RP Projects Sem2

8/6/2019 RP Projects Sem2

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Research Projects Semester 2, 2011

1. SOLVENT PROPERTIES CHARACTERIZATION: IMPACT OF THEPRESENCE OF SALTS AND OLIGOMERS ON ETHANOLAMINE /WATER MIXTURES

Project Supervisors: Ludo Dumee, Sandra Kentish

Number of Students 2 students

Suitable for Minor RP (CHEN90026)? NO

Abstract/Project Description:

This project involves a comprehensive characterization of mixed salts/solvent solutions used

in industrial carbon capture processes. The study will focus on determining the impact of various salts and oligomers typically reported as degradation products in CCS solvent captureunits on the viscosity, conductivity, surface tension and corrosivity of model solutions. Heatstable salts mixed with ethanolamine / water solutions will be used and the changes in thebulk solvent properties will be correlated to data obtained on two experimental rigs(Electrodialysis and Nanofiltration) designed to remove the salts from the mainstreams. Apublication is expected to be produced out of this work.

Required:- Motivated student willing to learn chemistry characterization techniques- Interest in co-writing a high impact systematic publication

2. SIMULATION OF GAS SEPARATION MEMBRANES FOR CARBONDIOXIDE CAPTURE

Project Supervisors: Colin Scholes, Sandra Kentish

Number of Students 1 student



The Cooperative Research Centre for Greenhouse Gas Technologies (CO2CRC) hasdeveloped an Aspen HYSYS simulation package of gas separation membranes for carboncapture from flue gas. The specific focus of the project will be the development of a hybridarrangement of membranes with cryogenic processing to achieve necessary carbon dioxiderecovery and purity from a coal-fired power station. The project will optimize the hybridprocess design to determine its viability relative to other carbon capture approaches

3. FACILITATED TRANSPORT MEMBRANES FOR CARBON DIOXIDECAPTURE


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Project Supervisors: Colin Scholes, Sandra Kentish




The Cooperative Research Centre for Greenhouse Gas Technologies (CO2CRC) isdeveloping novel membranes that have high CO2 flux as well as good CO2 selectivitycompared to N2, which will enable efficient carbon capture. This project will focus ondeveloping facilitated transport membranes, which utilize a CO2 selective carrier speciesinside a wetted membrane, to maximize CO2 permeability. The project will develop thefabrication process to produce a robust membrane that can withstand the temperaturesexperienced when separating CO2 from flue gas.

4. EVALUATION OF WATER AND SALT PERMEABILITY THROUGHCOMMERCIAL REVERSE OSMOSIS MEMBRANES FORDESALINATION AND INDUSTRIAL WASTE WATER TREATMENTAPPLICATIONS

Project Supervisors: Judy Lee and Sandra Kentish

Number of Students 1-2 students



A significant problem that is faced around the world is the scarcity of valuable freshwater resources. This is coupled with an increase in the concern for preservation of theenvironment. One of the most important environmental issues facing many industries,especially the mining and dairy industries, is hypersaline brine production. Recently,membrane processes have emerged as one of the most promising technologies for advancedwater reclamation and wastewater treatment. One of the widely used membrane processesis reverse osmosis (RO) and it has been proven to be a good barrier for inorganic ions as wellas emerging organic pollutants. The performance of a membrane as a selective barrier ispredominately determined by two parameters, water flux and salt rejection rate, which areboth influenced by charge of the membrane surface and feed conditions such as the type of

salt, pH, temperature and operating pressure.This project will involve the use of a cross flow RO rig, representative of a real industrialprocess, to investigate the water flux and salt rejection under various solution and operationalconditions. The charge on the membrane surface will also be examined by measuring thezeta potential using an electro-kinetic analyser under similar solution condition used in ROexperiment. From this project, students will gain an advanced understanding of membraneseparation processes and membrane properties, and apply mass transfer theories to appliedindustrial situations.

5. A STUDY OF THE PHYSICAL EFFECTS OF HIGH SHEAR MIXING ONDAIRY SOLUTIONS


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Project Supervisors: Apple Koh, Jayani Chandrapala, Muthupandian Ashokkumar and Sandra Kentish




Protein aggregates in dairy whey solution are broken down upon ultrasonic treatment at 20kHz. Increased solution clarity, reduced viscosity, reduced gelation times, increased gelstrength and increased heat stability are also observed. The reduction in viscosity of wheysolutions is significant as it may allow solutions of higher solids content to be processed inspray driers, evaporators and membrane filtration units with relative ease. Overall energyrequirements may also be reduced. In addition, there is a dramatic reduction in viscosity andaggregate size when sonication is applied to a heated solution of denatured and aggregatedproteins. This low viscosity is maintained even after re-heating and reconstituting. Thecombination of pre-heat and ultrasonic treatments is thus a feasible solution in overcoming a

key problem in dairy processing facilities whereby the heat stability of re-constituted powers ispoor.In this project, an Ultra-Turrax unit is used to investigate the physical effects of high shear mixing on various solids concentrations of reconstituted whey protein concentrate 80(WPC80) and fresh whey solutions by monitoring aggregate size, viscosity, gelation point andgel strength. The combination of pre-heating and high shear mixing is also studied. Usingidentical output powers in both the mixer and sonicator, a qualitative comparison of physicaleffects can be made

