October1st,2015

TheXLIVAnnualMeeting of the ItalianCrystallographicAssociation (AIC)was held inVercelli (September14-18th,2015)by theUniversitàdelPiemonteOrientaleAmedeoAvogadro.The conference is located in therenewedComplessoUniversitarioSanGiuseppe,PiazzaS.Eusebio5.The program, selected by the Scientific Committee, encouraged the discussion on emerging methods incrystallography, opening new fields for the investigation of the condensed matter world. Crystal Growth,Nanoscalephenomena,Organic,InorganicandBiomolecularSystemsarestudiednotonlyasstructuralimagesbut also inmotion,whileworking asChemicalMachines.Several events enriched the program: two satelliteworkshops on emerging topics in materials science [Program] and structural biology [Program] describednew possible ways of exploring the crystallographic world. The contributions, also from the scientificviewpoint,ofseveralcompanies,theSoftwareFayre,themeetingoftheCSDusersinItalyandaRoundTableonthelegacyoftheIYCrinItalyfurtherenrichtheconferenceprogram.[FullProgramDownload]Almost 90 abstract were submitted and the final number of registrations (including the satellites events)reached170peopleandmanyguests,fromoutsideItaly,enrichedthescientificprograms.Theuseof printeddocumentswas limited asmuch as possible to reduce the environmental footprint of theconference.Ononehand,thebookofabstractwasgivenonlyasdigitaldocument(forlaptop,e-bookreadersandmobile devices). On the other hand,most of the logistic information before and during the conferenceweregivenbymailorby theFacebookConferencepage,wherealsomanypicturesareavailable.Please likeandshareit!

GiuseppeZanotti-AICPresidentMarcoMilanesio-ChairofOrganizingCommitteeGianlucaCroce–WebsitemanagerandBookofAbstracteditor

ScientificCommitteeMarcoMilanesio (Chair);GiuseppeZanotti (AICPresident);EnricoMugnaioli;MauroGemmi;PatriziaRossi;SilviaRizzato;AngelaAltomare;AntoninoMartorana;AlessandroGualtieri;DorianoLamba

OrganizingCommitteeMarco Milanesio (Chair); Giovanni Ferraris (Honorary Chair); Simona Galli (Treasurer); Gianluca Croce;DomenicaMarabello;DavideViterbo;LucaPalin;EleonoraConterosito;ValentinaToson;EnricoBoccaleri

SteeringCommitteeGiuseppe Zanotti (AIC President); Michele Saviano; Diego Gatta; Simona Galli ; Annalisa Guerri; ConsigliaTedesco;MicheleZema;AntoniettaGuagliardi;AndreaZappettini;MarcoMilanesio

2

GOLDMEDALMARIOMAMMI

ThingsDoneandThingsYetToBeDone:CrystallographyatLarge,2015-2030

AngeloGavezzottiUniversitàdegliStudidiMilano

Having been active in the field for the last 45 years, the author presents a brief but substantial list ofaccomplishments:forexample,fromonemonthtoonehourforanX-raycrystalstructure,andtheextractionofcrucialinformationonchemicalstructureandchemicalbondingfromtheorganic,organometallic,inorganicand protein Databases. Topics that await further progress are fortunately more numerous, ensuring acontinuingbusinessforthefuturecrystallographer.Theauthorspeculatesonawishlist,atthetopofwhichisthepredictionandcontrolofthebirthandstructuringofcrystallinesolidsbycoagulationfromtheotherstatesofmatter,chiral resolutionbeingafringebenefit.Alongwithsomepromisingresults,acaveat isgivenaboutwrongpathspresentlybeing taken in thisdirection: chemistry is doneby electrons, and lookingat distancesbetweennucleiisnotgoingtohelp.

3

MARIONARDELLIPRIZE

CrystalEngineeringon“Tailor-Made”MultifunctionalZirconiumPhosphonates

FerdinandoCostantinoa,baDipartimentodiChimica,BiologiaeBiotecnologie,UniversitàdegliStudidiPerugia,Italy

bCNR-ICCOM,Firenze,Italy.ferdinando.costantino@unipg.itCrystal engineering is defined as the design and synthesis of molecular solid-state structures with desiredproperties,basedontheunderstandingandexploitationofintermolecularinteractions.Zirconiumphosphonatescanbeconsidered“tailor-made”materialsthatcanbedesignedbyexploitingthecrystalengineeringprinciples.They have been extensively used for many applications in solid state chemistry, such as heterogeneouscatalysis, nanocomposites chemistry, ion- exchange and separation and intercalation. The interest on thesematerialsmainly resideson theirhigh insolubility andon their chemicalversatility.This classof compounds,widelydevelopedfromthebeginningofthe70’s,islivingasecondyouthintherecentyearsduetotheuseofnovelandmoresophisticatedphosphonicligands.However, theirhighinsolubilityalsorepresentsadrawbackfortheircorrectstructuralcharacterizationandfor thecomprehensionof thestructure/reactivityrelationship.Indeed, thepossibilitytogetsinglecrystalsfromthesematerials isextremelylowandthereforeonlyab-initioXRPDstructuredeterminationmethodscangivesuitableinformationontheirstructure.Inthiscontributionasurvey on the structure and reactivity of zirconium phosphonates with layered and three dimensional openframework compounds is reported. A special attention will be devoted on the ab-initio XRPD structuredetermination methods working in the real space. The crucial role of the synthetic conditions and of non-covalentinteractionsasstructuralorientatingfactorswillbealsodiscussed.[1]R.Vivani,G.Alberti,F.Costantino,M.Nocchetti,MicroporousMesoporousMater.2008,107,58−70.[2]M.Taddei,F.Costantino,R.Vivani,S.Sabatini,S.-H.Lim,S.M.CohenChem.Commun.2014,50,5737-5739.

4

PHD'STHESISAWARDINCRYSTALLOGRAPHY

NewFormsofPolarandSpinOrderinginPb2(Mn,Co)WO6DoublePerovskites:SymmetryAnalysisofFerroicProperties

OrlandiFabioDipartimentodiChimica,UniversitàdiParma,ParcoAreadelleScienze17/A,43124Parma,Italy

fabio.orlandi@nemo.unipr.itInrecentyears,thescientificcommunityfocusedonthestudyofnewmultifunctionalmaterials,inwhichthesimultaneouspresenceofdifferentfunctionalitiescanmakecompoundsusefultofabricatesingledevicesableto handle several tasks. In this framework themultiferroicmaterials occupy a special place. In this type ofsystemsthesymmetryconstrains,dictatedfromthemagneticpointgroup,playanessentialroleregulatingallthe physical properties and in particular the magneto-electric coupling. In this talk I present the study ofdouble perovskite compounds, Pb2(Mn,Co)WO6, that reveals a complex and interesting magneto-electricmultiferroic character.Thework is basedon the accurate analysisof themagnetic symmetry, exploiting theuse of the coloured groups [1] and its generalization to the superspace formalism [2,3], joined with acomprehensive physical characterization, finally allowing to define in detail the complicated picture of thesystem properties. The study is mainly focused on the two end members of the solid solution and on theintermediatecompositioncontaininga60/40ratioofthetwoBsitecations.ThePb2MnWO6 compound displays a ferrielectric state characterized by the presence of two independentlead sublattices [4]. By lowering the temperature the system exhibits twomagnetic phase transitions and amagneticgroundstatecharacterizedbyanincommensuratetocommensurate(IC/C)magneticphasetransitionat 8K [5].Themagnetic structurewas solvedby theuseof the superspace formalism that allows to easilycharacterizetheIC/Ctransition.ThePb2Mn0.6Co0.4WO6compoundshows,atroomtemperature,acentrosymmetricorthorhombicstructure,defininganantiferroelectricsystem.Thecompoundpresentsafirstmagnetictransitionat190Kcharacterizedbyashortrangeordering,whereasasecondlong-rangemagnetictransitionisobservedat9K.Thelong-rangemagneticmodelisanantiferromagneticcollinearstructureshowinganacentricmagneticspacegroupimplyingthepresenceofaspontaneouselectricalpolarization,confirmedbypyroelectricmeasurements.Thecombineduse of the magnetic symmetry and of the electrical characterization suggests that the symmetric exchangestrictionmechanismisatthebasisoftheobservedphenomena.The cobalt endmember presents an incommensuratemonoclinic phase at room temperature undergoing, at230K,aphasetransitiontoanorthorhombicstructure.Themagneticsymmetryanalysis indicatea transitionto an incommensurate spin structure below 12 K, suggesting the presence of a spontaneous electricalpolarizationbelowthemagnetictransition.

[1]Shubnikov,A.V.,Belov,N.V.&others,1964(Oxford:PergamonPress1964)[2]PetricekV,FuksaJ.andDusekM.ActaCryst.2010,A66,649–655[3]Perez-MatoJ.M.,RibeiroJ.L.,PetricekV.andAroyoM.I.J.Phys.:Condens.Matter2012,24,163201.[4]OrlandiF.;RighiL.;CabassiR.;DelmonteD.;PernecheleC.;BolzoniF.;MezzadriF.;SolziM.;MerliniM.andCalestaniG.Inorg.Chem.2014,53,10283−10290.[5]OrlandiF.,RighiL.,RitterC.,PernecheleC.,SolziM.,CabassiR.,BolzoniF.andCalestaniG.J.Mater.Chem.C,2014,2,9215-9223

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PLENARYLECTURES

PL1.NewAdvancesinElectronDiffraction:fromAb-initioStructureSolutiontoRefinement

LukášPalatinusInstituteofPhysicsoftheASCR,Prague,CzechRepublic.palat@fzu.cz

Crystallography isabroadsubjectwithdiversesub-fieldsandmanydifferentoutcomes.Nevertheless, in theheart of crystallography there is still the search for the answer to the question Where are the atoms…Crystallographicinvestigationsusingelectrondiffractionhavebeenusedtoassist infindingthisanswersincemany decades ago.However, until recently, electron crystallography has been generally considered a usefulcomplementtoothermethods,butnotself-standing,independentmethodforstructureanalysis.This statusof electron crystallographyhas changedverymuchover the last decade.The changewasmadepossible by two key developments – electron diffraction tomography (EDT) and precession electrondiffraction(PED).EDTisawayofcollectingthree-dimensionaldiffractiondatafromasinglenanocrystalbyrotatingthecrystalaroundthegoniometeraxisinsmallsteps,andacquiringthediffractionimageateachstep[1,2].This approach is equivalent to the rotating crystalmethodused commonly also in single-crystal x-raydiffraction.Incontrast to the traditionalcollectionoforienteddiffractionpatterns,EDTdataset iseasierandquicker to collect, and, more importantly, it is much more complete. Moreover, because special zone-axispatternsareavoided,dynamicaldiffractioneffectsare suppressed in suchadata set.Further suppressionofthedynamicalcharacterof thediffracted intensitiescanbeachievedbyemployingPED.Althoughdevelopedalready in 1994 [3], it has become popularmuch later, and the real boom of its use has come after it wasassociatedwithEDT[4].EDTdatasets,possiblycombinedwithPED,yield3Ddiffractiondatasuitableforabinitiostructuresolutionby methods entirely equivalent to the procedures used in x-ray single crystal diffraction. Since itsdevelopment, a large number of structures have been solvedwith thismethod. Themain advantage of thisapproachisthepossibilitytoperformafullsingle-crystalexperimentonasinglemicro-orevennano-crystal.Themaindisadvantage is that thedynamical diffraction effects cannotbe entirely suppressed, andusing thekinematical theory of diffraction is just a very coarse approximation. Therefore, the quality of theab initiostructure solution is in general lower than from x-ray diffraction data. For the same reason the standardstructurerefinementyieldshighfiguresofmeritandrelativelyinaccuratestructuremodels.A remedy to the problem of kinematical approximation is the use of full dynamical diffraction theory in therefinement process. The refinements using dynamical diffraction theory aremore time consuming, but theylead to more reliable and more accurate structure refinements [5]. The accuracy of such refinements cancompetewiththerefinementsagainstx-raydiffractiondata,especiallyifonlypowderdataareavailable.Thedevelopmentsof the last fewyears,startingfromtheadoptionofEDTmethodsandprecessionelectrondiffraction, throughab initio structure solution to the accurate refinementusingdynamicaldiffraction theorymean that electron crystallography nowoffers to the crystallographic community a newwonderful tool – afullandaccuratestructureanalysisfromasinglenanocrystalassmallasfewtensofnanometres.[1]U.Kolb,T.Gorelika,C.Kübelb,M.T.Ottenc,D.Hubert.,Ultramicroscopy107,507(2007)[2]W.Wan,J.Sun,J.Su,S.Hovmoller,X.Zou.,J.Appl.Cryst.46,1863(2013)[3]R.Vincent,P.A.MidgleyUltramicroscopy53,271(1994)[4]E.Mugnaioli,T.Gorelik,U.Kolb,Ultramicroscopy109,758(2009)[5]L.Palatinus,V.Petricek,C.A.Correa,ActaCryst.A71,235(2015)

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PL2.Ab-initioModelinginCrystallographyBartolomeoCivalleri,aAlessandroErba,a,JeffersonMaul,aRobertoOrlando,aRobertoDovesia

aDipartimentodiChimica,UniversitàdiTorino,Torino,ItalySince the advent of the Kohn-Sham formalism 50 years ago, Density Functional Theory has shown aparamount success in the ab initiomodelling of solids fromphysics to chemistry, frommaterials science tocrystallography.Here, we will show how ab initio modelling, by means of DFT methods, can be used to predict variuosproperties of crystalline systems and how results can be fruitfully used by crystallographers and non-crystallographerstobetterunderstandtheirphysicalproperties.Exampleswillbereportedforthepredictionofstructure,vibrationalfeatures,ADPs,thermodynamicproperties,linearandnonlinearopticalproperties,chargedensitystudiesofdifferentcrystallinesolidsrangingfrommolecularcrystalstometal-organicframeworks.Allreportedresultshavebeencomputedbymeansoftheperiodicab-initioprogramCRYSTAL14[1,2].[1] R. Dovesi, R. Orlando, A. Erba, C. M. Zicovich-Wilson, B. Civalleri, S. Casassa, L. Maschio, M.Ferrabone,M.De La Pierre, P. D’Arco, Y.Noel,M. Causa,M. Rerat, B. Kirtman, Int. J. QuantumChem.2014,114,1287.[2]R.Dovesi,V.R.Saunders,C.Roetti,R.Orlando,C.M.Zicovich-Wilson,F.Pascale,B.Civalleri,K.Doll,N. M. Harrison, I. J. Bush, P. D’Arco, M. Llunell, M. Causà and Y. Noël, CRYSTAL14 User's Manual,UniversityofTorino,Torino,2014.(http://www.crystal.unito.it)

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PL3.WatchingMatterinMotion:TimeResolvedStudiesfromSynchrotronstoFELs

MarcoCammarataDepartmentofPhysics,CNRS/UniversityofRennes1,Rennes,France

marco.cammarata@univ-rennes1.frAtoms move in the tens of fs time scale (1fs = 10-15 s). While synchrotrons have long been used tounderstand kinetics, only recentlyXFELs are opening the doors towards the dynamical aspect ofmatter. Inthis contribution, Iwill briefly introduce fast (synchrotrons) andultrafast (XFEL)X-ray sourceswith somekeyparametersfortimeresolvedstudies.Iwillthenshowhowtechniquesrangingfromsolutionscatteringtocrystallography andX-ray absorption have been applied to study chemical reactions, biophysical processes,andmaterials.

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PL4.ElectronDiffractionandImagingofProteinandPharmaceutical3DNanocrystals

JanPieterAbrahamsa,baPaulScherrerInstitute,CH-5232Villigen,Switzerland.

bCenterforCellularImagingandNanoAnalytics,Biozentrum,UniversityBasel,DepartmentforBiosystemsScienceandEngineering,CH-4058Basel,Switzerland.jan-pieter.abrahams@psi.ch;

janpieter.abrahams@unibas.ch

High-energyelectronsprovide1000timesmoreinformationperGray(absorbedenergy,i.e.radiationdamage),comparedtoX-rays.HenceelectronsoutperformX-raysforstructuredeterminationwhenradiationdamageisthelimitingfactor.Unlike X-rays, electrons can not only be diffracted, but also imaged. However, when imaging transparentsamples, the total number of quanta per unit area determines the signal-to-noise ratio. When diffractingtransparentsamples,thenumberofinteractingquantaperunitareadeterminesthesignal-to-noiseratio.Measuringelectrondiffractionaccuratelyhasonlyrecentlybecomepossiblewiththeadventofquantumareadetectors.OneofthechallengesisthatanelectronmicroscopeisfloodedwithphotonradiationresultingfromBremsstrahlunggeneratedbythehigh-energyelectrons.Only an area detector that can discriminate between photon noise and electron signal is insensitive to thisnoise. This difference in signal-to-noise ratio was demonstrated in practice for electrons using a Timepixquantumareadetector.When imaging a 100 nm thick lysozyme protein crystal with electrons, typically one to two images of thesame location could be measured with significant details up to 3.5Å resolution. Subsequent images hadsufferedtoomuchfromradiationdamagetoshowsuchdetail.When diffracting similar crystals, hundreds of electron diffraction patterns with Bragg spots beyond 3 Åresolution could be measured from the same location. However, there is no such thing as a free lunch.Diffractioncomesataprice: thestructurefactorphasesare lost.Theycanonlyberetrievedusingadditional(prior)information,forinstanceobtainedfrom(afew)electronimages.Wedemonstratedthisstrategybyphasingthe3Dstructurefactorsofanano-crystallineamyloidicpeptide.

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MS1.ADVANCEDTHEORETICALANDEXPERIMENTALMETHODSINCRYSTALLOGRAPHY

TheMSfocusesonthemostrecentandinnovativemethodologicalapproachesdevelopedincrystallography,intheoretical,computingandexperimental field. Itcovers traditionalx-raycrystallographicmethodsaswellascomplementarytechniques(scattering,spectroscopic,calorimetric,molecularmodeling,microscopy,etc.).MS1spansfromsinglecrystaltomicro-andnano-powder,fromsmallmoleculetomacromolecule.Chair:AngelaAltomare(ICCNRBari)

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1KN1.Advancesinmethodsformacromolecularstructuresolution:abinitioandMRapproaches

BenedettaCarrozzini,aMariaCristinaBurla,abRoccoCaliandro,aGiovanniLucaCascarano,a

CarmeloGiacovazzo,aAnnamariaMazzone,aGiampieroPolidoriaaIstitutodiCristallografia(IC),CNR,Bari,Italy

bDipartimentodiFisicaeGeologia,UniversitàdegliStudidiPerugia,Perugia,Italybenedetta.carrozzini@ic.cnr.it

Newmethodshavebeenrecentlydevelopedtoimprovethestructuresolutionofmacromoleculesbyab initio(PattersonorDirectMethods)andnonabinitio(MolecularReplacement)approaches.Phasingproteinsatnon-atomic resolution is still a challenge for anyab initiomethod.The combined use ofdifferent algorithms [Patterson deconvolution and superposition techniques, cross-correlation function (C-Map), theVLD (Vive laDifference) approach included in theDirect SpaceRefinement (DSR) procedure, anewprobabilisticformulaestimatingtripletinvariantsandcapableofexploitingamodelelectrondensitymaps,theFREELUCH extrapolationmethod, anewFOM to identify the correct solution] allow to overcome thelack of experimental information. The new methods [1,2] have been applied to a large number of proteindiffractiondatawithresolutionupto2.1Å,under thecondition thatCaorheavieratomsare in thestructure.Results show that solving proteins at limited resolution is a feasible task, achievable even by new DirectMethodsalgorithms,againstthetraditionalcommonbelievethatatomicresolutionisanecessaryconditionforthesuccessofadirectabinitiophasingprocess.Anewprocedure(REVAN)[3,4],aimingatsolvingproteinstructuresviaMolecularReplacementanddensityguidedoptimizationalgorithms,hasbeenassembled.Itcombinesavarietyofprograms(REMO09,REFMAC,COOT) and algorithms (Cowtan-EDM, DSR, VLD, FREE LUNCH), and can successfully lead to thestructure solution alsowhen the sequence identity between target andmodel structures is smaller than 0.30and data resolution up to ~ 3Å. The application to a wide set of test structures (including difficult casesproposed by DiMaio et al. [5], solved by using MR procedures together with energy guided programs)suggests that REVAN is quite effective even far from atomic resolution and, in combination with EDMtechniques and sequence mutation algorithms, it is able to efficiently extend and refine the set of phases,reducingitsaverageerror.The final step of the automatic solving process (ab initio or MR approaches) is the application of anAutomatedModelBuildingprogram(i.e.Buccaneer,Nautilus,ARP-wARPorPhenix-Autobuild) in order torecoverthecorrectstructure.ResultssuggestthatthequalityofthephasesattheendofthephasingprocessisgoodenoughtoleadtheAMBprogramtosuccess.ThesenewefficientproceduresareimplementedinthecurrentversionofthesoftwarepackageSIR2014[6].[1]R.Caliandro,B.Carrozzini,G.L.Cascarano,G.Comunale,C.Giacovazzo&A.MazzoneActaCryst.D201470,1944-2006.[2]M.C.Burla,B.Carrozzini,G.L.Cascarano,C.Giacovazzo&G.PolidoriJ.Appl.Cryst.2015,submitted[3]B.Carrozzini,G.L.Cascarano,G.Comunale,C.GiacovazzoC.&A.MazzoneActaCryst.D 2013 69,1038-1044.[4]B.Carrozzini,G.L.Cascarano,C.GiacovazzoC.&A.MazzoneActaCryst.D2015,submitted.[5]F.DiMaio,T.C.Terwilliger,R.J.Read,A.Wlodawer,G.Oberdorfer,U.Wagner,E.Valkov,A.Alon,D.Fass,H.L.Axelrod,D.Das,S.M.Vorobiev,H.Iwai,P.R.Pokkuluri&D.BeckerNature,2011,473,540-543.[6] M.C. Burla, R. Caliandro, B. Carrozzini, G.L. Cascarano, C. Cuocci, C. Giacovazzo, M. Mallamo, A.Mazzone&G.PolidoriJ.Appl.Cryst.201548,306-309.

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1KN2.AdvancesinmicrostructureanalysisofmaterialswithdefectsMatteoLeoni,a

aDICAMUniversitàdegliStudidiTrento,Trento,Italymatteo.leoni@unitn.it

Inawidenumberoftechnologicallyrelevantcases,thefeaturespresentinthediffractionpatterncanhardlybedescribedusingmodern toolssuchas theRietveldmethod.Broad,asymmetricoranisotropicpeakshapesordisplacementof thepeaksfromtheirexpectedpositionsaresomeofthemostcommonmanifestationsof themicrostructureofthematerial.When the defects are diluted, the effects of structure andmicrostructure clearly contribute, respectively, totheintegratedintensityandtheprofileshape.This isaconsequenceof thepeculiar3Dnatureof theproblemand of the Fourier transform relationship between real and reciprocal space.When the quantity of defectsincreases, we can enter the regime where the global lattice approximation is no longer sustainable:configurationentropyandcomplexitystartplaying their role.Alocaldescription isstillpossible,but the localviewis insufficient todescribeagivenspecimeninfull.StochasticprocessessuchasMarkovchainscanbeemployed as compact descriptors to link the local to the global structure: the diffraction pattern providesinformationonagivenspecimenandisnolongerexpectedtobeuniqueforagivenmaterial.Wewillinvestigatesomerecentadvancesinmicrostructureanalysis[1],leadingtoaunifiedformalismfortheRietveld[2],WPPM[3]andmatrixmethods[4].[1]R.J.Koch,M.LeoniScientificReports.2015.Submitted.[2]R.A.Young,TheRietveldMethod,OxfordUniversityPress,Oxford,1993.[3]P.ScardiandM.Leoni,ActaCrystallogr.A2002,58,190.[4]V.A.Drits,C.Tchoubar,X-RayDiffractionbyDisorderedLamellarStructures.TheoryandApplicationstoMicrodividedSilicatesandCarbons,Springer-Verlag,Berlin,Heidelberg,NewYork,1990.

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1O1.QuantumMechanicalSimulationOfProteinCrystals:TheCaseOfTheSmallProteinCrambin

MassimoDellePianea,MartaCornoa,RobertoOrlandoa,PieroUgliengoa,RobertoDovesiaaUniversityofTorino,DepartmentofChemistry,viaP.Giuria7,10125Torino,Italy

massimo.dellepiane@unito.itMolecular simulations of proteins have been usually accomplished through empirical or semi-empiricalpotentials, due to the large size and inherent complexity of these biological systems. On the other hand, atheoretical description of proteins based on quantum-mechanical methods would provide an unbiaseddescription of their electronic properties, possibly offering a precious link between these and the finalbiological activity. Yet, such approaches have been historically hindered by the large amount of requestedcomputationalpowerandlimited,inpractice,tomixedQM/MMsimulations.Herewedemonstrate the applicationof theperiodicDensityFunctionalTheoryCRYSTAL14code [1], in itsefficient massively parallel version [2], to the description of the small plant’s seed protein crambin (46aminoacids)crystal,acommontestcase.WehaveemployedtheaccuratehybridB3LYPfunctional,coupledtoanempiricaldescriptionofLondon interactions (D*) tooptimize thecrambincrystalgeometry,startingfromanhighresolutionneutrondiffractionstructure[3],withan increasingamountofwatermolecules in thecell(up to 172H2O/cell, close to the actual crambin crystal). A good agreement with the experiment has beenachievedforbothproteingeometryandprotein-waterinteractions(seeFigure1).Inclusionofwaterprovedtobe essential for a correct description of the system. The energetics has been computed, obtaining accuratecrystal formation energies, protein-water, protein-protein and water-water interaction energies. The uniqueinformationobtainedfromafullyab-initiotreatmentofthesystemallowedtostudytheelectronicpropertiesofthe protein, such as its electrostatic potential and the charge transfer involved in its interactionwith water.Finally, the full infra-red spectrum of crambin has been modeled. These results proved that quantum-mechanical simulationsof smallproteinsarenowpossible ina reasonableamountof time, thanks tomodernHighPerformanceComputingarchitectures.

Figure1.Superpositionofexperimental(red)andB3LYP-D*optimized(blue)crambinstructures.

[1]Dovesi,R.;Orlando,R.;Erba,A.;Zicovich-Wilson,C.M.;Civalleri,B.etal.Int.J.QuantumChem.2014,114,1287[2]Orlando,R.;DellePiane,M.;Bush,I.J.;Ugliengo,P.;Ferrabone,M.;Dovesi,R.J.Comput.Chem.2012,33,2276.[3]Chen, J.C.-H.;Hanson,B.L.;Fisher,S.Z.;Langan,P.;Kovalevsky,A.Y.Proc.Natl.Acad.Sci. 2012,109,15301.rni

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1O2.Experimentalandtheoreticalchargedensitystudyofiodoperfluoroalkylimidazolesself-assembledthroughhalogenbond

AlessandraForni,aDavideFranchini,bStefanoPieraccini,a,bMaurizioSironi,a,bGiancarloTerraneo,cPierangeloMetrangolo,cGiuseppeResnati,cYuriiL.Yagupolkiid

aCNR-ISTM,InstituteofMolecularSciencesandTechnologies,Milan,ItalybDipartimentodiChimica,UniversitàdegliStudidiMilano,Milan,Italy

cNFMLab,DCMICPolitecnicodiMilano,viaMancinelli7,20131Milan,ItalydNationalAcademyofScience,Ukraine,Inst.OrganicChem.,UA-02094Kiev,Ukraine

alessandra.forni@istm.cnr.itHalogen bonding, namely any noncovalent interaction involving halogens as electrophilic sites, is a relativelynew item in the supramolecular toolbox and shares numerous properties with the better known hydrogenbonding.ThetopologicalanalysisoftheX-raymultipolerefinedchargedensityprovedtobeaneffectivetoolto elucidate the nature of halogen bonding [1] and in general of intermolecular interactions responsible formolecularcrystalsformation.Wepresentheretheresultsobtainedontwoiodotetrafluoroethylimidazolederivatives,whosecrystalstructureisdominatedbyformationofI∙∙∙Nhalogenbondsbetweenequivalentmolecules,andstabilizedbythepresenceofF∙∙∙F,C–H∙∙∙F,π∙∙∙πandotherweakinteractions.Theexperimentalchargedensitieshavebeenderivedfromsingle-crystal X-ray data collected at 100 K, using the aspherical atom formalism of Stewart [2] asimplemented in VALTOPO [3], as well as by accurate DFT and MP2 molecular modeling calculations.Information such as the topological features and nature of the involved interactions, as derived fromtopological analysis of electron density and its Laplacian, and the interaction energies associated to halogenbondingandtheweakerinteractions,willbepresented.

Figure1.InteractionsNetworkinIodotetrafluoroethylimidazole[1] (a)R.Bianchi,A.Forni,T.Pilati,Chem.Eur.J.,2003,9,1631-1638; (b)R.Bianchi,A.Forni,T.Pilati,ActaCrystallogr.Sect.B,2004,60,559-568;(c)A.Forni,J.Phys.Chem.A,2009,113,3403-3412.[2]R.F.Stewart,ActaCryst.Sect.A,1976,32,565-574.[3]R.Bianchi,A.Forni,J.Appl.Cryst.,2005,38,232-236.

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1O4.StructuralcharacterizationofLDHsamplesbyADTandTGA-GC-MS:thermalresponseandcontaminationinnitrateandorganic-exchanged

hydrotalcitesEleonoraConterosito,aLucaPalin,aDiegoAntonioli,aDavideViterbo,aEnricoMugnaioli,b,cUteKolb,cLuana

Perioli,dMarcoMilanesioaandValentinaGianotti.aaDipartimentodiScienzeeInnovazioneTecnologicaandNano-SiSTeMIInterdisciplinaryCentre

UniversitàdelPiemonteOrientale.Alessandria,Italy.eleonora.conterosito@unipmn.itbDipartimentodiScienzeFisiche,dellaTerraedell'Ambiente,UniversitàdegliStudidiSiena

cInstitutfürPhysikalischeChemie,JohannesGutenbergUniversität,Mainz,Germany.dDipartimentodiScienzeFarmaceuticheUniversitàdegliStudidiPerugia,Perugia,Italy

eleonora.conterosito@unipmn.it

Layered double hydroxides (LDH) are versatile materials used for intercalating bioactive molecules, both inpharmaceutical, nutraceutical and cosmetic fields, with the purpose of protecting them from degradation,enhancing their water solubility to increase bioavailability, to improve pharmacokinetics properties andformulation stability. The crystal chemistry of hydrotalcite-like compounds is investigated byX-ray powderdiffraction (XRPD)[1], automated electron diffraction tomography (ADT)[2],[3] and hyphenated TGA-GC-MS [4] to shed light on the mechanisms involved in ion exchange and absorption of contaminants, mainlycarbonateanions.ForthefirsttimeADTallowedtoobtainastructuralmodelofLDH_NO3fromexperiment,shedding light on the conformation of nitrate inside LDH and on the loss of crystallinity due to the layermorphology. The ADT analysis of a hybrid LDH sample (LDH_EUS) clearly revealed the increase ofdefectivity in this material. XRPD demonstrated that the presence of carbonate is able to influence theintercalation of organic molecules into LDH, since CO3 contaminated samples tend to assume d-spacingsroughly multiples of LDH_CO3 d-spacing. TGA-GC-MS allowed distinguishing and quantifying intercalatedandsurfaceadsorbedorganicmolecules,confirmingthepresenceandamountofcarbonate,especiallyatlow(below2%inweight)concentrationsandseparatingthedifferenttypesandstrengthofadsorption,inrelationwiththetemperatureofelimination.

Figure1.LDH_NO3structurebyADT,anionexchangereactionmodelandTGA-GC-MSdata.[1]E.Conterosito,G.Croce,L.Palin,C.Pagano,L.Perioli,D.Viterbo,E.Boccaleri,G.Paul,M.Milanesio,Phys.Chem.Chem.Phys.2013,15,13418.[2]E.Mugnaioli,T.Gorelik,U.Kolb,Ultramicroscopy2009,109,758–65.[3]U.Kolb,E.Mugnaioli,T.E.Gorelik,Cryst.Res.Technol.2011,46,542–554.[4] V. Gianotti, D. Antonioli, K. Sparnacci, M. Laus, T. J. Giammaria, M. Ceresoli, F. Ferrarese Lupi, G.Seguini,M.Perego,J.Chromatogr.A2014,1368,204–10.

15

1O5.PolymerBrushesandTheirCompositeswithSilverNanoparticles:AnX-RayReflectivityandPositronAnnihilationSpectroscopyStudyGianluigiMarra,aStefanoAghion,bRafaelFerragut,bGiovanniConsolati,cGuidoPanzarasad

aEniRenewableEnergy&EnvironmentalR&D,Novara,Italy.gianluigi.marra@eni.combL-NESS,DipartimentodiFisica,PolitecnicodiMilano,PoloTerritorialediComo,Como,Italy

cDipartimentodiScienzeeTecnologieAerospaziali,PolitecnicodiMilano,Milano,ItalydDipartimentodiScienzeeInnovazioneTecnologica,UniversitàdelPiemonteOrientale,Alessandria,Italy

Stimuli-responsive polymer brushes loaded with plasmonic nanoparticles are perfect optical sensors fortemperature and pH. Probing the distribution of nanoparticles in brushes is of paramount importance toproperly investigate and correlate the properties of the resultant nanocomposites. However, conventionalcharacterization techniques do not allow to reach such insight, at least without damaging the sample (e.g.sectionelectronmicroscopy).Thatmakesobtainingadetailedcharacterizationofpolymerbrushesandoftheircompositeswithembeddednanoparticlesachallengingtask.HereweshowhowX-RayReflectivity (XRR)andPositronAnnihilationSpectroscopy(PAS)canbeused toobtaindeepinsightonthecharacteristicsofsuchcomplexsystemswithunprecedenteddetail.Botharenon-destructivetechniques.XRRisabletomeasurethicknessesontheorderof1nmintherange0÷200nm.Otherinformationssuchasmassivedensityandinterfaceroughnesscanalsobeobtained.PASisamore unconventional technique, based on the implantation of positrons in amatrix and on the study of theannihilationfeatures.TheusefulnessofPASforthestudyofpolymercompositesarisesfromitssensitivitytoholesanddefectswithnanometerandsub-nanometersizeandalsoon thepossibility toextractdetailson thechemicalcompositionoftheprobedenvironment.In this work, PAS has been applied for the first time to a nanocomposite obtained by loading silvernanoparticles (NPs) into “grafting-from”–prepared poly(dimethylaminoethyl methacrylate) brushes.PDMAEMAisaweakpolyelectrolyteandsincepositrons implantationdependsalsoon the ioniccharacterofthematerial, a rapid and accurate discrimination between protonated and deprotonated states was obtained.XRRoutputsprovidedbasilarinputtoallowPASdatafitting,makingpossibletoidentifychangesinthemassdensityof thebrushesfilmsembeddedwithsilverNPsandthe introductionofnewdefectsassociated to thebrushes/NPsinterface.

16

1P1.ModellingTheCarbonateSubstitutionInHydroxyapatiteTowardsBoneComposition

MartaCorno,aMassimoDellePiane,aFrancescaPeccati,bGianfrancoUlian,cGiovanniValdrè,cPieroUgliengoaaDipartimentodiChimica,UniversitàdegliStudidiTorino,viaPietroGiuria7,10125,Torino,Italy

bDepartamentdeQuímica,UniversitatAutònomadeBarcelona,Bellaterra,08193,SpaincDipartimentodiScienzeBiologiche,GeologicheeAmbientali,UniversitàdiBologna“AlmaMater

Studiorum”,PiazzadiPortaSanDonato1,40126Bologna,Italy.marta.corno@unito.itHydroxyapatite[HA,Ca10(PO4)6(OH)2]isthemainconstituentoftheinorganicphaseofbonesandteethandis studied and applied as a biomaterial for tissues repairing and reconstructing. The biological HA ischaracterizedbythepresenceofvacanciesanddefects,themostrelevantbeingthecarbonateionsubstitutionin the lattice (about 6% in weight). The CO3

2- ion can be accommodated either in place of the hydroxylgroups (typeAdefect) or of thephosphategroup (typeB)of theunit cell.Thedetailedknowledgeof thesepossible HA defective structures has recently become fundamental to design improved prosthetic materials,since the carbonate incorporation can influence the adsorption processes at the mineral surface in thebiologicalenvironment.Theoreticalmethodscanbesuccessfullyappliedtoprovidestructuralinformationandsurfacepropertiesandtoofferacomparisonwithexperimentalmeasurements.In the present contribution, some recent results of our computational study on the role of carbonate ion inbothfullyandpartiallycarbonatedhydroxyapatitewillbepresented.Staticcalculationsat theDFTlevelhavebeen run to simulate structural, electronic and vibrational bulk properties of theA-,B- andAB-type defects[1,2,4].Moreover, ab initiomolecular dynamics simulations have been employed to provide insights on theCO3

2−mobility [3].Work is in progress tomodel and characterize different surfaces of carbonated apatite,bothplainandininteractionwithbiologicallyinterestingmolecules.

