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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Date and location: Wednesday, September 18th, 2013 – Amphitheatre CNRS, Montpellier, France. Scientific Committee: K. KURODA, M. OGAWA and Y. SUGAHARA, Waseda University, Tokyo, Japan, A. AYRAL, B. BOURY, M. WONG CHI MAN, Pôle Chimie Balard, Montpellier, France. Local organizers: A. AYRAL, B. BOURY, M. WONG CHI MAN.

Program 9h00: 9h15 - Professor Thomas ZEMB, Coordinator of the LabEx CheMISyst: Introductory remarks

9h15: 9h45 - Prof Kazuyuki KURODA, Department of Applied Chemistry, Waseda University, Tokyo, Japan: Utilization of Alkoxysilyl Groups for the Creation of Structurally Controlled Siloxane-Based Nanomaterials. 9h45: 10h15 - Dr Corine GERARDIN, ICGM, Montpellier, France: Dynamic polymer micelles as structuring and functionalizing agents of ordered mesoporous materials 10h15: 10h45 - Dr Alain IBANEZ, Institut Néel, CNRS, Grenoble, France: Fluorescent molecular nanocrystals grown in organosilicate matrices for biophotonics.

10h45: 11h00 – Coffee break

11h00: 11h30 - Prof Makoto OGAWA, Department of Earth Sciences, Waseda University, Tokyo, Japan: Designed nanostructures of silicate-organic hybrids. 11h30: 12h00 – Dr Anne JULBE, IEM, Montpellier, France: Design of membrane materials and multifunctionnal systems. 12h00: 12h30 – Prof Clément SANCHEZ, Collège de France, Paris, France: Some similarities between natural biomaterials and advanced hybrid materials.

12h30: 14h00 – Break for lunch

14h00: 14h30 - Dr Minoru OSADA, National Institute for Materials Science, Tsukuba, Japan: 2D Nanomaterials: To Graphene and Beyond? 14h30: 15h00 - Dr Agnès GRANDJEAN, ICSM, Marcoule, France: Mesoporous materials in the field of the nuclear fuel cycle. 15h00: 15h30 - Dr François BERTIN and Dr Amal CHABLI, CEA-DRT, Grenoble, France: Start-of-the-art on nanocharacterization of organic/inorganic nanostructured material.

15h30: 15h45 – Coffee break

15h45: 16h15 - Dr Naokazu IDOTA and Prof Yoshiyuki SUGAHARA, Department of Applied Chemistry, Waseda University, Tokyo, Japan: Selective Separation by Temperature Control using Smart Polymer-Grafted Materials. 16h15: 16h45 - Prof Frédéric LAMATY, IBMM, Montpellier, France: Synthesis and applications of macromolecule-based nanostructured materials.

16h45: 17h00 - Professor Thomas ZEMB and the members of the Scientific Committee: Concluding remarks.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Utilization of Alkoxysilyl Groups for the Creation of Structurally Controlled Siloxane-Based Nanomaterials Author: Kazuyuki KURODA, Department of Applied Chemistry, Waseda University, Tokyo, Japan

Short abstract: Silica-based materials have found many applications in various fields. Alkoxysilanes have been most widely used as precursors. Fine structural control of silica-based materials has become increasingly important for tuning their properties and for developing new functions. In this presentation, utilization of alkoxysilyl groups will be reviewed from the viewpoint of designing siloxane-based nanomaterials. Alkoxy groups have generally been used only as eliminating groups in the sol−gel processing; however, recent research has shown that they are useful for molecular assembly, for generating pores, for linking nanobuiliding blocks, and for selective synthesis of new oligosiloxane compounds.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Dynamic polymer micelles as structuring and functionalizing agents of ordered mesoporous materials Author: Corine GERARDIN, Institut Charles Gerhardt, Montpellier, France

Short abstract: A highly versatile and powerful preparation route of polymer functionalized ordered mesoporous materials will be presented: smart assemblies of hydrophilic diblock copolymers are used as innovative structuring and functionalizing agents for the direct synthesis, at room temperature and in water as the only solvent, of polymer-functionalized mesoporous silica. The new functional assemblies are dynamic reversible PolyIon electrostatic Complex micelles of double-hydrophilic block copolymers which are used as porogens and as agents of homogeneous functionalization of mesopores with polyacid or polybasic chains.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Designed nanostructures of silicate-organic hybrids Author: Makoto OGAWA, Department of Earth Sciences, Waseda University, Tokyo, Japan

Short abstract: The utilization of layered silicates as scaffolds for designing functional nanostructures will be discussed. Surface modification of smectites with organoammonium ions has given hydrophobic and microporous nature to uptake nonionic organic contaminants from environments. The states of the adsorbed nonionic organic compounds have been altered and varied by the modification of smectites as shown by the controlled release and specific catalytic reactions. Cationic species have been easily concentrated on smectites from aqueous phase and the states (orientation and distribution) have been controlled by the co-adsorption of both cationic and nonionic species. The grafting of organic functionality on hydroxyl bearing layered silicate was also conducted to immobilize such functional units as hydrophobic, acidic and polymerizable ones. The functions of silicate-organic hybrids derived from the precisely controlled nanostructures will be introduced.