6. DEVELOPING A MATLAB SCRIPT FOR THE MODELING OF ZINCRECOVERY FROM HOT-DIP GALVANISING EFFLUENT STREAMS BY

SOLVENT EXTRACTION

Project Supervisors: A/Prof. Sandra Kentish, William Lum




Hot-dip galvanising is a method that coats metals with a protective layer of zinc. Pickling

solution is used before the galvanising step to remove rust and mill-scale. However, theeffectiveness of the pickling solution reduces with time due to increasing heavy metal content,such as iron and zinc, and decreasing acidity of the bath. As such, galvanising plants usuallydispose of effluent in specialised landfills due to toxicity of the heavy metals. With increasingconcerns over process sustainability and environmental consciousness, plants are looking toreduce and recycle their wastes. Hence industries are gaining interest in treatment of spentpickling solution.The recovery of zinc from the effluent stream can be achieved through solvent extractionusing tri-butyl phosphate (TBP) as the extractant. TBP extracts zinc via reaction equilibrium.In order to model the solvent extraction reaction, the intrinsic equilibrium constant, K, isrequired. This can be determined through fitting of experimental and literature data. Due tothe complexity of the equations involved, fitting of K requires a program that can handle ahigh degree of iterative calculations and process large volumes of data quickly, such as

Matlab.


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Therefore, the focus of this project is to develop a Matlab script to determine the intrinsicequilibrium constant of zinc extraction by TBP, and predict the equilibrium concentrationsbased on initial conditions.

7. EFFECT OF SURFACTANT ON WAVE-FRONT FLOW DOWN AVERTICAL WALL

Project Supervisors: Malcolm Davidson

Number of Students 2

Suitable for Minor RP (CHEN90026)? YES


The motion of thin liquid films on solid surfaces is important to many processes in industry(e.g. coating flows) and in nature (e.g. rainwater on a window pane). In some casessurfactants are added to alter the spreading characteristics of the film, and sometimes thepresence of surfactant on the liquid-air film is unintentional and due to adsorption of impurities. Either way, when surfactant is present, the interfacial tension is reduceddepending on the surface concentration of surfactant; this modifies the film behaviour. Fluidflow redistributes the surfactant along the interface. This not only results in a non-uniforminterfacial tension but also sets up a surface tension driven flow due to Marangoni forces thatopposes the surfactant redistribution. Both effects can influence the spreading of the film.

Recently Schwartz & Davidson (2011) presented Computational Fluid Dynamic predictions of wave-front motion of a liquid film moving down a vertical wall when surfactant was present onthe interface. A linear relationship (equation of state) between surfactant concentration andinterfacial tension was assumed, valid for small enough concentrations. The aim of thisproject is to extent those predictions to non-linear equations of state, applicable to higher surfactant concentrations. The work will involve a background literature review, managementof computational simulations, and importantly, physical interpretation of the results.Knowledge of the particular numerical technique is not required.

8. HEAT TRANSFER FROM A PARTIALLY BURIED NATURAL GASPIPELINE

Project Supervisors: Malcolm Davidson, Dalton Harvie, James Holbeach (MSiKenny)




Large natural gas pipelines transport gas and liquid from installations offshore to onshoreprocessing plants, or other offshore installations. Issues such as corrosion, hydrate formation,hydraulics and liquid holdup need to be considered at the design stage to ensure that themost cost effective yet robust pipeline design is installed. In such pipelines, the gas will coolas it travels along the pipe. If the gas cools rapidly it can cause corrosion problems since therate of "top of line" (ToL) corrosion is driven by the local rate of heat transfer to thesurrounding sea.


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In order to mitigate ToL corrosion issues "cooling sections" of pipe are installed with corrosionresistant alloy to cool down the gas before it reaches the unprotected sections of the pipe.The corrosion resistant alloy is very expensive, however, and therefore the length of these"cooling sections" is critical to a cost effective design. When such pipelines sit on the seafloor, currents, tides and cyclones can cause significant movement of sand and mud which

may fully or partially bury the pipeline. This burial may have a significant impact on the rate of heat transport from the pipeline, in particular the cooling sections. Typically burial will causethe gas to cool less quickly and therefore will impact the length of the cooling sectionrequired.

Unfortunately heat transfer in the case of partial burial of pipes has received little study. In thisproject you will develop a computational fluid dynamics (CFD) model of a partially buried pipein order to determine the rate of heat transfer under various conditions. Of particular interestis the external heat transfer coefficient (also known as the film coefficient) for partially buriedpipes in the cases of natural convection (i.e. no bulk flow of the sea), and low sea currents.

9. EFFECT OF SURFACE CHARGE NON-UNIFORMITY ON IONCONCENTRATION AND FLOW FIELD IN ELECTRO-OSMOTIC FLOW

Project Supervisors: Malcolm Davidson




Understanding of microchannel flow characteristics (such as pressure distribution, ionconcentration, and flow pattern) is a pre-requisite for optimal design of the microfluidicdevices ranging from pH and temperature sensors to micro-pumps, mixers and valves, inanalysis of DNA and proteins, drug delivery and biomedical diagnosis. At micrometer scales,electrokinetic effects assume increased importance. Electrokinetic phenomena develop in achannel containing an electrolyte when the channel walls in contact with the liquid carry acharge. For example, in electro-osmotic flow, an applied electrical field will then drive flow byacting on the excess charge adjacent to the wall.