Figure.1.FullycarbonatedHAunitcell[Ca10(PO4)6CO3]viewedalongthec(left)anda(right)axes.[1]G.Ulian,G.Valdrè,M.Corno,P.Ugliengo,Amer.Miner.2013,98,410.[2]G.Ulian,G.Valdrè,M.Corno,P.Ugliengo,Amer.Miner.2013,98,752.[3]F.Peccati,M.Corno,M.DellePiane,G.Ulian,P.Ugliengo,G.Valdrè,J.Phys.Chem.C2014,118,1364.[4]G.Ulian,G.Valdrè,M.Corno,P.Ugliengo,Amer.Miner.2014,99,117.

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1P2.ChemicalselectivityinstructuredeterminationbytimedependentanalysisofinsituXRPDdata:aclearviewofXethermalbehaviorinsidea

MFIzeoliteLucaPalin,a,bRoccoCaliandro,cDavideViterbo,aMarcoMilanesioa,*

aDipartimentodiScienzeeInnovazioneTecnologica,UniversitàdelPiemonteOrientale‘‘A.Avogadro’’(Italy),ViaMichel11,I-15121Alessandria,Italy.E-mail:marco.milanesio@uniupo.itbNovaRess.r.l.,ViaDoloresBello3,28100Novara,Italy(http://www.novares.org)

cInstituteofCrystallography,CNR,viaAmendola122/o,Bari70126,Italy.X-ray diffraction methods in general provide a representation of the average structure, thus allowing onlylimitedchemicalselectivity.Asrecentlyshown[1],somestructural informationonasubsetofatomscanbeobtained by modulation enhanced diffraction (MED), thus proposing a new tool that is able to enhanceselectivityindiffraction.MEDusesaperiodicstimulussuppliedinsituonacrystal,whilediffractiondataarecollected continuously during one ormore stimulation periods. Such large data sets can then be treated bydifferentmethods.Herewepresent andcomparePhaseSensitiveDetection (PSD)andPrincipalComponentAnalysis(PCA)forinsituX-raypowderdiffraction(XRPD)datatreatment.TheapplicationofPCAtoMEDdata isdescribed for the first time in thepresentpaper.Simulated and experimentalMEDpowder datawereproducedbyusinganMFIzeoliteas static spectator, inwhichXe,actingasactive species, is adsorbedanddesorbedinaperiodicmanner.MEDallowedobtaining,bydemodulatingfirstsimulatedandthenexperimentaldata, the powder diffraction pattern of the responding scattering density, and selectively extractingcrystallographic informationonXebysolving thecrystalstructureof theactivespecies independentlyof thestatic zeolite framework. The “real world” experiments indicated that the PSD-MED approach has somelimitationsrelated to thedegreeof fulfilmentofsometheoreticalassumptions.Whenapplied to insituXRPDdata,PCA,despitebasedonblindstatisticalanalysis,gaveresultssimilartothoseobtainedbyPSD(basedonFourier analysis) for simulated data. Moreover, PCA is complementary to PSD, thanks to its capability ofgathering information on theXe substructure even in the presence of a non-periodic stimulus, i.e. using forinstance the most simple stimulus shape as a single temperature ramp. In particular PC1 resulted able toperfectly reproduce the corresponding 1Ω signal from a traditional PSD analysis. Moreover PCA can beapplied directly to raw non periodic XRPD data, opening the possibility of using it during an “in situ”experiment. PCA can thus be envisaged as a very useful fast and efficient tool to improve data collectionstrategyand tomaximizedataquality and their information content.To date however PSD remains superiorforsubstructuresolutionfromanalysisof2Ωdemodulateddata[2].[1]D.Chernyshov,W.vanBeek,H.Emerich,M.Milanesio,A.Urakawa,D.Viterbo,L.Palin,R.Caliandro,ActaCryst.2011,A67,327-335.[2] L. Palin, R. Caliandro, D. Viterbo, M. Milanesio, Physical Chemistry Chemical Physics, 2015, DOI:10.1039/C5CP02522B

18

1P3.NewadvancesofQUALX2.0,aqualitativephaseanalysissoftwarequeryingafreelyavailabledatabase

AngelaAltomare,aNicolaCorriero,aCorradoCuocci,aAureliaFalcicchio,aAnnaMoliterni,aRosannaRizziaaIC-CNR,SedediBari,ViaAmendola122/o,70126Bari,Italy.nicola.corriero@ic.cnr.it

Phaseidentificationofcrystallinematerialsbypowderdiffractiontechniqueisausefulapplicationindifferentscientificfields(e.g.,organicandinorganicChemistry,Mineralogy,Pharmaceutics,materialsscience,culturalheritage,..)aswellasinindustrialsectors(e.g.,controlofqualityofdrugs).QUALX[1]isaqualitativephaseanalysisfreesoftwarequeryingthePDF-2commercialdatabase,maintainedandupdated by ICDD [2]. It is a computer program searching for the database single-phase pattern(s) bestmatchingtheexperimentalpowderdiffractiondata.QUALX2.0 [3] is theupdatedversionofQUALX.QUALX2.0canperformall theprocedurescarriedoutbyQUALX and its main feature is querying also a freely available database (POW_COD). Consequently,QUALX2.0 is the only qualitative phase analysis program freely distributed and based on a free database.POW_CODisgeneratedbythestructureinformationcontainedintheCrystallographyOpenDatabase(COD)[4], an open-access collection of crystal structures of inorganic, metal-organic, organic compounds andminerals,continuouslygrowing(currentlyCODcontainsmore than315000entries).POW_CODisexportedinSQLite3format.Other novelties ofQUALX2.0: i) the possibility of reading a larger variety of formats of the experimentaldiffractionpatternASCIIfile,ii)newsearch-matchoptions.Since November 2014, QUALX2.0 and POW_COD are available at http://www.ba.ic.cnr.it/content/qualx-downloads, free for academic and non- profit research institutions after registration (number of downloads400).Veryrecently,newfeatureshavebeenintroducedinQUALX2.0concerningthepossibilityofactivelyusinginthe search-match process restraints on cell parameters, crystal density and/or symmetry. The structure ofPOW_CODhasbeensuitablyoptimizedinordertomakethesearchwithrestraintsfastandefficient.ThemainproceduresofQUALX2.0, its new features and some applications to experimental diffraction datawillbeoutlined.[1]A.Altomare,C.Cuocci,C.Giacovazzo,A.Moliterni,R.RizziJ.Appl.Cryst.200841,815.[2] ICDD The Powder Diffraction File. International Center for Diffraction Data, 12 Campus Boulevard,NewtonSquare,Pennsylvania19073-3273,USA,2003.[3]A.Altomare,N.Corriero,C.Cuocci,A.Falcicchio,A.Moliterni,R.RizziJ.Appl.Cryst.201548,598.[4]S.Grazulis,D.Chateigner,R.T.Downs,A.F.T.Yolochi,M.Quiros,L.Lutterotti,E.Manakova,J.Butkus,P.Moeck,A.LeBailJ.Appl.Cryst.200942,726.

19

MS2.INVESTIGATINGSTRUCTURE-PROPERTYRELATIONSHIPSINCOMPLEXMOLECULARSYSTEMSBYAMULTI-TECHNIQUE

APPROACH

The MS concerns the application of complementary techniques to study structure-property relationships indifferentclassesofcomplexmolecularsystemssuchas,forexample,MOForco-crystals.Chair:PatriziaRossi(U.Firenze)

20

2KN1.Newinsightintothepropertiesofindomethacinpharmaceuticalco-crystals

ValeriaFerretti,aAlessandroDalpiaz,aValerioBertolasi,aBarbaraPavanbaDipartimentodiScienzeChimicheeFarmaceutiche,UniversitàdegliStudidiFerrara,Ferrara,ItalybDipartimentodiScienzedellaVitaeBiotecnologie,UniversitàdegliStudidiFerrara,Ferrara,Italy.

frt@unife.itInthelastyears,thesynthesisofco-crystalscontainingactivepharmaceuticalingredients(APIs)hasbecomethe new frontier of the crystal engineering due to the great opportunity to modify the physico-chemicalpropertiesofsolidformsofdrugs.Actually, thepharmaceuticalco-crystalsdisplayintermolecularmotifsandhencecrystalstructuredifferentfromthepureAPIcomponent,andconsequentlycanexhibitdiversespecificphysicalproperties,suchassolubilityanddissolutionrate.Since the therapeuticefficacyofapharmaceuticalformulation depends on its bioavailability, i.e. the absorption extent and rate of the active pharmaceuticalingredient into the bloodstream following its administration, the solubility and dissolution properties of co-crystalscanallowtoincreasethebioavailabilityofpoorlywatersolubleAPIs.Even though it is currently believed that the co-crystallization strategy should not induce changes on thepharmacological profile of theAPIs, it is not yet clearwhether a co-crystalwould be defined as a physicalmixtureorasanewchemicalentity.Inorder toclarify theseaspects,wechoseindomethacin(Figure1a)asguestpoorlyaqueoussolublemoleculeandcompareditspropertieswiththoseofitscocrystalsobtainedwith2-hydroxy-4-methyl-pyridine (cocrystal1), 2-methoxy-5-nitroaniline (cocrystal 2) and saccharine (cocrystal3).Inparticular,weevaluatedviaHPLCanalysistheAPIdissolutionprofile(Figure1b),itsabilitytopermeateacross intestinal cell monolayers (NCM460) and its oral bioavailability in rat using the pure drug, its co-crystalsandtheirparentphysicalmixtures[1].This interdisciplinary studyhas shown for the first time thatdifferent effects canbe inducedbyco-crystalsand their parent physical mixtures on a biologic system, and at the same time has raised serious concernsabout the use of co-crystal strategy to improve API bioavailability without performing appropriateinvestigations.

Figure1.a)Indomethacin;b)dissolutionprofilesofindomethacinco-crystalsandphysicalmixtures

[1] V. Ferretti, A. Dalpiaz, V. Bertolasi, L. Ferraro, S. Beggiato, F. Spizzo, E. Spisni, B. Pavan, Mol.Pharmaceutics,2015,12,1501.

21

2KN2.Biomoleculesasligandstoconstructhigh-dimensionalcoordinationnetworks(bioMOFs):towardsarationaldesignofmorefeasible

biocompatibilityandhomochiralmaterialsDonatellaArmentano,aEmilioPardo,bGiovanniDeMunno.a

aDipartimentodiChimicaeTecnologieChimiche,UniversitàdellaCalabria,87036Rende,Cosenza,ItalybDepartamentdeQuímicaInorgànica,InstitutodeCienciaMolecular(ICMOL),UniversitatdeValència,

46980Paterna,València,Spaindonatella.armentano@unical.it

Amongthedifferentareasofchemicalsciences,thesynthesisofhigh-dimensionalmetal-ligandnetworks,so-calledMetal-OrganicFrameworks(MOFs),hasexperiencedprobably themorerapiddevelopmentduring thelastdecades.[1]Thereasonsaretwo-fold:first,fromacrystalengineeringpointofview,becauseofthelargevariety of intriguing topologies and fascinating structures they can show, and secondly, due to the wideplethoraofphysicalandchemicalpropertiestheycanexhibit,relatedtotheirintrinsicporouscharacter.A quite recent step forward towards the obtention of original examples of MOFs consisted to constructbioMOFs.[2]These novelmaterials,which can be obtained using ligands derived from the biologicalworld,may offer remarkable advantages over traditional MOFs, more feasible biocompatibility affording potentialmedical applications as well as the possibility to achieve homochiral materials in a rational and predictablemanner due to the enantiopure nature of the employed biomolecules, capable of transmitting their “chiralinformation”tothestereochemistryofthemetalatoms,andsuitableforapplicationinchiraldiscriminationorseparation.Asanextensionofourrecentworkwiththerelatedmonosubstitutedoxamatoderivatives[3a]andcytidine,[3b]wehavenow focusedon a familyof enantiopuredisubstitutedoxamidato ligandsderived fromnatural amino acids (scheme 1) and cytidine 5’-monophosphate,[3c]which offermultiple coordination sitesandgoodperspectivesaschiralinducers.Wereporthereinanovelexampleofprotonconducting,homochiralbioMOFfamily.

Figure1.(left)Chemicalstructuresofthechiralbis(aminoacid)oxalamideligands;(right)Perspectiveviewof

the3Dopen-frameworkof{CaIICuII6[(S,S)-L]3(OH)2(H2O)4}.32H2O.[1]J.R.LongandO.M.Yaghi,Chem.Soc.Rev.,2009,38,1213;(b)G.Férey,Chem.Soc.Rev.,2008,37,191;(c)S.KitagawaandR.Matsuda,Coord.Chem.Rev.,2007,251,2490.[2]C.Martí-Gastaldo,D.Antypov, J. E.Warren,M. E.Briggs, P. aChater, P.VWiper,G. J.Miller,Y. Z.Khimyak,G.R.Darling,N.G.Berry,andM.J.Rosseinsky,Nat.Chem.,2014,6,343.[3](a)T.Grancha,J.Ferrando-Soria,M.Castellano,M.Julve,J.Pasán,D.Armentano,andE.Pardo,Chem.Commun.,2014,50,7569;(b)D.Armentano,T.F.Mastropietro,M.Julve,R.Rossi,P.Rossi,G.DeMunno,J.Am.Chem.Soc.,2007,129,2740;(c)N.Marino,D.Armentano,E.Pardo,J.Vallejo,F.Neve,L.DiDonnaandG.DeMunno,Chem.Sci.,2015,inpress,DOI:10.1039/C5SC01089F

22

2O1.MolecularRotorsinPorousCovalentFrameworksandSupramolecularArchitectures

SilviaBracco,AngiolinaComotti,FabioCastiglioni,DonataAsnaghi,PieroSozzaniDipartimentodiScienzadeiMateriali,UniversitàdegliStudidiMilano-Bicocca,Milano,Italy.

silvia.bracco@mater.unimib.itHighlyporousmaterialsareattractinglargeattentionintherecentliteraturefortheirapplicationsinthefieldofgasstorage,selective recognitionandmolecularconfinement.Thediscoveryofultra-fastmolecular rotors inporous covalent frameworks allowed us to look at them from a new perspective [1,2]. The unusualcombination of remarkable porosity with fast dynamics enabled the reversible speed-regulation of matrixrotors by the interaction with I2 vapors entering the galleries of the porous compounds. Molecular rotors,especiallywhenbearingdipoles,areachallengingresearchfieldentailinganumberofusefulphenomena,suchasswitchableferroelectricity,andthefabricationofdynamicelementsofmolecularmotorsinsolids.Recently,fastrotatingorganicelementsbearingcarbon-fluorinedipoleshavebeenfabricatedinporousorganic-inorganichybrid periodic architectures [3]. The reactivity of the pivot bonds allowed halogen addition and motionregulation.A first example ofmolecular rotors in porousmolecular crystals is presented.Disulfonated rotor-containingmolecular rods were self-assembled with alkylammonium salts to fabricate porous supramoleculararchitecturesheld togetherbycharge-assistedhydrogenbonds [4].The rotors are exposed to the crystallinechannels,whichabsorbCO2andI2vaporsatlowpressure.TherotordynamicscouldbeswitchedoffandonbyI2absorption/desorption,suggestingtheuseofporouscrystalsinsensingandpollutantmanagement.Moreover, crystals with permanent porosity were exploited in an unusual way to decorate crystal surfaceswith regulararraysofdipolar rotors.The insertedmoleculescarryalkylchainswhichare includedasguestsintothechannel-ends[5].Therotorsstayatthesurfaceduetoabulkymolecularstopperwhichpreventstherotors fromentering thechannels.Thehost-guest relationshipswereestablishedby2Dsolid-stateNMRandlowrotationalbarrierswerefoundbydielectricspectroscopy.[1]A.Comotti,S.Bracco,P.Valsesia,M.Beretta,P.SozzaniAngew.Chem.IntEd.,2010,49,1760.[2]A.Comotti,S.Bracco,T.Ben,S.Qiu,P.SozzaniAngew.Chem.,Int.Ed.,2014,53,1043.[3]S.Bracco,M.Beretta,A.Cattaneo,A.Comotti,A.Falqui,K.Zhao,C.Rogers,P.Sozzani,Angew.Chem.IntEd.,2015,54,4773.[4]A.Comotti,S.Bracco,A.Yamamoto,M.Beretta,T.Hirukawa,N.Tohnai,M.Miyata,P.SozzaniJ.Am.Chem.Soc.,2014,136,618.[5]L.Kobr,K.Zhao,Y.Shen,A.Comotti,S.Bracco,R.K.Shoemaker,P.Sozzani,N.A.Clark,J.Price,C.Rogers,J.MichlJ.Am.Chem.Soc.2012,134,10122.

23

2O2.Characterizationofthesolidstatedynamicbehaviourofcyclicpeptoids

ConsigliaTedesco,aEleonoraMacedi,aAlessandraMeli,aAndrewN.Fitch,bVincentJ.Smith,cLeonardJ.Barbour,cIreneIzzo,aFrancescoDeRiccardisa

aDipartimentodiChimicaeBiologia,UniversitàdegliStudidiSalerno,Fisciano,ItalybESRF,Grenoble,France

cDept.ofChemistryandPolymerScience,UniversityofStellenbosch,Stellenbosch,SouthAfrica.ctedesco@unisa.it

Cyclic alpha-peptoids hold the attention of both synthetic and supramolecular chemists for their biostabilityandpotentialdiversitybutalsofortheirelegantandintriguingarchitectures[1].Peptoidsdifferfrompeptidesinthesidechains,whichareshiftedbyonepositionalongthepeptidebackbonetothenitrogenatomtogiveN-substitutedoligoglycine.ThelackoftheamideprotonpreventstheformationofNH···OChydrogenbondsandweakerinteractions,asCH···OChydrogenbondsandCH-piinteractions,playakeyrole.Inter-annularCH···OChydrogenbondscanprovidefacetofaceorsidebysidearrangementofmacrocyclesmimickingbeta-sheetsecondarystructureinproteins[2].In particular, the role of side chains in the solid state assembly of peptoidmacrocycleswill be discussed toshowhowtheycanpromotetheformationofapeptoidnanotubebyactingaspillars,extendingverticallywithrespecttothemacrocycleplanes[3,4].Conformational flexibility is a key feature of peptoids and may be exploited to lead to functional materials.Exampleswill begiven as the suitable choiceof the side chainshas akey role indetermining the solid statedynamicbehaviouruponsolventuptakeandrelease.Thermalanalysis,hot-stagemicroscopy,in-situgasabsoprtionX-raypowderdiffractionandsinglecrystalX-raydiffractionconcurredtotheassessmentofthesolidstatedynamicbehaviouroftheexaminedcompounds.

Figure1.Reversiblesinglecrystaltosinglecrystaltransformationuponacetonitrilereleaseanduptakeforthe

cyclicpeptoidcyclo-(Nme-Npa2)2,Nme=N-(methoxyethyl)glycine,Npa=N-(propargyl)glycine.

EUFP7-People- IRSESgrant number 319011 "Synthesis and characterization of porousmolecular solids" isgratefullyacknowledged.[1]J.Sun,R.N.Zuckermann,ACSNano2013,7,4715.[2]C.Tedesco,L.Erra,I.Izzo,F.DeRiccardisCrystEngComm2014,16,3667.[3]N.Maulucci,I.Izzo,G.Bifulco,A.Aliberti,C.DeCola,D.Comegna,C.Gaeta,A.Napolitano,C.Pizza,C.Tedesco,D.Flot,F.DeRiccardis,Chem.Commun.2008,3927.[4]I.Izzo,G.Ianniello,C.DeCola,B.Nardone,L.Erra,G.Vaughan,C.Tedesco,F.DeRiccardis,Org.Lett.2013,15,598.

24

2O3.PromisingLow-Dielectric-ConstantMaterials:Metal-organicFrameworksandCoordinationPolymersCompared

SimonaGallia,*AlessandroCimino,a,bCarlottaGiacobbe,aGiovanniPalmisano,aAngeloMaspero,a,*JoshuaF.Ivy,bChiYang,bSammerTekarli,bandMohammadA.Omaryb,*

aDipartimentodiScienzaeAltaTecnologia,Universitàdell’Insubria,Como,Italy.bDepartmentofChemistry,UniversityofNorthTexas,Denton,Texas.simona.galli@uninsubria.it,angelo.maspero@uninsubria.it,

omary@unt.edu.Identifyingnovel low-dielectric-constant (low-k)materials for integrated circuit (IC) use is amain challengeforthemicroelectronicsindustry.Fluorousmetal-organicframeworks(FMOFs)andnon-porouscoordinationpolymers (FN-PCPs)built upwithpoly(azolate) ligandsarepromisingalternatives to currently applied low-kdielectrics, as their properties can be modulated through a sensible choice of nodes and spacers, with theadded value of the high thermal stability imparted by theN-donor struts. Surprisingly, in spite of this, fewreports,regardingsolelyMOFs,haveappearedtodateondielectricproperties.To improve theknowledgeon this scarcelyexplored field,we reporthere,asacasestudy,on thestructuralfeatures, the thermal behaviour and the dielectric constant of a number of FBTB- and FTZ-basedmaterials(FBTB=1,4-bis-(tetrazol-5-ate)tetrafluorobenzene;FTZ=3,5-bis(trifluoromethyl)-1,2,4-triazolate).As retrieved by state of the art PXRD, bothCu(FBTB) andAg2(FBTB) show 3-D networks: the former,possessingpts topology, features1-D rhombicchannelsaccounting for30%of theunit cellvolumeand fortheso-called‘breathing’observedasafunctionoftemperature(bothupto523Kanddownto90K);duetothe exo-octa-dentate coordination mode adopted by the spacer,Ag2(FBTB) is non porous and remarkablyrigid, as also proved by N2 adsorption at 77 K. Finally,Ag2(Ag4FTZ6) [1] possesses a nanotubolar 3-Darchitecture.Asforeseen,ligandsfluorinationisdefinitelybeneficial,asit1. enhances thermal stability: asdemonstratedbycouplingTGAandVT-PXRD,Cu(FBTB) andAg2(FBTB)decompose in air at 260 and 400 °C, respectively (vs. Tphase change = 100 °C and Tdec = 380 °C for theisostructuralcounterpartsCu(BTB)[2]andAg2(BTB)[3]).2.favoursstabilitytowardwater(k~80):notonlyAg2(FBTB) is recovered intactafteronemonthexposureto water vapours, yet it shows measured contact angles up to ~75° (vs. ~50° for Ag2(BTB)). Even moreperforming, in this respect, isAg2(Ag4FTZ6): in spite of porosity, measured contact angles reach ~160º,allowingtoclassifyitasasuper-hydrophobicmaterial.3.reducesvalues:impedanceroomtemperaturemeasurementsupto2MHzdisclosedadielectricconstantaslow as 2.59(3) and 2.44(5), for Ag2(FBTB) and Cu(FBTB), respectively (vs. 3.79(4) for Ag2(BTB)).Moreover,after72hexposure towatervapours,Ag2(FBTB) increases toonly2.63(5).Finally,preliminarytests onAg2(Ag4FTZ6) revealed values lower than 2.5. Noteworthy, to the best of our knowledge, theobserveddielectricconstantsconstituteanewworldrecord(k<2.8)forMOFsandPCPs.Workisinprogresstocompletethisstudyandexploitmetal-ligandcombinationswhich,thoughpreservingtheobserved promising properties, increase the stability up to the ~450 ºC needed for the dielectrics to surviveprocessingandpost-processingstepsforICapplications.[1]C.Yang,X.Wang,M.A.OmaryJ.Am.Chem.Soc.2007,129,15454.[2]M.Dincă,A.F.Yu,J.R.LongJ.Am.Chem.Soc.2006,128,8904.[3] A.Maspero, S. Galli, V. Colombo, G. Peli, N.Masciocchi, S. Stagni, E. Barea, J.A.R. Navarro Inorg.Chim.Acta2009,362,4340.

25

2O4.FiftyYearsofSharingCrystalStructuresStephenMaginn,ColinGroom,SuzannaWard,MatthewLightfoot

CambridgeCrystallographicDataCentre(CCDC),12UnionRoad,CambridgeCB21EZ,UK.maginn@ccdc.cam.ac.uk

Crystallographershavebeenresponsibleforsomeremarkableachievements,demonstratedbythemultitudeofNobelprizesawarded in the field.Thecrystallographiccommunitycanalsoclaima remarkableachievement:theoutputofeverystructuredeterminationeverpublishedisavailableforall.Notonlycanwelearnfromtheseindividualstructures,butwecanlearnfromthecollection.TheCambridgeStructuralDatabase(CSD)[1]isoneofthecollectionsofcrystallographicdataanditcontainsallthesmallmoleculeorganicandmetal-organiccrystalstructureseverpublished.Thankstothehardworkingcrystallographic community this valuable resource now contains nearly 800,000 crystal structures, and therateofgrowthoftheCSDcontinuestorise.This presentation, timed to coincide with the 50th anniversary of the Cambridge Structural Database, willdiscusstrendsinstructuralchemistry,fromauthorshiptouseofstructures,fromcrystallographicstatisticstopolymorph propensities.We will also look at examples of the extraordinary, curious and bizarre within thedatabase.[1]F.H.AllenActaCrystallographicaB58.2002,380-388

26

2P1.HomochiralSelf-AssemblyofBiocoordinationPolymers:Anion-TriggeredHelicityandAbsoluteConfigurationInversion

NadiaMarino,a,bDonatellaArmentano,aEmilioPardo,cJuliaVallejo,cFrancescoNeve,aLeonardoDiDonna,a

GiovanniDeMunnoaaDipartimentodiChimicaeTecnologieChimiche,UniversitàdellaCalabria,Italy

bDepartmentofChemistry,SyracuseUniversity,UnitedStatescInstitutodeCienciaMolecular(ICMOL),UniversitatdeValència,Spain

nadia.marino@unical.it,nmarino@syr.eduWe report hereinon twoquasi-identicalhomochiral1Dbio-coordination polymers built from the direct self-assembly of cytidine 5’-monophosphate (CMP) and Cu(II) ions, in the presence of two different counter-anions(perchlorateortriflate)comingfromthecopper(II)source.Wefoundtheaniontoplayacentralroleinthehomochiral resolutionprocess, leadingtoahelixwithP (right-handed)orM (left-handed)chirality in thecaseof theperchlorate or the triflate, respectively (seeFigure1).Thehandnessof the twoobtainedhelicescan be quickly inverted, in a reversible way, by switching the anion, as revealed by circular dichroismexperiments,bothinsolutionandinthesolidstate.SinglecrystalandpowderX-raydiffraction,togetherwithelectrosprayexperiments,wellsupportourhypothesis.[1]

Figure1.SideviewoftheP(right-handed),left,andM(left-handed),right,helicespresentedinthiswork.[1]N.Marino,D.Armentano,E.Pardo,J.Vallejo,F.Neve,L.DiDonna,G.DeMunnoChem.Sci.2015,DOI:10.1039/c5sc01089f,inpress.

27

2P2.NaphthalenediimidecocrystalsbasedonhalogenbondDavideCapucci,aAlessiaBacchi,aMarcoBarbieri,aAnnaGatti,aPaoloPelagatti,aMariannaPiolia

aDipartimentodiChimica,UniversitàdegliStudidiParma,Parma,Italydavide.capucci@unipr.it

Naphthalene imides (NI), naphthalene diimides (NDI), perylene diimides and their derivatives are commonlyemployed for their absorption and luminescence properties [1]: they are indeed one of the most promisingclassofelectronacceptingmaterials.Theirrigidaromaticcorefavoursπ-πstackinginteractionswhich,alongwithdifferenttypesofweakinteractions,couldleadtoabroadrangeofcompellingcompounds.In thisworkwepresent the first sets of cocrystalsmadeupwithDPNDI (N,N-di-(4-pyridyl)-naphtalene-1,4,5,8-tetracarboxydiimide) and halogenated aromatic derivatives interacting throughhalogen bonds.Recentinterest in this specific kind of interactions [2] is certainly ascribable to the capacity to tune and designspecificandvalidself-assemblystructures.Formationofnewcrystalline compounds,obtained through the combinationof twodifferentmolecules (co-crystals), is possible by using suitable molecular partners. Despite NDI molecules remain unchanged incocrystal form, its specific properties are subjected to an evident variation. For this reason we haveinvestigated and correlated different cocrystals and their absorption properties to the crystalline packing andhowNDIsmolecules andpartners interact in the solid state inorder to establish aunivocal relationbetweeneachother.Thedegreeof inclinationinaπstackingsystemcanbedescribedbytwoanglescalled“pitch”(P)and“roll”(R) as reported in previous works [3] so as to properly correlate halogen bonds to the ultimate crystallinestructure.

igure1.Diiodobenzene-DPNDIcocrystal.

[1]SheshanathV.Bhosale,ChintanH.Jani,S.J.Langford,Chem.Soc.Rev.,2008,37,331-342[2]P.Metrangolo,G.Resnati,Cryst.GrowthDes.2012,12,5835-5838[3]M.D.Curtis,J.Cao,J.W.Kampf,J.Am.Chem.Soc.2004,126,4318-4328

28

2P3.Fromcrystallographytoapplications:nonlinearopticalpropertiesofβ-D-fructopyranosealkalinehalidesMOFs

DomenicaMarabello,a,bPaolaAntoniotti,aAlessandroBarge,cPaolaBenzi,abCarloCanepa,aCarlaDivieto,d

LeonardoMortati,dMariaPaolaSassidaDipartimentodiChimica,UniversitàdegliStudidiTorino,Torino,Italy

bCrisDi-InterdepartmentalCenterforCrystallography,UniversityofTorino,ItalycDipartimentodiScienzaetecnologiadelfarmaco,UniversityofTorino,Italy

dINRIM–IstitutoNazionalediRicercaMetrologica,Torino,Italy

Many physical properties of crystals are strictly correlated to their symmetry elements and packing of theirconstituents. It is thecaseof thesecondharmonicgeneration (SHG)property, that is stronglydependentonthe absence of the inversion centre in the crystal structure [1]. Furthermore, in a non-centrosymmetriccrystal, the presence of asymmetric molecules can introduce an additional electronic asymmetry and highhyperpolarizability,thatseemstobestrictlyrelatedtotheSHGintensity[2].MetalOrganicFrameworks(MOFs)representan idealcategoryofcompounds todesignfunctionalmaterialswithphysicalpropertiesdependentoncrystalsymmetry.Inparticular,carbohydrates represent good asymmetric poly-dentate ligands for the formation of MOFs. The SHGefficiencyofmanymono-,di-andtri-saccharideshavebeenexamined,andacorrelationbetweentheircrystalsystemsandSHGefficiencieshasbeenevidenced, i.e. the lower is thespacegroupsymmetryof thecrystalthelargeristheSHGefficiency[3].In our previouswork [4], twoMOFs obtained from fructose andCaCl2, [Ca(C6H12O6)(H2O)2]Cl2 (1) and[Ca(C6H12O6)2(H2O)2]Cl2∙H2O(2),were studied and itwas demonstrated that the coordination of fructoseon the calcium ion causes an improvement of the SH intensity with respect to the fructose itself. Thetheoreticalcalculationssuggeststhat,attheexcitationangularfrequency,theSHintensityisinfluencedbyboththepositionoftheresonantfrequencyandthesecond-ordersusceptibility.In this work we aim to better understand the correlation between the structural features and the SHGefficiencyof newMOFsobtained from fructose andMX2 (M=Ca,Sr;X=Cl,Br), of formula [Ca(C6H12O6)(H2O)2]Br2(3)and[M(C6H12O6)2(H2O)2]X2∙H2O(4,5).The metal-carbohydrate based MOFs analyzed in this work show a favorable combination of thermal andchemical stability, transparency, and second-order optical nonlinearity, and are thus potential candidate forapplicationsinelectro-opticsdevices.

Figure1.Infinitenetworkofcalcium,chlorideandsugarinthe[010]directionforcompound2.[1]D.S.Chemla, J.ZyssNon linear optical properties of organicmolecules and crystals,Academic Press:NewYork,1:2,1987[2]O.R.Evans,W.LinAcc.Chem.Res.,2002,35,511-522[3]G.Bournill,K.Mansour,K.J.Perry,L.Khundkar,E.T.Sleva,R.Kern,J.W.PerryChem.Mater.,1993,5,802-808[4]D.Marabello,P.Antoniotti,P.Benzi,C.Canepa,E.Diana,L.Operti,L.Mortati,M.P.SassiJ.Mater.Sci.,2015,50,12,4330-4341

29

2P4.StudiesoftheconformationalchangesontheribosomalGTPaseEFL1usingSAXS

DritanSiliqia,NuriaSanchez-Puigb,EugeniodelaMorab,AlfonsoMéndez-Godoyb,DavideAltamuraa,CinziaGianninia,TeresaSibillanoaandMicheleSavianoa

IstitutodiCristallografia,CNR,ViaG.Amendola122/0,70126Bari,ItalyInstitutodeQuímica,UniversidadNacionalAutónomadeMéxico,CircuitoExterior,CuidadUniversitaria,

MéxicoD.F.,México.Ribosomebiogenesisiscloselylinkedtothecellgrowthandproliferation.Dysregulationofthisprocesscausesseveraldiseasescollectivelyknownasribosomopathies.OneofthemistheShwachman-DiamondSyndrome,andtheSBDSproteinmutatedinthisdiseaseparticipateswithEFL1inthecytoplasmicmaturationofthe60Ssubunit. SBDS couples the energy liberated from the hydrolysis of GTP by EFL1 to release eIF6 from thesurface of the 60S ribosomal subunit [1,2]. The eIF6 protein prevents the premature association of theribosomalsubunitsbybinding to theB6 inter-subunitbridgeandadditionallycontacting thesarcin-ricin loop,Rpl23 andRpl24 (3,4).EFL1belongs to theP-loop familyofGTPases and is homologous to the elongationfactorEF-G/EF-2 (5).EFL1probably removeseIF6 from the60Ssurface throughaconformationalchangesimilartothattriggeredbyEF-2duringelongationintheproteinsynthesis.Recently,wehaveshownthattheinteraction of EFL1with SBDS resulted in a decrease of theMichaelis-Menten constant (KM) for GTP andthus SBDS acts as aGEF for EFL1 [3]. Subsequent studies demonstrated that SBDS greatly debilitates theinteractionofEFL1withGDPwithoutalteringthatforGTP.TheinteractionofEFL1aloneorincomplexwithSBDS to guanine nucleotides is followed by a conformational rearrangement. Understanding the molecularstrategy used by SBDS to disrupt the binding ofEFL1 forGDP and the associated conformational changeswill bekey tounderstand theirmodeof action and alterationsoccurring in thedisease.The structureof theGTPaseEFL1isnotknownanditscrystallizationhasbeenunsuccessfulatleastinourhands.In thisstudy,weaimtoshowtheconformationalchangesresultingfromthe interactionsbetweenEFL1andits binding partners, the SBDS protein and the guanine nucleotides using SAXS technique [4,5]. SAXSwillprovide structural information of the proteins and their conformational changes [6]. For the SAXS dataanalysiswehavebuiltmodels ofEFL1usingbyEF-2 as homology template andofSBDSusing the crystalstructuresofthearchaeaorthologues.Theauthors acknowledge financial supportPGR2015 "Con il contributo delMinistero degliAffariEsteri edallaCooperazioneInternazionale,DirezioneGeneraleperlaPromozionedelSistemaPaese".[1]Finch,A.J.,Hilcenko,C.,Basse,N.,Drynan,L.F.,Goyenechea,B.,Menne,T.F.,GonzalezFernandez,A.,Simpson,P.,D'Santos,C.S.,Arends,M.J.,Donadieu,J.,Bellanne-Chantelot,C.,Costanzo,M.,Boone,C., McKenzie, A. N., Freund, S. M., andWarren, A. J. (2011) Uncoupling of GTP hydrolysis from eIF6releaseontheribosomecausesShwachman-Diamondsyndrome.GenesDev25,917-929.[2]Menne,T.F.,Goyenechea,B.,Sanchez-Puig,N.,Wong,C.C.,Tonkin,L.M.,Ancliff,P.J.,Brost,R.L.,Costanzo, M., Boone, C., and Warren, A. J. (2007) The Shwachman-Bodian-Diamond syndrome proteinmediatestranslationalactivationofribosomesinyeast.NatGenet39,486-495[3]Gijsbers,A.,Garcia-Marquez,A.,Luviano,A.,andSanchez-Puig,N.(2013).Guaninenucleotideexchangein the ribosomalGTPaseEFL1 ismodulatedby theproteinmutated in theShwachman-DiamondSyndrome.BiochemBiophysResCommun437,349-354[4]Altamura,D.,Lassandro,R.,DeCaro,L.,Siliqi,D.,LadisaM.&Giannini,C.(2012).X-raymicroimaginglaboratory(XMI-LAB).J.Appl.Cryst.45,869–873(2012)[5] Svergun,D,Koch,MichelH.J., Timmins, P.A. andMay,R.P (2013). "SmallAngleX-Ray andNeutronScatteringfromSolutionsofBiologicalMacromolecules".OxfordUniversityPress.[6]Petoukhov,M.V.,Franke,D.,Shkumatov,A.V.,Tria,G.,Kikhney,A.G.,Gajda,M.,Gorba,C.,Mertens,H.D.T.,Konarev,P.V.andSvergun,D.I.(2012).NewdevelopmentsintheATSASprogrampackageforsmall-anglescatteringdataanalysis.J.Appl.Cryst.45,342-350.