References Okada, T., Ide, Y. and Ogawa, M. "Organic-inorganic hybrids based on ultrathin oxide layers - Designed nanostructures for molecular recognition” Chem. Asian J. 7, 1980-1992 (2012). Okada, T. and Ogawa, M. “Organo-smectite adsorbents; Designed nanostructures for smart adsorbents”, Clay Sci. 15, 103-110 (2011). Ogawa, M. "Clay mineral organic interactions" in Bergaya, F., Theng, K.G.B. and Lagaly, G. (editors)"Handbook of Clay Science" Elsevier (2006). Ogawa, M. "Photoprocesses in clay-organic complexes " in Auerbach, S.M., Carrado, K.A. and Dutta, P.K. (editors) "Handbook of Layered Materials" Marcel Dekker, (2004).

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Fluorescent molecular nanocrystals grown in sol-gel thin films or in silicate particles for biophotonics Author: Alain IBANEZ, Institut Néel, CNRS, Grenoble, France

Short abstract: We have developed the confined nucleation and growth of organic nanocrystals into the pores of silicate matrices. This spatial confinement of nanocrystals, accurately modulated through the sol-gel chemistry, provides narrow size distributions, prevents the coalescence of nanocrystals, and stabilizes them through one-step processes. Thus, depending on the experimental conditions, nanocrystal diameters ranging between 20 and 500 nm can be obtained with narrow size distributions of around 10%. These hybrid organic-inorganic nanocomposites combine high fluorescence efficiency and photostability of nanocrystals with the easy shaping and transparency of the inorganic amorphous matrix. The organic nanocrystals, being constituted of high numbers of molecules, exhibit high cross section absorptions and high fluorescence intensities while having single spectroscopic signatures. We have optimized the preparation of fluorescent nanocrystals grown in silicate thin films for the development of a new type of signalization function for biological sensors based on fluorescence quenching and turn-on emission. Indeed, the adsorption of a probe molecule at the nanocrystal surface quenches their fluorescence. This quenching is very efficient due to the excitation delocalization throughout the nanocrystals that exhibit nanoemitter behaviors. Then, to develop high sensitive biochips, organic nanocrystals grown in sol-gel thin films were made directly available to biological aqueous solutions through a controlled dissolution of the sol-gel surface by using basic aqueous solutions leading to nanocrystals emerging only by a few nanometers from the sol-gel surface. We have demonstrated that in presence of DNA-probe solutions, the nanocrystal fluorescence is strongly quenched by Förster Resonance Energy Transfer, by grafting onto the surface of nanocrystals DNA-probe fragments. Recently, we have also undertaken a new shaping of organic nanocrystals embedded in silicate spheres by using an original spray-drying process. These new 0D hybrid nanocomposites, constituted by crystalline organic cores surrounded by amorphous silicate shells, are promising for bio-imaging. Indeed they exhibit very bright fluorescence properties and the particle size can be adjusted between 40 and 800nm. Moreover, large amounts of these tracers can be prepared (several grams in the lab), while their silicate shells are transparent in the visible and biocompatible with hydrophilic character that is crucial for their dispersion in biological media and their furtivity in vivo. Finally, we will introduce our last results on the rare earth (RE) - complexes dispersed in gel-glass nanoparticles for the development of high stable labels in biological solutions. We have involved different types of silicon akoxides used as gel-glass precursors to adjust the hydrophilic character and closed porosity of nanoparticles to optimize their biocompatibility and dispersion in aqueous solutions and also to avoid the decomplexation of the RE-complexes. The stability in aqueous solutions of the complexes inserted in different sol-gel matrices was followed by luminescence spectroscopy.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Design of Membrane Materials and Multifunctional systems for gas/vapor treatment and separation. Author: Anne JULBE, Institut Européen des Membranes, Montpellier, France