The aim of this project is two-fold. First, you will carry out a literature review on electrokineticflows with heterogeneous wall charge. Then you will numerically simulate electro-osmotic flowin the presence of non-uniform wall charge to quantify the effect on the ion concentrationsand the flow field. An existing computational fluid dynamic (CFD) model will be utilised.

Knowledge of the particular numerical technique is not required.

10. FABRICATION OF MICROSTRIPES OF NANOSHEETS BY ANEVAPORATION DRIVEN PROCESS

Project Supervisors: Xuahua Zhang, Dan Li (Monash Uni), Yufei Wang (MonashUni)




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When a drop of coffee gets dry on the desk, a ring can always been observed. Themechanism for the formation of the coffee stain has been studied since 1990s (Deegan, R.D. et al. Nature 389, 827829 (1997)). Basically, in a drying droplet the pinning of theair/solvent/solid contact line leads to a radial flow of liquid from the centre of the droplet to the

contact line of the droplet. This flow compensates the volume loss of the liquid at the edgeand carries the solute inside the liquid to the contact line. When the contact line eventuallyretreats, the solute is left behind along the line. These days this mechanism has been widelyused to fabricate advanced materials of regular layers or patterns on surfaces. (For example,TERRY P. BIGIONI, et al, Nature Materials 2006, 5, 265-270 ).

The success to disperse nanosheets of graphene into water (Dan Li, et al NatureNanotechnology, 2008, 3,101-105.) makes it possible to use this mechanism for thefabrication of functional microscale patterns of nanosheets on surface. Compared tonanoparticles, the single atomic thickness of nanosheets may give the sheets great flexibilityunder the forces applied by the meniscus of the solvent. It is very interesting to see how thesingle atomic sheets assemble driven by the evaporation process. The self-assembly will beinfluenced by the evaporation rate, the concentration of the graphene, the wettability and

roughness of the surface, and possibly the size of the sheets. In this project, we will controlthe evaporation conditions (such as temperature, solution concentration) to obtain regular stripes of graphene. Such materials can be potentially used as conductive electrodes. Thepreliminary results have shown the feasibility of this project.

11. LIFE CYCLE ANALYSIS OF CARBON DIOXIDE CAPTURETECHNOLOGIES

Project Supervisors: Kathryn Mumford, Clare Anderson, Geoff Stevens




The development of technologies to capture carbon dioxide from mayor emission sourcessuch as power plants is well underway. Efficient techniques to compare and contrast theperformance of these are required. Traditionally, performance indicators such as energyusage, operational and capital costs have been utilised for this purpose. These techniques failto incorporate issues such as use of hazardous/potentially environmentally damagingmaterials amongst others. This project is a desktop study comparing different carbon dioxide

capture technologies using a Life Cycle Approach. The term "Life Cycle" refers to the major activities in the course of the product/process life span from manufacture, use andmaintenance to its final disposal. By including the impacts throughout it provides acomprehensive view of the environmental aspects and a more accurate picture of the trueenvironmental trade-offs.

12. MICROSCOPY AND LIGHT SCATTERING TECHNIQUES FOR THECHARACTERIZATION OF CASEIN MICELLES IN MILK

Project Supervisors: Dr Lydia Ong and Dr Sally Gras



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This project will be conducted at The Bio21 Institute and Department of Chemical and

Biomolecular Engineering and is suitable for Chemical Engineering or Chemical andBiomolecular Engineering Students.

Many food properties such as flavour and texture are critically dependant on the distribution of food components on a micron-scale, known as the microstructure of food. Of particular importance is the microstructure of milk proteins, such as casein micelles. These particlesare the building blocks of many dairy products including cheese.

The first aim of this project is to characterize casein micelles within the milk produced byvarious mammals including cow, buffalo, sheep and goat. The project student will learn arange of particle sizing techniques such as dynamic light scattering and learn to assessparticle sizes from microscopic images generated by confocal laser scanning microscopy(CLSM), cryo- scanning electron microscopy (SEM) or transmission electron microscopy

(TEM).

One challenge of casein micelle characterisation is that the protein components in milk oftenrequire dilution to very low concentrations, which may change the native structure of thecasein micelles. The second aim of this project is therefore to investigate the effect of varioussolvents on the accuracy of casein micelle size determination using dynamic light scatteringand to compare the results with those obtained using microscopy techniques.

The project has high industrial relevance. It is part of an ongoing Cheese Microstructureproject currently running within the group and part of a collaboration with Dairy InnovationAustralia and four major dairy processors. The data collected will also be compared to datarecently obtained at The Australian Synchrotron.