30

2P5.StackingmotivesinmetallatesaltsofmethyleneblueStefanoCanossa,AlessiaBacchi,ClaudiaGraiff,PaoloPelagatti,GiovanniPredieri

DipartimentodiChimica,UniversitàdeglistudidiParma,Parma,Italy.stefano.canossa@studenti.unipr.itThe study focuses on the π-π stacking geometry exhibited in the solid state by 3,7-bis(dimethylamino)phenothiazin-5-ium,alsoknownasmethylenebluecation (MBC)associatedwithdifferentcounter-anions,inparticularmetallateions.Thepreparationsofall thecompoundswerecarriedout in thesolidstate,bygrindingMBCchloridetogetherwith several transition metal salts. The resulting powders have been characterized through X-ray powderdiffraction, inorder tocheck the reactionsproductsand toconfirm thecrystallinenatureof thecompoundsobtained.All the productswere subsequently dissolved in adequate solvents and several crystallization trialswere set up.Someof themafordedcrystals suitable for single crystalX-raydiffraction and their structureshavebeensuccessfullysolved.In theobservedcrystallinephasesMBCgivesrise toseveraldifferentπ-πstackings,whichcanbedividedintwomain classes. In the first class, themost abundant one,MBCexhibits an infinite π-π stacking. In thesecases the geometrical operator connecting one molecule to the next in the stacking array is not a simpletranslation, as themolecule is also rotated on its ownplane.The second class consists of rare caseswhereMBCformsdimersboundtogetherthroughπ-πinteraction,withnosignificantstackings.In order to find a rationale for the different dispositions of MBC, several parameters must be taken intoaccount, e.g. the geometryof the involved counter-anion, its charge, the presenceof solventmolecules andtheir geometry and polarity. Hence, a statistical approach is required to simplify the data processing and toevaluatetheelectrostaticandstericinfluenceonthecrystalpackinginallthecrystalphasesobserved.

Figure1.TwodifferentexamplesofstackinggeometryofMBCasobservedintwocrystallinephasesinwhich,respectively,a[HgCl4]2-anion(left)anda[AuCl4]-(right)ispresent.Theanionicspeciesareomitted

forclarity.

31

MS3.FROMNATURETOADVANCEDMATERIALS:STRUCTURECHARACTERIZATIONATTHENANOSCALE

The development of complex advancedmaterials and the need for a deeper understanding of nature requirecrystallographic knowledge at a nanoscopic level. Macroscopic materials properties are strictly linked withatomicstructure,defectivityandhierarchicalarrangementofcrystallinenanodomains.LabX-raydiffractionmethodsneedtobeintegratedbyotherstructureinformation,availablebysynchrotronsources,spectroscopies,neutron and electron diffraction, electron and atomic force microscopy. Speakers are invited to presentinnovativeapproachesand case-studies for the characterizationof complexmaterials,with special regard totheidentificationofnanoscopicstructuralfeatures.Chair:MauroGemmi(IITPisa);EnricoMugnaioli(U.Siena)

32

3KN1.RotationelectrondiffractionasacomplementarytechniquetopowderX-raydiffractionforphaseidentificationandstructuresolution

WeiWan,JieSu,JunliangSun,SvenHovmöllerandXiaodongZouaBerzeliiCenterEXSELENTonPorousMaterials,StockholmUniversity,SE-10691Stockholm,Sweden,andbInorganicandStructuralChemistry,DepartmentofMaterialsandEnvironmental

Chemistry,StockholmUniversity,SE-10691Stockholm,Sweden.wei.wan@mmk.su.sePhase identification and structure determination of submicrometre-sized crystals are important in materialsscienceandcrystallography.Themostwidelyusedtechniquefor thesepurposes ispowderX-raydiffraction(PXRD).However, the use of PXRD is limited inmultiphase samples, especially those containing unknownphases. Due to the strong interaction between electrons and matter, submicrometre-sized crystals can bestudied as single crystals using electron diffraction. Electron crystallography has proven a promisingalternative for studying individual phases in multiphase crystalline samples containing submicrometre-sizedparticles.The recentlydevelopedelectrondiffraction tomographymethods, forexampleautomatedelectrondiffractiontomography (ADT) [1] and rotation electron diffraction (RED) [2,3] and can be used to collect completethree-dimensionalelectrondiffraction(ED)datafromsinglecrystalsofsub-micrometresizesinaTEM.REDcombinesdiscretegoniometertiltsteps(typically2–3°)withveryfinestepsofbeamtilt(typically0.05–0.20°)and data collection is controlled entirely by software on a conventional transmission electron microscope.Since there is no need to align the crystal, data collection is made very simple and fast. In RED dataprocessing,3Dreciprocalspaceofthecrystalisreconstructedandtheunitcellaswellasthespacegroupcanbeeasilydetermined.Thereflectionsare then indexedanda listofhklwith intensities isoutput forab initiostructuresolutionusingstandardphasingmethods,forexampledirectmethods[4].Today it has become routinework to collect essentially complete three-dimensional electron diffraction datafromcrystalsassmallastensofnanometersandsolvethestructures.However,atpresentelectrondiffractiondataneeds tobecombinedwithPXRDforacompletestructuredeterminationwhich includesbothstructuresolutionandreliablerefinement,duetothefactthattheelectrondiffractionintensitiesareoflowerquality.Thebest approach is to combine three-dimensional ED and PXRD [5,6].We expect that three-dimensional EDmethods will become more and more important for phase identification and structure solution of complexmaterialsinthenearfuture.[1]U.Kolb,T.Gorelik,C.Kübel,M.T.Otten,D.HubertUltramicroscopy2007,107,507.[2]D.Zhang,P.Oleynikov,S.Hovmöller,X.D.ZouZ.Kristallogr.2010,225,94.[3]W.Wan,J.Sun,J.Su,S.Hovmöller,X.D.ZouJ.Appl.Cryst.2013,46,1863.[4]G.M.SheldrickActaCryst.2008,A64,112.[5]Y.F.Yun,X.D.Zou,S.Hovmöller,W.WanIUCrJ2015,2,267.[6]E.Mugnaioli,U.KolbZ.Kristallogr.2015,230,271.

33

3KN2.Howdifficultistosolvecomplexstructures:thecaseofEniCarbonSilicates

MichelaBellettatoEniS.p.A.,Research&TechnologicalInnovation,DownstreamR&D,PhysicalChemistryDept.,ViaF.

Maritano26,I-20097SanDonatoMilanese,Italy.michela.bellettato@eni.com

EniCarbonSilicate(ECS)materialsformanewfamilyofcrystallinehybridorganic-inorganicmetallo-silicatesrecentlydiscovered in theeni’s laboratories [1].Theyarepreparedbyhydrothermal treatmentat100°Cofareaction mixture composed by a source of trivalent metal ion (e.g. NaAlO2), a base (NaOH and/or KOH),demineralized water and a bridged silsesquioxane of general formula (R’O)3Si–R–Si(OR’)3 (R = alkyl,aromaticoralkyl-aromaticgroup;R’=MeorEt)assourceofsilica.Today, theECSfamilyiscomposedby20+phasesobtainedbyvaryingthenatureofthebridgingorganicgroup,thetrivalentmetalion(i.e.,Al[1],B[2], Ga [3]) and the composition of the reaction mixture. A detailed characterization of these phases isnecessary for answering to some important questions related to the integrity of the bridged silsesquioxanemoieties, to their assembly in the crystalline lattice, to the roleof the trivalentmetal ions, to thepresenceofopen porosity, etc.All this information can be obtained once the structure of thematerial is determined andrefined. In the case of ECSs, the structural characterization proved to be a challenging problem because oftheircomplexity,whilethenanocrystallinenatureofthesampleshamperedtheapplicationoftheconventionalsingle crystalX-raydiffraction techniques.Therefore, a suitable protocol,which includes elemental, thermal(TG-DTA-MS)andtextural(N2adsorption/desorptionisotherms)analyses,MASNMR(29Si,27Al,11B,71Ga,13C,1H),electronmicroscopy(FESEM-EDS,HRTEM)andlaboratoryX-raydiffraction(XRD),wasappliedforapreliminarycharacterizationof theECSsamplesand forderiving thenecessarydata for thesuccessivestructuredetermination.High-resolutionsynchrotronX-raypowderdiffractiondatawerecollectedforall theECS phases and in some cases (ECS-17 and ECS-14, Fig. 1) they were employed for solving the crystalstructurebydirectmethods[4,5].Forothermaterials,however,itwasnecessarytoapproachtheproblemina differentway, exploiting advanced crystallographic techniques recently developed, such as theAutomatedDiffraction Tomography (ADT), which allowed the collection of single-crystal electron diffraction data onvery small specimen (<0.5μm). In thisway, itwas possible to determine the structure ofECS-3 (with63independentnon-Hatomsintheasymmetricunit,actuallythemostcomplexstructuredeterminedbyADT[6])(Fig.1)andofECS-5,whichcrystallizeinformofverythinplatelets(<0.1μm)[2].The successful resultsobtained so fardemonstrateoncemorehow the integrationof conventional andnon-conventional techniques is fundamental for solving challenging problems in the structural characterization ofnewmaterialsandthiscanbeachievedonlythroughateamworkinvolvingthenecessaryskills.

Figure1.StructureofECS-17(left),ECS-14(middle)andECS-3(right).[SiO3C]tetrahedrainyellow,[AlO4]tetrahedraincyano,Naionsinblue,phenyleneringingrey.

[1] G. Bellussi, A. Carati, E. Di Paola, R. Millini, W. O. Parker Jr., C. Rizzo, S. Zanardi MicroporousMesoporousMater.2008,113,252[2]S.Zanardi,G.Bellussi,W.O.Parker Jr.,M.Bellettato,G.Cruciani,A.Carati, S.Guidetti,C.Rizzo,R.MilliniDaltonTrans.2014,43,10617[3] G. Bellussi, A. Carati, S. Guidetti, C. Rizzo, R.Millini, S. Zanardi, E.Montanari,W. O. Parker Jr.,M.BellettatoChin.J.Catal.2015,36,813[4]G.Bellussi,R.Millini,E.Montanari,A.Carati,C.Rizzo,W.O.ParkerJr.,G.Cruciani,A.deAngelis,L.Bonoldi,S.ZanardiChem.Commun.2012,48,7356[5]M.Bellettato,L.Bonoldi,G.Cruciani,C.Flego,S.Guidetti,R.Millini,E.Montanari,W.O.ParkerJr.,S.ZanardiJ.Phys.Chem.C2014,118,7458[6]G. Bellussi, E.Montanari, E.Di Paola, R.Millini, A. Carati, C. Rizzo,W.O. Parker Jr.,M.Gemmi, E.Mugnaioli,U.Kolb,S.ZanardiAngew.Chem.Int.Ed.2012,51,666

34

3O1.3DInvestigationoftheReciprocalSpaceofNano-CrystalsbyElectronDiffractionTomographyJérémyDavida,MauroGemmia,LukášPalatinusb

aCenterforNanotechnologyInnovation@NEST,IstitutoItalianodiTecnologia,Pisa,ItalybInstituteofPhysicsoftheASCR,Prague,CzechRepublic

jeremy.david@iit.itElectronDiffractionTomography(EDT)1isarecentcrystallographytechniquethatuntilnowhasmainlybeenused to solve unknown structures. It consists of taking a set of diffraction patternswhile tilting the samplearound the goniometer axis of themicroscope,with a specific angular step (typically 0.5-1°) andwithin anangularrangedependingonthegoniometerthatisused(inourcasefrom-60°to60°).Itcanbecoupledwithprecession,inordertoobtainquasi-kinematicalintensities.However,evenifsolvingstructuresisthemaingoalofEDT,itisonlyoneofthepossibilitiesofthispowerfulandversatiletechnique.Infact,apartfromgoingthroughthewholestructuresolutionprocess,a3D-reconstructionofthereciprocalspace(RS)canbeperformedandusedasapowerfulvisualizationtool.Furthermore, thisfeaturealsoallowstobuild sectionsof theRS thatdonotpass through itsorigin,makinga finer investigationof the reciprocalspacepossible.This3D-reconstructionthenmakesiteasiertounderstandwhathappensinthestructure,andspecificweakfeatureslikestructuremodulationanddiffusescatteringcanbedetectedanddirectlyvisualizedinconnectionwiththeunderlyingBraggscattering.The case of a modulated structure (Bi8Pb5O17) will first be discussed. The visualization allows us tounderstand thegeometryand thesymmetryof themodulation, that in thiscase is two-dimensional,andhowthis one affects the average structure.Apreliminary structuralmodel has been derived in a five-dimensionalsuperspaceusingtheSuperflipsoftwareandJANA2006.AsecondexamplewillconcernthereciprocalspaceanalysisofInSbnanowires, inwhichthereciprocalspacereconstructionshowsastonishingstarshapespotsprobablyconnected toacore shell structure inducedbydifferent relaxedstructures in the radialdirectionofthewire.A thirdexamplewill show thediffuse scatteringof themineral cesarolite as a roadmap towardsamodulatedcrystalstructure.

Figure1.3-dimensionalreconstructionofthereciprocalspaceofanInSbnanowire.

ThemaindrawbackofEDT,likeallthetechniquesinwhichelectronsareinvolved,isthedifficultytouseitonbeam sensitivematerials. This is overcomewith a fast EDT[2] procedure: the diffraction patterns are takenwhile the sample is tilted continuously, reducing dramatically the dose suffered by the sample. Then newpossibilitiesareemerging,likethestudyofpharmaceuticalcompoundsandproteinsforexample.[1]U.Kolb,T.Gorelika,C.Kübelb,M.T.Ottenc,D.Hubert.,Ultramicroscopy107,507(2007)[2]M.Gemmi,M.G.I.LaPlaca,A.S.Galanis,E.F.Rauch,S.Nicolopoulos,J.Appl.Cryst.48(2015)

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3O2.Structuredeterminationusingab-initiomethodsandsimulatedannealingfromPEDtomography

ParthaP.Das1,3,IreneMargiolaki2,StavrosNicolopoulos31ElectronCrystallographySolutions,Madrid,Spain,2DepartmentofBiology,UniversityofPatras,Patras,

Greece,3NanoMEGASSPRL,Brussels,Belgium.partha@ecrystsolutions.comDespitethesuccessofX-Raycrystallographyinsolvingstructuresthereisa limitationtoworkwithnmsizecrystals. Since the invention of precession electron diffraction (PED) [1] in Transmission ElectronMicroscope (TEM), many structures have been solved either collecting several zone axis (ZA) data orcollecting the data by diffraction tomography technique. During the ab-initio structure determination fromelectrondiffractiondata incombinationwithPED, it ispossible that the light atomsarenot foundusingab-initiostructuresolutionor theirpositionsarefounddistortedduetopoorqualityof thecollectedEDdata.Inthis work we present how combination of ab-initio structure solution and simulated annealing can help torecovercorrectlyallatompositionsfromlowqualityelectrondiffraction(ED)data.Using automated diffraction tomography (ADT) in combination with PED, a tilt sequence of several non-orientatedelectrondiffractionpatternsaroundanarbitrarytiltaxiswithfixedtiltstepcanbecollected[2].ThecollectedPEDpatternscanbeanalyzedbyADT3Dsoftware to extract theunit cell and intensity.Suchdatamayhave lowcompletenessdue to the restrictionof theTEMgoniometer and/or thequalityof theEDdatamaybepoorduetobeamsensitivityortothelowdynamicrangeofCCDcameraused;allthosefactorsmayhaveanegativeimpactontheab-initiostructuresolution.As a test case, ED data fromLiFe0.20Al0.80Si2O6 samplewith space groupC 2/c was collected with a tiltrange of +-300, ES500W Erslangshen 12 bit CCD camera. From the extracted intensity ab-initio structuresolutionwasperformedwithdirectmethods(SIR2012)andchargeflippingalgorithmsbutitwasnotpossibleto determine Li atom position. After using same extracted intensity data set and using simulatedannealing/potentialenergyminimizationalgorithm(Endeavoursoftwarepackage) [3] itwaspossible todetectLiatom[Figure1]atpositionwhichmatchwiththepositionobtainedfromX-raydiffractiondata.

Figure1.CrystalstructuremodelofLiAl0.2Fe0.8Si2O6,asobtainedbyEndeavourSoftware

[1]R.Vincent,P.A.Midgley,Ultramicroscopy,1994,53,271.[2]E.Mugnaioli,T.Gorelik,U.Kolb,Ultramicroscopy,2009,109,758.[3]H.Putj,J.C.Schon,M.Jansen,J.Appl.Crystallogr.1999,32,864.

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303.Organizedarchitectureofdyesinzeolitechannels:aneffectivetransportofelectronicexcitationenergy

LaraGiglia,RossellaArlettia,b,JennyG.Vitilloc,GianmarioMartrad,GabrieleAlbertod,GloriaTabacchic,EttoreFoisc,SimonaQuartierie,GiovannaVezzalinif

aDipartimentodiScienzedellaTerra,UniversitàdegliStudidiTorino,Torino,ItalybInterdepartmentalCentre“NanostructureInterfacesandSurfacesNIS”,Torino,Italy

cDipartimentodiScienzaedAltaTecnologia,UniversitàdegliStudidell’Insubria,-Como,ItalydDipartimentodiChimica,UniversitàdegliStudidiTorino,Torino,Italy

eDipartimentodiFisicaeScienzedellaTerra,UniversitàdegliStudidiMessina,MessinaS.Agata,ItalyfDipartimentodiScienzeChimicheeGeologiche,UniversitàdegliStudidiModenaeReggioEmilia,

Modena,Italylara.gigli@unito.it

The Assembly of chromophore molecules, using the one-dimensional channel framework of zeolite L (ZL)allow to induceorganizedarchitectures [1],or functional supramolecular systems (e.g.Dye−ZLcomposites)[2],withefficientFRETandimpressiveantennapropertiesforlightharvesting,transport,andtrapping[3].Ithas been shown [4], that the properties of dye-ZL systems depend on the molecular packing inside thechannels,controllingtheintermolecularandthedyes/frameworkinteractionsInthisworkwepresentsastudyontheopticalpropertiesofatwo–dyesantennasysteminwhichfluorenonemolecules(FL,donormolecule)andthionine(Th,acceptormolecule)areorganizedinZeoliteLporosities.To interpret theopticalpropertiesof thehybridsadetailedstructuralstudyatatomistic levelwasmandatory.Due to the impossibility of studying from the structural point of view a two–dyes systems, two “one-dye”hybrids(ZL/FLandZL/Th)werefirstlysynthesizedandcharacterizedtoinvestigatetheintermolecularandthedyes/frameworkinteractions[5].Theresultsofthermogravimetric,IR,andX-raystructuralrefinementscarriedoutfortheone-dyeZL/FLandZL/Thsystemsestablishedthat1.5and0.3moleculesperunitcellarethemaximumloadingspossibleforFLandTh, repectively.TheFLcarbonylgroupstrongly interactswithaK+ion in theZLchannel.On theotherhand,shortdistancesbetweenthecarbon,sulfurandnitrogenatomsofThwithtwowatermoleculesites,inturn at bond distance from the oxygen atoms of the main channel, suggested a water-mediated Th-ZLinteractions.TheenergytransferfromexcitedFLmolecules,formingthenon-covalentnano-ladder in theZLchannel,andTh,depositedontheexternalsurfaceofZLparticles,iscurrentlyunderinvestigation.Inconclusion,concerningtheopticalpropertiesofourcomposites,noevidenceofDavydovsplittingemergedfrom our study, indicating that one of the main competitors of the FRET mechanism is not operativenotwithstanding the close packed arrangement of FL. We believe that this feature is of overwhelmingrelevanceinviewofapplicationofsuchasysteminartificialantennadevices.The authors acknowledge the Italian Ministry of Education, MIUR-Project: “Futuro in Ricerca 2012 -ImPACT-RBFR12CLQD”.[1]A.D.Schlüter,Top.Curr.Chem.2005,245.[2]J.W.Steed,SupramolecularChemistry,Wiley,NewYork,2000.[3] G. Calzaferri; R. Méallet-Renault.; D. Brühwiler; R. Pansu; I. Dolamic.; T. Dienel; P. Adler; H. Li; A.Kunzmann,ChemPhysChem.2011,12,580.[4]G.Calzaferri;K.Lutkouskaya,Photochem.Photobiol.Sci.,2008,7,879.[5] L.Gigli., R.Arletti.; G. Tabacchi.; E. Fois.; J.G.Vitillo;G.Martra.;G.Agostini.; S.Quartieri. andG.Vezzalini.,J.Phys.Chem.C.2014,118,15732.

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3O4.StructuralevolutionoftungstenoxidenanocrystalsinvestigatedbyPairDistributionFunctionandModulationEnhancedDiffraction

RoccoCaliandro,aCinziaGiannini,aPantaleoDavideCozzoli,bcRiccardoScarfiello,bdJonathanC.Hanson,e

EricDooryheee,fTeresaSibillano,aBennyDaniloBelviso,gMicheleMancadaIstitutodiCristallografia(IC),CNR,Bari,Italy

bDipartimentodiMatematicaeFisica"E.DeGiorgi",UniversitàdelSalento,Lecce,ItalycIstitutodiNanotecnologia(CNR-NANOTEC),Lecce,Italy

dCenterforBiomolecularNanotechnologies@UNILE,IstitutoItalianodiTecnologia,LecceItalyeChemistryDepartment,BrookhavenNationalLaboratory,Upton,NY,UnitedStates

fPhotonSciences,BrookhavenNationalLaboratory,Upton,NY,UnitedStatesgCentreforBiomolecularScience,UniversityofNottingham,Nottingham,England

rocco.caliandro@ic.cnt.itA static and dynamic structural characterization of selected crystal-phase-controlled samples of colloidaltungstenoxidenanorods,synthetizedbyanon-hydrolyticrouteunderrigorouswater-andair-freeconditions[1], then subject to prolonged air exposure, has been carried by combining the Modulation EnhancedDiffraction (MED) technique [2] and PairDistribution Function (PDF) analysis [3]. The samples have beencharacterizedwithanunprecedentedaccuracy,whichhasalloweddeterminingthethermalmotionandpositionofsingleatoms,andrevealingsubtlestoichiometrydeviationsfromthereferencecrystalphasesavailableinthedatabase. The crystal phases present in the sampleswere identified bymeans of a Rietveld analysis againstseveral reference phases and an atomic pair PDF refinement of the best candidates.The sampleswere thenput in contact with air at ambient temperature and their structure was monitored by time-dependent X-raymeasurements, using a synchrotron facility for monitoring within the first 24 hours, and a homediffractometerformonitoringoveraperiodofseveralmonths.ThePDFanalysisofthesedatasetsrevealedapeak broadening and an increased atomic thermal motion. This static analysis was complemented with adynamicinvestigation,performedbymeansoftheMEDtechniqueappliedtothewholesetofmeasurements.TheMEDtechniquehasbeenrecentlyproposedasatooltocapturestructuralfeaturesofcrystalsystemsthatarevarying inphaseuponapplicationof someexternal stimuli, like forexample temperatureorpressure [4].MED is basedon the joint analysis of a series ofXPDprofiles, collected as long as the external stimulus isbeingvaried[5,6].ThistechniquehasbeenhereappliedtoPDFanalysisforthefirsttime,andcomplementedbyanovelmultivariate approach.The time-dependentbehaviorof the samplesproducedunder air exposure,obtainedfromXPDandPDFanalysisonthebasisofamultivariateanalysis,hasbeeninterpretedasresultingfrom an appreciable increase of the thermal motion of oxygen atoms within the most oxygen-rich crystalplanes.Themethodsandthealgorithmsproposedinthisstudycanbepotentiallyappliedtoanynanomaterial,tomonitoritsstructuralpropertiesinresponseofaninsituappliedexternalperturbation.[1]Lee,K.,Seo,W.S.,Park,J.T.(2003).J.Am.Chem.Soc.125,3408-3409.[2]Chernyshov,D.,vanBeek,W.,Emerich,H.,Milanesio,M.,Urakawa,A.,Viterbo,D.,Palin,L.,Caliandro,R.(2011).ActaCryst.A67,327-335.[3] Egami, T. & Billinge, S. J. L. (2013). Underneath the Bragg Peaks: Structural Analysis of ComplexMaterials,2nded.Amsterdam:Elsevier.[4]Caliandro,R.,Chernyshov,D.,Emerich,H.,Milanesio,M.,Palin,L.,Urakawa,A.,vanBeek,W.,ViterboD.(2012).J.Appl.Cryst.45,458-470.[5]vanBeek,W.,Emerich,H.,Urakawa,A.,Palin,L.,Milanesio,M.,Caliandro,R.,Viterbo,D.,Chernyshov,D.(2012).J.Appl.Cryst.45,738-747.[6]Milanesio,M., Palin, L.,Viterbo,D., Caliandro,R.,Urakawa,A., vanBeekW.,ChernyshovD. (2014).ActaCryst.A70,C1471.

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3P1.ElectrondiffractionstudyofpolyphasicnanocrystallineM2O-Al2O3-WO3(M=Na,K)system

EnricoMugnaioli,aIrynaAndrusenko,bYaşarKrysiak,bTatianaE.Gorelik,bDianaNihtianova,cUteKolb,b,daDipartimentodiScienzeFisiche,dellaTerraedell’Ambiente,UniversitàdegliStudidiSiena,Siena,Italy

bInstitutfürPhysikalischeChemie,JohannesGutenberg-Universität,Mainz,GermanycInstituteofMineralogyandCrystallography,BulgarianAcademyofSciences,Sofia,BulgariadInstituteofAppliedGeosciences,DarmstadtUniversityofTechnology,Darmstadt,Germany

enrico.mugnaioli@unisi.itIn the last century,X-ray crystallography allowed the determination of the atomic structure of hundreds ofthousandsofmaterials.Still,single-crystalX-raydiffractioncanbeperformedonlyoncrystallinedomainsofsome cubicmicrons,whilemany new synthetic phases do not grow in crystals of such dimensions.X-raypowder diffraction may be problematic for polyphasic samples and structures characterized by large cellparametersorpseudo-symmetry.On theotherhand, electrondiffraction is able todeliver3Dstructuraldatafromsinglecrystallitesoffewnanometers.Thisabilityderivesfromthehighcrosssectionbetweenelectronsandmatterandthepossibilitytofocustheelectronbeamintoananometricprobe.Inthelastyears,automateddiffraction tomography (ADT) emerged as an efficient method for acquiring complete and quasi-kinematicelectrondiffractiondataforab-initiostructuredeterminationofsub-micrometricphases[1-2].M2O-Al2O3-WO3 (M = alkaline metals) system attracted the attention of the scientific community becausesomeofitsmembersshowedpotentialapplicationsassinglecrystallinemediafortunablesolidstatelasers.Asystematic investigation of these phases is nonetheless hampered because it is impossible to produce largecrystalsandonlyinfewcasesapuresyntheticproductcanbeachieved.Inthisworkwepresentthestructurecharacterizationoftwohithertoundeterminedcompounds,K5Al(W3O11)2andNaAl(WO4)2,byacombinationofADTandprecessionelectrondiffraction [3].Ab-initio structuredeterminationwasobtainedbydata takenfrom single crystallites less than 100 nm in size, eventually sampled in polyphasic mixtures. Structuredeterminationwascomplicatedby thepresenceofpseudo-symmetry, thatwas revealedby3Dsingle-crystaldiffractiondata[4].K5Al(W3O11)2wasfoundtocrystallizeinmonoclinicspacegroupC2.Weakreflectionshk0withh=1,3,5maymisleadspacegroupassignmentforpoorcrystallographicdata,andprobablyarethereasonforthefailureofpreviousattemptsofstructuresolution.NaAl(WO4)2 can be synthesized only in a polyphasic mixture together with Na2W2O7, whose structure isknown from literature [5]. Both NaAl(WO4)2 and Na2W2O7 have a pseudo-hexagonal cell that must bereducedrespectivelytoC-centeredorthorhombicandC-centeredmonocliniccellsinordertoachievestructuredetermination.Actually, thestructureofNaAl(WO4)2, solved inspacegroupC2/c,was found tobe isotypicwithNaFe(MoO4)2structure,inagreementwithpreviousproposalsonthebasisofcompositional,metricandsymmetryresemblancesobservedinorientedelectrondiffractionzonepatterns.[1]U.Kolb,T.Gorelik,C.Kübel,M.T.Otten,D.HubertUltramicroscopy2007,107,507.[2]U.Kolb,E.Mugnaioli,T.E.GorelikCryst.Res.Technol.2011,46,542.[3]E.Mugnaioli,U.Kolb,T.GorelikUltramicroscopy2009,109,758.[4] I. Andrusenko,Y.Krysiak, E.Mugnaioli, T.E.Gorelik,D.Nihtianova,U.KolbActaCrystallogr. B, doi:10.1107/S2052520615007994.[5]K.Okada,H.Morikawa,F.Marumo,S.IwaiActaCrystallogr.B1975,31,1200.

39

3P2.AverageandLocalstructuralcomparisonofBaTi1-xCexO3byPairDistributionFunction

GiorgiaConfalonieria,MonicaDapiaggia,VincenzoBuscagliab,GiovannaCanubandAndreaBernasconicaDepartmentofEarthSciences,UniversityofMilan,Milano,Italy.giorgia.confalonieri@unimi.it

bIENI-CNR,Genova,ItalycEuropeanSynchrotronRadiationFacility(ESRF),Grenoble,France

BaTiO3isconsideredasatypicalferroelectricmaterial.Itpresents,withatemperaturedecrease,theclassicalphase transition from a paraelectric cubic structure to ferroelectric phases (progressively: tetragonal,orthorhombicandrhombohedral).ThesolidsolutionswithotherBaMIVO3perovskites(M=Sn,Zr,Hf,Ce)canstronglymodifythesetransitionsandtherelatedpolarbehaviors.Somematerialsshow,dependentlyfromthedopant type and amounts, a variation fromconventional ferroelectric, via diffuse ferroelectric transition to aclearrelaxorstateandfurthertodipolarglassbehaviour[1].ConsideringthatBaTiO3-basedsolidsolutionsareenvironment-friendly dielectricswith similar performances asmany toxic Pb-based electroceramics [2], thestudyof thesecompoundsbecomesa topicofgreat interest andacurrentmatter.Different researcheshaveinvestigated these systems, but the relation with the average crystallographic structure, the local order andelectric properties is still mostly unknown. Just few previous studies, as for the BaTi1-xZrxO3 [3], haveaddressed the issue demonstrating the existence of a structural local disorder linked to the evolution of thepolarbehaviour.InthisworkBaTi1-xCexO3ceramicsolidsolutionswithdifferentceriumamounts(x=0.05,0.10,0.20)arepresented.ThissystemrepresentsalimitandinterestingcaseduetoalargedifferenceintheTiandCe atomic radius ( rCe4+= 0.87Å and rTi4+= 0.605Å), and because this kind of substitution does notinvolve the creation of charge compensating lattice defects. As indicated by dielectric permittivitymeasurements, the three samples under study correspond to a different polar behaviour: conventionalferroelectric (x= 0.05) but close to the so-called pinched transition, diffuse phase transition (x= 0.10) andnon-ergodicrelaxor(x=0.20).TotalscatteringdatahasbeencollectedID22highresolutionbeamline,ESRF(EuropeanSynchrotronRadiationFacility;Grenoble,France)inarangebetween100and400Kevery100Ktoexplorethephasetransitionsassociatedtoeachsample.PairDistributionFunction(PDF)refinementshavebeenperformedwiththeaimofunderstandingtheinduceddifferencesbetweenaverageandlocalstructureasa function of composition and temperature. The Rietveld and average PDF results show a good agreementwiththestructuralhypothesissuggestedbythedielectricpermittivitymeasurements.Ontheotherhand,PDFsanalysis also highlights a clear local disorder for all the samples. Often local and average structure haverequired different space groups to be fitted appropriately. PDFs comparison and structural refinementsdemonstrate in fact a clear local evolution of Ti-O and Ce-O bond distances with temperature and by theincreaseoftheceriumamount.

[1]V.V.ShvartsmanandD.C.LupascuJ.Am.Ceram.Soc.2012,95(1),1-26.[2]C.Ciomaga,M.Viviani,M.T.Buscaglia,V.Buscaglia, L.Mitoseriu,A. Stancu, P.Nanni J. Eur.Ceram.Soc.2007,27,4061-4064.[3] V. Buscaglia, S. Tripathi, V. Petkov,M. Dapiaggi,M. Deluca, A. Gajovic, Y.J. Ren J. Phys.: Condens.Matter.2014,26,065901.

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3P3.PhotocatalyticShapingofSilverNanoprismsSelf-AssembledonAnataseThinFilms

GianluigiMarra,aGuidoPanzarasa,bGuidoSoliveri,cSilviaArdizzonecaEniRenewableEnergy&EnvironmentalR&D,Novara,Italy

bDipartimentodiScienzeeInnovazioneTecnologica,UniversitàdelPiemonteOrientale,Alessandria,Italy.guido.panzarasa@unipmn.it

cDipartimentodiChimica,UniversitàdegliStudidiMilano,Milano,ItalyFilms made of highly photoactive titanium dioxide (anatase) were deposited on silicon substrates by anelectrochemically-assisted technique. Citrate-stabilized silver nanoprisms (mean side length 40 nm, meanthickness 5 nm) were then self-assembled on titania. The process was aided by functionalizing the filmsurfacewith 3-aminopropyltriethoxysilane (APTES) to exploit the electrostatic interaction betweenpositivelychargedaminegroups andnegatively charged silvernanoprisms.Silvernanoprismsdistributedevenlyon thesurfaceandtheirshapewasnotaffectedbythedepositionprocessasconfirmedbyelectronmicroscopy.However, by irradiation with 365 nm-UV light for less than 1 h, dramatic changes in both the shape andsurfacedistributionofattachedsilvernanoprismswereobserved(Figure1).Whilethebiggerprismschangedinto discoidal particles, the smaller dissolved. Such new particles displayed different plasmonic propertiescomparedtopristinenanoprisms.Titaniumdioxideisknowntoproducehighlyreactiveoxygenspecies,suchas hydrogen peroxide and hydroxyl radical, underUV irradiation. Silver nanoprisms are sensitive to reactiveoxygen species and display relevant optical properties (surface plasmon resonance).Both photocatalytic andplasmonicaspectsmustthenbeconsideredtodelineatethephotoshapingmechanism.By performing the irradiation through a photomask, defined patterns with micrometer resolution could beeasilyobtained evenon transparent substrates, openingnew scenarios, for example, development of surfaceenhancedRamanscattering(SERS)sensors.

Figure1.Self-assembledsilvernanoprismsonAPTES-functionalizedtitaniumdioxideinthedark(left)andafterUVirradiation(right).