Short abstract: Advances in membrane materials and fabrication technology are, among many potential solutions, one of the most direct, effective and feasible approaches to solve many issues associated to resource depletion, record high oil prices, clean water shortages, high costs of pharmaceuticals, and changing climate conditions. The treatment, separation and/or filtration of gases and vapors are key areas specifically addressed in our group, in view of the huge potential of membrane technologies for solving key issues in both energy and environmental emerging systems. For these key applications, meso-, micro-porous or quasi-dense membranes are required, with specific transport properties, high thermal and chemical stability and sometimes with coupled functionalities such as separation & catalytic activity, adsorption or electrochemical properties. In this very challenging background, where the industrial requirements are increasingly heavy, imagination has no limit as far as the development of original membranes (designs, concepts, materials or synthesis strategy) could afford significant breakthrough. Complex membrane architectures are being developed in our Institute with oxides, non-oxides, hybrid or composite materials, and new reaction pathways are also investigated to orient the formation of stable material designs. In this presentation our general strategies for the development of original membrane materials will be described, involving self-assembling approaches, supercritical CO2- or microwave assisted- soft chemistry, Plasma-Enhanced Chemical Vapor Deposition, Atomic Layer Deposition or Polymer Derived Ceramic route. A special focus will be dedicated to the design of ultra-thin steam-stable molecular sieve non-oxide membranes for He or H2 separation up to 400°C.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Some similarities between natural biomaterials and advanced hybrid materials Author: Clément SANCHEZ, Collège de France, Paris, France

Short abstract: Today targets and ambitions of main researchers working in the Chemistry of Materials field is to produce both fundamental and applied research at the frontier between nanosciences, biology, medicine, energy, and environment by pushing to their limits: nanochemistry developed with inorganic or hybrid matter and innovative processing techniques. Their ultimate aim is to achieve a comprehensive view of fundamental synthesis and processing concepts in order to be able to tailor materials by fully controlling all involved mechanistic aspects. The control of molecularly designed chemical complexity will be the next achievement of the chemistry of materials. Following this way, a first step concerns the development of integrative synthesis pathways, clearing the track to tailored complex materials as those found in nature. Elucidating the basic components and building principles selected by evolution allow to construct more reliable, efficient and environment respecting materials. Indeed, materials found in nature combine many wonderful features such as sophistication, miniaturization, hierarchical organizations, hybridation, resistance and adaptability. Biomimetic or bio-inspired approaches are strongly motivating the materials chemistry community. Taking mesoporous materials and hybrid self-healing materials as an example, this lecture will describe some similarities between natural biomaterials and advanced hybrid materials.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: 2D Nanomaterials: To Graphene and Beyond? Author: Minoru OSADA, National Institute for Materials Science, Tsukuba, Japan

Short abstract: Two-dimensional (2D) nanosheets, which possess atomic or molecular thickness and infinite planar lengths, have been emerging as important new materials due to their unique properties. In particular, the recent development of methods for manipulating graphene has provided new possibilities and applications for 2D material systems; many amazing functionalities such as high electron mobility and quantum Hall effects have been discovered. This breakthrough has opened up the possibility of isolating and exploring the fascinating properties of 2D nanosheets of other layered materials, which upon reduction to single/few atomic layers, will offer functional flexibility, new properties and novel applications. We are working on the creation of new oxide nanosheets and the exploration of their novel functionalities in electronic applications [1,2]. Recently,

we found that titania- or perovskite-based nanosheets exhibit superior high- performance (r = 100–320) even at a few-nm thicknesses, essential for next-generation electronics [3]. Additionally, nanosheet-based

high- capacitors exceeded textbook limits, opening a route to new capacitor devices. One more interesting concept using 2D oxide nanosheets is designing complex nanodevices and superstructured nanohybrids such as all nanosheet FETs [2], artificial ferroelectrics [4], spinelectronic devices [5], magneto-plasmonic metamaterials [6], Li-ion batteries [7] etc. With these unique aspects, 2D nanosheets will become an important research target in the form of “oxide graphene”.

[1] M. Osada and T. Sasaki, Adv. Mater., 24, 209 (2012). [2] M. Osada and T. Sasaki, J. Mater. Chem. 19, 2503 (2009). [3] M. Osada et al., Adv. Mater. 18, 1223 (2006); ACS Nano 3, 1097 (2009); ACS Nano 4, 4966 (2010); ACS Nano 4, 5225 (2010); Adv. Funct. Mater. 21, 3482 (2011). [4] B. W. Li, M. Osada et al., ACS Nano 4, 6673 (2010); Chem. Mater. 24, 3111 (2012). [5] M. Osada et al., Adv. Mater. 18, 295 (2006); PRB 73, 153301 (2006); JACS 128, 4872 (2006); APL 92, 253110 (2008); APL 93, 093112 (2008); Chem. Mater. 21, 4366 (2009). ACS Nano 5, 6871 (2011). [6] M. Osada et al., J. Mater. Chem. C, 1, 2520 (2013). [7] X. Xu et al., Energy Environ. Sci., 4, 3509 (2011).