13. ANALYSIS AND MODELLING OF SHEARED BATCH SEDIMENTATION

Project Supervisors: Dr Shane Usher, Prof Peter Scales




Many industries, particularly the mineral processing and water treatment industries, employlarge scale gravity thickeners to recover water and valuable process liquor whileconcentrating residue solids to reduce the environmental footprint in tailings disposal. Thesethickeners are often greater than 40m in diameter and cost in excess of $10 million to buildyet, even after 100 years of research, accurate sizing is still a challenge. Laboratory scalebatch sedimentation tests have long been used to produce solids dependent flux data that areinput to models used for the design of thickening processes. The method works well for non-aggregated suspensions but would nominally result in designs that are typically 1-2 orders of magnitude oversized for flocculated particulate suspensions. A reason for the discrepancybetween model and reality is that low rate shear processes can alter the structure of flocculated aggregates significantly and cause them to settle quicker. For the first time, a newanalysis technique has been developed to accurately characterise the effect of shear onaggregate settling. In this project, this new tool will be used to analyse experimental data andpredict the influence of shear rate on the rate and extent of aggregate restructuring in


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sedimentation and compression. The project will involve analysis of experimental data andvalidation of results using tools developed at The University of Melbourne

14. MEASUREMENT OF SHEAR YIELDING BEHAVIOUR OFSUSPENSIONS UNDER COMPRESSIVE LOAD

Project Supervisors: Dr Anthony Stickland, Ms Hui-En Teo, Prof Peter Scales




Particulate suspensions are commonplace in households and industries throughout Australiaand the world, ranging from formulated products such as paints and ceramics to industrialprocess streams such as mineral slurries and wastewater treatment sludges. Whilst the flowand yielding behaviour of such suspensions are commonly measured in response to either shear or compressive forces in isolation, investigation of combined shear and compression isrelatively unexplored. In part this is due to the difficulties associated with experimentalinvestigations in this area. However understanding combined shear and compressivedeformation is critical in many industrially important processes such as the drying of films,paints and coatings as well as in the behaviour of flocculated suspensions in mineralprocessing.This project aims to measure, using recently constructed equipment, the shear yieldbehaviour of particulate networks whilst under compressive loads, with the expectation thatthey are inter-dependent. The materials include alumina and kaolin. If successful, thesemeasurements would be the first of their kind for these materials and the outcomes of thiswork will form a core testing capability for an ongoing fundamental research program.

15. ANALYSIS OF SHEAR RHEOLOGY DATA FOR COAGULATEDALUMINA SUSPENSIONS

Project Supervisors: Dr Anthony Stickland, Mr Ashish Kumar, Prof Peter Scales




The shear flow of Newtonian fluids is well defined by constant viscosity. Concentratedsuspensions, on the other hand, show complex viscoelastic shear behaviour with solid-likeelastic response at low applied stresses and shear-rate dependent viscosity at high stresses,with a transition regime exhibiting characteristics of both solids and liquids depending on thetime-scale of the deformation. This has significant implications for the design, scale-up andoperation of suspension processing operations such as pipe-flow, coating, spreading, etc.Traditionally, the transition from solid to liquid-like behaviour for suspensions has beencharacterised in terms of a yield stress; many models of flow behaviour such as Bingham or Herschel-Bulkley use a yield stress. However, a significant amount of work shows that thetransition is not simply described by a yield stress such that it is not the appropriate yieldcriterion. The aim of this project is to undertake an analysis of recently measured rheological

data for coagulated alumina systems to quantify the behaviour during the transition regime.The data is from stress relaxation (a step strain is applied and the residual stress is


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measured), creep (a constant stress is applied and the strain measured) and creep recovery(the stress is removed and the elastic response recorded). The analysis requires a goodbackground in data manipulation and curve fitting and is well suited to those with amathematical inclination.

16. MATERIAL PERMEABILITY FROM TRANSIENT CENTRIFUGALSETTLING

Project Supervisors: Dr Shane Usher, Ms Feng Qian, Prof Peter Scales




Dewatering processes are common throughout industry. Processes such as centrifugation,thickening, filtration and evaporation are used from the minerals to wastewater industries toseparate the solids and liquids in suspensions. The dewatering behaviour of suspensionscan be described in terms of its compressibility and permeability. Armed with good materialproperty information, engineers can confidently design and optimise dewatering equipment.However, without this information, scale-up and operation are based purely on heuristics andcostly errors can be made.A number of techniques are required in order to characterise the dewatering properties of asuspension from dilute (i.e. single particle in an infinite material) to concentrated (e.g. filter cakes). One method for characterising suspensions at intermediate concentrations is to usecentrifugal settling the interface or mud-line of a suspension is tracked as a function of timeas it settles under centrifugal acceleration in a centrifuge tube. Our group has recentlydeveloped a method for extracting useful information from such settling tests. The aim of thisproject is to perform a series of centrifuge experiments on a model alumina system to showthat the data extracted from centrifugal characterisation aligns with properties measured usingalternative methods such as gravitational settling or filtration.