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MS4.NEWTOPICSINCRYSTALGROWTHRESEARCH

What’s new on experimental and theoretical aspects of crystal growth and its applications. Topics may alsoinclude but are not limited to: crystallization in nano-composites or nanospace; crystals for energyconversion and storage; growth, characterization and technological developments of new crystallinematerials; innovative growthmethods; newperspectives in crystallizationand resolutionof chiral systems;new theoretical and experimental approaches for the control of crystal polymorphism and crystal habitmodifications.Chair:SilviaRizzato(U.Milano)

42

4KN1.Uncoveringtheroleofsolventinorganiccrystalsnucleationandgrowth

MatteoSalvalaglio,a,b,caInstituteofProcessEngineering,ETHZurich,CH-8092Zurich,Switzerland,

bFacoltàdiInformatica,IstitutodiScienzeComputazionali,UniversitàdellaSvizzeraItalianaViaG.Buffi13,CH-6900Lugano,Switzerland,

cpresentaddress:ChemicalEngineeringDepartment,UniversityCollegeLondon,TorringtonPlaceLondon,WC1E7JE,UnitedKingdom,matteo.salvalaglio@gmail.com

Nucleation and growth of crystals from solution are important and yet only partially understood physical-chemical transformations, playing key roles in a wide variety of systems both in nature and in the processindustry. Understanding crystallization at the molecular level is key to control and predict properties ofcrystals. Reaching towards this goal is a multidisciplinary challenge that greatly benefits from the interplaybetweentheory,simulationsandexperimentaltechniques.In this seminar the use of advancedmolecular simulationmethods [1] to investigate both crystal nucleationandgrowthwillbediscussed.The paradigmatic case of urea will be analyzed. In fact, despite being a rather simple organic molecule, itdisplaysarichcrystallizationbehavior.Ureanucleationfromsolutionhasbeenfoundtofolloweitherasingle-step or a two-stepmechanism depending on the solvent.Moreover in the early stages of urea nucleation, acompetition between polymorphic structures has been observed to take place [2-4]. Also concerning thedevelopmentof solvent-specific crystalmorphologiesurea represents an interestingcase study.Experimentalevidenceshighlightthat thesolutioncompositionaffectsureacrystalhabitsallowingaccessingawidevarietyofmorphologies:fromelongatedneedle-likeprismstocompacttetrahedra.Inthiscontextenhancedsamplingsimulations allow to assess the role of both solvents and additives, to uncover face-specific growthmechanisms[5]andtopredictsteadystatemorphologiesobtainedfordifferentsolutions[6].

Figure1.Ureanucleationandgrowthfollowsolvent-dependentroutesandgenerateavarietyofmorphologies.[1]A.Barducci,G.Bussi,andM.ParrinelloPhys.Rev.Lett.,100:020603,2008.[2]F.Giberti,M.Salvalaglio,M.Mazzotti,Parrinello,M.,Chem.Eng.Sci.121,51-59,2015,[3]M.Salvalaglio,C.Perego,F.Giberti,M.MazzottiandM.Parrinello,Proc.Natl.Acad.Sci.,112(1),E6-E14,2015.[4]M.Salvalaglio,M.MazzottiandM.Parrinello,FaradayDiscuss.doi:10.1039/C4FD00235K2015.[5]M.Salvalaglio,T.Vetter,F.Giberti,M.MazzottiandM.ParrinelloJ.Am.Chem.Soc.134,17221–17233,2012.[6]M.Salvalaglio,T.Vetter,M.Mazzotti,M.Parrinello.Angew.Chem.Int.Ed.52,13369–13372,2013.

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4KN2.Theroleoftheadhesionenergyinsurfaceandinterfacegrowthprocesses:apatitesandalkali-halides.

LindaPasteroa,DinoAquilanoaaDipartimentodiScienzedellaTerra,UniversitàdegliStudidiTorino,Torino,Italy.

linda.pastero@unito.itTheadhesionenergy(βadh) is theunderlying themeofseveralsurfaceand interfacialphenomenaas twinningandepitaxially ruledgrowthofcrystallinephases.Related to theadhesionenergy, theconceptof thesurfacewettingcangiveanimmediateimageofwhatcouldhappenintwo-ormorephasessystems:thewettingcouldrange from inexistent to better than perfect, generating or not structured interfaces, according to thethermodynamicconditions.A geometrical approach (the theoretical analysis of the surface and interface structure) followed by thecalculationofthesurfaceenergyandoftheinterfaceenergy[1,2,3,4]arequantitativeandunambiguouswaysto decode a sometimes weird-looking growth behavior of crystals. This method can be applied tohomogeneous and heterogeneous systems, and then can be related to apparently unrelated phenomena astwinningoradsorptionfollowedbyepitaxy.Inthiscontribution,theunifyingroleoftheadhesionenergywillbediscussedfromtheexperimentalpointofview, focusing on the growthmorphology and association of some interesting phases as apatites and alkali-halides.

Figure1.a)andb)twinnedsyntheticapatites,c)alizarinred,epitaxiallygrownonNaCl,d)KClgrowninthepresenceoflead

[1]R.KernCryst.Res.Technol.,2013,48(10),727-782,doi:10.1002/crat.201200704[2]D.Aquilano,M.Bruno,M.Rubbo, F.R.Massaro,L. PasteroCryst.GrowthDes.,2014, 14 (6), 2846–2852,doi:10.1021/cg5001478[3]D.Aquilano,M.Bruno,M.Rubbo,L.Pastero,F.R.MassaroCryst.GrowthDes.,2015,15 (1),411–418,doi:10.1021/cg501490e[4] M. Bruno, M. Rubbo, L. Pastero, F. R. Massaro, F. Nestola, D. Aquilano Cryst. Growth Des., 2015,doi:10.1021/acs.cgd.5b00389

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4O1.TurningliquiddrugsintocrystalsAlessiaBacchi,DavideBalestri,DavideCapucci,PaoloPelagatti

DipartimentodiChimica,UniversitàdegliStudidiParma,Parma,Italy

alessia.bacchi@unipr.itTheobjectiveof thisworkis tofindasystematicwaytoembedliquidorvolatilemolecules insidecrystallinematerials,with themultiple aimsof stabilizing them,of tuning theirpossiblewaysofdelivery inmedicineoragrochemistry,andtoexplorenewregulatoryandintellectualpropertiesissues.Liquidorvolatileformulationsof active pharmaceutical ingredients (APIs) are intrinsically less stable and durable than solid forms; in factmost drugs are formulated as solid dosage because they tend to be stable, reproducible, and amenable topurification.Mostdrugsandagrochemicalsaremanufacturedanddistributedascrystallinematerials,andtheiraction involves the delivery of the active molecule by a solubilization process either in the body or on theenvironment.Thepoorsolubilityofpharmaceuticalactive ingredients (API)or the reverse toohighsolubilityofagrochemicalsareproblemsoftenencounteredintheirformulationsincethesephenomenalimitrespectivelythe bioavailability of the API or the duration of the action of the agrochemical. However some importantcompounds for the human health or for the environment occur as liquids at room temperature. We havedefined a benchmark ofmolecules relevant to humanhealth and environment that have been combinedwithsuitable partners according to the well known methods of crystal engineering in order to embed them incrystallinehosts.Ourapproachistwofoled,byusingcocrystalsandMOFs.Theformationofco-crystalshasbeendemonstratedasameansoftuningsolubilitypropertiesofsolidphases,and therefore it is widely investigated by companies and by solid state scientists especially in the fields ofpharmaceuticals, agrochemicals, pigments, dyestuffs, foods, and explosives. In spite of this extremely highinteresttowardsco-crystallizationasatooltoaltersolubility,practicallynoemphasishasbeenpaidtousingitasameanstostabilizevolatileorlabileorliquidproducts.InthisworkwetrapandstabilizevolatileandliquidAPIsandagrochemicals incrystallinematricesbyengineeringsuitableco-crystals.Thesenewmaterialsalterthephysicstateoftheactiveingredientsallowingtoexpandthephasespaceaccessibletomanufacturinganddelivery.We also explore the possibility to include liquid APIs inside the pores of suitable designedMOFs,againwiththeaimofstabilizingtheirsolidstateformulation(Figure).

Figure1.ElectrondensitymapofnicotineembeddedintheMOFPCN6.

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4O2.Exploitingdimensionalvariabilityincoordinationpolymers:solventpromotesreversibleconversionbetween3Dandchiral1Darchitectures

MarzioRancan,a,bLidiaArmelaoa,baDipartimentodiScienzeChimiche,UniversitàdegliStudidiPadova,Padova,Italy

bCNR-IENI,Padova,Italy.marzio.rancan@unipd.itCoordination polymers generated frommetal centres and polytopic ligands have attracted increasing interestalong the last two decades. Indeed, they are an excellent bench test for self-assembly concepts and awidesourceofnewfunctionalmaterials.Despitethemassiveattentiondevotedbyresearcherstothesecompounds,thepredictabilityof the finalnetworkanddimensionality is still anopenchallenge. In fact, the self-assemblyprocess involves competing reversible and simultaneous interactions among the metal, the ligand, thecounteranion and the solvent. In particular, the solvent has themost ambiguous and unpredictable role. Thecoordinating ability of some solvents can play a crucial role in promoting the network dimensionality, asevidencedbyfewbutsignificantworks.Inthiscontext,westudiedtheself-assemblybetweenCu(II)ionsand4,4´-bipyridine (bpy) in the presence of the highly coordinating DMSO solvent and we showed that itpromotes a reversible conversion between a 3D network and a chiral 1D Cu-bpy based polymer. DMSOpromotestheformationofboththearchitecturesaswellasthedimensionalvariabilitybyblockingadifferentnumberofcoordinativesitesofCu(II)ions.Thisallowstoselectivelyandreversiblyobtaina3Dnanoporousnetwork and a 1D chiral polymer. The crystal growth of the 1D or 3D architecture can be tuned throughchemico-physical parameters such as the presence of a co-solvent or the evaporation rate.Notably, the 1Dchiral architecture is obtained from achiral building blocks and it displays spontaneous resolution during thecrystallizationleadingtoaracemicmixtureofenantiomericpuresinglecrystals.[1]M.Rancan,L.Armelao,submitted2015.

46

4O3.Catalyst-freevapour-phasegrowthofGa2O3nanowiresandnanobelts

AlabiAderemia,CalestaniDavideb,CoppedèNicolab,VillaniMarcob,LazzariniLaurab,FabbriFilippob,ZappettiniAndreab

aDepartmentofPhysics,UniversityofIlorin,Ilorin,Nigeria,bCNR-IMEM,Parma,Italy.

zapp@imem.cnr.itGalliumoxide is a transparent conductingoxide (TCO)with awide transparency range (bandgap energy isabout 4.9eV), high chemical stability, n-type conductivity, and strong blue photoluminescence (PL). Itcrystallizes in five known crystallinemodifications (α, β, γ, δ and ε phases), amongwhich β-Ga2O3 is themost stable polymorph. The β-phase Ga2O3 is characterized by a monoclinic crystal structure with twodistinct gallium sites (six-and four-coordinated) and threeoxygen sites (three- and four-coordinated).Nativepoint defects are known to form readily in this complex oxide lattice and are responsible for a range ofimportantphysicalproperties.Specifically,oxygenvacancieshavebeenproposed to lead to the formationofshallowdonorstateswhichareconsideredtobethesourceofn-typeelectricalconductivity.In recent years, low-dimensional β-Ga2O3 structures including NWs, nanobelts, nanorods and nanosheetshave attracted growing attention of researchers due to their superior properties as compared to their bulkcounterpart.Onevery importantadvantageofβ-Ga2O3NWs is their large surface tovolume ratioprovidingmore surface states to interactwith the surroundings.The strongblue light emissionpropertyof theGa2O3nanobelts also suggests them as new candidates for fabricating functional optoelectronic nanodevices andnanosizesensors.In this work we report the successful synthesis of β-Ga2O3 nanowires/nanobelts using simple a physicalevaporation technique, derived from previous experiments on the vapour phase growth of metal oxidenanostructures fromasimplemetal source.Nanostructureshavebeengrownondifferentkindof substrates(silicon,alumina,sapphire)startingfrommetallicGasourcethat,intheproperalternationofargonandargon-oxygenmixtureatmospheres,evaporates,depositsandfinallyfeedsthegrowingnanocrystalsbyreactionwithoxygeninthepropertemperaturerange.Nocatalysthavebeenusedtoforcethenucleationofnanowiresandnometal-organicprecursorhavebeenused,sothatonlyhighpurityβ-Ga2O3nanostructurescanbeobtained.Asacaseofstudy,nanowireshavebeengrownalsoonAuandPtfilmsforcomparison.Themorphological, structural andoptical properties of theobtainednanostructures havebeen characterized,revealingthin(mainlyrangingfrom5to20nm)andlong(uptotensofmicrometers)nanowire-ornanobelt-shaped crystals. Their properties have been studied by means of SEM and TEM microscopy as well ascathodoluminescence,mainlycomparingresultsobtainedfordifferentgrowthconditionsandsubstrates.

Figure1.SEMimageofβ-Ga2O3nanowiresandnanobeltsobtainedonaluminasubstrate.

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4O4.NewFluorinatedMetal-OrganicFrameworksSelf-AssembledviaHalogenBonding

GiancarloTerraneo,VijithKumar,FranciscoFernández-Palacio,GabriellaCavallo,PierangeloMetrangolo,GiuseppeResnati

NFMLab,D.C.M.I.C.“GiulioNatta”,PolitecnicodiMilano,ViaL.Mancinelli7,20131,Milan,Italy.giancarlo.terraneo@polimi.it

Metal–organic frameworks (MOFs) are composed of organic linkers and coordinating metals that self-assemble to form a crystallinematerial with tunable porosity. Their synthetic modularity and inherent long-rangeordercreateopportunitiesforuseasnewfunctionalmaterialswithapplicationsinareasasgasstorage,separationandcatalysis[1].Recently, the useful properties of fluorinated molecules prompted the preparation of MOFs containingfluorinated linkers (F-MOFs).Enhanced thermalandchemical stability,highhydrophobicityof theporesandlow surface energy are expected. Up to now only a few F-MOFs have been reported and they are mainlyrelatedtogasabsorption,especiallyH2[2].TuningthepropertiesofthenetworkviastructuralcontrolisoneofthekeychallengesintheMOFsfield.Coordinationbonds(CBs)areclearlythemaindrivingforceinMOFsself-assembly, but other supramolecular interactions could play a significant role. The strong electron-withdrawing effect of fluorine makes iodinated perfluoro-motifs ideal for the formation of strong halogenbonds (XBs). Here we report the exploitation of a cooperative approach between XB and CB for the self-assembly of F-MOFs. A new Cu(II)-F-MOF containing unsaturated metal centres shows selective andreversiblesolventabsorptionaccompaniedbysolvatochromiceffect.[3][1](a)Li,J-R.;Kuppler,R.J.;Zhou,H-C.Chem.Soc.Rev.2009,38,1477-1504.(b)Lee,J.G.;Fahra,O.K.;Roberts,J.;Scheidt,K.A.;Nguyen,S.T.;Hupp,J.T.Chem.Soc.Rev.2009,38,1450-1459.[2] (a) Yang, C.; Wang, X.; Omary, M. A. J. Am. Chem. Soc. 2007, 129, 15454-14455. (b) Hulvey, Z.;Falcao,E.H.L.;Eckert,J.;Cheetham,A.K.J.Mater.Chem.2009,19,4307-4309.[3] (a) Bertani, R.; Sgarbossa, P.; Venzo, A.; Lelj, F.; Amati, M.; Resnati, G.; Pilati, T., Metrangolo, P.;Terraneo, G. Coord. Chem. Rev. 2010, 254, 677-695. (b) Martì-Rujas, J.; Colombo, L.; Lü, J.; Dey, A.;Terraneo,G.;Metrangolo,P.;Pilati,T.;Resnati,G.Chem.Commun.2012,48,8207-8209.

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4P1.Cu2-xSultrathinfilmsobtainedbyelectrodeposition:astructuralcharacterization

AndreaGiaccherinia,FrancescoDiBenedettob,SerenaCinottia,GiordanoMontegrossic,AnnalisaGuerria,FrancescoCarlàd,RobertoFelicid,MassimoInnocentia

aDepartmentofChemistry,UniversityofFlorence,ViadellaLastruccia3-13,50019SestoFiorentino(Florence),Italy

bDept.EarthSciences,Univ.Florence(Italy),ViaLaPira4,50121Firenze,ItalycIGG,IstitutodiGeoscienzeeGeorisorse,CNR,viaG.LaPira4,50121,Firenze,Italy

dESRF,6,RueHorowitz,F-BP220,38043,Grenoble,Cedex,Franceannalisa.guerri@unifi.it

Recentdevelopmentsinthefieldofthinfilmmanufacturingresultedintheproductionofawiderangeofnewmaterials for photovoltaic application [1]. A particular interest focuses on thin films realized by mildapproaches, as electrochemical deposition, giving the opportunity of working under standard laboratoryconditionswithout requiring expensivevacuumequipments. In this contributionwe report about our studiesdevotedtothegrowthofsemiconductors,of interest in thesolarenergyconversionfield,preparedusing theE-ALD(ElectrochemicalAtomicLayerDeposition)method to synthesizeap-n junction ina single step.Theelectrodepositedfilmsareusuallyultrathinandrequirespecificinvestigationmethodstobefullycharacterized.Inourcase,thestructureofthegrowthfilmswasstudiedbymeansofSXRD(SurfaceX-RayDiffraction).In-situ and ex-situ SXRD measurements were performed at the ID03 Surface Diffraction beamline of theESRF(Grenoble).Thein-situmeasurementsaimedtotheinvestigationofthegrowthmechanismofCu-Sultrathin films on the (111) crystal plane of a silver single crystal, commonly used as aworking electrode. ThegrowthofthefilmwasmonitoredbyfollowingtheevolutionofthediffractionpatternaftereachE-ALDstep.Bragg peaks, characteristic of the growth film, became observable after R 15 E-ALD cycles and theirevolutionhasbeenfollowedupto60E-ALDcycles.BreadthandprofileanalysisoftheBraggpeaksleadtoaqualitativeinterpretationofthegrowthmechanism,inthenormaland in-planedirections,with respect to theAgsurface.Namely, thecontributionofcrystal strainandcrystallitesizewereidentifiedbythewidthanalysisoftheBraggreflections.

Figure1.Mappingofthereciprocalspaceofthethinfilmsonthe(h,k,1.05)planeofthesilverlattice,bymeansofanhexagonalcell

Thepreliminaryinterpretationoftheexperimentalreciprocallattice,coupledtotheSEMinvestigation,suggeststhat thesamplesshowapseudosinglecrystaldiffractionpattern.Thiscanbedescribedbyanewhexagonalunit cell. The crystal structure of this electro-deposited Cu2-xS could be related to that of chalcocite, inparticularconsideringthelayeringoftriangularCusitesandoctahedralCusites.Theinfluenceoftheappliedelectricpotentialonthestabilityoftheelectro-depositedcrystalstructurehasbeenmonitored bymeans of SXRDmeasurements performed during the switch off of the potential.A structuralchange was, in fact, registered, and correlated to the occurrence of the stable phases under conventionallaboratoryconditions.[1]B.W.GregoryandJ.L.Stickney,J.Electroanal.Chem.,1991,300,543

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4P2.Recrystallizationbehaviorofamorphousvenlafaxinefreebasepreparedbymelttechnique

LorellaGiovannelli,LorenaSegale,RobertoNegri,GiovanniBattistaGiovenzana,FrancoPattarinoDipartimentodiScienzedelFarmaco,UniversitàdegliStudidelPiemonteOrientale“A.Avogadro”,Novara,

Italy;lorella.giovannelli@uniupo.itVenlafaxine, a bicyclic phenylethylamine-based compound, is an antidepressant administered orally ashydrochloride (VHC).VHC is relatively aggressive towardshandling equipment and it is irritating to the skin[1].Venlafaxinefreebase(VB)iseasiertohandle,butsignificantlylesssolubleinwatercomparedtoVHC.Asreportedinliterature,VBmayexistinthreecrystallinephases(FormI,FormIIandFormIII)[2].Crystalline-to-amorphousphase transformationrepresentsoneof theapproachesable to improve thesolubilityofpoorlywater-soluble drugs. Compared to the crystalline counterpart, the amorphous materials are endowed withhigher molecular mobility and enhanced thermodynamic properties. These features lead to high apparentsolubility and dissolution rate, and so potentially enhancing the bioavailability [3]. However, due to theirmetastable nature, amorphous solids are often characterized by a notable spontaneous crystallization. Thepurposeofthisstudywastoevaluatesolid-solidphasetransformationthatmayoccurintheamorphousformof VB prepared by melt process. VB was melted at 80 °C and analyzed by DSC and XRPD immediately(VBmelt)andafter24hoursstorageatroomtemperature(VBmelt-1d).Figure 1a shows that crystalline VB was in Form I (Tmelt ~75 °C); during the temperature scanning, VBtransformedintoadifferentcrystallinephase,consistinginamixtureofFormIIandIII(Tmelt~77°Cand78°C, respectively). The drug analyzed immediately after the melt process (VBmelt) was fully amorphous. Aspontaneoussolid-solid interconversionoccurredwithin1day:DSCprofileofVBmelt-1dshowedthat itwascomposedofForm IIIwith small percentagesofForm II.The comparisonofXRPDdiffractogramsof thethree formsofVB[4]with those reported inFigure1bevidenced thatVBmelt-1dwasamixtureofFormIIandFormIII.AmorphousVBcompletelyrevertedbacktothecrystallinestatewithin1day.Toavoidpatentingissuesandtofollowtheregulatoryrequirements,nucleationandcrystalgrowthofamorphousdrugsduringtheshelflifeofpharmaceuticalproductsmustbeprevented.

Figure1.a:DSCprofilesofVB,VBmelt,VBmelt-1d(endoup)andb:XRPDofVBandVBmelt-1d.

[1]R.Keltjens,F.Picha,C.Escol.USPatent,2003/0191347A1.[2]J.Th.H.vanEupen,W.W.J.Elffrink,R.Keltjens,P.Bennema.Cryst.GrowthDes.2008,8,71.[3]R.Laitinen,K.Löbmann,C.J.Strachan,H.Grohganz,T.Rades.Int.J.Pharm.2013,453,65.[4]J.Th.H.vanEupen,R.Westheim,M.A.Deij,P.Bennema,E.Vlieg.Int.J.Pharm.2009,368,146.

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4P3.AcomputationalapproachtothestudyofepitaxyMarcoBruno,aMarcoRubbo,aLindaPastero,aFabrizioNestola,bDinoAquilanoa

aDipartimentodiScienzedellaTerra,UniversitàdegliStudidiTorino,Torino,Italy,bDipartimentodiGeoscienze,UniversitàdegliStudidiPadova,Padova,Italy

marco.bruno@unito.itCrystallineinterfacesarethemostcommonmicrostructures.Theydeterminechemicalandphysicalpropertiesof devices for applications in mechanics, electronics, medicine, in material chemistry for designing andengineeringofcompositematerials.Thisworkisacontributiontothecharacterizationofepitaxialinterfaces.When,attheinterfacewhereepitaxyoccurs, the misfit between 2D lattice is low, interfaces relax with negligible in plane stress and adhesionenergy can be calculatedwithout the need of considering interface dislocations.We are interested to naturalsystemsandtothecontributionthatcrystalgrowththeorycangivetounravelquestionssuchas:canolivine,(Mg,Fe)2SiO4,nucleateonsomediamondfacesinconditionofnegativeaffinity?Avalidcontributiontotheseitemscanonlycomebythecouplingofthelaboratoryandfieldobservationswiththecalculationsofadhesionandinterfaceenergy.In thiscontribution the theoreticalandcomputationalaspects related to thedeterminationsof the(i) interfacestructure, (ii)adhesionenergyand (iii) interfacialenergyofa systemcomposedby twocrystallinephases inepitaxialrelationship,arediscussed.Specifically,wedescribethepossible2Dlatticecoincidencesbetweentwophases in epitaxial relationship, as well as all of the possible initial interface configurations which generatewhen different surface terminations of the phases put in contact are taken into account. Then, in order toelucidatethesetheoreticalaspects,wehavestudiedthefollowingepitaxiesinanaturalsystem:{110}-diamond(C)/{101}-forsterite (Mg2SiO4), {001}-diamond/{001}-forsterite and {111}-diamond/{001}-forsterite [1].Theoptimizedinterfacestructuresandtheiradhesionenergiesweredeterminedatabinitiolevel.

Figure1.{110}-diamond/{101}-forsteriteinterfaceviewedalongthe[010]directionofforsterite.[1]M.Bruno,M.Rubbo,L.Pastero,F.R.Massaro,F.Nestola,D.AquilanoCrystalGrowth&Design.2015,doi:10.1021/acs.cgd.5b00389.

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4P4.Facileintercalationoforganicmoleculesintohydrotalcitesbyliquidassistedgrinding:yieldoptimizationbyachemometricapproach

ValentinaToson,aEleonoraConterosito,aLucaPalin,a,bEnricoBoccaleri,a

MarcoMilanesio,aValentinaGianottiaaDISIT,UniversitàdelPiemonteOrientale“A.Avogadro”,Alessandria,Italy

bNovaRes,Novara,Italy.valentina.toson@uniupo.itInarecentwork,afastandconvenientmethod,namelyliquidassistedgrinding(LAG),forthepreparationoffunctional materials based on organic molecules intercalated into hydrotalcite (LDH) was developed anddemonstrated1. LAG can profitably produce hybridmaterialswith facile preparation routes,mild conditions,low solvent consumption, short reaction times and high yields. It can also allow an easy scale up of thesynthesis to industrial production.The currentwork employs a chemometric approach to optimize theLAGparameters for sulfonic intercalation in nitrate exchanged hydrotalcite (HTLC-NO3). Six suitable molecules,three aliphatic sulfonic surfactants and three naphthalensulfonic acids,were employed as negatively chargedintercalants to evaluate the conditions and the efficiency of LAG method. The completeness of theintercalationandtheyield(%intercalation,calculatedas(LDH_2-NSA/(LDH_2-NSA+LDH_NO3))*100)wereestimated and quantified using XRPD analysis with Rietveld refinement, using Topas TA4 and single peakrefinements. Using the same standard recipe (hydroalcoholic liquid phase, stoichiometric intercalant/nitrateratio,grindingtime)differentintercalationyieldsforthemoleculeswerefound,demonstratingtheclearroleofthemoleculesstructuralandchemicalfeaturesintheprocess.Asacasestudy,theintercalationyieldvariabilityof2-naphtalenesulfonicacid(2-NSA)wasinvestigatedusingadesignofexperiment(DoE)approach,inordertoachievethebestconditionsformaximumintercalationyieldscase.Experiments were performed in accordance to factorial design2 and Simplex3 algorithms, varying twoexperimentalfactors,theamountofNaOHandpercentofEthanolintheliquidcomponentoftherecipe,whiletheprocedureandtheotherparameterskeptconstant.Froma starting intercalationyieldof 2-NSAof about 40-50%using the reference recipe, a preliminaryDoEapproach using the Factorial Design resulted able to improve it of up to 66%. However, this method wasconsiderednotfullysuitableforyieldoptimization,forthelimitedvariabledomainexplorationandtheiraprioridefinition on the basis of previous OVAT (One Variable At Time) experiments. Conversely, the Simplexalgorithm resulted the optimalDoE tool to reach the best conditions in few experiments, also in absence ofpreliminaryexperiments.ExperimenttrackwithSimplexledtoa2-NSAintercalationyieldimprovementupto76%, which can be considered a physico-chemical limit of the system for one-step intercalations (higheryieldswere achieved by repeated LAG exchanges of LDH-NSA samplewith freshNaOH/Ethanol solution).Simplex evidences highlighted also an antagonist effect between NaOH and EtOH, undetectable with OVATmethods. The LAG-obtained compounds, despite the completely different reaction conditions (i.e. solvent-free),resultedsimilartosolvent-intercalatedproducts,asdemonstratedbyXRPD,TGAandDR-UV-Visdata.[1] E. Conterosito,W. Van Beek, L. Palin, G. Croce, L. Perioli, D. Viterbo, G. Gatti, M.Milanesio,Cryst.GrowthDes.2013,13,1162.[2]R.A.Fisher,J.MinistryAgric.1926,33,503.[3]W.Spendley,G.R.Hext,F.R.Himsworth,Technometrics.1962,4,441[4]A.A.Coelho,J.Appl.Cryst.2005,38,455.

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4P5.NewCo-crystalsofSalicylicacid:fromscreeningtosynthesisandstructuralcharacterization

AnieleZ.Tier,a,bAndreiL.Belladona,aClarissaP.Frizzo,aMarcosA.P.Martins,aLuciaCarlucci,bDavideM.Proserpio,bc

aNUQUIMHE,DepartmentofChemistry,FederalUniversityofSantaMaria,SantaMaria,BrazilbDipartimentodiChimica,UniversitàdegliStudidiMilano,Milano,Italy

cSamaraCenterforTheoreticalMaterialsScience,SamaraStateUniversity,Samara,Russia.annetier@gmail.com

Fewareasof crystal engineeringhave, in recent times, received the sameamount of attention that has beenlavisheduponalmostanytopicdealingwithco-crystals.Manyco-crystalshavebeenpreparedthroughstronghydrogenbonds,notablybetweenacarboxylicacidandanN-grouphydrogen-bondacceptor.[1]Toassesstheutilityof these synthons,wepresenthereour studieson the supramolecular reactionsbetween salicylic acid(SA) with six co-formers (tyramine (Tyr), 1,2-Phenylendiamine (Phen), paracetamol (Par), ibuprophen(Ibu), diglycine (Dig) and triglycine (Trig)). The co-crystals are first screening usingDifferential ScanningCalorimetry (DSC) and synthesized byLiquidAssistedGrinding (LAG).A single crystal ofSA•••Phen andSA•••Trig were obtained by slow evaporation method using methanol as solvent in the first case and amixture of methanol:water (9:1) in the second case. The mixtures were characterized by thermal analysis(DSC and Thermogravimetric Analysis (TGA)), Powder X-RayDiffraction (PXRD), infrared spectroscopy(IR) and Single Crystal X-Ray Diffraction (SCXRD) when possible. From the initial screening and dataobtainedsofar, itcanbeconcluded:(i)Theco-formersstudied,SA•••PhenandSA•••Trig formedasinglecrystaland thestructureswerecharacterizedusingSCXRD. (ii)SA•••IbuandSA•••Dig,showedpotentialto form co-crystals by screening conducted using DSC. Furthermore, the PXRD spectrum showed somesignificant changes in the samples prepared through the LAG method. (iii) SA•••Par need furtherinvestigation, includingnewcrystallizations and studyofnew ratiosbetween the components.Dataobtainedfor the SA•••Par (1:1), prepared through the slow evaporation of the solvent and LAG method, are notconclusivetoobserveinteractionsbetweenthesecomponents.

Figure1.Newco-crystalsfromsalicylicacid.[1]C.B.Aakeröy,J.Desper,B.M.T.ScottChem.Comm.2006,1445.

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4P6.MorphologicalandStructuralEffectsofGelsonCoordinationPolymersCrystallization.

SilviaRizzatoa,MassimoMoretc,MarcoMerlinib,AlbertoAlbinatia,FabioBeghiaaDipartimentodiChimica,UniversitàdiMilano,ViaGolgi19,Milano,Italy

bDipartimentodiScienzedellaTerra"ArditoDesio”,UniversitàdiMilano,ViaBotticelli23,Milano,ItalycDipartimentodiScienzadeiMateriali,UniversitàdiMilanoBicocca,ViaRobertoCozzi55,Milano,Italy.

silvia.rizzato@unimi.itTheuseofgelsorviscousmaterialsasgrowthmediaforawiderangeofcompounds,includingproteinsandinorganicandorganiccompoundshasbeenreportedintheliterature.Inthepresenceofgel,sedimentationandconvection currents are greatly suppressed and the mass transport of the molecules mainly occurs bydiffusion,resulting,usually,inalowernucleationdensityandabettercrystalquality.[1a]Here we report some new interesting phenomena observed in crystallization experiments of coordinationcompounds,suchas,“coordinationpolymers”,byusinggelsasdiffusionmedia.[1b]By using a semi-liquid silica-gel system as a dispersionmatrix, we were able to increase the quality of thecrystals but also slow down the solvent loss, stabilizing the partially dehydrated structure of a very flexibleporousframework.Thishasenabledanaccuratedeterminationofthedynamicbehaviorofthesystemduringthe desolvation process by using single crystalX-raydiffraction. Unit cells and structure solution has beenobtainedatanypointduringtheprocess.Theimprovedstabilityofthecrystalsandthelargeflexibilityofthenetworkhavealsomadepossibletocarryoutin-situhigh-pressurediffractionmeasurements.Other important results concern the effects of gels on the macroscopic crystal shape and on themicromorphologyofthecrystalsurfaces(Figure),andthecapacityofgelmediatopromotetheconcomitantcrystallizationoftopologicalisomerswithamonotropicrelationship.[2]FundingfromtheCariploFoundationunderthegrant‘‘2012‐0921”isgratefullyacknowledged.

[1]a)K.H.Henisch,CrystalsinGelsandLiesegangRings,CambridgeUniversityPress,Cambridge,1998;b)L.Carlucci,G.Ciani,J.M.Garcìa-Ruiz,M.Moret,D.M.ProserpioandS.RizzatoCryst.GrowthDes.,2009,9(12),5024-5034.[2]S.Rizzatoetal.,unpublishedresults.

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MS5.NANOSTRUCTURESANDNANOSCALEPHENOMENAAdvanced structural studies are essential to establish structure-properties relationships and taylor newnanomaterials for a wide range of applications. The micro symposium “Nanostructures and Nanoscalephenomena” is focussed on experimental techniques (such as XAS, NPD, XRPD, also under operativeconditions)andproceduresof structuralanalysis (simulationofEXAFS spectra,PairDistributionFunction,DebyeFunctionAnalysis)particularlysuitedforMaterialsScience.Chair:AntoninoMartorana(U.Palermo)

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5KN1.Characterizationofnano-structuredmaterialsbysynchrotronradiationtechniques

LorenzoMino,aElisaBorfecchia,aAngeloAgostino,aMarcoTruccato,bChiaraGroppo,cDanieleCastelli,c

GemaMartinez-Criado,dCarloLamberti,a,eaDepartmentofChemistry,CrisDiandNISinterdepartmentalcenters,UniversityofTurin,ItalybDepartmentofPhysics,CrisDiandNISinterdepartmentalcenters,UniversityofTurin,Italy

cDepartmentofEarthSciences,UniversityofTurin,ItalydEuropeanSynchrotronRadiationFacility,ID22,Grenoble,France

eSouthernFederalUniversity,Rostov-on-Don,Russia.carlo.lamberti@unito.itSynchrotron radiation X-ray micro- and nano-beams are emerging characterization tools with broadimplications for science, covering solid state physics catalysis, geology, cultural heritage, biology andmedicine. In the field of materials characterization, they are becoming a key tool for the space-resolveddetermination of structural (XRD) and electronic (XANES/EXAFS) properties and for chemical speciation(XRF)ofnano-structuredorcompositematerials[1].In this contribution, recent advances in focusing devices available at III generation synchrotron radiationsources will be briefly reviewed and selected examples will be afterward presented. In particular, (i) thecompletecharacterizationofaMulti-QuantumWellsElectroabsorption-ModulatedLaser[2],employedinhighfrequency optical communications over long propagation spans, (ii) the structural investigation ofsuperconductingwhiskers [3] (Figure 1a) and (iii) the Fe3+/ΣFe in a zoned garnetmicrocrystal geologicallyrelevanttounderstandsubductionprocesses(Figure1b)[4]willbemoredeeplydiscussed.

Figure1.(a):Nano-XRDinvestigationofacurvedYBCOwhisker.(b):QuantitativespatialvariationoftheFe3+/ΣFeratioobtainedforageologically-relevantgarnetsamplefromthemicro-XANESanalysis.

[1] G. Martinez-Criado, E. Borfecchia, L. Mino, C. Lamberti, “Micro and nano X-ray beams” in:CharacterizationofSemiconductorHeterostructuresandNanostructures IIEd., (C.Lamberti andG.AgostiniEds.)Elsevier,Amsterdam,2013,pp.361-412;L.Minoetal.,J.Phys.D-Appl.Phys.,2013,46,423001.[2]L.Minoetal.,Adv.Mater.,2010,22,2050;J.Anal.At.Spectrom.,2010,25,831;Small,2011,7,930.[3] S. Cagliero et al., J. Synchrotron Radiat., 2009, 16, 813; Supercond. Sci. Technol., 2011, 24, 035009;Supercond.Sci.Technol.,2012,25,125002.A.Pagliero,NanoLett.,2014,14,1583.[4]Borfecchiaetal.,J.Anal.At.Spetrosc.2012,27,1725.L.Minoetal.,Catal.Today,2014,229,72.