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Mesoporous materials in the field of nuclear industry Author: Agnès GRANDJEAN, Institut de Chimie Séparative de Marcoule, Marcoule, France

Short abstract: Innovative concepts in the nuclear fuel cycle are needed to achieve higher levels of security and ressource efficiency as well as a higher resistance towards nuclear proliferation. In this context, mesoporous materials, which are already widely found in applications such as catalysis, sensing and optics are expected to make their way in the field of nuclear power production. Up to now, some (hybrid) mesoporous solids have already been investigated (i) in separation chemistry for actinide extraction or for the development of selective sorbents and/or getters; (ii) in waste management for the confinement of mobile or volatile radioactive species inside the porosity of such materials (using soft treatment to close the porosity); (iii) in the design of new fuel forms, which can accommodate gaseous fission product and sustain the important associated pressure increases and (iv) but also as model materials to investigate radiation defects, as possible nuclear waste disposal form and as functional materials to be placed in or close to new forms of nuclear waste matrices [1].

[1] Philippe Makowski, Xavier Deschanels, Agnès Grandjean, Daniel Meyer, Guillaume Toquer, Frédéric Goettmann, New Journal of Chemistry, 2012, 36, 531-541.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Start-of-the-art on nanocharacterization of organic/inorganic nanostructured material Author: François BERTIN and Amal CHABLI, CEA-DRT, Grenoble, France

Short abstract: The controlled fabrication of nanostructured material relies on the ongoing progress in the characterization techniques. Up to now microelectronics industry has been a major driver to push the limit and assess the measurement protocols of a wealth of analytical tools such as: transmission/scanning electron microscopy, spectroscopic ellipsometry, focus ion beam, x-ray reflectivity/diffraction… These techniques are mainly devoted to the characterization of inorganic material and, with the growing demand of characterization techniques for organic/inorganic nanostructured material, an effort must be put to develop new characterization techniques and protocols based on existing knowledge. In particular 3D noninvasive and in-situ techniques are highly desirable. In this context we will show new progress in term of instrumentation and analytical protocol which could meet these needs. We will present new development suitable for nanoporosimetry characterization such as porosimetry ellipsometry, positrons annihilation, X-ray and neutron based techniques. To deal with composite materials progress in term of new sources (Ar-cluster, low energy electron), sample preparation and techniques (peak-force acquisition mode in atomic force microscopy) are under progress and will be presented.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Selective Separation by Temperature Control using Smart Polymer-Grafted Materials Author: Naokazu IDOTA and Yoshiyuki SUGAHARA, Department of Applied Chemistry, Waseda University, Tokyo, Japan

Short abstract: In this study, we designed smart polymers comprising thermoresponsive poly(N-isopropylacrylamide) incorporated with functional comonomers to specifically interact with target compounds, and the selective adhesion and detachment on the surfaces were controlled simply by temperature changes using the smart polymer-grafted materials.

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First international seminar on nanoporous and nanostructured materials for

energy, environment and health

Title: Synthesis and applications of macromolecule-based nanostructured materials Author: Frédéric LAMATY, Institut des Biomolécules Max Mousseron, Montpellier, France

Short abstract: The mild conditions used in sol-gel process allow the preparation of hybrid materials containing an organic and an inorganic part. The organic part may be a polymer, and new materials owning the properties of the macromolecule can be synthesized and used in various chemical and biological applications. In a first approach, a polyether-functionalized mesoporous silica was prepared and used as support for palladium particles with applications in catalysis [1]. In a second approach, the macromolecule is a peptide and the hybrid material obtained present catalytic or anti-fouling properties [2,3]. Furthermore, by exploiting the properties of self-assembly of the peptide unit, a range of bio-inspired nanostructured materials was prepared.

[1] A. F. Grandsire, C. Laborde, F. Lamaty, A. Mehdi, Applied Organometallic Chemistry 2010, 24, 179. [2] S. Jebors, C. Enjalbal, M. Amblard et al., J. Mater. Chem. 2013, in press. [3] S. Jebors, C. Enjalbal, M. Amblard et al., Tetrahedron 2013, in press.

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