17. SYNTHESIS OF THERMOREVERSIBLE SILICA GELS

Project Supervisors: Dr Anthony Stickland, Prof Peter Scales




The flow and deformation (that is rheology) of suspensions can be highly non-Newtonian andviscoelastic. The material response to an applied stress or strain is dependent on theproperties of both the solid and liquid phases of the suspension. A major variable isinterparticle forces in simple terms, particles that repel each other will be dispersed whereasparticles that attract will be agglomerated. We have recently developed a theory of suspension rheology that requires the testing of a range of models systems with well-understood interparticle forces under well-defined conditions. However, one issue that ariseswhen measuring the properties of agglomerated systems is that they can be shear sensitive,such that the act of loading a rheometer with the material changes the properties of thematerial and therefore gives questionable results. One way to avoid this complication is toperform the agglomeration in situ by loading the suspension into the test device in adispersed state, changing a key parameter and letting the material agglomerate in the device.An ideal system for such studies is thermoreversible gels (composed of octadecyl coated


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silica particles suspended in decalin), which gel below a critical temperature. Therefore,material can be loaded into a rheometer at high temperature and then cooled to perform insitu agglomeration.The aim of this project is to synthesise thermoreversible gels using the Stber method, whichinvolves the base catalysed hydrolysis of tetraethyl-orthosilicate in an ethanol medium. Theresulting particles will be characterised using a variety of methods including dynamic light

scattering and SEM. A student with strong organic or inorganic chemistry laboratory skills isrecommended.

18. PRECIPITATION SYSTEMS FOR CO 2 CAPTURE

Project Supervisors: Dr Dimple Quyn and Prof Geoff Stevens




Solvent absorption is presently the only commercially viable technology for post combustioncapture of CO 2 from power station flue gases. In order to reduce the large circulation rates of solvent in a carbon capture plant, and consequently reduce the reboiler energy duty,precipitating carbonate/bicarbonate solvents are being investigated by leading researchgroups, including the CO2CRC at the University of Melbourne. An exciting new processbased on a precipitating solvent has been developed; however a number of challenges needto be addressed before it can be implemented. These include the best ways of handlingslurries, different configurations of absorption columns etc. This project will include a literaturereview of current global projects and patents, particularly in relation to energy duties, ratepromoters and solids handling. Special attention will also be paid to column internals for precipitating processes, along with laboratory measurement of appropriate properties of thesesystems.

19. ENVIRONMENTAL FACTORS CONTRIBUTING TO FIBRILLARDISEASES

Project Supervisors: Dave Dunstan




Despite the increasing prevalence of several major diseases related to mis-folded proteinsand amyloid fibril formation, little is known about the epidemiology and environmental factorswhich cause these diseases. This project will review the literature regarding the possible andknown environmental factors that contribute to Alzheimers disease.

20. A REVIEW OF DUMBBELL MODELS OF POLYMERS IN FLOW


Number of Students 2 studentsSuitable for Minor RP (CHEN90026)? YES


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Since Kuhn first introduced the elastic Dumbbell in 1933 it has become the corner stone of polymer dynamics. Models of polymers in flow attribute the hydrodynamic forces to affect the

beads with a Stokes drag term and include and elastic restoring force or Hookean spring toembody the elastic entropic contribution from the chain. This project will review the essentialassumptions of this model and review the predictions and modifications required in order topredict polymer flow behaviour.

21. REVIEW OF POLYMER FLOW BIREFRINGENCE





Polymers in flow exhibit visco-elastic behaviour. In flow, the polymer molecules are thought toalign and cause anisotropy in the optical behaviour. This is often measured as differences inthe refractive index parallel and perpendicular to the flow direction. The so-calledbirefringence has been measured in a number of geometries and the so-called stress opticlaw has seen that there is a generally observed linear relationship between the stress anddifference in refractive index. This project will review the literature and try to make sense of the different measurements and coefficients.

22. P13 KINASE ROLE AND INHIBITORS IN CANCER





The protein P13 Kinase has been identified as a key protein in a number of prevalentcancers. A number of research groups have focussed on the development of inhibitingmolecules which restrict the activity of the protein. A number of drugs have been consideredwithout success to date. This project will review the role of P13K in cancer and the modelcompounds which have been identified as possible inhibitors. Key structural characteristicswill be used to identify new naturally occurring candidates as possible therapeutics.

23. POWER LAW FLUIDS





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Polymer shear thinning behaviour can be modelled using several simplified equations. Thepower law model describes the region of shear thinning and relates the viscosity to the shear rate raised to the power, (power law), of the fluid. The effect of solvent quality, molecular weight and polymer type on the power law exponent will be reviewed. Summarising the

literature will enable key aspects of the polymer behaviour to be identified.

24. AMYLOID INHIBITORS: A NATURALLY OCCURRING COMPOUND

Project Supervisors: Dave Dunstan, Greg Qiao, Sian-Yang Ow




Amyloid Fibrils are a key signature of a number of diseases including Parkinsons,Alzheimers and Type II diabetes among others. Recent work in the Complex Fluids grouphas identified a naturally occurring compound that inhibits amyloid fibril formation in-vitro. Thesize of the natural molecules suggests that it will not cross the blood-brain barrier. Using thekey physical attributes of the compound, we have designed a molecule which will be smallenough to cross the BBB. The project will undertake the synthesis of this molecule with thepossibility of conducting preliminary tests for the in vitro inhibition using the syntheticcompound.

25. **THE EFFECT OF FREEZING ON BUFFALO MILK QUALITY

Project Supervisors: Hanh Nguyen, Dr Lydia Ong and Dr Sally Gras




This project is suitable for a Chemical Engineering or Biomolecular and Chemical Engineeringstudent. It will be located largely at The Bio21 Institute.