56

5KN2.ApplicationofTotalScatteringMethodstotheInvestigationofCleanEnergyMaterials

LorenzoMalavasi,aaDipartimentodiChimicaandINSTM,UniversitàdegliStudidiPavia,Pavia,Italy

lorenzo.malavasi@unipv.itThe knowledge of the structural properties of crystalline materials is one of the most essential piece ofinformation we need to obtain in order to make reliable correlations with physical properties, especially infunctional materials. Traditional crystallographic methods based on single crystal and powder X-ray andneutron diffraction are the preferredmethods to look at theaverage structure of a crystallinematerial. Theprogress in thesynthesisofcomplexmaterialswithenhancedproperties showed thata fullunderstandingoftheir structural featuresmaynot be obtainedwith the use of diffraction alone.Materialswhich are not fullyperiodic, likenanocrystallineorhighlydisorderedcompounds, requirenewexperimental approaches that cantackle the structural issues to a high degree of accuracy [1]. In this context, materials for clean energyapplications, suchashighlydefectiveoxidesandnanocrystallinecompounds (whicharebecomingextremelypopular in this area) for a range of applications (solid oxide fuel cells, lithium batteries, hydrogen storagematerials)needtobetreatedwithanewapproachthatcouldopenthepossibilitytostudytheirlocal structureand unveil structural features which cannot be assessed with traditional crystallographic methods. Thisapproach centres around the atomic pair distribution (PDF) technique. In the past, PDF analysis has beenusedformanyyearsforstudyingmaterialswithnolong-rangeordersuchas liquidsandglasses.TheadventofhighpowerX-rayandneutronsourcesallowedtoapplythePDFanalysistotheinvestigationofcrystallinematerials.Theessentialdifferencewithrespecttothetraditionalcrystallographicmethods,whichmakeuseofthe structural information contained in the Bragg peaks, is the use of the total scattering coming from thesamplewhich include theBragg anddiffuse scattering [1].This part of the sample scattering becomemoreandmoreimportantasthelong-rangeorderbreaksontheatomic-scaleandthePDFtechniqueallowtorevealtheshortandintermediateorderofthematerialregardlessofthedegreeofdisorder.InthistalkwearegoingtogivefirstaconcisedescriptionofthePDFtechniqueandthenanoverviewaboutthe successful application of total scattering methods to the investigation of crystalline materials for cleanenergy applications.We should stress that,with respect to other classes ofmaterials, the application of thePDF technique tomaterials for energetics ismore recent.However, such new approach already showed itspower in order to provide information at the atomic scale level that are essential to give new insights, forexample, about the mechanisms involved in the carrier motion, study the defects structure and findcorrelationsbetweendifferentcrystalstructureofamaterial[2-6].[1] T. Egami and S. J. L. Billinge,Underneath the Bragg peaks: structural analysis of complex materials,2012,Pergamon,Amsterdam;Boston.[2]L.Malavasi,H.Kim,S.J.L.Billinge,Th.Proffen,C.TealdiandG.Flor,J.Am.Chem.Soc.,2007,129,6903.[3]L.Malavasi,C.A.J.Fisher,M.S.Islam,Chem.Soc.Rev.,2010,39,4370.[4]L.Malavasi,A.Orera,P.R.Slater,P.M.Panchmatia,M.S.Islam,Chem.Comm.,2011,47,51.[5]L.Malavasi,DaltonTrans.,2011,40,3777.[6]A.Mancini,V.Barbieri,J.C.Neufind,K.Page,L.Malavasi,J.Mater.Chem.A,2014,2,17867.[7]L.-E.Kalland,A.Magrasó,A.Mancini,C.Tealdi,L.Malavasi,Chem.Mater,2013,25,2378.

57

5O1.DisclosingtheRhombohedralStructureofColloidalLeadChalcogenidesQuantumDots,theirstoichiometryandtheirshape

evolutionthroughtheDebyeFunctionAnalysisFedericaBertolotti,aDmitryDirin,b,cMariaIbáñez,b,cMaksymV.Kovalenko,b,c

AntonioCervellino,dRuggeroFrison,e,fNorbertoMasciocchiaandAntoniettaGuagliardifaDipartimentodiScienzaeAltaTecnologiaandTo.Sca.Lab,Universitàdell’Insubria,Como,Italy

bDepartmentofChemistryandAppliedBiosciences,ETH,Zürich,SwitzerlandcEmpa-SwissFederalLaboratoriesforMaterialsScienceandTechnology,Dübendorf,Switzerland

dSwissLightSource-PaulScherrerInstitut,Villigen,Switzerland.eDepartmentofChemistry,UniversityofZürich,Zürich,Switzerland.

fIstitutodiCristallografiaandTo.Sca.Lab,CNR,Como,Italy.e-mail:federica.bertolotti@uninsubria.it

Colloidal lead chalcogenides Quantum Dots (QDs) are an increasingly important class of nanocrystallinematerials.Duetostrongquantum-sizeeffects,theyareverypromisingmaterialsinsolarcellsapplications[1],photodetectors[2]andthermoelectricdevices[3].Size-tuneableQDsareusuallysynthesizedusinglongorganicligands(controllingtheirgrowthandpreventingthemfromaggregation)providingmetal-richnanocrystals(NCs).Controllingtheirstructureattheatomiclevelisthekeytofullyunderstandingtheirpeculiarpropertiesandtuningtheirfunctionalities.A lotofworkhasbeendoneon this side, thatmainly indicate the formationofnon-stoichiometriccore-shellNPs,withanexcessofPbatomsatthesurface,coordinatedbythecappingligands[4].AlsothepresenceoflocalPbdisorderhasbeendeeplyanalysedwithseveraltechniques(PDF[5],EXAFS[6])inmicrocrystallinepowders, but it is still stronglydebated.UsingunconventionalWide-AngleX-rayTotalScattering techniquesand a core-shell model relying on the Debye Scattering Equation, we characterized highly monodispersedoleate-cappedPbSandPbSeQDs(withnominalsizesinthe3-8nmrange)incolloidalsuspensionsintermsofcrystalstructure,size,sizedistributionandstoichiometry.Datawerecollectedat theMS-X04SAbeamlineoftheSwissLightSource.StructuralmodellingwasperformedusingtheDebussyProgramSuite[7].By this innovative approach we were able to obtain very unexpected findings about QDs crystal structure,stoichiometry andmorphology that could bring new lights on the understanding of their complex functionalproperties.Theseresultswillbepresentedindetailswithinthiscommunication.[1]1C.Piliego,L.Protesescu,S.ZulkarnaenBisri,M.V.Kovalenko,M.A.Loi,EnergyEnviron.Sci.2013,6,3054.[2]M.Böberl,M.V.Kovalenko,G.Pillwein,G.Brunthaler,W.Heiss,Appl.Phys.Lett.2008,92,261113-1.[3]SN.Girard,JHXiaoyuanZhou,D.Shoemaker,C.M.Jaworski ,C.Uher,V.P.Dravid ,J.P.Heremans,M.G.Kanatzidis,J.Am.Chem.Soc.2011,.133(41),16588.[4]I.Moreels,Y.Justo,B.DeGeyter,K.Haustraete,C.Martins,Z.Hens,ACSNano2011,5,2004.[5]a)E.S.Božin,C.D.Malliakas,P.Souvatzis,T.Proffen,N.A.Spaldin,M.G.Kanatzidis,S.J.L.Billinge,Science2010,330,1660;b)KSKnight,J.Phys.:Condens.Matter2014,26,385403-1.[6]T.Keiber,F.Bridges,B.C.Sales,Phys.Rev.Lett.,2013,111,095504-1.[7]a)A.Cervellino,C.Giannini,A.Guagliardi,J.Appl.Cryst.2010,43,1543;b)A.Cervellino,R.Frison,F.Bertolotti,A.Guagliardi,DEBUSSY2.0 - thenewreleaseofaDebyeUserSystem fornanocrystallineand/ordisorderedmaterials,submitted.

58

5O2.Spatiallyresolvedphotoemissionspectromicroscopy:apowerfultoolforthecharacterizationofnanostructurednovelmaterials.

LucaGregoratti,aMatteoAmati,aHikmetSezenaaElettra–SincrotroneTriesteSCpA,inAreaSciencePark,Trieste,Italy

luca.gregoratti@elettra.euDuetotheshortescapedepthofelectrons,usuallylessthanafewnm,photoelectronspectroscopyisthebestsurface sensitiveanalytical technique forprobingchemical compositionandelectronicpropertiesof surfacesand top layers of samples. Nevertheless the standard approach to this technique suffers from two majorlimitations:1)spatialresolution(materialgap)and2)therequirementforhigh-vacuumenvironment(pressuregap).The Scanning PhotoEmissionMicroscope (SPEM) uses a direct approach to add the spatial resolution andcharacterize chemically surfaces and interfaces at the submicron scale i.e. theuseof a small focusedX-rayphoton probe to illuminate samples. Focusing ofX-ray beams is performed by Fresnel lenses (zone plates)while elemental selectivemaps are obtained by scanning samples with respect to the focused beam. In theSPEMhostedattheESCAmicroscopybeamlineattheElettrasynchrotronlightsource,theX-raybeamcanbedownsizedtoadiameterof120nmwhichallowsimagingresolutionoflessthan50nm[1].Theuniquepropertiesofphotoemissionspectroscopy toshed lighton thechemicalandelectronicpropertiesofsurfacesofferapowerfultoolofanalysisforawideclassofscientificandtechnologicaltopics.ThemainresultsobtainedbyusingtheSPEMinthecharacterizationofmaterialsusedforthefabricationsofsolidoxidefuelcells[2],nanomaterialsinmodelredoxreactions[3]andelectrochemicaldeviceswillbepresentedaimingtodisseminatepropertiesandperformanceofthisnoveltypeofmicroscopy.Onlyrecentlythedevelopmentofelectronenergyanalyzerswithdifferentiallypumpedlenssystemsallowedtoperform in situXPSmeasurementsup to fewmbar (nearambientpressure (NAP)).Due to severe technicalconstrains it was not possible to implement these solution on photoemission microscope so far. The firstresultsofinoperandospatiallyresolvedNAPphotoemissionmeasurementsobtainedatElettrawithinnovativesetupswillbepresentedanddiscussed.

Figure1.SPEMimageofverticallyalignedmultiwallcarbonnanotubeshavingadiameterof60nm.[1]S.Guenther,B.Kaulich,L.GregorattiandM.Kiskinova,Prog.Surf.Sci.,2002,70,187.[2]B.Bozzini,M.Amati,L.Gregoratti,K.Kiskinova,ScientificReports,2013,3,2848.[3]M.Dalmiglio,M.Amati,L.Gregoratti,O.T.Mentes,M.A.Nino,L.FelisariandM.Kiskinova,J.ofPhys.Chem.C,2010,114(40),16885.

59

5O3.microEXAFSandmicroXANESforthestudyofSolidOxideFuelCells

FrancescoGiannici,aGiovannaCanu,bMariannaGambino,aAlessandroLongo,cMurielleSalomé,dMassimoVivianib

aDipartimentodiFisicaeChimica,UniversitàdegliStudidiPalermo,Palermo,ItalybCNR-IENI,Genova,Italy

cNetherlandsOrganizationforScientificResearch,Grenoble,FranceandCNR-ISMN,Palermo,ItalydEuropeanSynchrotronRadiationFacility,Grenoble,France.francesco.giannici@unipa.it

Chemical and structural compatibility betweenmaterials is a critical point in all-ceramic devices working atvery high temperatures: in this respect, the degradation of the cell performance is often the critical factorlimitingtheworkinglifeofSOFC.Awell-studiedexampleistheformationofaresistivelayerofLa2Zr2O7 attheinterfacebetweenlantanum-containingperovskitecathodesandzirconiaelectrolytes.LaNbO4 dopedwith2%Ca2+ (LNC) represents the last real breakthrough in the field of proton-conductingoxides for use as electrolytes in SOFC, showing improved stability and high conductivity with respect toperovskites [1]. To develop efficient and robust devices based on LNC, the electrical performance andchemicalcompatibilityofvariouselectrodematerialswithLNCwasextensivelytestedinrecentliterature.[2]We recently applied X-ray microspectroscopy to evaluate the chemical and local structural fate of cationsinterdiffusing across an LNC/cathode bilayer (where the cathode is either La0.6Sr0.4MnO3,La0.6Sr0.4Co0.8Fe0.2O3, etc.) after prolonged annealing at high temperatures (1150 °C), to simulate theoperating conditions of a fuel cell. The interfaces of the devices were studied with space-resolved X-rayabsorption spectroscopy (XAS) using the focused submicrometer-sized beam available at the SXM-IIendstationontheID21beamlineofESRF.WecollectedmicroXANESandmicroEXAFSspectraattheNbL3,LaL3, CaK, FeK andMnK edges. ThemicroXRF compositionmaps spectrawere also collected, givinginformationon thedistributionof cations. In somecases,microXANESspectra showmarkedvariations, sothatchemical-contrastmapscanbeacquiredbychangingslightlythebeamenergy.Awealthofinterestingresultsareobtainedbycombiningchemically-resolvedmapsandmicrospectroscopy.Ingeneral, an unexpected and impressive exsolution of theCa2+ dopant from the LNC electrolyte towards thecathodeisobservedinallsamples.[3]TheCaandNbchangeofcoordinationnumberandgeometrybetweentheperovskitecathodeandtheLNCelectrolyteiswellsupportedbymicroXANESsimulations,pinpointingthegreaterstructuralflexibilityoftheperovskitestructureasthedrivingforcebehindtheincorporationofcationsfrom theelectrolyte.FeandMnedgemicroXANESspectraalsoshow interestingvariationsasa functionofthedistancefromtheinterface,hintingatsomekindofoxygenvacancyaccumulationattheinterface.AttheLa,FeandMnedges,highqualitymicroEXAFSspectrawerecollectedandmodeleduptoabout8Å-1.These results represent the firstapplicationofX-rayabsorptionmicrospectroscopy to thestudyofmaterialscompatibility in SOFC. Such an approach can be extended to other kinds of SOFC materials, includingceramicanodes,cermets,andoxide-ionconductors,reproducingdifferentworkingconditionsofrealdevices:thisisexpectedtogiveunprecedentedinsightonthemechanismsgoverningelectrolyte-electrodecompatibilityandelectrochemicalperformanceinsolidoxidefuelcells.[1]R.Haugsrud&T.NorbyNatureMater.2006,5,193-196.[2]K.V.Kravchyketal.Int.J.HydrogenEnerg.2011,36,13059.[3]F.Giannicietal.Chem.Mater.2015,27,2763.

60

5P1.Asupercellapproachfortherefinementofcarbonatehydrotalcitesaffectedbystackingfaults

LucaPalin,a,bEleonoraConterosito,aValentinaToson,aEnricoBoccaleri,aMarcoMilanesioaa Dipartimento di Scienze e Innovazione Tecnologica, Università del Piemonte Orientale ‘‘A. Avogadro’’(Italy),ViaMichel11,I-15121Alessandria,Italy.E-mail:marco.milanesio@uniupo.itbNovaRess.r.l.,ViaDoloresBello3,28100Novara,Italy(http://www.novares.org)Carbonatehydrotalciteisknowntocrystallizeintotwodifferentpolitipes:athree-layerrhombohedralpolytype(3R1), and a two-layer hexagonal polytype (2H1). The 3R1 polytype has a metal hydroxide layer stackingsequenceofAbCCaBBcAAbC,andthe2H1polytypehasastackingsequenceofAbCCbAAbC,whereAbCstands forametalhydroxide layer.Theuppercase letters stand for thehydroxyl ionpositions,and the lowercaselettersstandforthecationpositions.Dependingonthesynthesismethodispossibletoobtainordered3R1samplesorfaultedsample.Arecentpaper(1)showsthat faultedsamplesaresimulatedwithDIFFaXcorresponding to the3R1polytypewith30%2H1stackingfaults.However,itisimportanttonotethattheDIFFaXformalism,unliketheRietveldtechnique, does not include a least-squares fit of the whole profile, but is a simple simulation of the XRDpatternofanygivenmodelstructurethatpermitstheinclusionofstructuraldisorderandpredictstheresultantlineshape.InthisworkwepresentthenewsupercellapproachforthetreatmentofstackingfaultsimplementedinTopasV5,werewerefinedbothsimulatedandrealdatatoorderedandfaultedhydrotalcitesamples.[1]R.ShivaramaiahandA.NavrotskyInorg.Chem.,2015,54,3253-3259.

61

5P2.StressmeasurementsatthenanoscalebyZnONanorods-modifiedCarbonFibers

CulioloMaurizio1,DelmonteDavide1,VillaniMarco1,MarchiniLaura2,BercellaRocco2,CalestaniDavide1,CoppedèNicola1,SolziMassimo3,ZappettiniAndrea1

1IMEM-CNR,Parma(Italy),2Bercellas.r.l.,Varanode’Melegari(PR),(Italy),3DipartimentodiFisicaeScienzedellaTerra“MacedonioMelloni”–UniversitàdegliStudidiParma,Parma(Italy),

zapp@imem.cnr.itCarbon fiber based composites (CFC), owing to the exceptional ratio between mechanical properties andweight, represent a fundamental technology for several applications, ranging from aerospace to automotive,fromcivilinfrastructuretobiomedicalengineering.Duetotheintensemechanicalstressofteninvolved,strainanddeformationonCFCmadestructureshavetobeconstantlymonitored.Furthermoreunivocalmechanicalmodelsdoesn’texist,sincecarbonfiber(CF)patchescanbetexturedwithCForientedindifferentdirectionsdependingonnecessity.Nowadays strain sensing onCFC is carried outwith optical fiber and piezoelectric ceramics.However thistechnologiespresent threemaindrawbacks, thatare largesize (compared toCFsize),weightaddition to thestructure and use of precious metals wires. Recently the use of different materials functionalized withpiezoelectriczincoxide(ZnO)nanostructuresstartedtogetafootholdforsensingandenergyharvesting.Piezoelectric effect, owing to its dual peculiarity relating deformationwith electric properties, lends itself toboth sensing and actuating applications. Therefore functionalization of CF with ZnO piezoelectricnanostructures allow to realize a fully integrated piezoelectric sensor/actuator within CFC structure, thanksalsotothefactthatconductiveCFthemselvesactaselectricalwires.TheZnOin-situgrowthismadebyalow-temperatureandlow-costtwo-stepprocess:functionalizationofCFwithZnO seed-layer bySuccessive IonicLayerAdsorption andReaction (SILAR) technique and growth ofZnOnanorodsbychemicalbathdeposition.Measuring the piezoelectric effect in ZnO nanostructures is still a debatable topic, since the typical I-Vcharacterization is not generally accepted. In thiswork piezoelectric investigation is carried out for the firsttime on such structure using ferroelectric virtual ground, PUNDandDHM techniques.The emergence of avoltage-invariantcapacitancevariationuponstressapplicationisascribedasthefingerprintofpiezoelectricity.

Figure1.Depictionofthedevicestructure:crossedCFfunctionalizedwithZnOseed-layerandnanorods

62

5P3.TheDebUsSySuite2.0:apowerfultoolforcharacterizingnanosizedmaterialsthroughtheDebyeScatteringEquation

AntoniettaGuagliardia,RuggeroFrisona,b,FedericaBertolottic,AntonioCervellinodaIstitutodiCristallografia,CNR,&To.Sca.Lab,22100Como,Italy

antonella.guagliardi@ic.cnr.itbUniversityofZurich,Zurich,Switzerland

cUniversitàdell’Insubria&To.Sca.Lab,22100Como,ItalydPaulScherrerInstitut,Villigen,Switzerland

TheDebyeScatteringEquation(DSE)providesthetotal(X-ray,NeutronorElectron)scatteringpatternofanensemble of nanoparticles through the distribution of their interatomic distances,without any assumption ofperiodicityandorder [1].DSE is thereforeapowerful approach forquantitativelydetermining structural andmicrostructural properties of nanoscaled materials and nanocomposites, at both the atomic and nanometerlengthscales.DebUsSy is a suite of programs implementing the DSE for the analysis of powder diffraction data fromnanocrystalline,defectiveandnon-periodicobjects[2].ItencodesanalgorithmmakingtheDSEcalculation,inprincipleveryintensivefromthecomputationaltimepointofview,extremelyfastandaccurate.TheSuitehasbeen successfully applied in modeling different kind of nanomaterials (metals, alloys, oxides, bioceramics,moleculardrugs,QDsandmetal-organiccompounds)[3,4,5].Inthiscontribution,thenew2.0releaseoftheDebUsSySuite[6]willbepresented.Itincludesdifferentkindsofoptimizationalgorithmsenabling toextractquantitativemicro-structuralvaluesofmono-orbi-variate log-normal function to deal with the sample-size distribution, size-dependent lattice expansion, atomic siteoccupationfactorsandthermalparameters.DisorderofparacrystallinenaturecanbemodeledaccordingtotheWelberry’stheory[7].Apython-basedGraphicalUserInterfacemakeseasytorunanyoftheprogramswithintheSuite and todisplaypredefinedor customizedplotsof the results.Additionally, a satellite suiteofutilitieshas been developed for correcting the experimental data from absorption and instrumental effects, andsubtractingextra-samplescatteringcontributions.[1]P.Debye,Phys.Z.191531,797–798.[2]A.Cervellino,C.Giannini,A.Guagliardi,J.Appl.Cryst.2010,43,1543.[3]G.Cernuto,S.Galli,F.Trudu,G.M.Colonna,N.Masciocchi,A.Cervellino,A.Guagliardi,Angew.Chem.Int.Ed.2011,50,10828.[4]R. Frison,G.Cernuto,A.Cervellino,O. Zaharko,G.M.Colonna,A.Guagliardi,N.Masciocchi, Chem.Mater.2013,25,4827.[5] J.M. Delgado-López, R. Frison, A. Cervellino, J. Gómez-Morales, A. Guagliardi, N. Masciocchi, Adv.Funct.Mat.2014,24,1090.[6]A.Cervellino,R.Frison,F.Bertolotti,A.Guagliardi,submitted.[7]A.Cervellino,A.Maspero,N.Masciocchi,A.Guagliardi,Cryst.Growth.Des.2012,12,3631.

63

5P4.Core-shellcobalt/cobaltoxidenanoparticles:aDebyefunctionXRDpatternsimulation

AntoninoMartoranaa,AlessandroLongob,FrancescoGiannici,aLuisaSciortinoaaDipartimentodiFisicaeChimica,UniversitàdegliStudidiPalermo,Palermo,Italy

bCNR-ISMN,Palermo,Italy.antonino.martorana@unipa.itCobalt nanoparticles have long attracted the interest of structural investigations, from the point of view ofstructural modelling [1] and for structure-properties correlations [2-4]. We have recently coped with thestructural analysis of cobalt nanoparticles prepared by thermal decomposition ofCo2(CO)8, and proposed anewmodelallowingforstackingfaultsinthesequenceoftheCobasalplanes[5].Accordingtothemodel,thepositionof each layerof the stack isprobabilistically influencedby theblockof the fourneighbouringones,giving rise to XRD patterns showing the simultaneous presence of both the hcp and ccp signatures. Themodel, validated by simulation runs based on the Debye Function Analysis (DFA), allowed to treat thestructure of cobalt nanostructured samples on the basis of a unique statistical ensemble, overcoming thequestionable approach of summing up two different contributions bearing separately the hcp and ccpcharacters[6].The nanostructuredCo experimental patterns showed also a contribution thatwas attributed to a disorderedoxide phase. This likely constitutes a shell of variable thickness growing over the metal core, as it is alsoconfirmed by TEM data. The occurrence of the oxide phase can be effectively taken into account in thepattern fitting procedure by a background line, such as aTchebicheff polynomial of suitable degree.On theotherhand,asimulationinvolvinga thoroughphysicalmodel[7]couldgive important informationinviewofapplicationsofnanostructuredcobaltasmagneticorcatalyticmaterial.In this paperwe report about thewholepattern simulationof core-shell cobalt nanostructured samples.TheshellcontributioniscalculatedbyDFA,weighingthedistancetbetweencouplesofscattererswiththevolumecommontotheshapefunctionanditst-shiftedimage.Theissuestakenintoconsiderationare:i.theinteractionbetweenthemetalcoreandtheoxideshell;ii.thecobaltoxidationstate;iii.thethicknessoftheoxideshell;iv.the oxide lattice constants; v. the degree of long rangeorder of the shell.The integrationof shell simulationintothealgorithmofwholepatternfittingallowedastructuralanalysisbasedentirelyonaphysicalmodel.[1]A.J.C.WilsonProc.R.Soc.Lond.A1942,180,277.[2]M.A.Zalich,V.V.Baranauskas,J.S.Riffle,M.Saunders,T.G.St.PierreChem.Mater.2006,18,2648.[3]V.A. de la PeñaO’Shea, P. Ramírez de la Piscina,N.Homs,G.Aromí, J. L.G. Fierro,Chem. Mater.2009,21,5637.[4]Q.A.Pankhurst,N.K.T.Thanh,S.K.Jones,J.Dobson,J.Phys.D:Appl.Phys.2009,42,224001.[5]A.Longo,F.Giannici,L.Sciortino,A.MartoranaJ.Appl.Cryst.2014,47,1562.[6] J.Sort,S.,Suriñach, J.Muñoz,M.Baro',M.Wojcik,E. Jedryka,S.Nadolski,N.Sheludko, J.Noguès,Phys.Rev.B2003,68,014421.[7]R. Frison,G.Cernuto,A.Cervellino,O. Zaharko,G.M.Colonna,A.Guagliardi,N.MasciocchiChem.Mater.2013,25,4820.

64

5P5.StructuralAnalysisofHighlyDefectivePt@SiO2NanorodsthroughSynchrotronX-RayTotalScatteringTechniques

NorbertoMasciocchi,aDanieleMoschenia,FedericaBertolottia,AntonioCervellino,bAntoniettaGuagliardic

aDip.ScienzaeAltaTecnologiaandTo.Sca.Lab,UniversityofInsubria,Como,ItalybSwissLightSynchrotron,PaulScherrerInstitut,Villigen,Switzerland

cIstitutodiCristallografiaandTo.Sca.lab,CNR,Como,ItalyIn the last years, pushed by a large scientific and technological interest, the knowledge of nanocrystallinematerials has enormously increased, making their range of application extremely vast. The functionalproperties ofmetals, semiconductors, dyes and drugs depend not only on the crystal andmolecular atomicstructure, but also on particle size and shape distribution [1,2] and on the presence of various kind ofdefectiveness.Inlinewiththeseobservations,varioussyntheticapproacheshavebeensuccessfullyaddressedto control these fundamental parameters [3], but robust characterization methods at the nanoscale are stillmissing. Indeed,portraying thesecomplexsystems is still achallenging taskand isusuallyachieved throughthecombinationofdifferent techniques, fromspectroscopy tomicroscopyanddiffraction. In the lastyears,newWideAngleX-rayTotalScatteringTechniques(WAXTS)haveemergedassuitablecharacterizationtoolsfornanomaterials.Withoutbeingrestrictedtoideallyperiodicandorderedmaterials,WAXTS,andparticularlytheDebyeScatteringEquation (DSE) approach (recently rejuvenatedby the availabilityof fast andpowerfulcomputationalmethods), can suitablymodel diffuse scattering, between andbelowvery broadBraggpeaks,normallyneglectedinconventionalpowderdiffractometry.Here, the DSE method has been targeted to derive important structural and microstructural features of Ptnanocrystals (Figure 1) grown in amesoporous SiO2 matrix, starting from impregnation of hign nuclearitycarbonyl clusters and thermally induced CO desorption. The occurrence of faulted Pt clusters ofmarkedlyanisotropicshape(asexpectedforconstrainedgrowthwithinthemesoporoussilicachannels),determinedbyDSE, is further supplemented by the detection of partly amorphousmetallic Pt by real-space PDF analysis,bothperformedonhigh-qualitysynchrotronWAXTSdatacollectedattheSwissLightSourceatPSI.

Figure1.Faultedandunfaultedclustermodelsforrod-likePtnanoparticles,grownalong[111].

The authors are indebted toProf.StefanoZacchini,UniversityofBologna, for the synthesisof theplatinumcarbonylprecursors.PartialfundingfromFondazioneCARIPLO,ProjectNo.2011-2009.[1]C.Binns,IntroductiontoNanoscienceandNanotechnology,2010,Wiley,Hoboken,NewJersey[2] See for example: G. Cernuto, N. Masciocchi, A. Cervellino, G. M. Colonna, A.Guagliardi,J.Amer.Chem.Soc.,2011,133,3114-3119.[3]L.H.Reddy,J.L.Arias,J.Nicolas,P.Couvreur,Chem.Rev.,2012,112,5818-5878.

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MS6.CRYSTALCHEMISTRYOFINORGANICCOMPOUNDSFORTHEUNDERSTANDINGOFTHEIRPROPERTIESANDSTABILITY

Thissessionwelcomesinnovativecontributionsdealingwiththecrystallographyandcrystalchemistryofbothnaturalandsyntheticinorganiccompoundssensulatosuchasnanophasesandmicroporousmaterials,aimedtothe understanding of their physical-chemical and technological properties and stability fields(temperature/pressure).Chair:AlessandroGualtieri(U.ModenaeReggioEmilia)

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6KN1.TimeforChanges:NanosizedMagnetiteClustersontheRunNorbertoMasciocchi,aRuggeroFrison,b,cAntonioCervellino,dAntoniettaGuagliardib

aDipartimentodiScienzaeAltaTecnologiaandTo.Sca.Lab,Universitàdell’Insubria,Como,Italye-mail:norberto.masciocchi@uninsubria.it

bIstitutodiCristallografiaandTo.Sca.Lab,ConsiglioNazionaledelleRicerche,Como,ItalyaDepartmentofChemistry,UniversityofZurich,Zurich,SwitzerlandbSwissLightSource,PaulScherrerInstitut,Villigen,Switzerland

Very small superparamagnetic iron oxide nanoparticles were characterized by innovative synchrotron X-raytotal scattering methods and Debye function analysis. Using the information from both Bragg and diffusescattering, size-dependent core–shell magnetite–maghemite compositions and full size (number- and mass-based)distributionswerederivedwithinacoherentapproach. [1]Verybroadsuperstructurepeaksproducedby the polycrystalline nature of the surface layers were experimentally detected even in room temperatureoxidized samples.Effectivemagnetic anisotropy constants, derivedby taking theknowledgeof the full size-distributions into account, show an inverse dependence on the NPs size, witnessing a major surfacecontribution. These iron oxide nanoparticles concomitantly show size-driven expansion and oxidation-drivencontraction,botheffectsinfluencingtheaccuracyoflatticeparameterandofstoichiometrydetermination.[2]Finally, insituoxidationexperimentsperformedatdifferent temperaturesallowedkineticand thermodynamicparametersofmagnetiteoxidationtobesuitablydetermined.

Figure1.Anexampleoftherelativevariationoftheweightfractions,wt%,oftheFe3O4coreandtheγ-Fe2O3oxidizedshell(seeinset)asafunctionoftheparticlesizewithinthemass-basedpopulation.

[1]R.Frison,G.Cernuto,A.Cervellino,O.Zaharko,G.M.Colonna,A.Guagliardi,N.MasciocchiChem.Mater.2013,25,4820.[2]A.Cervellino,R.Frison,G.Cernuto,A.Guagliardi,N.MasciocchiJ.Appl.Cryst.2014,47,1755.

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6KN2.Trackingstructuralandelectronicpropertiesofcoordinationcompounds:theroleofsynchrotronradiation

ElisaBorfecchiaaaDept.ofChemistry,NISandINSTMReferenceCenters,UniversityofTurin,Turin(Italy),

elisa.borfecchia@unito.itThis contribution aims to provide an overview of the potential of synchrotron-based X-ray techniques toelucidate the structural and electronic properties of crystalline coordination compounds, and to track theirevolutionduringchemically-relevantprocesses[1].Besides thewell-establishedanamalousdiffractionandX-rayabsorptionspectroscopy(XAS),inbothnear(XANES)andpost(EXAFS)edgeregions,morespecializedtechniques currently emerging in the panorama of synchortron characterization will be introduced, with anemphasis onX-ray emission spectroscopy (XES) and small/wideX-ray scattering (SAXS/WAXS)methods.Furthermore,advancedexperimentalapproachesdesignedtomonitor theevolutionandto track thereactivityof the investigated system in controlled conditions will be presented, including multi-technique insitu/operando setups and quick/dispersive EXAFS methods. Synchortron approaches will be criticallycompared tomoreconventionaldiffractometricandspectroscopic laboratory techniques (suchasXRD,UV-vis,NMR,EPR and FTIR), evidencing both the added value of synchrtron probes and the importance of amulti-technique approach to maximize the information level in the analysis of complex nanomaterials. Inaddition, thekey roleofcomputationalmodelling fora reliable interpretationof structural andelectronicdatawillbediscussed.

Figure1.Pictorialrepresentationofthepotentialitiesofsynchrotron-basedX-raytechniquesinelucidatingstructuralandelectronicpropertiesofcoordinationcompounds,andtrackingtheirevolutionalongchemically

relevantprocesses.The potentialities of the above-mentioned methods and setups, further empowered by their synergicintegration,willbeexemplifiedbya selectionof relevantapplications, focusingon long/short rangestructureandreactivityinMOFsandfunctionalizedderivatives[2],electronic/structuralpropertiesandcatalyticactivityofexchangedmetalsites inzeolite-basedcatalysts[3], intra-molecular interactionsandelectronicstructure intransitionmetalmolecularcomplexes[4],andmulti-techniqueinsitu investigationofcrystallizationprocesses[5].Finally,aperspectivesummaryofthekeyadvancesexpectedtoimpactthesynchrotroncharacterizationfieldintheforthcomingfuturewillbepresented.[1]C.Garinoetal.,Coord.Chem.Rev.2014,277,130;S.Bordigaetal.,Chem.Rev.2013,113,1736.[2]L.Valenzanoetal.,Chem.Mater.2011,23,1700;S.Øienetal.,Chem.Mater.2015,27,1042.[3]E.Borfecchiaetal.,Chem.Sci.2015,6,548;T.V.W.Janssensetal.,ACSCatal2015,5,2832.[4]K.A.Lomachenkoetal.,Phys.Chem.Chem.Phys.2013,15,16159;C.Garinoetal.,Phys.Chem.Chem.Phys.2012,14,15278.[5]D.Grandjeanetal.,J.Am.Chem.Soc.2005,127,14454.

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6O1.Adsorption/DesorptionOfFuelBasedPollutantsConfinedwithinZSM-5:aCombinedInSituHigh-TemperatureSynchrotronPowderX-

RayDiffractionandChromatographicStudyElisaRodegheroa,GiuseppeCruciani,LuisaPastibandAnnalisaMartuccia

aDepartmentofPhysicsandEarthSciences,UniversityofFerrara,Ferrara,Italy.rdglse@unife.itbDepartmentofChemistry,UniversityofFerrara,Ferrara,Italy

Removalof fuel-basedcompoundsfromnaturalwater isofconsiderable interestdue to theirharmfuleffectson the environment, even at very lowconcentration.Toluene (TOL), 1,2-dichloroethane (DCE) andmethyl-tert-butyl-ether (MTBE) are of special relevance since they are toxic and commonly found in surface andgroundwater. Recently, high-silica zeolites, have been shown to be environmental friendlymaterials able toefficientlyadsorb fromwater fuelbasedpollutants[1].Moreover,zeolitescanbeeasily thermally regeneratedat low cost without changing their initial adsorption [2]. In this work, the in situ high-temperature (HT)synchrotronX-ray powder diffraction (XRPD), is used as a key to continuousmonitoring theDCE,MTBEandDCE-MTBEmixturedecompositionprocessaswellasthestructuralmodificationsundergoingonZSM-5uponatemperature-programmedthermaltreatment.Kineticsandadsorptionisothermbatchdatawereobtainedvia Headspace Solid Phase Microextraction-GC. Thermal analyses were performed in air up to 900°C at10°C/min. HT-XRPD data (temperature range 30°-600°C) were collected on the ID31 beamline (ESRF,Grenoble).RietveldrefinementsdemonstratedthatregenerationofZSM-5iseffectivewhenthermallytreatingthe adsorbent in mild conditions (~300°C). Once regenerated and reloaded, thermogravimetric,chromatographic (Figure1)anddiffractometricanalyses (Figure2) indicates thatbothorganics locationandcontentremainsubstantiallyunchangedthushighlightingZSM-5isabletore-adsorbtheselectedpollutantsinamountscomparable to that adsorbed in the first cycle.XRDanalysisdemonstrates that the regeneratedandreloaded zeolite does not show any significant crystallinity loss, as well as perfectly regains thecrystallographicfeaturesoffreshmaterial(Figure2).Theregeneration/adsorptionprocessalsooccurswithoutanysignificantdeformationsinthechannelapertures.Inconclusion,theuseofthisadsorbentwithunchangedadsorption performances after thermal regeneration undermild conditions appears very promising also overseveralcyclesoftheadsorption/desorptionprocess.