This project will look at the effect of freezing on buffalo milk quality. Buffalo milk is oftentransported frozen due to the long distances involved in milk transport in Australia yet there islittle information on the effect of freezing on buffalo milk quality and microstructure. Theproject will involve techniques such as confocal microscopy to assess the microstructure of the milk and any damage to the native milk fat globule membrane that occurs as a result of freezing. The calcium present in solution or in micelles will also be assessed before and after freezing and the changes in the rheological properties of the milk determined. Sonication willalso be explored as a possible method to prevent or reduce damage induced during freezing.

26. ** BIOMASS PYROLYSIS SIMULATIONS USING REACTIVEMOLECULAR DYNAMICS

Project Supervisors: Dr. Gabriel da SilvaNumber of Students 2 students


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Woody biomass (comprising cellulose, hemi-cellulose, and lignin) is a low-grade solid fuel thatis being widely investigated as a source of renewable energy. One promising technologyinvolves pyrolysis over a catalyst to produce liquid hydrocarbons for transportation fuels,along with other useful chemicals [1]. The fundamental chemical reactions taking placeduring biomass pyrolysis are not well understood, however, and are difficult to studyexperimentally and theoretically due to the complex and heterogeneous chemical structure of this material. This study will use reactive molecular dynamics [2,3], a new theoreticaltechnique, to investigate the pyrolysis chemistry of biomass components. Reactive molecular dynamics (as implemented in the ReaxFF software package) is ideally suited to studyingbiomass pyrolysis, as it allows for the incorporation of reactive events (unlike classicalmolecular dynamics) and can be readily applied to systems containing hundreds or eventhousands of atoms (unlike quantum mechanics).

[1] Huber, G. W.; Iborra, S.; Corma, A., Synthesis of transportation fuels from biomass:Chemistry, catalysts, and engineering Chemical Reviews 2006 , 106 , 4044.

[2] van Duin, A. C. T.; Dasgupta, S.; Lorant, F.; Goddard, W. A., III, ReaxFF: A reactiveforce field for hydrocarbons Journal of Physical Chemistry A 2001 , 105 , 9396.

[3] Chenoweth, K.; van Duin, A. C. T.; Goddard, W. A., III, ReaxFF reactive force fieldfor molecular dynamics simulations of hydrocarbon oxidation Journal of Physical Chemistry A 2008 , 112 , 1040.

27. ** SEPARATION OF TIMESCALES IN CHEMICALLY ACTIVATEDREACTIONS

Project Supervisors: Dr. Gabriel da Silva




Gas-phase reactions are critical to understanding the composition of flames, atmospheres,and the interstellar medium. The empirical insights of Arrhenius, codified into transition statetheory almost a century ago, provided a means of rigorously treating single-step thermallyactivated reactions. The association of two compounds in the gas-phase, however, results intheir chemical activation, making them vibrationally hot relative to the surrounding bath gas;the further reaction of activated species can no longer be described as a function of temperature within the framework of canonical transition state theory, and instead requiresmicrocanonical treatment of rate constants as a function of energy along with time-dependentmodelling of collisional energy transfer between the activated molecule and the surroundinggas, using theoretical methods which are more recent but now relatively robust. In manyinstances chemical activation and thermal activation take place on comparable timescales,and the separation of the two processes becomes non-trivial (see Figure 1). This project willattempt to develop a mathematical procedure to effectively separate the chemical and thermalactivation events in complex gas-phase reactions, by applying an instantaneous reactionassumption to the chemically activated component. Conventional constants will be fit to thethermally activated processes at long time scales to provide a means of extrapolating back totime zero. The developed method will be compared with detailed time-dependent reactionsimulations [1], and incorporated into a computer program for automated rate constantextraction.


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Figure 1: Product yields vs. time in a complex gas-phase reaction (C 3H3 + C 4H2) [1].

[1] da Silva, G.; Trevitt, A. J. Chemically activated reactions on the C 7H5 energy surface:Propargyl + diacetylene, i -C5H3 + acetylene, and n -C5H3 + acetylene Physical Chemistry Chemical Physics 2011 , doi: 10.1039/c1cp20112c.

28. ** KILLER CLOUDS: MODELLING THE IN-CLOUD FORMATION OFCARCINOGENIC COMPOUNDS

Project Supervisors: Dr. Gabriel da Silva




The highly carcinogenic nitrosamine NDMA has been detected in urban cloud droplets,although it is not known if it forms in the gas-phase or in the droplets themselves [1]. Thisstudy will apply a mathematical model of the nitrosation mechanism [2] to investigate thekinetics of in-cloud NDMA formation, including the previously-unconsidered effects of I - andBr - catalysis.

[1] Hutchings, J. W.; Ervens, B.; Straub, D.; Herckes, P., N -Nitrosodimethylamineoccurrence, formation and cycling in clouds and fogs Environmental Science and Technology 2010 , 44 , 8128.

[2] da Silva, G.; Dlugogorski, B. Z.; Kennedy, E. M., Elementary reaction step model of the N -nitrosation of ammonia International Journal of Chemical Kinetics 2007 , 39 ,645.

29. ** DEVELOPMENT OF A KINETIC MODEL FOR IN VIVO NITROSAMINE

FORMATIONProject Supervisors: Dr. Gabriel da Silva


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Carcinogenic nitrosamine compounds form by reaction of the nitrite ion with amines under acidic conditions, according to a nitrosation mechanism. All of the reagents required for nitrosamine formation are found in the human stomach, and while it is generally accepted thatnitrosamines are formed in vivo , the reaction rate and detailed mechanism are not known. Arecent reaction model of the nitrosation process suggests that in the human stomachnitrosamine formation can be catalysed by common halides. This project will develop amathematical model of the stomach to incorporate with the existing reaction model, allowingus to predict nitrosamine formation under realistic physiological conditions, revealing the trueimportance of these newly proposed catalysts.

30. INCLUDING EXPLICIT WATER MOLECULES IN DENSITYFUNCTIONAL THEORY MODELLING OF CARBOXYLIC ACIDS INSOLUTION

Project Supervisors: Dr. Gabriel da Silva, A/Prof. George Franks, Catherine Sutton




Carboxylic acids exist as both neutral and ionic species in solution. In order to understandhow they interact and react with other species, it is useful to know how they exist individually.Of particular interest is whether or not acids and surfaces are protonated or deprotonated.pK a is the pH at which 50% of the acid molecules have dissociated. Sometimes it is notpossible to experimentally measure the p K a of a molecule and so it is useful to be able tocalculate this value. Furthermore, accurate replication of known p K a values indicates that asuitable model is being used to perform these calculations and gives confidence to proceedand model other interactions.The p K a of acids can be determined using thermodynamic cycles, where the energies of molecules are calculated using quantum mechanical modelling using a Density FunctionalTheory computer package. Representation of the way in which molecules interact with their surroundings has a significant impact on the accuracy of these calculations. The aqueous

environment can be modelled with a continuum representing water, surrounding themolecules of interest, or with explicit water molecules interacting with the molecules, or acombination of the two.The objective of this research project is to determine how best to use explicit water moleculesin the calculation of p K a . This includes choice as to the most appropriate number of water molecules and the configuration of the water molecules around the acidic molecule of interest.

J. Ho and M. L. Coote, A Universal Approach for Continuum Solvent pKa Calculations: AreWe There Yet? Theor Chem Acc, 2010. 125 : p. 3-21.Liptak, M.D. and G.C. Shields, Accurate pK(a) calculations for carboxylic acids using Complete Basis Set and Gaussian-n models combined with CPCM continuum solvationmethods. Journal of the American Chemical Society, 2001. 123 (30): p. 7314-7319.


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31. STRUCTURAL CHARACTERISATION OF COMPLEXMACROMOLECULES VIA MATRIX ASSISTED LASER DESORPTIONIONISATION TIME-OF-FLIGHT (MALDI TOF) MASS SPECTROMETRY

Project Supervisors: Dr. Anton Blencowe and Prof. Greg Qiao

Number of Students 2 students (1 Major RP and 1 Minor RP)



Background;

MALDI ToF is a soft ionization mass spectrometry technique allowing for the analysis of biomolecules (biopolymers such as proteins , peptides and sugars ) and large organic molecules (such as polymers ,dendrimers and other macromolecules ), which tend to be fragile and fragment when ionized by moreconventional ionization methods. [1,2] The analyte is first co-crystallized with a UV absorbing matrix andthen subjected to pulsed laser radiation. This causes the vaporization of the analyte/matrix crystalsand produces ions, which are directed into a flight tube. The mass of an ion is measured by the time ittakes to arrive at the detector (smaller ions are faster, larger ions are slower). The time is thenconverted to mass to charge ratio.

MALDI ToF not only provides exact mass data, but also allows for detailed structuralcharacterisation of complex macromoleculesto be conducted. [2,3] For example, theanalysis of poly(ethylene glycol) (PEG), awidely used synthetic polymer, enablesdetermination of the molecular weightcharacteristics and structural informationrelating to the polymers end-groups anddefects ( Figure 1 ).

Figure 1 : MALDI ToF spectrum of 2 kDaPEG.

Project Outline;

Given that the characterisation of macromolecules is fundamental to understanding their structurerelated properties, this project will focus upon the MALDI ToF analysis of complex synthetic polymersprepared via different polymerisation methods. In order to obtain detailed and reliable data it will benecessary to optimise the conditions used for the analysis by varying the type of matrix and

instrument parameters. Once spectra have been collected for a series of polymers the data will beanalysed to determine their exact structure and molecular weight characteristics. Complementarytechniques, such as gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR)spectroscopy will be also be employed to support the results obtained from MALDI ToF.

References:[1] Karas, M.; Bahr, U., "Laser Desorption Ionization Mass Spectrometry of Large Biomolecules",

Trends Anal. Chem. 1990 , 9: 3215.[2] Schrepp, W.; Pasch, H., MALDI ToF Mass Spectrometry of Synthetic Polymers, 2003 , Berlin:

Springer-Verlag, ISBN 3-540-44259-6 .[3] Wu, K. J.; Odom, R. W.; "Characterizing synthetic polymers by MALDI MS", Analytical

chemistry, 1998 , 70, 456A461A.