References:[1]L.Pasti,A.Martucci,M.Nassi,A.Cavazzini,A.Alberti,R.Bagatin,Micropor.Mesopor.Mater.2012,160,182-193.[2]A.Martucci,E.Rodeghero,L.Pasti,V.Bosi,G.Cruciani.InpressonMicropor.Mesopor.Mater.

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6O2.AfteracenturyofBraggdiffraction,howwelldoweknowthestructuresofinorganiccompounds?

RossJAngel,aFabrizioNetsolaaaDipartimentodiGeoscienze,UniversitàdegliStudidiPadova,Padova,Italia.rossjohn.angel@unipd.it

The atomic structure provided by refinement to the Bragg intensities obtained in a diffraction experimentprovidesapictureoftheaveragestructureofamaterialattheatomicscale.Thisaveragestructureisnotonlythefoundationforunderstandingthethermodynamicsandphysicalpropertiesofbulkmaterials,butisalsothebasis for defining a variety of structural modifications such as defects, compositional order/disorder,dynamical disorder, incommensurate modulations and the structures of nanoparticles. With the recentadvances in technology,weasked thequestion:“Howwell are structuresdetermined in routineexperiments,onecenturyafterthediscoveryofX-raydiffraction?”Toanswer thisquestionwehaveundertakenasystematicstudyofhowwellwecandeterminewithmodernlaboratory equipment the structures of two major Earth minerals; anorthite as an example of the feldsparfamily which comprises 60% of the Earth’s crust, and olivine the major component of the Earth’s uppermantle.We used sub-100um size crystals,measuredwith a commercial instrument, theOxfordDiffractionSuperNovadiffractometerequippedwithaMo-targetmicrosource,andaPilatus200Kareadetector.We found that a partial data collection of just 90 seconds on anorthite is sufficient to determine the bondlengthstoanaccuracyof0.02Åandthustheessentialarchitectureofthestructure!Afulldatasetto2θmax=60ocollectedin48minutesyieldsesd(T-O)=0.004Å,equivalenttotheresultsfrom6daysdatacollectionin1990,orseveralyears in the1950s!Adatacollectionwith2θmax=100o (81hours)has>28,000 reflectionsandgivesesd(T-O)=0.0005Å.Refinedstructuresofanorthiteshownosignificantdifferencesinbondlengthswith either changing resolution (2θmax from 60o to 100o for MoKα) or with increasing exposure time atconstant resolution in fulldatasets.Theesdsscaleapproximatelywith the inversesquare rootof thenumberof reflections used in the refinement. This means that modern diffraction data themselves are precise andaccurate.Conventionalrefinementsofolivinewithindependentatommodelsshowthatthesiteoccupanciesarestronglydependent on data resolution and give systematically wrong chemical compositions. The reason is that thediffraction intensities are sufficiently precise to include the diffraction effects of the non-spherical electrondistributiondue tobonding in the crystal.Theuseof refinementmodels such as the electron-in-bondmodelprovidescorrectcompositions(andbyinferencecorrectsiteoccupancies)independentofdataresolution.These testsshowthatmodernstructure refinements,properlyperformed,arenot limitedby theaccuracyorprecisionofmodernlaboratoryX-raydiffractiondatawhichprovideanunbiasedmapof theelectrondensityof thecrystal.Thelimitationsofmodernstructurerefinementsare in therefinementmodelsusedto interpretthedata.Thus,whilebondlengthsandanglesaredeterminedconsistentlybydifferentmodels,siteoccupancyrefinements are biased to the wrong results by the conventional independent atom model, but can beaccuratelydeterminedwithphysically-meaningfulbutsimplerefinementmodels.ThisworkwassuppportedbyERCStartingGrant307322(Indimedeaproject)toF.Nestola.

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6O3.Crystal-fluidinteractionsinopen-frameworkmaterialsathighpressure

PaoloLotti,aRossellaArletti,bG.DiegoGatta,aSimonaQuartieri,cGiovannaVezzalini,dMarcoMerlinia,LindaPasterob

aDipartimentodiScienzedellaTerra,UniversitàdegliStudidiMilano,Milano,ItalybDipartimentodiScienzedellaTerra,UniversitàdiTorino,Torino,Italy

cDipartimentodiFisicaeScienzedellaTerra,UniversitàdiMessina,Messina,ItalydDipartimentodiScienzeChimicheeGeologiche,UniversitàdiModenaeReggioEmilia,Modena,Italy

paolo.lotti@unimi.itThenumberofexperimentsonthehigh-pressurebehaviorofopen-frameworkmaterialsincreasedsignificantlyin the last decade [1,2]. The framework topology, the chemical composition and the so-called “host-guest”interactions (between the framework and the extraframework components) were found to significantlyinfluence the responseof zeolites to the appliedpressure.However, theHP-behaviorof zeolitesmayalsobeinfluenced by crystal-fluid interactions when P-transmitting fluids (PTF) are used to generate hydrostaticcompression,andinparticularwhenthePTFis“pore-penetrating”.Insuchacase,theP-inducedpenetrationofPTFmoleculesintothezeolitestructuralvoidsleadstoachangeofthephysical-chemicalpropertiesofthestudiedmaterial,forexampleinducingastiffeningoftheelasticbehaviororleadingtothehyperconfinementofsupramolecularaggregates(inthezeolitechannels)withfunctionalproperties[3].In this study, we describe the HP-behavior and the crystal-fluid interactions of two synthetic zeolites withempty channels and cages, i.e. all-silica ferrierite (Si-FER) and ALPO4-5 (AlPO4), compressed with non-penetrating (silicone oil, s.o.) and potentially pore-penetrating PTF. The compression of Si-FER in s.o.evidences the remarkable flexibility of this framework: a first displacive phase transitionwas observed fromthe Pmnn to the P121/n1 space group at ~ 0.7 GPa. A second displacive phase transition, involving asignificantunit-cellvolumecontraction,wasobservedat~1.24GPafromtheP121/n1totheP21/n11spacegroup (through an intermediate P-1 structure, “type-II” transition according to Christy [4]). The high-PP21/n11polymorphwasfoundtobestableat leastupto3.00(7)GPa,whereas-uponpressurerelease- thestartingPmnn structurewas fully recovered.The threepolymorphswere found to share avirtually identicalbulkelasticbehavior,being their averagevolumecompressibilityβV: 0.051(4), 0.056(9) and0.055(3)GPa-1,respectively. The compression of Si-FER and ALPO-5 in potentially pore-penetrating PTF showed a lowerbulk compressibility, different phase-transition paths (for Si-FER) and diverse atomic-scale deformationmechanismswith respect to the compression in silicone oil, suggesting the onset of significant crystal-fluidinteractions,likelyduetotheP-inducedpenetrationofPTFmolecules.Inaddition,theHP-behaviorofSi-FERisstronglyinfluencedbytheprocesskinetics,whichwasfoundtocontroltheP-inducedmolecules intrusionphenomenaand,asconsequence,theP-inducedphasetransitionsinthismaterial.

The authors acknowledge the Italian Ministry of Education, MIUR-Project: “Futuro in Ricerca 2012 -ImPACTRBFR12CLQD”.[1]G.D.Gatta,Y.LeeMineral.Mag.2014,78,267-291. [2]G.Vezzalini,R.Arletti,S.QuartieriActaCryst.2014,B70,444-471.[3]M.Santoro,F.A.Gorelli,R.Bini,J.Haines,A.VanderLeeNat.Commun.2013,4,1557-1563.[4]A.G.ChristyActaCryst.1993,B49,987-996.

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6O4.Insituhigh-temperatureX-raydiffractionandspectroscopicstudyoffibroferrite,FeOH(SO4)5H2O

GennaroVentruti,aGiancarloDellaVentura,bFabioBellatreccia,bAlessandroF.Gualtieri,cCorradoCuocci,d

EmanuelaSchingaroaaDipartimentodiScienzedellaTerraeGeoambientali,UniversitàdiBari,Bari,Italy.

gennaro.ventruti@uniba.itbDipartimentoScienzeGeologiche,UniversitàdiRomaTre,Roma,Italy

cDipartimentodiScienzeChimicheeGeologiche,UniversitàdegliStudidiModenaeReggioEmilia,Modena,Italy

dIstitutodiCristallografia–CNR,Bari,ItalyFe-sulfatesarefoundinavarietyofgeologicalsettings,andarealsoconsideredtoberelativelywidespreadinMarswhere they are considered important carriers forwater [1]; they are currently recognized as sensitiveenvironmental indicators and play an important role in the acid drainage mobilization of metals and themonitoringofwaterquality[2].Decomposition products of iron-bearing sulfates are extremely important in technological processes;applications include uses in selective catalysis, pigments, coatings, sensor technologies, ion exchangers, anddatastoragematerialsandindevelopingnewelectrodematerialsforlithium-ionbatteries[3].Thepresentstudyisfocusedonaparticularironhydratedsulfate,fibroferrite,FeOH(SO4)5H2O.The crystal structure of fibroferrite is based on [Fe3+(OH)2(H2O)2O2] octahedra linked via cis octahedralverticestoformhelicalchainsrunningparalleltothecaxis.SO4groupssharetwooxygencornerswithFe3+-octahedraprovidingfurtherintra-chainlinkages.Adjacentchainslinkbothbydirecthydrogenbonding,andbyanadditionalandcomplexhydrogen-bondingnetworkinvolvingfreewatergroups.Thethermaldecompositionoffibroferritewasstudiedbyamultimethodologicalapproach,combiningRietveldrefinement of in-situ high-temperature (HT) synchrotron X-ray powder diffraction data, HT-FTIRspectroscopy, thermogravimetricanalysisandmassspectrometry.Theresults fromthese techniquesallowedtocloselyaddress thestructuralchangesof the initialcompound,determining thestability fieldsandreactionpathsand thehigher temperatureproducts.Sixmaindehydration/transformationstepshavebeen identified intheheatingtemperaturerange25-800°C.Above760°C,hematiteisthefinalphase.Temperaturebehaviorofthedifferentphaseswasanalyzedandthestructuralchangesinducedbyheatingarediscussed.Infrared spectraarecharacterizedbyacomplex systemofSO4

2- andH2Ointernalmodes. Insitu HT-FTIRdata,collectedupto600°Cbothonpowdersandsingle-crystals,showasuccessionofstructuraltransitionsaccompanying the lossofwatermolecules andOHgroups, in agreementwithHTX-raypowderdiffractionresultsandmasslossstepsfromthermogravimetry.[1]H.Bai,Y.Kang,H.Quan,Y.Han,J.Sun,Y.FengBioresour.Technol.2013,128,818–822.[2]M.D.Lane,J.L.Bishop,M.D.Dyar,P.L.King,M.Parente,B.C.HydeAm.Mineral.2008,93,728-739.[3]M.A.Gomez,G.Ventruti,M.Celikin,H.Assaaoudi,H.Putz,L.Becze,K.E.Leea,G.P.DemopoulosRSCAdvances.2013,37,16840-16849.

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6O5.StructuralcharacterizationofmagnetoresistivePb2FeMoO6

FrancescoMezzadri,aDavideDelmonte,bFabioOrlandi,aChiaraPernechele,cRiccardoCabassi,bFulvioBolzoni,bAndreaMigliori,dManuelPascal,eMassimoSolzi,cGianlucaCalestaniaandEdiGiliolib

aDipartimentodiChimica,UniversitàdegliStudidiParma,Parma,Italy.francesco.mezzadri@unipr.itbIMEM-CNR,Parma,Italy.

cDipartimentodiFisicaeScienzedellaTerra,UniversitàdegliStudidiParma,Parma,Italy.dIMM-CNR,Bologna,Italy.

eISISFacility,STFC,RutherfordAppletonLaboratory,Chilton,Didcot,Oxfordshire,UK.Pb2FeMoO6 belongs to the class of double perovskites (general formula A2BB’O6), which represent aninterestingplayground in thematerial researchfield,beingcharacterizedby thehighstabilityand tolerance tochemicalsubstitutionstypicalofperovskites,withtheadditionofB-sitesplitting,allowinginprinciplethefine-tuningofcationordering,magneticexchangeinteractionsandelectricalproperties.Asaresult,alargenumberofpeculiarstructuralandphysicalpropertiescanbeobserved,includingmultiferroism,spinpolarizedcarriers,magnetoresistanceorcatalyticproperties.Pb2FeMoO6isapoorlystudiedmemberofthefamily,needinghighpressure and high temperature conditions to be synthesized. It is reported [1] to display ferromagnetic-likepropertiesbelowabout250Kandmagnetoresistanceeffects.Wepresenthereaseriesofthoroughstructuralcharacterizations allowing the effective interpretationof thephysical properties of the systemmakinguseofelectron diffraction, synchrotron powder X-Ray diffraction and neutron time of flight measurements. TheroomtemperaturecrystalstructureofPb2FeMoO6wasdeterminedforthefirsttime,beingcharacterizedbyasuperstructurewithFm-3msymmetryandlatticeparametera’=2ap(apindicatesthesimpleperovskite).B-sitecation ordering is detected, with the relevant presence of antisite defects. The lead atoms are statisticallyshiftedoffthehighsymmetrypositiongivingrisetolocalpolarproperties.Themagneticstructurewassolvedin the I4/mm’m’ coloredspacegroup (seeFig.1), involving theatomicmomentsof ironandmolybdenumtobecoupledinantiparallelway,givingrisetoaferrimagneticresultantoverwhichacentralroleisplayedbytheantisite defects. The results of the structural analysis are compared with the physical characterizationsrevealingexcellentagreement.

Figure1.MagneticstructureofPb2FeMoO6.

[1]Y.Xueping,X.Mingxiang,C.YanbinAppliedPhysicsLetters2013,103,052411.

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6P1.Twinning:structuralpeculiaritiesandopportunitiesincoordinationpolymers

EmanuelePriolaaaDipartimentodiChimica,UniversitàdegliStudidiTorino,Torino,Italy

The phenomenon of twinning in the chemical crystallographic community is commonly perceived as aprobleminanaccuratestructuralresolution.However,twinscanbeanopportunityinthematerialscience,i.e.the peculiarmeccanical properties ofmetallicmaterials obtained from deformation twinning. [1] In a widersense,allthepropertieswithatensorialnaturecanbemodeledthrougharationaldevelopmentofthedifferentkindoftwinning:thepointgroupsymmetryoftheentirecrystaledificediffersfromthepointgroupsymmetryofthetwin’sindividuals,andthismakepossibletochangetherelationsbetweenthetensorcomponentsfromthesinglecrystaltothetwinnededifice.[2]Rationalcontroloftensorialpropertiesisofgreatinterestfortheirapplications inNLOmaterials and advanced optics .Within this background, a less developed study of thenature, problems and opportunities of twinning is the investigation of this phenomenon in the structure ofcoordinationpolymers,organometalliccompoundswithaninfiniterepetitionofmetalcentersandligandinoneor more dimensions. The study of this family of polymers has been developed in the last decades for theinvestigationof the peculiar structural features and the consequent properties .However, a screeningon thestructuralliteratureonthisfieldshowsaverycommonoccurrenceoftwinninginthiskindofstructures.Theoccurrenceofthesephenomenahasbeendeeplystudiedandunderstoodinmineralogy,butscarcelydevelopedfromaninorganic-organometallicpointofview.Themainaimofthiscontributionisatentativetocorrelatethestructural pattern of the coordination polymers and their weak interactions responsible of the crystallinearchitecture, with the presence of twinning, in order to obtain a better knowledge of his occurrence in thecrystal growth.The peculiar symmetries of the twin’s individualswill be examined in the framework of thepolychromaticgrouptheory,adevelopmentofthestudyofShubnikovgroups.[3]Thisapproachisinterestingtodoamoreformalandrigorousdescriptionofthetwinningandcouldbeimportantforanexactdescriptionofthecrystalstructure,intheframeworkofthemoderngeminography.[1]Yu,Q.,Shan,Z.W.,Li,Ju,Xiao,L.,Sun,J.,Ma,E.,Nature,463,2009,335-338[2]Wadhawan,V.K.,ActaCryst.,A53,1997,546-555[3]Nespolo,M.,Z.Kristallogr.,219,2004,57-71

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6P2.ImproperFerroelectricstateinadoubleperovskitesystemwithacollinearmagneticstructure

OrlandiFabio,†*RighiLara,†§MezzadriFrancesco,†§ManuelPascal,¶KhalyavinDmitry,¶CabassiRiccardo,§

BolzoniFulvio,§SolziMassimo‡andCalestaniGianluca†§†DipartimentodiChimica,UniversitàdiParma,ParcoAreadelleScienze17/A,43124Parma,Italy

‡DipartimentodiFisicaeScienzedellaTerra,UniversitàdiParma,ParcoAreadelleScienze7/A,43124Parma,Italy

¶ISISFacility,STFC,RutherfordAppletonLaboratory,Chilton,Didcot,OxfordshireOX11-0QX,UK§IMEM-CNR,ParcoAreadelleScienze37/A,43124Parma,Italy

The physical characterization and the careful crystallographic study of the double perovskite systemPb2Mn0.6Co0.4WO6indicateanimproperferroelectricstateinducedbythemagneticordering.Thecompoundshows a centrosymmetric orthorhombic double perovskite structure, s.g.Pmcm.1', strongly distorted fromthe lead stereoactivity, joined with twomagnetic transitions at 190 K and 10 K. The time of flight neutrondiffractiondata,performedat theISISfacilityontheWISHinstrument[1], indicates thepresenceofdiffusescattering below the first transition temperature and the rise of extra reflections below 10 K. These newreflections, ascribable toa long rangemagneticordering, canbe indexedwith twopropagationsvectors1=(000) and 2=(½00). The symmetry analysis of the magnetic transition, performed with the help of theISODISTORTandJana2006software[2,3],indicatethebreakingofbothtimeandspatialinversionsymmetryat themagnetic transition from themmm.1' to them'm21' point group. The symmetry reduction allows thegenerationofaspontaneouselectricalpolarizationconfirmedbytheelectricalcharacterizations.Themagneticstructure is described by a collinear pseudo-E type structure propagating in the {111}plane of the primitiveperovskitecell.Theobservedelectricalpolarization isproducedbysymmetricexchangestrictionmechanismbetween the interacting spins, as supportedby themagnetic symmetryanalysis that exclude thepresenceofspiral magnetic structure and, as consequence, of inverse Dzyaloshinskii-Moriya mechanism. Theexperimental electrical polarization is modelled on the basis of the observed magnetic structure and of thesymmetric exchangemechanism, taking intoaccount also the small rangeordering, evidenced in the timeofflightdatafromthediffusescatteringinthehighd-spacingregion.Thiscaseofstudyisameaningfulexampleoftherolethatthemagneticsymmetryanalysisandinparticulartheuseofthecolouredsymmetrycanplayinexplainingthestructure-propertiesrelationshipincomplexmultifunctionalmaterialslikemultiferroics.[1] Chapon L.C. , Manuel P., Radaelli P.G. , Benson C., Perott L., Ansell S., Rhodes N.J. , Raspino D.,DuxburyD.,SpillE.,andNorrisJ.NeutronNews2011,22,22-25.[2]CampbellB.J.,StokesH.T.,TannerD.E.andHatchD.M.,J.Appl.Cryst.,2006,39,607-614.[3]Petricek,V.;Dusek,M.;Palatinus,L.Z.Kristallogr.2014,229,345–352.

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6P3.CO2adsorptioninFaujasitesystems:asynchrotronX-RayPowderDiffractioninvestigation

RossellaArlettia,b,LaraGiglia,FrancescoDiRenzoc,SimonaQuartierid,aDipartimentodiScienzedellaTerra,UniversitàdegliStudidiTorino,Torino,ItalybInterdepartmentalCentre“NanostructureInterfacesandSurfacesNIS”,Torino,Italy

cInstitutCharlesGerhardtdeMontpellier,UMR5253CNRS-UM2-ENSCM-UM1,Montpellier,FrancedDipartimentodiFisicaeScienzedellaTerra,UniversitàdiMessina,MessinaS.Agata,Italy

rossella.arletti@unito.itTheseparationofCO2fromotherlightgaseshasbeenlargelypracticedinthepast.Inparticular,muchofthework concerned the separation of CO2 for the purification of natural gas [1]. Several different approacheshavebeenproposedtoremoveCO2fromfluegasesonalargescale[2-5].Amongthese,zeolitesarestronglypreferredfortheirhighadsorptioncapacity,selectivity,irreversibilityoftheadsorptionprocessesandrelativelylowproductioncost[6].In this work - through in situ X-Ray Powder Diffraction (XRPD) experiments - we describe the CO2molecules penetration and their interactions with zeolite cavities/extraframework cations. Three differentzeolitesamples[NaX,NaYandCaLSX]-sharingthesameFAUframeworktypebutwithdifferentSi/Alratiosanddifferentcationcontents-wereinvestigated.XRPD experiments were carried out at the MCX beamline at Elettra Sincrotrone Trieste source. ThepowderedsamplesweredegassedatT=400°CinordertoremovethewaterandthensaturatedwithCO2at1barfor30minutes.XRPDpatternswerecollected.InordertostudytheCO2desorption,aseriesofpatternswerecollecteduponheatingfromroomTto600°C.After thedegassingat400°Cand theconsequentwater release, theextraframeworkspeciesunderwenta re-organization.Oncethesystemsweresaturatedat1bar,itwaspossibletolocatethehostmoleculesadsorbedinthecavities.ThediffractiondatacollectedonNa-Yallows localizing48CO2molecules in theFAUsupercage,distributedovertwoindependentcrystallographicsites.Themoleculesformclustersatthecenterofthecage.FortyCa-coordinated CO2 molecules were located in the supercage of Ca-LSX, as well. On the contrary, the datacollectionperformedonthesaturatedNaXallowstolocatefiveNa-coordinatedCO2moleculesinthesodaliticcage,andacarbonate-likespeciesnearthesupercage.DuetothelownumberofCO2moleculesfoundbythisstructurerefinement,itisnotpossibletoexcludethefurthermoleculesoccupyingthecageswithadisordereddistribution.Upon heating up to 600°C, the Na-samples underwent a complete release of all previously adsorbed CO2molecules. On the contrary, Ca-LSX retained 25 CO2 molecules in the channels, suggesting a strongerbondinginteractionwiththecations.[1]S.Sridhar,B.Smitha,T.M.AminabhaviSep.Purif.Rev.2007,36,113.[2] R. T. Yang Gas Separation by Adsorption Processes, Imperial College Press, London, 1997. [3] R.Bredesen,T.A.PetersMembraneTechnol.,Vol.2,Wiley-VCH,Weinheim,2008.[4]P.L.Llewellyn,etal.,Langmuir2008,24,7245.[5]A.R.Millward,O.M.Yaghi,J.Am.Chem.Soc.2005,127,17998.[6]S.Choi,J.H.Drese,C.W.JonesChemSusChem.2009,2,796andreferencesherein.

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6P4.Crystallographicandchemicaltransformationofasbestiformerioniteandchrysotileasbestosincellenvironment

RuggeroVigliaturo,aArmandaPugnaloni,dSilvanaCapella,aElenaBellusoa,b,caDipartimentodiScienzedellaTerra,UniversitàdegliStudidiTorino,viaValpergaCaluso,35,10125,

Torino,ItaliabIGG,CNR,Torino,ItalycIGC-NIS,Torino,Italy

dDip.diScienzeClinicheeMolecolari,UniversitàPolitecnicadelleMarche,Marche,Ancona,ItalyChrysotileishistoricallyawellknownmaterialwithexceptionaltechnologicalproperties,aswellasfamousfortherelatedhealth issuescausedwhenbreathedinhighdoses.Erioniteneverhadan industrialuse,butasanyzeolite it bears rare physical and chemical properties and unfortunately also its fibers can cause diseases,specificallymesothelioma(akindofcancer).Chrysotile is themainserpentinesheetsilicate thatoccurswithasbestiformhabit and owing to its tubular sheet arrangement it is amicroporousmineral having high tensilestrenght, flexiblility, excellent thermal and acoustic absorption properties, chemical and biological strentgh .Erionite can occur in fibers or prismatic crystals, having a framework characterized by several channelsdevelopped along its structure forwhich it can be classified as amicroporousmineral. The internal surfacearea is particularly extended, giving to it the possibility to absorb the 20% of its weight in water, also ionexchangeproperties comes from this aspect.These twodifferentmicroporousminerals cancause the samediseases in human. The present study aims to evidence common characteristics and differences in theinteractionamongthesemineralsandthehumancellenvironment(invitroexperiment).Fibersohbothmineralswerecharacterizedusingtransmissionelectronmicroscopyanddiffractionbeforetheinteraction with the cell cultures and after 48 hours and 96 hours of interaction (Fig. 1). Many intensemorphologicalandcrystallinitymodificationsarevisibileinchrysotilesamples,whilsthigherchemicalvariationhappensinasbestiformerionitesamples,withalargemotionofextra-frameworkcations.Aftertheinteraction,bothmineralsshowasmorestablestructuralcomponentthetetrahedralcoordinatedcations, inchrysotilethesurfaceandnear-surfacespeciesarehydrolizedandcarriedintosolution.Inerionitefibersthecationexchangeisnotonlyasurfaceornear-surfacephenomenon,butinvolvestheinteriorofthemineralthatactsasabuffer.

Figure1.HRTEMevidenceofanerionitefibershowinghighcrystallinitydegreeafter96hoursinteractionwithabronchoalveolarcell.Onthetop,theunitcellorientedasinthebottomTEMimageisshown

77

6P5.Compressibilityandhigh-pressurebehaviourofleadfeldsparNadiaCuretti,PieraBenna,EmilianoBruno

DipartimentodiScienzedellaTerra,ViaValpergaCaluso35,I-10125Torino,Italy:piera.benna@unito.itCrisDiInterdepartmentalCenterforCrystallography,ViaP.Giuria5,I-10125Torino,Italy.

High-pressure in situ X-ray diffraction was performed on synthetic lead feldspar. The crystals, withcomposition PbAl2Si2O8, were synthesized from melt as in a previous work and thermally treated at T =1150°C for 12 h and further annealed at T = 1000°C for 70 h [1]. A single crystal of lead feldspar waspreliminary characterized by using aGeminiRUltraX-ray diffractometer (CrisDi,University ofTorino).Atroomconditiontheunit-cellparametersarea=8.3936(4),b=13.0498(7),c=14.3258(8)Å,β=115.281(6)°,V=1418.9(1)Å3;spacegroup:I2/c;Qod=0.7.ThesamplewasloadedinanETH-typediamondanvilcell(DAC)andtheunit-cellparametersweremeasuredinthePrange0.0001-8.4GPaatroomT,usingaSiemensP4diffractometerandSINGLEsoftware[2].Theevolutionwithpressureoftheunit-cellparametersandvolumeshowsastrongdiscontinuitybetween7.7and8.2GPaindicatingafirstorder-phasetransition.InthePrange0.0001-7.7GPathetrendshownbytheaxialcompressibility ( a > c> b) is similar to that observed in the previous HP powder diffraction study,performedonleadfeldsparusinghigh-brilliancesynchrotronradiationupto7.1GPa[3].InthePrange0.0001-4.3GPaatroomT,theP-VdataoftheI2/cleadfeldsparwerefittedwitha2nd-orderBirch-MurnaghanEoS,usingEosFit7csoftware[4].Theparametersobtainedare:V0=1422.2(1)Å3andKT0= 76.4(9) GPa. At P > 4.27 GPa, the volume values deflect from the BM2 curve and show a volumesoftening, precursor of the reportedHPphase transition.Also in strontium feldspar a volume softeningwasrecentlyobservedabove4.2GPa[5].Another crystal of lead feldspar of the same synthesis was loaded in the DAC to investigate the structuralchanges with increasing pressure. Single-crystal diffraction intensities were collected with GeminidiffractometeratP=0.0001,2.4,3.1,5.4,6.0,7.2,8.4,9.7GPa.Themeasurementsup to7.2GPashowedonlya(h+k=even,l=even)andb-type(h+k=odd,l=odd)reflections(I2/cspacegroup).Theappearanceof c (h+k = even, l = odd) and d-type (h+k = odd, l = even) reflections at P = 8.4, the analysis of thesystematic absenceand the structural refinements indicate that theHP first-order transformation is an I2/c -P21/cphasetransition.[1]P.Benna,M.Tribaudino,E.BrunoAm.Mineral.1996,81,1337.[2]R.J.Angel,L.W.FingerJ.Appl.Cryst.2011,44,247.[3]M.Tribaudino,P.Benna,E.Bruno,M.HanflandPhys.Chem.Minerals.1999,26,367.[4]R.J.Angel,J.Gonzalez-Platas,M.AlvaroZ.Kristallog.2014,229,405.[5]F.Pandolfo,T.BoffaBallaran,F.Nestola,M.KochMuller,M.Mrosko,E.BrunoAm.Mineral.2011,96,1182.

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6P6.Alkaliactivatedmaterialsfromsulfate-bearingkaolins:prosandconsOcchipintiR.1,TarantinoS.C.1,GaspariniE.1,RiccardiM.P.1,ZemaM.11 Dipartimento di Scienze della Terra e dell’Ambiente, Università di Pavia, 27100 Pavia, Italy.roberta.occhipinti01@ateneopv.itThe feasibility of using low-grade kaolins containing sulfates to synthesize alkali activatedmaterials (AAMs)has been assessed.Alunite,KAl3(SO4)2(OH)6, is present in kaolin deposits deriving from trachyte, rhyolite,andsimilarpotassium-richvolcanicrocks,andnormallyhinderstheuseoftheseclaysintheceramicindustryduetothereleaseathightemperatureofSOx,whichdamagesfurnacesrefractories.Metakaoliniteobtainedbyannealingalunite-containingkaolinsatT=550°C,i.e.belowdesulfationtemperature,hasbeenusedforalkaliactivation.AAMshavebeensynthesizedfrommetakaolinandsodiumsilicatesolution,nominalcompositionoftheslurryis given by SiO2/Al2O3 and Al2O3/Na2O molar ratios of 4.6 and 1.04, respectively. Specimens have beencuredinair-tightmoldsat52°Candfor19h.Sampleshavebeenpreparedbyusingthealunite-bearingkaolinfromPilonidiTorniellamine(alunite5%wt)asstartingmaterialandbymixing10%wt.alunitetohigh-qualitykaolinite to better identify sulfate by-products in the AAMs. The results are promising as the synthesizedsamplesrevealedtobecomposedmainlybyanamorphousgelandcharacterizedbyhighthermalstabilityandstrength, with compressive strength higher than 80 MPa. All samples have been characterized by thermalanalysis, X-ray powder diffraction and infrared spectroscopy. A petrographic approach has been used toanalyzethetexturalfeaturesofgeopolymersatdifferentlengthsofscalebyusingopticalandscanningelectronmicroscopies.More studies are needed in order to improve the sulfate retention aswell as to identify all the silico-sulfatephases and understand the possible interactions between precipitated nanocrystalline sulfate phases andgeopolymerbinder.

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6P7.HTphasetransitioninoliveniteandthermalbehaviourofolivenite-groupminerals

SerenaC.Tarantinoa,b,MicheleZemaa,b,MassimoBoiocchic,AthosM.CallegariaaDipartimentodiScienzedellaTerraedell’Ambiente,UniversitàdegliStudidiPavia,viaFerrata1,I-27100

Pavia,Italy.serenachiara.tarantino@unipv.itbCNR-IGG,SezionediPavia,viaFerrata1,I-27100Pavia,Italy

cCentroGrandiStrumenti,UniversitàdiPavia,ViaBassi21,I-27100Pavia,ItalyOlivenite, Cu2(AsO4)(OH), is the only mineral among those of the olivenite group showing at roomtemperature amonoclinicP21/n crystal structure, although characterized by aβ angle close to 90° [1]. Allothermineralsof thegroup,whichcomprisesseveralarsenatesandphosphates,suchasadamite, libethenite,eveite,zincolivenite,zincolibetheniteandauriacusite,crystallizeintheorthorhombicPnnmspacegroup[2].Referring to theorthorhombic crystal structure, twocation sites, having respectivelyoctahedral and trigonalbipyramidalgeometries,are typicallyoccupiedbyCu2+orZn2+ ions.Octahedrashareedges to formstraightchains along c. Such chains are cross-linked by isolated PO4 or AsO4 tetrahedra via corner-sharing, thusforming an open networkwith channels extending in the c direction. Trigonal bipyramids share an edge toform dimers, which lie in these channels. Dimers are connected to octahedra chains and to tetrahedra bycorner-sharing.Ahydroxylgroupissharedbytwooctahedralandonetrigonalbipyramidalcoordinatedions.In this work, a natural olivenite single crystal has been submitted to in situ high-temperature (HT) single-crystal X-ray diffraction from room temperature (RT) to 773 K, i.e. until dehydration and collapse of thecrystalstructure.Unit-cellparametershavebeenmeasuredatregularintervalsof25K,andcompletedatasetscollected every 100 K. Evolution of unit-cell parameters and structure refinements indicates that oliveniteundergoes a structural phase transition from P21/n to Pnnm at ca. 473 K, and eventually becomesisostructuralwiththeothermembersofthemineralfamily.Thesametransitionhasbeenobservedinsyntheticlibethenite at 160 K [3]. Volume expansion with temperature is larger in the monoclinic phase than in theorthorhombicone.Anisotropyofaxialthermalexpansionisrationalisedintermsofpolyhedraconnectivity.Thermalbehaviouroftheoliveniteorthorhombicphasehasbeencomparedwiththoseoflibethenite,Cu2(PO4)(OH) [1] and adamite, Zn2(AsO4)(OH) [2]. When the evolutions of the three orthorhombic structures arecompared,similarvolumeexpansioncoefficientsareobserved(Fig.1).AxialexpansionsindicatethatthetwoCu‑bearingmembersbehavesimilarlytoeachother,whileaxialexpansioncoefficientratiosareratherdifferentinadamite.

Figure1.Volumeexpansionsofolivenite,libetheniteandadamite.[1]C.Li,H.Yang,R.T.DownsActaCrystallogr.E.2008,64,i60-i61.[2]S.J.Mills,A.R.Kampf,G.Poirier,M.Raudsepp,I.M.SteeleMiner.Petrol.2010,99,113-120.[3]A.A.Belik,P.Naumov,J.Kim,S.TsudaJ.SolidStateChem.2011,3128-3133.[4]M.Zema,S.C.Tarantino,A.M.CallegariMineral.Mag.2010,74,555-567.[5]M.Zema,S.C.Tarantino,M.Boiocchi,A.M.CallegariMineral.Mag.submitted.

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MS7.IMAGINGBIOMOLECULARMACHINESINACTIONTHROUGHCRYO-ELECTRONDIFFRACTIONANDCRYO-

ELECTRONMICROSCOPY

Structures at near-atomic resolution are no longer the prerogative of X-ray crystallography or nuclearmagnetic resonance spectroscopy. The old dreamof being able to use fewdozen protein 3Dnano-crystals todeterminebyelectronmicroscopyatomic-resolutionstructuresmayfinallycometrue.Thecombinationofdirectelectrondetectorsandreliableimageprocessingprogramsiskeepingthefieldmovingforwardatarapidrate.Precise knowledgeof the structureofmolecularmachines in thecell is essential forunderstandinghow theyfunction.Structuresoflargemacromoleculesintheirmultitudeofdifferentconformationscannowbeobtainedat near-atomic resolution by averaging thousands of electron microscope images recorded before radiationdamage accumulates. This microsymposium will highlight the major methodological advances for highresolution imaging of biomolecular machines in action through cryo-electron diffraction and cryo-electronmicroscopy.Chair:DorianoLamba(ICCNRTrieste)

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7KN1.Theatomicstructureofthehumangamma-secretasecomplexXiao-chenBaia,ChuangyeYanb,GuanghuiYangb,PeilongLub,DanMab,LinfengSunb,RuiZhoub,andYigong

Shib,SjorsH.W.ScheresaaMRCLaboratoryofMolecularBiology,CambridgeBiomedicalCampus,Cambridge,UK.

bMinistryofEducationKeyLaboratoryofProteinScience,Tsinghua-PekingJointCenterforLifeSciences,CenterforStructuralBiology,SchoolofLifeSciences,TsinghuaUniversity,Beijing100084,China.

xcbai@mrc-lmb.cam.ac.uk

For many years, structure determination of biological macromolecules by cryo-electron microscopy (cryo-EM)waslimitedtolargecomplexesorlow-resolutionmodels.Withrecentadvancesinelectrondetectionandimage processing, the resolution by cryo-EM is now beginning to rival X-ray crystallography. A newgenerationofelectrondetectorsrecordimageswithunprecedentedquality,whilenewimage-processingtoolscorrect for samplemovements and classify images according todifferent structural states.Combined, theseadvancesyielddensitymapswithsufficientdetailtodeducetheatomicstructureforarangeofspecimens.Nowthequestionarisesastowherethenewsizelimitslie.Theribosomeandvirusmightbeconsideredeasytargets for cryo-EM because they are relatively large, and the latter also has high symmetry. Currently, thesmallest complex subjected to the new methodology is γ-secretase. This asymmetric membrane complexcomprises four different proteins with a total molecular weight of 170 kDa. Imaging on a K2 detector incounting mode and performing reconstruction with a modified motion correction and 3D classificationalgorithm led to near-atomic resolution 3.4Å, which proved sufficient for de novo model building. Thisstructure represents another breakthrough for the emerging technique of high-resolution cryo-EM, and alsoserves as a molecular basis for mechanistic understanding of γ-secretase function and disease-causingmutations.

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7KN2.MolecularmechanismsofasymmetriccelldivisionsSaraMaria,SimoneCulurgionib,SaraGallinia,andMarinaMapellia

aEuropeanInstituteofOncology,Milano,Italy.bDiamondLightSourceLtd,Oxford,UK.marina.mapelli@ieo.eu

TheAsymmetric cell divisions are attained by unequal segregation of cell-fate defining components, and bydifferential positioning of siblings within the tissue. In several vertebrate stem cell systems, only daughtersretaining contact to specialized microenvironment called niches maintain stemness. On these premises, itbecomes clear that asymmetric divisions require the coordination between cellular polarity and the divisionplane, and hence the mitotic spindle axis. Spindle coupling to cortical polarity is attained by pulling forcesexertedonastralmicrotubulesbyNuMA:LGN:GαicomplexesboundtoDynein.Whatinstructstherecruitmentoftheseforce-generatingdevicesatthecorrectcorticalsitesistodatelargelyunclear.TheadaptorInscuteable(Insc) has been considered the molecular bridge between the apical polarity proteins Par3:Par6:aPKC andLGN.InDrosophilaneuroblastsandinmurineneuralstemcellsandskinprogenitors,InschasbeenshowntointeractbothwithPar3andLGN.Howeverthemolecularbasisforitsfunctionstillremainelusive.IwillpresentthecrystallographicstructureofDrosophilaLGNincomplexwithInsc.Thestructurerevealsastable tetrameric arrangement of intertwined molecules, in which each Insc chain contacts two LGNTPR

domains.Biochemical analyses showed that Insc:LGN tetramers constitute stable cores for the assembly ofthe Par3-Insc-LGNGαiGDP apical complexes. Importantly, such oligomeric arrangements are conservedthroughoutspecies,andarecompetitivewiththebindingofLGNtoNuMA.Collectivelytheseresultssuggesta novel cortical function ofLGN, independent frommicrotubulemotors and specific for asymmetric apico-basal divisions. Based on this evidence, we propose a model in which two independent pools of LGNcontribute to asymmetry in different ways: the Insc-bound pool by coordinating the distribution of fatedeterminants includingPar3, and themore abundantNuMA-bound pool by providing cortical information toorientthedivisionplane.

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7O1.MembraneNAPE-PLDlinksmajorplayersinlipidhomeostasiswithmajorplayersinlipidmediatedsignaling

EleonoraMargheritis,aRobertoMarotta,bPaolaMagotti,cGianpieroGarauaaStructuralBiophysics,ItalianInstituteofTechnology,Genoa,Italy.

bNanochemistry,ItalianInstituteofTechnology,Genoa,Italy.cIRBMSciencePark,Pomezia(Roma),Italy.gianpiero.garau@iit.it

NAPE-hydrolyzing phospholipase D is a membrane enzyme that produces fatty acid ethanolamides (FAEs),essential biactive lipidmediators involved in highly conserved biological functions, such as innate immunity,energybalance,andstresscontrol[1].ThecrystalstructureofhumanNAPE-PLDat2.6Åresolutionshowsitformshomodimerspartlyseparatedbyaninternal~9-Å-widecannelanduniquelyadaptedtoassociatewithmembrane phospholipids. Structural and biophysical analysis reveal bile acids bind with high affinity tospecific pockets of the protein membrane interface, enhancing dimer assembly and enabling catalysis [2].Experimentsof3DEMreconstructionof theproteinassociated tomembranevesiclesareunderway.Theseinsights might cast an interesting light on NAPE-PLD as a point where signaling of bile acids and FAEsconverge[3].

Figure1.Regulationofbioactivelipidamidesignalsbybileacids[1]M.Lucanic,J.M.Held,M.C.Vantipalli,B.W.Gibson,G.J.Lithgow,M.S.Gill2011,Nature473,226.[2]P.Magotti,I.BauerI,M.Igarashi,R.Marotta,D.Piomelli,G.Garau.Structure2015,23(3),598.[3]M.Kostic.Chemistry&Biology2015,22,428.

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7O2.PoreflexibilityunderliesthepoorselectivityofCNGchannels:astructural,functionalandcomputationalanalysis

LuisaM.R.Napolitanoa,MatteoDeMarcha,InaBishab,ArinMarchesib,ManuelArcangelettib,NicolaDemitria,MonicaMazzolinib,AlexRodriguezb,AlessandraMagistratob,c,SilviaOnestia,AlessandroLaiob&

VincentTorrebaStructuralBiologyLaboratory,Elettra-SincrotroneTriesteS.C.p.A.,AreaSciencePark,Trieste,Italy.

bNeurobiologySector,InternationalSchoolforAdvancedStudies(SISSA),Trieste,Italy.cCNR-IOM-DemocritosNationalSimulationCenterc/oSISSA,Trieste,Italy.matteo.demarch@elettra.eu

Cyclic nucleotide-gated (CNG) ion channels, despite a significant homology with the highly selective K+channels, do not discriminate among monovalent alkali cations and are permeable also to several organiccations [1,2]. We combined X-ray crystallography with electrophysiology and molecular dynamics (MD)simulationstodemonstratethattheporeofCNGchannelsishighlyflexible.WhenaCNGmimiciscrystallizedin thepresenceof avarietyofmonovalent cations, includingNa+,Cs+anddimethylammonium(DMA+), thesidechainofGlu66intheselectivityfiltershowsmultipleconformationsandthediameteroftheporechangessignificantly. MD simulations indicate that Glu66 and the prolines in the outer vestibule undergo largefluctuations, which are modulated by the ionic species and the voltage. The differences in position, ionoccupancy and ion size in the Li+, Na+, Rb+, Cs+, MA+ and DMA+ complexes also result in small butsignificant structural changes in the polypeptide lining the pore lumen arise from both a small lateraldisplacementof thebackbonechainanda reorientationofmain-chaincarbonyls.This flexibilityunderlies thecouplingbetweengatingandpermeationandthepoorionicselectivityofCNGchannels.

Figure1.StructuralanalysisoftheCNGmimicchannelincomplexwithdifferentions.

[1]D.A.Doyle,J.MoraisCabral,R.A.Pfuetzner,A.Kuo,J.M.Gulbis,S.L.Cohen,B.T.Chait,R.MacKinno.Science.1998,280,5360.[2]Y.Jiang,A.Lee,J.Chen,M.Cadene,B.T.Chait,R.MacKinnon.Nature.2002,417,6888.

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7O3.Haveyourphosphateandeatit:structureandfunctionofabacterialPhoXphosphatase

PietroRoversia,b,SheeChienYonga,JamesLillingtonb,FernandaRodrigueza,MartinKrehenbrinka,OliverZeldina,ElspethGarmana,SusanLeab,andBenBerksa.

aOxfordBiochemistryDepartment,OxfordUniversity,Oxford,England,UK.bSirWilliamDunnSchoolofPathology,OxfordUniversity,Oxford,England,UK.

pietro.roversi@bioch.ox.ac.uk

When phosphate is unavailable in the environment, alkaline phosphatases enablemicroorganisms to generatetheir own phosphate supply by breaking down phosphate-containing compounds. We have determined thecrystal structureof thewidelyoccurringmicrobial alkalinephosphatasePhoX.Thepurified enzyme showedan unexpected purple colour – and turned out to be structurally and mechanistically distinct from so farcharacterised alkaline phosphatases. Its active site comprises two antiferromagnetically coupled ferric ironions, three calcium ions, and an oxo group bridging three of the metal ions. Notably, the main part of thecofactor resemblessyntheticoxide-centred triangularmetalcomplexes.Threeadditionalcrystal structuresofPhoX in complexwith a substrate analogue, a transition state analogue and phosphate, collectively implicatethe cofactor oxogroup in the catalyticmechanism.Aswell as offering some intriguing chemistry to followup, these findings also have ecological implications: PhoX is as widely distributed as the PhoA family ofalkaline phosphatases amongst oceanmicrobes.Thediscovery thatPhoX requiresFe andCa, in contrast toPhoA which requires Zn and Mg, raises the question of how these organisms may juggle with these twoenzymes in order to secure their phosphatemeal in areas of the oceanwhere Zn, Fe and phosphate are allsimultaneouslyscarce.

Figure1.LowphosphatelevelsinthewaterpromptoceanicbacteriatoexpressPhoXandsecurephosphateviacatalysisatitsCa3Fe2Oactivesite.

[1]YongSC,RoversiP,LillingtonJ,RodriguezF,KrehenbrinkM,ZeldinOB,GarmanEF,LeaSM,BerksBC.Acomplexiron-calciumcofactorcatalysingphosphotransferchemistry.Science2014,345(6201),1170.

86

7O4.Howtobuildahost-parasiteinteractome:aproofofconceptforSchistosomamansoni

AdrianaE.Mielea,GiovannaBoumisa,AndreaBellellia,SylvieRicard-Blumb,RomainSalzab,MarieFatoux-Ardoreb,SofianeBadaouib,GiancarloTriac

aDept.BiochemicalSciences,“Sapienza”UniversityofRome,Italy.bUMR5086,CNRSUniversité“ClaudeBernard”Lyon1,France.cEMBLHamburgoutstation,Hamburg,Germany.adriana.miele@uniroma1.it

Eukaryoticvector-borneparasitesrepresentahugeburdenforhumanhealthworldwide.Malaria, Schistosomiasis and Leishmania are the first causes of morbidity and death worldwide, affectingabout 1 billion people living between the tropics. Each parasite has evolved to evade the host immuneresponse,whilefindingitsfinaldestination,independentlyoftheentrypoint.Itisthereforeimportantforbothdiagnosticsandtherapeuticstoknowwhicharethemolecularplayersinthissurvivalgame.Underthisrespectwehaveundertakenahighthroughputscreeningoftheinteractionsbetweenthe secreted proteins from the human parasite Schistosoma mansoni and the components of the humanextracellularmatrix.S.mansoniisanextracellularparasitictrematode,whichlivesattachedtotheveinsoftheportalsystemaroundthe liver.Before attaining this final site, the infectious cercaria travels from the epidermis to thederma, thenreachesonecapillaryandheadstothelungs,whereitmaturesintothejuvenileform,whichthentravelstothefinaltropismandreachesthesexualadultstage.Previous studies of the secretomes of these three stages have evidenced the presence of a handful proteinsalwaysexpressedandsecreted,andanumberspecificforeachstage[1,2].In order to set up a proof of concept we have selected three of these proteins, which also display amoonlightingbehaviour:enolase,proteindisulfideisomeraseandthioredoxinglutathionereductase.Thenwehavescreenedwithsurfaceplasmonresonanceimagingfortheirhumanpartnersamong78proteins,glycoproteins,andglycosaminoglycans(GAG)knowntobethemajorcomponentsoftheextracellularmatrix.ThosepositivehitsweresubsequentlytestedforcomplexformationbysmallangleX-rayscattering, inordertorevealboththestoichiometryandthestructureofthecomplexes.Here we present the results on SmEnolase, whose major interacting protein partners are plasminogen,tropoelastin, tumor endothelial marker 8 (TEM8), while the major interacting GAGs are dermatan andchondroitinsulfate.In parallel we have screened live promastigotes of 24 strains of 6 species of Leishmania, dividing them bytropism (visceral, cutaneous andmucocutaneous) against the same subset of humanECM components [3].Very interestingly, common partners have been found between S. mansoni and L. donovani, L. infantum,which share a common visceral tropism,while a very small number of different partners could be used asmarkersfortropism.[1]C.L.Cass,J.R.Johnson,L.L.Califf,T.Xu,H.J.Hernandez,M.J.Stadecker,J.R.3rdYates,D.L.WilliamsMolBiochemParasitol.2007155,84-93.[2] D. Ditgen, E.M. Anandarajah, K.A.Meissner, N. Brattig, C.Wrenger, E. LiebauBiomed Res Int. 20142014,964350.doi:10.1155/2014/964350.[3]M.Fatoux-Ardore,F.Peysselon,A.Weiss,P.Bastien,F.Pratlong,S.Ricard-BlumInfectImmun201482,594-606.doi:10.1128/IAI.01146-13

87

7P1.PlatinumbindingtohumancopperchaperoneAtox1BelvisoBennyDaniloa,RoccoCaliandrob,AngelaGallianic,FabioArnesanoc,GiovanniNatilec

aCentreforBiomolecularScience,UniversityofNottingham,Nottingham,UK,bInstituteofCrystallography,ConsiglioNazionaledelleRicerche,Bari,Italy.

cDepartmentofChemistry,UniversityofBari‘‘Aldo.Moro’’,Bari,Italy.benny.belviso@nottingham.ac.uk

Interaction between platinum ion and intra and extra cellular proteins plays a key role in platinum-basedanticancerdrugresistance.Particularly,proteinsinvolvedincoppertransportandregulationareabletomediatethe cellular uptake, sequestration, and efflux from cell of platinum-based drugs, affecting their anticanceractivity.ThecopperchaperoneproteinAtox1,which is involved incopperhomeostasis,hasbeenreported to interactwithcisplatinininvitroandincellexperiments[1].Here, the interaction betweenAtox1 protein and platinum from oxaliplatin, belonging to the third-generationplatinumdrugs,hasbeeninvestigatedbyusingX-raycrystallographyandX-rayabsorptionspectroscopy.OurstructureshowsthatAtox1proteindimerizesinthepresenceofplatinum,whichlosestheamineligandsfromthe starting drug. A platinum ion binds the Cys12 and Cys15 sulfur atoms of two Atox1 proteins in anunexpected tetrahedral coordination, present also in a previously reported platinum-mediated Atox1 dimerstructure [2]. However, in this structure, a severe clash between the amine ligands and the sulfur atomsappears, as platinum preserves their native ammine ligands, suggesting that platinum loses all of its ligandsbeforebindingthesulfuratomsofthecage,asoccursinourstructure.Differently from thepreviousAtox1dimer structure,our structure shows thepresenceof a loweroccupiedbindingsiteontheCys41ofoneofthetwochainsformingthedimer,where,onceagain,platinumlosesallitsligandsfromnativedrug.In solution measurements (FPLC-SEC, ESI-MS, and SAXS), performed by using both cisplatin andoxaliplatin, show that monomeric Atox1 adducts containing a platinum ion coordinated to amine ligands isinitially formedand thatproteindimerization takesplaceat longer timewith lossof theamines, inagreementwith the crystal structure. This process is reminiscent of the copper-promoted formation ofAtox1 dimers,whichhavebeenproposedtobeabletocrossthenuclearmembraneandactasatranscriptionfactor[3].

Figure1.CrystalstructureoftheAtox1proteincrystallizedinthepresenceofoxaliplatin.[1]a)A.Galliani,M.Losacco,A.Lasorsa,G.Natile,F.Arnesano.JournalofBiologicalInorganicChemistry2014,19,705;b)F.Arnesano,L.Banci,I.Bertini,I.C.Felli,M.Losacco,G.Natile.J.Am.Chem.Soc.2011,133,18361.[2]A.K.Boal,A.C.Rosenzweig.J.Am.Chem.Soc.2009,131(40),14196-14197.[3]a)S.Itoh,H.W.Kim,O.Nakagawa,K.Ozumi,S.M.Lessner,H.Aoki,K.Akram,R.D.McKinney,M.Ushio-Fukai,T.Fukai.J.Biol.Chem.2008,283,9157;b)S.Itoh,K.Ozumi,H.W.Kim,O.Nakagawa,R.D.McKinney,R.J.Folz,I.N.Zelko,M.Ushio-Fukai,T.Fukai.FreeRadic.Biol.Med.2008,46,95-104.

88

7P2.Single-particlecryo-EMstudyoftheAMPAreceptorinthedesensitizedstate

RitaDeZorzi,a,*KatharinaL.Duerr,bEricGouaux,b,cThomasWalza,#aDepartmentofCellBiology,HarvardMedicalSchool,Boston,MA02115,USAbVollumInstitute,OregonHealthandScienceUniversity,Portland,OR97239,US

cHowardHughesMedicalInstitute,USA*Presentaddress:DipartimentodiScienzeChimicheeFarmaceutiche,Trieste34127,Italy

#Presentaddress:TheRockefellerUniversity,1230YorkAvenue,NewYork,NY10065,USArita_dezorzi@hms.harvard.edu

The neurotransmitter glutamate mediates most of the excitatory synaptic responses in the central nervoussystem. Glutamate released from the pre-synapticmembrane binds to ionotropic glutamate receptors in thepost-synapticmembrane,causingtheopeningofthereceptor’scationchannelandatransientdepolarizationofthemembrane[1].Deactivationoccurswhenglutamateisreleasedandthereceptorreturnstotheapo restingconformation. However, while the agonist is still bound, the receptor can undergo other conformationalchanges thatdecoupleagonistbinding from theactivationof the ionpore, leading toadesensitizedstate [2].Despite theimportanceof ionotropicglutamatereceptors, thedynamicsof intactreceptorsandthestructuralchanges between distinct functional states are not yet fully understood. In particular, questions remainconcerningthemechanismsthatunderliethedesensitizationofthesereceptors.Among glutamate receptors, α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) receptors,whosenamereflectstheiraffinityforthisartificialglutamateanalog,areresponsibleforfastsignalingandhavekinetics of activation, deactivation and desensitization in the scale of milliseconds [1]. First structuralinformation forAMPA receptors came fromnegative-stainEMstudies of heterotetrameric receptors isolatedfrommouse brains,which revealed that the extracellular domains are organized as dimers of dimers [3].Alater X-ray crystal structure of an engineered homotetrameric AMPA receptor in an antagonist-bound stateconfirmedtheEMstructureandprovidedinsightsintoligandbindingandactivationofthefull-lengthreceptor[4]. Since then, both EM andX-ray crystallographic studies aimed at understandingmechanistic aspects ofAMPAreceptorfunction[5,6].Thedesensitizedstate,inparticular,seemstobecharacterizedbyaseparationof the extracellular domains, and the conformational changes that trigger this flexibility are not yet fullyunderstood.Here,wepresentacryo-EMstudyof theAMPAreceptor in thedesensitizedstate,which ischaracterizedbytheseparationof itsextracellulardomains,consistingof theamino-terminaland ligand-bindingdomains.Asaresult, the extracellular domains lose the 2-fold symmetry observed in the X-ray structure [4] and adopt acontinuumofconformations.We imagedvitrified samplesbycryo-EMandcollected~250,000particles.3Dclassificationoftheseparticlesyieldedstructuresofthereceptorinvariousconformations,reflectingdifferentseparationsof the extracellular domains. Inparticular, the structures allowedus toobserve the coupling anduncouplingof the ligand-bindingdomains that lead to themajor conformational changes involving thewholeextramembranousdomain.[1]R.Dingledine,K.Borges,D.Bowie,S.F.TraynelisPharmacolRev.1999,51(1),7.[2]K.B.Hansen,H.Yuan,S.F.TraynelisCurrOpinNeurobiol.2007,17(3),281.[3]T.Nakagawa,Y.Cheng,E.Ramm,M.Sheng,T.WalzNature.2005,433(7025),545.[4]A.I.Sobolevsky,M.P.Rosconi,E.GouauxNature.2009,462(7274),745.[5]K.L.Dürr,L.Chen,R.A.Stein,R.DeZorzi, I.M.Folea,T.Walz,H.S.Mchaourab,E.GouauxCell.2014,158(4),778.[6] J.R.Meyerson, J.Kumar,S.Chittori, P.Rao, J. Pierson,A.Bartesaghi,M.L.Mayer, S.SubramaniamNature.2014,514(7522),328.

89

7P3.Three-dimensionalstructureandligand-bindingsiteofcarpFishelectin(FEL)

StefanoCapaldi,BeniaminoFaggion,MariaElenaCarrizo,LauraDestefanis,MaríaCeciliaGonzález,MassimilianoPerduca,MicheleBovi,MonicaGallianoandHugoL.MonacoBiocrystallographylaboratory,DepartmentofBiotechnology,UniversityofVerona,Verona,Italy.

hugo.monaco@univr.itCarp FEL (fishelectin or fish egg lectin) is a 238 amino acid lectin that can be purified from the fish eggsexploiting its selective binding to Sepharose followed by elution with N-acetyl glucosamine.We previouslyreported its amino acid sequence and other biochemical properties. The glycoprotein has four disulphidebridgesandthestructureoftheoligosaccharideslinkedtoAsn27wasdescribed(1).Theposterwilldescribe the three-dimensionalstructureofapocarpFEL(cFEL)andof itscomplexwithN-acetyl glucosamine determined byX-ray crystallography to resolutions of 1.35 and 1.70Å respectively (2).Themolecule folds as a six-blade β-propeller and internal short consensus amino acid sequences have beenidentifiedinalltheblades.Acalciumatombindsatthebottomofthefunnelshapedtunnellocatedinthecentreofthepropeller.Twoligandbindingsites,αandβarepresentineachofthetwoprotomersinthedimer.Thefirstsite,α,iscloser to theN terminusof thechainand is located in thecrevicebetween thesecondand the thirdbladewhilethesecondsite,β, is locatedbetweenthefourthandthefifthblade.Theaminoacidsthatparticipateinthecontactshavebeenidentifiedaswellastheconservedwatermoleculesinallthesites.Bothsitescanbindthetwoanomers,αandβofN-acetylglucosamine,clearlyrecognizableintheelectrondensitymaps.Thelectinpresentssequencehomologytomembersofthetachylectinfamily,knowntohaveafunctionintheinnate immune system of arthropods and homologous genes are present in the genome of other fish andamphibians (3).This structure is the firstofaproteinof thisgroupand,given thedegreeofhomologywithothermembersof the family,weexpect itwillbeuseful toexperimentallydetermineothercrystal structuresusingthecoordinatesofcFELassearchprobeinmolecularreplacement.

Figure1.RibbondiagramoftheFELmolecule..

[1]Galliano,M.,Minchiotti,L.,Campagnoli,M.,Sala,A.,Visai,L.,Amoresano,A.,Pucci,P.,Casbarra,A.,Cauci,M.,Perduca,M.&Monaco,H.L.Structuralandbiochemicalcharacterizationofanewtypeof lectinisolatedfromcarpeggs.Biochem.J.2003376,433-440.[2]Capaldi,S.,Faggion,B.,Carrizo,M.E.,Destefanis,L.,Gonzalez,M.C.,Perduca,M.,Bovi,M.,Galliano,M.&MonacoH.L.(2015)Three-dimensionalstructureandlignad-bindingsiteofcarpFishelectin(FEL)ActaCryst2015D71,1123-1135.[3Chen,S.C.,Yen,C.H.,Yeh,M.S.,Huang,C. J.&LiuT.Y. (2001)Biochemicalproperties andcDNAcloningoftwonewlectinsfromtheplasmaofTachypleustridentatus.JBiolChem.,2001276,9631-9639.]

90

7P4.Structuralstudiesofhumanacidicfibroblast-growthfactor(FGF1)mutantswithaprobableanticanceractivity

MaríaCeciliaGonzález,StefanoCapaldi,MariaElenaCarrizo,LauraDestefanis,MicheleBovi,MassimilianoPerducaandHugoL.Monaco

BiocrystallographyLaboratory,DepartmentofBiotechnology,UniversityofVerona,Verona,Italy.mariacecilia.gonzalez@univr.it

Lectins are carbohydrate-binding proteins ubiquitously present in nature. They play a role in biologicalrecognitionphenomenainvolvingcellsandproteins.Theinteractionlectin-carbohydrateishighlyspecific,andcanbeexploitedforthedevelopmentofnanoparticlescontainingontheirsurfacelectinsspecificallydirectedtocarbohydrateresiduespresentonlyonmalignantcellsandabsentonhealthyones[1].Lectinshavebeenfoundtopossessanticancerpropertiesandtheyareproposedastherapeuticagents,bindingtocancer cellmembranesor their receptors, causingcytotoxicity, apoptosis and inhibitionof tumorgrowth.SomelectinsareabletopreventtheproliferationofmalignanttumorcellsbecausetheyrecognizetheT-antigen(Galβ1–3GalNAc)foundspecificallyonthesurfaceoftumorcells[2].ThemainproblemisthattheiruseasadetectionagentfortheT-antigeninclinicalstudiesisnotpossiblebecausetheimmunesystemcanrecognizethemasforeignmoleculesanddevelopanimmuneresponse.Previous studies with X-ray crystallography made in our laboratory have characterized a lectin found inmushrooms called BEL β-trefoil which has antiproliferative activity on tumor cell lines, because it containsthree binding sites for the T-antigen. Unlike other lectins with this property, BEL β-trefoil shows structuralhomology with a human protein, acidic Fibroblast Growth Factor (FGF1) [3]. Superposition of theirstructuressuggeststhatthehumanproteincouldbemutatedtocontainatleastoneofthebindingsitesfortheT-antigen.Suchmutations should create inFGF1 the potential capacity of recognizing tumor cellswith lessimmunogenicity than the fungalprotein.FGF1 ismitogenicandchemotactic, andmediatescellular functionsbybinding to transmembrane receptors,whichareactivatedby ligand-induceddimerization requiringheparinasco-receptor.Toreachourpurpose,theFGF1cDNAwasclonedintoabacterialplasmidandthenmutatedinfourdifferentpositions to eliminate its mitogenic activity and to engineer in the protein the T-antigen binding capacity.AttemptstocrystalizethemutantsofFGF1weremadeusingthehangingdroptechniquewiththefinalaimtocarryouttheirstructuralcharacterizationbyX-raydiffractionanalysisofthecrystals.[1]LisHandSharonN.Lectinsasmoleculesandastools.AnnuRevBiochem.1986.55(1):p.35-67.[2] Ju T, Otto VI, Cummings RD. The Tn antigen-structural simplicity and biological complexity. AngewChemIntEdEngl.2011.50(8):p.1770-1791.[3]BoviM,CenciL,PerducaM,CapaldiS,CarrizoME,CivieroL,ChiarelliLR,GallianoM,MonacoHL.BELβ-trefoil: a novel lectin with antineoplastic properties in king bolete (Boletus edulis) mushrooms. 2013.Glycobiology.23(5):p.578-592.

91

7P5.UnravelingtheantitumoralpropertiesofArundodonaxlectinMassimilianoPerduca,MicheleBovi,LauraDestefanis,MartaBonaconsa,

MariaElenaCarrizo,HugoL.MonacoBiocrystallographylaboratory,DepartmentofBiotechnology,UniversityofVerona,Verona,Italy.

massimiliano.perduca@univr.itLectins are proteins that recognize specific carbohydrate structures and thereby participate in molecularrecognition events of fundamental relevance in a variety of biological processes [1]. They are promisingligandsfortargeteddrugdeliverybecausetheybindrapidlyandspecificallytomembrane-linkedcarbohydratesorglycoproteinstoinitiatereceptor-mediatedendocytosis[2].In recent years several lectin-functionalized nanoparticles have been described and, in particular, the well-knownwheat germagglutininhas beenused for the selectivedeliveryof nanoparticles loadedwith awidelyusedanticanceragent[3].Inour laboratorywehavebeguntocharacterizeanovel lectin thatpresentsasignificantsequencehomologywithwheatgermagglutininandexhibitscytotoxicactivityagainstepithelialcancercells(Fig.1).Thelectinisisolated in very high yields (500 mgs per Kg of the starting material) and with a very simple purificationmethodfromtherhizomesofthecommongiantreedArundodonax,oneofthemostreadilyavailablesourcesof biomass on the Earth because of its fast growing rate and its ability to grow in different soil types andclimaticconditions.WecalltheproteinADLwhichstandsforArundodonaxlectin[4].Thegoalofourprojectistostructurallyandfunctionallycharacterizethelectin,i.e.todefineindetailitsligandbinding specificity using several biophysical techniques and, in particular, X-ray crystallography. We havealreadyprepareddiffractionqualitycrystalsandare in theprocessof solving its three-dimensional structure.In the future we intend to prepare ADL conjugated nano-sized particles for the selective delivery of anti-tumoralagentstoneoplasticepithelialcells.

Figure1.ADLcytotoxicactivityagainstepithelialcancercells.[1]DebbageP.Targeteddrugsandnanomedicine:presentandfuture.CurrPharmDes.,2009;15(2):153-72.[2] C.M. Lehr, Lectin-mediated drug delivery: the second generation of bioadhesives, J. Control. Release,2000;65:19–29.[3]MoY, LimLY. Preparation and in vitro anticancer activity ofwheat germ agglutinin (WGA)-conjugatedPLGAnanoparticlesloadedwithpaclitaxelandisopropylmyristate.J.Control.Release,2005;107(1):30-42.[4] Kaur A, Singh J, Kamboj SS, Sexana AK, Pandita RM, Shamnugavel M. Isolation of an N-acetyl-D-glucosaminespecificlectinfromtherhizomesofArundodonaxwithantiproliferativeactivityPhytochemistry,2005;66(16):1933-1940.

92

7P6.StructuralCharacterizationOfProteinsInvolvedInHelicobacterpyloriMotilityAndAdhesion

ValentinaLoconte,FrancescaVallese,PaolaBerto,AlessandroNegroandGiuseppeZanottiDepartmentofBiomedicalSciences,UniversityofPadua,Padua,Italy.valentina.loconte@studenti.unipd.it

Helicobacter pylori is strongly associated with the development of atrophic gastritis, which is a precursorlesiontogastriccancer.TheGram-negativebacteriumispresentinhalfofhumanpopulation,butonly15%ofinfectedpeopleshowgastricandduodenalulcers[1].The infection isoftencontractedbefore theageof tenyears,byfecal-oralororal-oralinfection.AllH.pylori-infectedpatientsdevelopchronicgastricinflammation,butthisconditionusuallyisasymptomatic.TwooftheprincipalcausesofH.pylori stomachcolonizationarebacteriummotility and adhesion to gastric epithelium [2]. Themotion is due to flagella,which can serve asadhesiveappendagesintheinitialphasesofcolonization.Thereisevidencethatlessmotilestrainarelessableto colonize or survive in the host and the degree ofmotility is correlatedwith the degree of infection. Theorganization of theH. pylori flagellum consists of basal body, hook and flagellar filament. The basal bodyincludes the rings, motor and switching proteins. The filament is masked by a sheath and extends 3-5 μmfrom the cell; the flagella are polar and are between 2 and 6 per cell. A flagellum includes flagellins FlaA(HP0601)andFlaB,necessaryforthefullmotility.SeveralcopiesofFlgE(HP0870)composethehook,whichis a flexible structure that links the filament to the driving apparatus in the basal body. A set of about tenchaperons is included among the flagellar proteins in order to avoid protein axial polymerization [3]. FlgNbelongstothisgroupandisthoughttointeractwiththehookjunctionproteinsFlgLandFlgK.WhilstFlaAandFlgEarestillongoingin investigation,FlgNhasbeenclonedstartingfromthecorrespondinggenehp1457, expressed inE.coli BL21(DE3) and transformed using a pETite vector. After size-exclusionchromatographypurification,theproteinwasidentifiedasmonomericanddimericspecies.Crystalshavebeenobtained for the monomeric form at different concentrations. Further investigation should be carried on toimproveFlgNcrystalsquality.Adherenceofthebacteriumtothehostcellisamechanismthathelpstoprotectitfromthedisplacementduetoperistalsis. It damages the epitheliumand induces inflammation, eventually delivers toxins [4].Oneof theproteinsinvolvedinthispathogenicprocessis theHelicobacterpylori adhesinA(HpaA), formallydesignatedHP0797.HpaAwasexpressedfusedwithsfGFP1-10[5]inordertofacilitateproteincrystallizationandtohelptosolvethecrystalstructurebymolecularreplacement,usingGFPatomiccoordinates.Crystalswereobtainedin several conditions, but they turned out to be only GFP. New crystallizations attempts are on the way inordertoincreasecrystallizationkineticsagainstdegradation.[1]Dunn,B.E.;HartleyCohen,H.;Blaser,M.J.;J.Microbiol.,1997,10(4),720.[2]MontecuccoC.;Rappuoli,R.;Nat.Rev.Mol.Cell.Biol.,2001,2(6),457.[3]KawagishiI.;Homma,M.;Williams,A.W.;MacnabR.M.;J.Bacteriol.,1996,178(10),2954.[4]O'Toole,P.W.;Lane,M.C.;Porwollik,S.;MicrobsInfect.2000,2(10),120.[5]PedelacqJ.D.;CabantousS.;TranT.;TerwillingerT.C.;WaldoG.S.;Nat.Biotechenol.2006,24(1),79.

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7P7.Multi-Target-DirectedLigandsinAlzheimer’sDiseaseTreatmentAlessandroPesaresia ,SarahSamezᵃ,ᵇ,ManuelaBartolinic ,JureStojand,GregoryE.GarciaeXiaomingZhaf,

MariaLauraBolognesic ,DorianoLambaᵃᵃIstitutodiCristallografia,ConsiglioNazionaledelleRicerche,Trieste,Italy.

ᵇDipartimentodiScienzeChimicheeFarmaceutiche,UniversitàdiTrieste,Trieste,Italy.ᶜDipartimentodiFarmaciaeBiotecnologie,UniversitàdiBologna,Bologna,Italy.

dInstituteofBiochemistry,MedicalFaculty,UniversityofLjubljana,Ljubljana,Slovenia.eUSArmyMedicalResearchInstituteofChemicalDefense,AberdeenProvingGround,USA.

fJiangsuCenterforDrugScreening,ChinaPharmaceuticalUniversity,Nanjing,China.doriano.lamba@ts.ic.cnr.it

Alzheimer's disease (AD) is a complex neurodegenerative disorder arising from multiple molecularabnormalities including a progressive forebrain cholinergic deficiency, accumulation of misfolded proteindeposits as amyloid β plaques and a redox system impairment which lead to increased levels of reactiveoxygen species and to theconsequent radicalsmediated injury.Todate, theonly licensedAD treatments areacetylcholinesterase (AChE) inhibitors andmemantine,which are valuable in restoring cholinergic deficit butofferonlyamodestandtemporarybenefitstopatients[1].In the fight ofAD recently has been proposed amove from the classic “one protein, one target, one drug”strategytoastrategyofdevelopingdrugsthatsimultaneouslytargetmultipletargets[2].Wereportonthestructure-activityrelationshipsof twonovelmultitargetanti-Alzheimercompoundsdesignedby combining a tacrine fragment and a juglone [3] or benzofuran moiety respectively, with a linker of asuitablelength.Invitro, both compounds displayed excellent AChE inhibitory potencies and interesting capabilities to blockamyloid-β aggregation and anti-oxidants properties. The X-ray analysis of the Torpedo californicaAChE –inhibitorcomplexesallowedastructure-basedrationalefortheoutstandingactivitydata.

Figure1.Interactionofthetacrine-juglonehybridinhibitor(PanelA)andofthetacrine-benzofuranhybridinhibitor(PanelB)withintheTcAChEactivesite.

[1]M.Rosini,E.Simoni,A.Minarini,C.MelchiorreNeurochem.Res.2014,39,1914.[2] A. Cavalli, M.L. Bolognesi, A. Minarini, M. Rosini, V. Tumiatti, M. Recanatini, C. Melchiorre J. Med.Chem.2008,51,347.[3] E. Nepovimova, E. Uliassi, J. Korabecny, L.E. Peña-Altamira, S. Samez, A. Pesaresi, G.E. Garcia, M.Bartolini,M.Andrisano,C.Bergamini,R.Fato,D.Lamba,M.Roberti,K.Kuca,B.Monti,M.L.Bolognesi J.Med.Chem.2014,57,8576.

94

7P8.TheStructureoftheT190MMutantofMurineα-DystroglycanatHighResolution:InsightintotheMolecularBasisofaPrimary

DystroglycanopathyAlbertoCassettaᵃ,SoniaCovaceuszachᵃ,,ManuelaBozzib,MariaGiuliaBigottic,SaskiaBannisterd,Wolfgang

Hübnerd,FrancescaSciandrae,AndreaBrancaccioc,e,DorianoLambaᵃᵃIstitutodiCristallografia,ConsiglioNazionaledelleRicerche,Trieste,Italy.

ᵇIstitutodiBiochimicaeBiochimicaClinica,UniversitàCattolicadelSacroCuore,Roma,Italy.ᶜSchoolofBiochemistry,UniversityofBristol,Bristol,UK.

dDepartmentofPhysics,UniversityofBielefeld,Bielefeld,Germany.eIstitutodiChimicadelRiconoscimentoMolecolare,ConsiglioNazionaledelleRicerche,,c/oUniversità

CattolicadelSacroCuore,Roma,Italy.doriano.lamba@ts.ic.cnr.itThe severe dystroglycanopathy known as a form of limb-girdle muscular dystrophy (LGMD2P) is anautosomalrecessivediseasecausedbythepointmutationT192Minα-dystroglycan[1].Functionalexpressionanalysis in vitro and in vivo indicated that the mutation was responsible for a decrease in posttranslationalglycosylationofdystroglycan,eventuallyinterferingwithitsextracellular-matrixreceptorfunctionandlamininbindinginskeletalmuscleandbrain.TheX-raycrystalstructureofthemissensevariantT190MofthemurineN-terminaldomainofα-dystroglycan(50-313)hasbeendetermined[2],andshowedanoverall topology(Ig-likedomain followedbyabasket-shapeddomain reminiscentof thesmall subunit ribosomalproteinS6)verysimilar to that of the wild-type structure [3]. The crystallographic analysis revealed a change of theconformationassumedby thehighly flexible loopencompassing residues159–180.Moreover,a solvent shellreorganizationaroundMet190affects the interactionbetween theB1–B5anti-parallel strands formingpartofthe floor of the basket-shaped domain, with likely repercussions on the folding stability of the proteindomain(s) and on the overallmolecular flexibility.Chemical denaturation and limited proteolysis experimentspoint to a decreased stability of the T190Mvariantwith respect to itswild-type counterpart. Thismutationmay render the entire L-shaped protein architecture less flexible. The overall reduced flexibility and stabilitymayaffectthefunctionalpropertiesofα-dystroglycanvianegativelyinfluencingitsbindingbehaviortofactorsneeded for dystroglycan maturation, and may lay the molecular basis of the T190M-driven primarydystroglycanopathy.

Figure1.SuperimpositionoftheWTandT190MmutantS6domains.[1]Y.Hara,B.Balci-Hayta,T.Yoshida-Moriguchi,M.Kanagawa,etal.NEnglJMed.2011,364,939.[2]D.Bozic,F.Sciandra,D.Lamba,A.BrancaccioJBiolChem.2004,279,44812.[3]M.Bozzi,A.Cassetta,S.Covaceuszach,M.G.Bigotti,etal.PLoSOne.2015,10,e0124277.

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7P9.APPPPlatformatElettra:achievementsandfutureperspectivesBarbaraGiabbai,MartaSemrau,CristinaBusatto,VincenzoRiccio,WendalinaTigani,PaolaStorici

StructuralBiologyLab,Elettra-SincrotroneTriesteSCpA,AreaSciencePark,Basovizza-Trieste,Italy-paola.storici@elettra.eu

Expression,purificationandstructuredeterminationofrecombinantproteinsisafundamentalrequirementforavarietyofbiologicalapplications,fromexploratoryresearchtopharmaceuticaldrugdiscovery.The PROTEO project, granted by the Cross-Border Cooperation Program Italy - Slovenia 2007-2013, hascreated a network of scientific collaborations among research laboratorieswith a common focus on cancertherapy research and development of diagnostic devices for early cancer detection(www.elettra.eu/Prj/PROTEO).WithinthisframeworkwehaveimplementedaproteinproductionplatformintheStructuralBiologyLabofElettraprovidingspecializedsupporttoexpressandpurifyrecombinantproteinsfor functional and structural studies.Weperform semi-automated cloning and expressionofmultipleproteintargetsinE.coli and insectcell systems.Mammalianexpression isalsosupportedwithamanual throughput.The core unit is equipped to clone/express/purify proteinswith high efficiency, using rapid cloningmethodssuchasLigation-Independent,Gateway,Restriction-FreeorGibsoninmulti-sampleparallelprotocolsandNi-NTA affinity small-scale purification on a robotic platform (Freedom Evo 150 – Tecan). The unit is alsoequippedforscale-upproteinproductionandpurificationand toevaluateproteinstabilitybyTSAandproteinactivitybyfunctionalassays.Otherbiochemicalandbiophysicalassaysaredoneaccordinglywiththeproteinrequirements.ProteincrystallizationtrialsaresetupatthecrystallizationfacilityofElettra.Currently, about 10 projects are run in parallel with a focus on protein targets that are relevant for cancerdiagnostic and therapy. The main interest is on two classes of proteins: the human kinases and thedeubiquitinases. In this work we will present the workflow of the newly established protein productionplatform,takingexamplesfromthemostsignificantresultsobtainedfromtheprojectsinprogressinthelab.

96

7P10.StructuralstudiesofPOL(PleurotusostreatusLectin),afungallectinofmedicalinterest

LauraDestefanisa,MicheleBovia,MassimilianoPerducaa,HugoL.Monacoa.aBiocrystallographylaboratory,DepartmentofBiotechnology,UniversityofVerona,Verona,Italy.

laura.destefanis@univr.it

Lectins are proteinswidely diffused in nature that interact non-covalentlywith carbohydrates [1].Of all themushroomproteins, lectins areprobably themost extensively investigatedbecause it hasbeenobserved thattheycanexhibitantitumouractivityonhumancancercells[2].Wehaveisolateda373aminoacidlectinfromthe fruiting bodies of the edible oystermushroomPleurotus ostreatuswhich is able to inhibit the growth ofhuman neoplastic cells [3]. The lectin, named POL, Pleurotus ostreatus lectin, was purified using twochromatographic steps: a hog gastric mucin or melibiose column followed by a carboxymethyl-cellulosecolumnoraSephacrylS-100gel filtrationcolumn.Twoalternativewaysofelution fromtheaffinitycolumn(withlactose0.2MandwithEDTA5mM)gaveapproximatelythesameyield(2-5mg)ofproteinstartingwith500 g ofmushrooms.Crystals of 0.1-0.3mmcan be grown in two crystallization conditions: 1) 0.1MNaHepespH7.5inthepresenceof0.8Mpotassium/sodiumtartratetetrahydrateat20°Cand4°Cand2)1.6MAmmoniumsulphate,0.1MESpH6.5and10%v/vDioxane.InitialX-raydiffractiondataofthesecrystalsforthe solution of the phase problemwere collected on a copper rotating anodeX-ray source, available in thebiocrystallographylaboratory.Aftersolvingthestructure,thefinaldatawerecollectedatvariousbeamlinesofthe European Synchrotron Radiation Facility (ESRF) in Grenoble, France. The structure was solved byMultiple Isomorphous Replacement (soaking crystals in Mercury, gold and Platinum solutions). The modelwasbuiltwiththeprogramCootv.0.7andrefinementwascarriedoutwithdatacollected fromapocrystalsat 2.05 Å using RefMac 5. The unknown preliminary amino acid sequence of the polypeptide chain wasobtained from the electron density maps. The crystals grown in the two above mentioned crystallizationconditionswereallhexagonal(spacegroupP6122)withcellparameters:a=b=153.07Åandc=145.81Åwitha singlemolecule in theasymmetricunitcontaining twopseudosymmetricdomainsanda totalof22β-strands: 10 forming the domain closest to theN terminus and 12 nearest theC terminus.The twodomainspack face to faceand theβ-sheet strandsare radiallyarrangedaroundacentral tunnel.Crystals soakedwithlactose diffracted to a resolution too low (4-4.5 Å) for ligand fitting in the electron density maps and datacollectedafterdifferentsoakingtimesgaveavariationintheunitcellparameters.Forinstance,ifthecrystalswere frozen after three seconds of interaction with lactose, a and b measured 152.96 Å and c measured143.94Å,beingindicativeofthefactthattheligandinteractswithPOLandforcesthelectininthecrystaltoassume a different conformation with variations in the unit cell parameters. Themaps show clear electrondensity for twoN-acetyl-D-glucosamines (NAGs) (β-1,4-glycosidic linkage) in three N-linked glycosylationsites(displayingtheconsensussequenceforglycosylationN-X-T)involvingAsn78,Asn298andAsn321ofthechain.Thelectinshowsalsoaweakβ-glucosidaseactivity(Vmax=87.21±1.5nmolsec-1mg-1,kcat=0.044s-1andKm=240±0.26µM)andhastwoCalciumatomscoordinatedtotwosites.TheidentityofthemetalwasverifiedbyX-rayFluorescenceanalysisofthecrystals.POLwasalsotestedonhumanpancreaticcancercells(MiaPaCa-2) and on HepG2 cells, a cell line of human liver carcinoma cells, and its apoptotic effect wasevident.RecombinantPOL,whoseexpressionwasoptimized inE.coli, crystallized in several conditions andtheenzymaticandhemagglutinatingactivitieswerepreserved.Encapsulationand/orbinding topoly(lactic-co-glycolic acid) nanoparticles of POL might be exploited both to direct PLGA towards tumours and also topreparePOL-fillednanoparticlesfortherapeuticpurposes.

[1]H.Lis,N.Sharon.Lectins:Carbohydrate-SpecificProteinsThatMediateCellularRecognition.ChemRev.1998.98(2):637-674.[2] J. Erjavec, J.Kos,M.Ravnikar.Proteins of higher fungi from forest to application. Trends Biotechnol.2012.30(5):259-73.[3]H.Wang,J.Gao,TB.Ng.AnewlectinwithhighlypotentantihepatomaandantisarcomaactivitiesfromtheoystermushroomPleurotusostreatus.BiochemBiophysResComm.2008.275:810-816.

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7P11.Fingerprintingofproteinmixturesasatoolformonitoringthelignocellulosedegradation

ChiaraCattaneo,SaraIcardi,StefanoSpertino,LaraBoatti,MariaCavalettoDISITDipartimentodiScienzeeInnovazioneTecnologica,UniversitàdelPiemonteOrientale,Alessandria,

Vercelli,Italy.chiara.cattaneo@uniupo.itTwo-dimensional electrophoresis (2-DE) is a powerful tool to discriminate and “visualize” single proteinspeciesbasedontheirisoelectricpointandmolecularweight.Thedevelopmentofmassspectrometryappliedtoproteomicsallowedtheidentificationofmanyproteinsequencesandthecollectionofhugeamountsofdata,representing an invaluable resource for biochemistry scientists. The combined use of 2-DE and massspectrometry is a faster approach to determine the composition and possible chemical modifications of acomplexproteinmixture, thusweproposethisasa“proteinfingerprinting”approachfor thecharacterizationof cellulase cocktails. Lignocellulosic biomass is recalcitrant to enzymatic degradation due to its crystallinecore structure, a mixture of fungal cellulases and hemicellulases is needed to obtain a good biomasshydrolysis.Wereportedthemapofanaturalsecretome,derivedfromthefungusP.decumbensgrownon lignocellulose.Thecomplexenzymemixture representedanoptimalmodel to follow for thedesignofcommercial cellulasecocktails.Moreover,wecharacterized twocommercialmixtures,Celluclast 1.5LandNovozyme188,whichare routinelyemployed incellulosicbiomassdegradation,andcompared themwith the“natural”one[1].Theobtained results confirmed the doubly usefulness of this approach, which provides a novel tool for thepreparation of new cellulase cocktails and represents a further simple and intuitive support to monitor thestabilityofcommerciallyavailableenzymaticmixtures.

Figure1.Outlineoffingerprintingofproteinmixtures.[1]C.Cattaneo,S.Spertino,L.Boatti,S.Icardi,M.CavalettoAnalyticalMethods.2014,6,4046.

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MISCELLANEOUS

MP1.CrystalStructureofFunctionalizedCroconainesErnestoMesto,aMariaLacalamita,aEmanuelaSchingaro,aVincenzoFino,bClaudiaCarlucci,bGianlucaMaria

Farinola.b

aDipartimentodiScienzedellaTerraeGeoambientali,UniversitàdegliStudidiBari“AldoMoro”,Bari,Italy.ernesto.mesto@uniba.it

bDipartimentodiChimica,UniversitàdegliStudidiBari“AldoMoro”,Bari,Italy.Croconaine(CR)dyeshavebeenthesubjectofmanyrecentinvestigationsowingtotheirexcellentopticalandelectronicproperties.Their intramolecularcharge-transfer (CT)characteraswellas theextendedconjugatedπ-electronnetworkgiverisetotheintensebandsobservedinthevisibletonear-infrared(NIR)region.Thesepeculiarity together with their stability promoted their exploitation in a number of applications i.e.:photoconductivity,lightemittingfield-effecttransistors,solarcells,etc.[1-5].TheirphotochemistryhasbeenextensivelystudiedandmanyderivativesoftheCRmoietieshavebeensynthesized,especiallyasinfrared(IR)probesandnon-linearoptical(NLO)materials[6].TheCRpropertiesdependbothonthefunctionalizationofthemoleculeandonthecrystalstructure.Inthiscontext,herewedescribetheresultsofaSCXRDstudyofthreeCRmolecules (seeFigure).The I- andBr-substituted crystals resulted to bemonoclinic (S.G.P21/n,10.818<a<11.163Å,10.02<b<10.11Å,23.15<c<23.15Å,103.1<β<103.4°),while the lastone istriclinic(S.G.P-1,a=11.08Å,b=14.65Å,c=28.65Å,=66.2°,=81.9°,=72.3°)fortheoccurrenceofembeddedsolventmoleculesintothecrystalstructure.BondvalenceanalysesallowedtocheckH-positions.Itturns out that CR stereochemical arrangements are affected by intramolecular N-H...O bonds, whereas thecrystalpackingsaredrivenby-interactionbetweenC=Ogroupsandsometimesbetweenaryl-arylgroupswhichallowanextendedconjugatedπ-electronnetwork.

Figure1.Sketchofthestudiedcroconainesmolecules(X=H,Br,I).[1]R.R.Avirah,K.Jyothish,D.RamaiahJ.OrgChem.2008,73,275.[2]X.Zhang,C.Li,X.Cheg,;X.Wang,;B.ZhangSensorsandActuatorsB2008,129,152.[3]K.Takechi,P.V.Kamat,R.R.Avirah,K.Jyothish,D.Ramaiah,Chem.Mater.2008,20,265.[4]G.T.Spence,G.V.Hartland,B.D.SmithChem.Science2013,4,4240[5]G.T.Spence,S.S.Lo,C.Ke,H.Destecroix,A.P.Davis,G.V.Hartland,B.D.SmithChem.Eur. J.2014,20,12628.[6]Z.Li,Z.-H.Jin,K.Kasatani,H.OkamotoPhysicaB2006,382,22.

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SOFTWAREFAYRE

TheEXPOprogramC.Cuocci-IC-CNR,SedediBari,ViaAmendola122/o,70126Bari,Italy.corrado.cuocci@ic.cnr.it

ThemainfeaturesofEXPO2014*[http://wwwba.ic.cnr.it/content/software],asoftwareforcrystalstructuredeterminationfromX-raypowderdiffractiondata,willbegivenbyexplicativeexamples.The preliminary steps will be described: download and installation of software; preparing the input file forEXPO2014; indexing thediffractionpatternbymeansofanew tool,whichcombinescell solutionsobtainedfromdifferent indexingprograms; identifying thespacegroup.Theprogram isable toperform thestructuresolution by using Direct Methods and/or the Real Space Methods approaches: examples related to bothmethodswillbedisplayedandappliedtoorganicandinorganiccompounds.Usefulsuggestions tobeadoptedwhenEXPO2014default strategies failwillbegiven.AbriefdescriptionoftheRietveldrefinementperformances inEXPO2014andof tools forvisualizationandmanipulationofcrystalstructureswillbealsoproposed.

*A.Altomare,C.Cuocci,C.Giacovazzo,A.Moliterni,R.Rizzi,N.CorrieroandA.Falcicchio,"EXPO2013:akit oftoolsforphasingcrystalstructuresfrompowderdata",J.Appl.Cryst.(2013).46,1231-1235.

TheSIRprogramG. L. Cascarano - IC-CNR , Sede di Bari, Via Amendola 122/o, 70126 Bari, Italy.gianluca.cascarano@ic.cnr.it

The SIR (Semi-Invariants Representation) package [ http://wwwba.ic.cnr.it/content/software] has beendevelopedforsolvingcrystalstructuresbyavarietyofmethods(DirectandPattersonMethods,VLD,DirectSpaceMethods,MolecularReplacement).Thepresentversionof theprogram,Sir2014 (v.15.07), isdesigned to solveab initio structuresofdifferentsizeandcomplexity,up toproteins,provided thatdata resolution isno lower than2.0.Datacanbecollectedwith X-Ray or electron sources. The program can also be applied to Molecular Replacement problemsprovidingapowerfulpipeline to solveand refineprotein structures.NewfeaturesandanewGraphicalUserInterfacewillbeshown.

TheCRYSTALprogramB.Civalleri-DipartimentodiChimica,UniversitàdiTorino,Torino,Italy,bartolomeo.civalleri@unito.it

Ab initio modeling has become an ever-increasing area of interest in solid state chemistry, physics andmaterialsscience.CRYSTAL[http://www.crystal.unito.it] is a general-purpose program for the study of crystalline solids, andthefirst tohavebecomeavailable to thescientificcommunity. ItadoptsGaussian typefunctionsasbasissetandallowscalculationsatHF,DFTandvariousflavorsofHF/DFThybrid(e.g. B3LYP, PBE0, ...) levels of theory. The program may be used to perform consistent studies of thephysical and chemical properties of crystalline solids, surfaces, nanotubes, polymers and molecules. Thesymmetryofthesystemisautomaticallyhandledandfullyexploitedinthecalculations.Basic, advanced andnewcapabilities of the latest versionof the code (CRYSTAL14)*will be presented andillustratedwithhands-ontutorialsorganizedinthepracticalsession.

$ R. Dovesi, R. Orlando, A. Erba, C.M. Zicovich-Wilson, B. Civalleri, S. Casassa, L.Maschio,M. Ferrabone,M. De La Pierre, P.D’Arco,Y.Noel,M.Causa,M.Rerat,B.Kirtman.“CRYSTAL14:AProgramfortheAbInitioInvestigationofCrystallineSolids”Int.J.QuantumChem.(2014)114,1287.

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ROUNDTABLE

TheFutureofCrystallographyandtheLegacyofIYCrinItalyM.Zemaa,b,A.Bacchic

aInternationalUnionofCrystallography,Chester,UKbDipartimentodiScienzedellaTerraedell’Ambiente,UniversitàdiPavia,Pavia,Italy,

michele.zema@unipv.itcDipartimentodiChimica,UniversitàdegliStudidiParma,Parma,Italy

alessia.bacchi@unipr.itLa comunità dei cristallografi italiani ha aderito con entusiasmo all’Anno Internazionale della Cristallografia(IYCr2014), proponendouna serie di iniziative locali distribuite su tutto il territorio nazionale, e alcune azionigenerali rivolte in specialmodo a insegnanti e studenti delle scuole superiori. Sono stati organizzati oltre 50eventi locali per la divulgazione della cristallografia a vari livelli. Alcune iniziative sono ancora in corso e siproiettano nel 2015. Questa tavola rotonda ha l'obiettivo di presentare alcune tra le attività più positive eproporrestrategiepercostruireprogettididivulgazioneevisibilitàperiprossimianni.17:15-17:30Lamostraitinerante"Cristalli!"(AlessiaBacchi)17:30-17:45Cristallografia:lavisioneairaggiX(SimonaGalliePietroRoversi)17:45-17:55ConcorsoNazionaledicrescitacristallina(MarcoBruno)17:55-18:10Crystallographymatters...more(MicheleZema)18:10-18:45Opendiscussion

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COMMERCIALPRESENTATIONS

ProgressinX-rayCrystallographicMethodology:ShutterlessDataCollection

EricHovestreydt,aHolgerOtt,aMichaelRufbaBrukerAXSGmbHKarlsruheGermany,eric.hovestreydt@bruker.com

bBrukerAXSIncMadison,Wisconsin,USAInstrumentation for single crystal structure analysis has advanced greatly over the last decade. Theseimprovements include the introduction of area detectors, in particular CCD detectors with high dynamicranges;aswellasmajorsoftwareimprovements.In mid-2011 Bruker AXS introduced the PHOTON 100 detector; the first CMOS active pixel sensor forlaboratory crystallography. Since then, CMOS technology has been rapidly displacing CCD detectors and alarge number of D8 QUEST and D8 VENTURE systems are now used in laboratories throughout theworld.CMOStechnologyoffersnumerousadvantagescomparedtoCCDdetectors:-CMOSsensorsareavailableinlargersizes-CMOSsensorshavelowerpowerconsumptionthanCCDsandprovideexcellentsignal-to-noiseratiosevenwhenonlymoderatelycooled.Thisallowsthedesignofair-cooleddetectors.CCD detectors and imaging plates operate in the conventional still-imagemode involving numerous shutter-open/shutter-close, goniometer ramp-up/ramp-down and detector readout steps. Next to overhead-time thisprocessintroducesmechanicaljitter.ThePHOTON100detectorcannowoperateinacompletelyshutterlessread-outmode.Thisenablescontinuousdatacollectionwithout theneed tofrequentlyopenandclose theX-rayshutter,resultinginlessmechanicalwearandfaster,moreaccuratemeasurements.

Figure1.shutterless,continuous-scanmodeallowsformoreefficientexperimentsatsameorbetterdataquality(left)orgreatlyimproveddataqualityatsametimeascomparedtoshutteredmode

XRPDSolutionstoIndustrialApplicationFieldsAlessandroTorboli

GNRsrl,AgrateConturbia,Italy.gnrx_ray@gnr.itThepaper aim is todescribehowXRPD (X-RayPowderDiffraction) analytical technique canbe applied toindustrial applications as a reliable tool for quality assurance and quality control practices.All the developedsolutionstakeadvantageofthemainfeaturesofXRPDasstructuredeterminationandQPA(quantitativephaseanalysis)moreoveritisanon-destructive.Inthispaperaretakenintoaccountmanufacturing,pharmaceuticalandhealthhazardapplications.Inmanufacturingprocesses,XRPDissuccessfullyusedtodetermineresidualstress[1]andretainedaustenite[2].Residualstressesare thecompressiveand tensilestresses that remain inamaterialonceanexternal loadhas been applied. Most of the manufacturing processes (mechanical, thermal, chemical), which leads toinhomogeneousdeformation, inhomogeneousvolumechanges,etc. induceresidualstresses intocomponents.Theextentofinducedresidualstressdependsontheprocess.Effectsvaryfrom“nearsurface”region,causedbymachining,grinding,etc.,toinnercomponentregionscausedbycasting,welding,heat-treatment,etc.Austenite isaveryusefulstructuralconstituentofadvancedhigh-strengthsteels. Itsability forstrengtheninginmanydifferentwaysofferspossibilitiestoobtainauniquerangeofmechanicalandtechnologicalpropertiesthusitsamount(retainedaustenite)needtobedetermined.Anespeciallyimportantfeatureofaustenitephaseisitsabilitytotransformtomartensiteortoformtwinnedmicrostructuresduringstraining.In health hazard field, XRPD is successfully used to quantify silica dust concentration. Silica is one of themost commonminerals in the earth crust and canbe found in three crystalline forms (polymorphs): quartz,cristobalite and tridymite. Nowadays, it is well known that crystalline silica dust inhalation can cause both

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silicosis and lung cancer, being a health hazard especially formining, construction and foundryworkers. Inorder topreventoccurrenceofpathologies,severalnationaland internationalnormsregulate theoccupationalexposure to silica dust [3], by defining procedures for sampling airborne particles on filters and theirconcentration estimation. XRPD is particularly effective for quantification of silica dust concentration onfilters:infact,ontheonehandeachpolymorphcanbeinvestigatedandquantified;ontheotherhandpotentialoccurrenceofinterferingcrystallinemineralphasesisdetected.In Pharmaceutical field,XRPD is successfully used to determine the crystal structure the presence and therelativeamountsofdifferentpolymorphsandcrystallinitydegree.Solid-state properties of drugs is a major contributing factor to both bioavailability and formulationcharacteristics.Most pharmaceutical drugs are solids and exist in many different physical forms, includingamorphous,polymorphiccrystallineorhydratedforms.Thepolymorphism,isoneofthemostimportantsolidstate properties of drugs because it can affect the pharmaceutically, important chemical and physicalproperties,suchasmeltingpoint,chemicalreactivity,solubility,dissolutionrateandtabletingbehavior.XRPDisapowerfultooltoidentifydifferentphasesbytheiruniquediffractionpattern.[1] UNI - UNI EN 15305, Non-Destructive Testing - Test Method for Residual Stress Analysis by X-RayDiffraction.[2] ASTM E975-13, Standard Practice for X-Ray Determination of Retained Austenite in Steel with NearRandomCrystallographicOrientation,ASTMInternational,WestConshohocken,PA,2013.[3]NIOSH7500,OSHAID143,MDHS14/3,UNICHIM2398

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INDEXIntroduction

GOLDMEDALMARIOMAMMI-ThingsDoneandThingsYetToBeDone:CrystallographyatLarge,2015-2030

MARIONARDELLIPRIZE-CrystalEngineeringon“Tailor-Made”MultifunctionalZirconiumPhosphonates

PhD's THESIS AWARD in CRYSTALLOGRAFY - New Forms of Polar and Spin Ordering inPb2(Mn,Co)WO6DoublePerovskites:SymmetryAnalysisofFerroicProperties

PLENARYLECTURES

PL.1NewAdvancesinElectronDiffraction:fromAb-initioStructureSolutiontoRefinement

PL2.Ab-initioModelinginCrystallography

PL3.WatchingMatterinMotion:TimeResolvedStudiesfromSynchrotronstoFELs

PL4.ElectronDiffractionandImagingofProteinandPharmaceutical3DNanocrystals

MICROSYMPOSIA

*MS1.AdvancedTheoreticalandExperimentalMethodsinCrystallography

1KN1.Advancesinmethodsformacromolecularstructuresolution:abinitioandMRapproaches

1KN2.Advancesinmicrostructureanalysisofmaterialswithdefects

1O1.QuantumMechanicalSimulationOfProteinCrystals:TheCaseOfTheSmallProteinCrambin

1O2. Experimental and theoretical charge density study of iodoperfluoroalkylimidazoles self-assembledthroughhalogenbond

1O4. Structural characterization of LDH samples by ADT and TGA-GC-MS: thermal response andcontaminationinnitrateandorganic-exchangedhydrotalcites

1O5.PolymerBrushesandTheirCompositeswithSilverNanoparticles:AnX-RayReflectivity andPositronAnnihilationSpectroscopyStudy

1P1.ModellingTheCarbonateSubstitutionInHydroxyapatiteTowardsBoneComposition

1P2.ChemicalselectivityinstructuredeterminationbytimedependentanalysisofinsituXRPDdata:aclearviewofXethermalbehaviorinsideaMFIzeolite

1P3.NewadvancesofQUALX2.0,aqualitativephaseanalysissoftwarequeryingafreelyavailabledatabase

*MS2. Investigating Structure-PropertyRelationships inComplexMolecular Systems by aMulti-TechniqueApproach

2KN1.Newinsightintothepropertiesofindomethacinpharmaceuticalco-crystals

2KN2. Biomolecules as ligands to construct high-dimensional coordination networks (bioMOFs): towards arationaldesignofmorefeasiblebiocompatibilityandhomochiralmaterials

2O1.MolecularRotorsinPorousCovalentFrameworksandSupramolecularArchitectures

2O2.Characterizationofthesolidstatedynamicbehaviourofcyclicpeptoids

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2O3. Promising Low-Dielectric-ConstantMaterials:Metal-organic Frameworks and Coordination PolymersCompared

2O4.FiftyYearsofSharingCrystalStructures

2P1. Homochiral Self-Assembly of Biocoordination Polymers: Anion-Triggered Helicity and AbsoluteConfigurationInversion

2P2.Naphthalenediimidecocrystalsbasedonhalogenbond

2P3. From crystallography to applications: non linear optical properties of β-D-fructopyranose alkalinehalidesMOFs

2P4.StudiesoftheconformationalchangesontheribosomalGTPaseEFL1usingSAXS

2P5.Stackingmotivesinmetallatesaltsofmethyleneblue

*MS3.FromNaturetoAdvancedMaterials:StructureCharacterizationattheNanoscale

3KN1. Rotation electron diffraction as a complementary technique to powder X-ray diffraction for phaseidentificationandstructuresolution

3KN2.Howdifficultistosolvecomplexstructures:thecaseofEniCarbonSilicates

3O1.3DInvestigationoftheReciprocalSpaceofNano-CrystalsbyElectronDiffractionTomography

3O2.Structuredeterminationusingab-initiomethodsandsimulatedannealingfromPEDtomography

303.Organizedarchitectureofdyesinzeolitechannels:aneffectivetransportofelectronicexcitationenergy

3O4. Structural evolution of tungsten oxide nanocrystals investigated by Pair Distribution Function andModulationEnhancedDiffraction

3P1.ElectrondiffractionstudyofpolyphasicnanocrystallineM2O-Al2O3-WO3(M=Na,K)system

3P2.AverageandLocalstructuralcomparisonofBaTi1-xCexO3byPairDistributionFunction

3P3.PhotocatalyticShapingofSilverNanoprismsSelf-AssembledonAnataseThinFilms

*MS4.NewTopicsinCrystalGrowthResearch

4KN1.Uncoveringtheroleofsolventinorganiccrystalsnucleationandgrowth

4KN2.Theroleoftheadhesionenergyinsurfaceandinterfacegrowthprocesses:apatitesandalkali-halides.

4O1.Turningliquiddrugsintocrystals

4O2. Exploiting dimensional variability in coordination polymers: solvent promotes reversible conversionbetween3Dandchiral1Darchitectures

4O3.Catalyst-freevapour-phasegrowthofGa2O3nanowiresandnanobelts

4O4.NewFluorinatedMetal-OrganicFrameworksSelf-AssembledviaHalogenBonding

4P1.Cu2-xSultrathinfilmsobtainedbyelectrodeposition:astructuralcharacterization

4P2.Recrystallizationbehaviorofamorphousvenlafaxinefreebasepreparedbymelttechnique

4P3.Acomputationalapproachtothestudyofepitaxy

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4P4.Facileintercalationoforganicmoleculesintohydrotalcitesbyliquidassistedgrinding:yieldoptimizationbyachemometricapproach

4P5.NewCo-crystalsofSalicylicacid:fromscreeningtosynthesisandstructuralcharacterization

4P6.MorphologicalandStructuralEffectsofGelsonCoordinationPolymersCrystallization

*MS5.NanostructuresandNanoscalePhenomena

5KN1.Characterizationofnano-structuredmaterialsbysynchrotronradiationtechniques

5KN2.ApplicationofTotalScatteringMethodstotheInvestigationofCleanEnergyMaterials

5O1. Disclosing the Rhombohedral Structure of Colloidal Lead Chalcogenides Quantum Dots, theirstoichiometryandtheirshapeevolutionthroughtheDebyeFunctionAnalysis

5O2. Spatially resolved photoemission spectromicroscopy: a powerful tool for the characterization ofnanostructurednovelmaterials.

5O3.microEXAFSandmicroXANESforthestudyofSolidOxideFuelCells

5P1.Asupercellapproachfortherefinementofcarbonatehydrotalcitesaffectedbystackingfaults

5P2.StressmeasurementsatthenanoscalebyZnONanorods-modifiedCarbonFibers

5P3. The DebUsSy Suite 2.0: a powerful tool for characterizing nanosized materials through the DebyeScatteringEquation

5P4.Core-shellcobalt/cobaltoxidenanoparticles:aDebyefunctionXRDpatternsimulation

5P5.StructuralAnalysisofHighlyDefectivePt@SiO2NanorodsthroughSynchrotronX-RayTotalScatteringTechniques

*MS6.CrystalChemistryofInorganicCompoundsfortheUnderstandingofTheirPropertiesandStability

6KN1.TimeforChanges:NanosizedMagnetiteClustersontheRun

6KN2. Tracking structural and electronic properties of coordination compounds: the role of synchrotronradiation

6O1. Adsorption/Desorption Of Fuel Based Pollutants Confined within ZSM-5: a Combined In Situ High-TemperatureSynchrotronPowderX-RayDiffractionandChromatographicStudy

6O2.AfteracenturyofBraggdiffraction,howwelldoweknowthestructuresofinorganiccompounds?

6O3.Crystal-fluidinteractionsinopen-frameworkmaterialsathighpressure

6O4.Insituhigh-temperatureX-raydiffractionandspectroscopicstudyoffibroferrite,FeOH(SO4)5H2O

6O5.StructuralcharacterizationofmagnetoresistivePb2FeMoO6

6P1.Twinning:structuralpeculiaritiesandopportunitiesincoordinationpolymers

6P2.ImproperFerroelectricstateinadoubleperovskitesystemwithacollinearmagneticstructure

6P3.CO2adsorptioninFaujasitesystems:asynchrotronX-RayPowderDiffractioninvestigation

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6P4. Crystallographic and chemical transformation of asbestiform erionite and chrysotile asbestos in cellenvironment

6P5.Compressibilityandhigh-pressurebehaviourofleadfeldspar

6P6.Alkaliactivatedmaterialsfromsulfate-bearingkaolins:prosandcons

6P7.HTphasetransitioninoliveniteandthermalbehaviourofolivenite-groupminerals

* MS7. Imaging Biomolecular Machines in Action through Cryo-Electron Diffraction and Cryo-ElectronMicroscopy

7KN1.Theatomicstructureofthehumangamma-secretasecomplex

7KN2.Molecularmechanismsofasymmetriccelldivisions

7O1.Membrane NAPE-PLD links major players in lipid homeostasis with major players in lipid mediatedsignaling

7O2. Pore flexibility underlies the poor selectivity of CNG channels: a structural, functional andcomputationalanalysis

7O3.Haveyourphosphateandeatit:structureandfunctionofabacterialPhoXphosphatase

7O4.Howtobuildahost-parasiteinteractome:aproofofconceptforSchistosomamansoni

7P1.PlatinumbindingtohumancopperchaperoneAtox1

7P2.Single-particlecryo-EMstudyoftheAMPAreceptorinthedesensitizedstate

7P3.Three-dimensionalstructureandligand-bindingsiteofcarpFishelectin(FEL)

7P4.Structuralstudiesofhumanacidic fibroblast-growth factor(FGF1)mutantswithaprobableanticanceractivity

7P5.UnravelingtheantitumoralpropertiesofArundodonaxlectin

7P6.StructuralCharacterizationOfProteinsInvolvedInHelicobacterpyloriMotilityAndAdhesion

7P7.Multi-Target-DirectedLigandsinAlzheimer’sDiseaseTreatment

7P8. The Structure of the T190M Mutant of Murine α-Dystroglycan at High Resolution: Insight into theMolecularBasisofaPrimaryDystroglycanopathy

7P9.APPPPlatformatElettra:achievementsandfutureperspectives

7P10.StructuralstudiesofPOL(PleurotusostreatusLectin),afungallectinofmedicalinterest

7P11.Fingerprintingofproteinmixturesasatoolformonitoringthelignocellulosedegradation

*MISCELLANEOUS

MP1.CrystalStructureofFunctionalizedCroconaines

*SOFTWAREFAYRE

TheEXPOprogram

TheSIRprogram

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TheCRYSTALprogram

ROUNDTABLE-TheFutureofCrystallographyandtheLegacyofIYCrinItaly

*COMMERCIALPRESENTATIONS

ProgressinX-rayCrystallographicMethodology:ShutterlessDataCollection

XRPDSolutionstoIndustrialApplicationFields

108