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32. SYNTHESIS OF DRUG LOADED AMINO ACID-BASED STARPOLYMERS FOR DRUG DELIVERY APPLICATIONS

Project Supervisors: Dr. Anton Blencowe, Adrian Sulistio and Prof. Greg Qiao




Background;

Central to the proposed project is a type of star polymer recently developed by our group and composedof naturally occurring amino acids, making them biodegradable and biocompatible. [1] Over the last year our group has developed a facile one-pot approach to prepare highly functionalised polypeptide-basedstar polymers from amino-acid N -carboxyanhydride (NCA) derivatives. These star polymer can beloaded with drugs and functionalised with targeting moieties for targeted drug delivery applications. Thisproposal will focus on PEG- b-poly(L-glutamic acid) arm poly(L-cystine) core ((PEG- b-PLGA)arm PLC core ) star polymers, since the linker and drug conjugation chemistries for PLGA-based macromolecules is alreadywell established. [2] The protected stealth star S1 possess pendent benzyl ester groups (Bn) located inthe inner-shell; these groups will be modified with hydrazine, through which chemotherapeutic drugssuch as doxorubicin can be conjugated via acid liable hydrazone linkages to afford the drug loadedstealth star S2 (Scheme 2 ). The hydrazone linkage is stable at basic and neutral pH values, butundergoes hydrolysis below pH 6.5, which is ideal for the desired, site specific release of drugs in theendosomal environment of cancer cells.

Project Outline;

The student will synthesize the star S2 as outlined ( Scheme 2 ) and investigate the drug loading andrelease. The drug loading will be determined via changes in molecular weight or UV-vis spectroscopy,since drugs like doxorubicin have distinctive absorbances. After drug loading the stars will be purifiedvia dialysis to ensure that any free drug is removed. The drug release kinetics of the star S2 will be

studied in vitro at various pH values and various reducing conditions to mimic the acidic and reducingenvironment of the cancer cell endosome.


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References:[1] A. Sulistio, et al. , Chem. Commun. , 2011 , 47, 1151.[2] K. Kono, et al. , Biomaterials , 2008 , 29, 1664.

33. ** SYNTHESIS OF HYDROGEL SCAFFOLDS FOR TISSUEENGINEERING APPLICATIONS

Project Supervisors: Dr. Anton Blencowe, Berkay Ozcelik and Prof. Greg Qiao




Hydrogels are a potential type of biomaterial that have shown great promise as scaffolds for tissue engineering applications. [1] These materials have tissue-like water contents, may beformed in situ for ease implantation and can encapsulate cells as they crosslink. [2] Thephysical and biological properties of the hydrogel play an important role in the development of engineered tissues. The hydrogel scaffold must be biodegradable, biocompatible, have goodmechanical properties and also have open pore morphology to promote cell adhesion,growth, migration and differentiation function. [3] Therefore, the aims of this research projectare to synthesize hydrogel scaffolds with appropriate properties for tissue engineeringapplications. A simple technique used to produce chemically cross-linked hydrogels is the co-polymerization of monomers with cross-linkers to generate networks with biodegradable ester linkages. In this study poly(ethylene glycol) (PEG)-based star polymers will be cross-linkedwith suitable acid chloride monomers to afford novel hydrogels composed of hydrolysableester linkages. PEG is chosen in the formulation due to several attractive characteristics, suchas, biocompatibility and low toxicity. Moreover, the materials have been approved by Foodand Drug Administration (FDA) and have been utilized widely in tissue engineeringapplications. The mechanical properties and degradation rate of the hydrogels will be tailoredthrough variation of the monomer to cross-linker ratio, monomer concentration and monomer structure.

The student involved in this project will investigate the preparation of hydrogels, optimisingthe procedure to produce materials with desired mechanical, degradation and biologicalproperties that can potentially be used as scaffolds for in vitro or in in vivo applications.

References 1. K. Lee, D. Mooney et al, Chemical Reviews. , 2001, 7 , 1869-79.2. R. J. LaPorte, Hydrophilic Polymer Coatings For Medical Devices , Technomic

Publishing company, Lancaster, PA, 1997, pp 20.

3. H. Qingpu, A. D. B. Paul, M. S. Kevin, J. Mater. Chem ., 2004, 14 , 1915-1923.

34. ** BIOENERGY PRODUCTION FROM MICROALGAE - ENHANCINGTHE DISRUPTABILITY OF MICROALGAE CELLS FOR BIODIESELPRODUCTION

Project Supervisors: Greg Martin, Sandra Kentish and Ian OlmsteadLaboratory-based project



Background


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There is increasing interest in the possibility of large-scale cultivation of microalgae as asource of renewable liquid fuel. Microalgae offer numerous advantages over traditionalrenewable fuel crops (e.g. wheat, soy, corn, sugar, date palms etc.) including rapid, year-round, high-density production and the ability to be grown on non-arable land using saline or grey water sources. However, current production technologies are not economically viableand major advances need to be made. This project and the next investigate the viability

and/or optimisation of various aspects of this process:


In order for biodiesel production from microalgae to be economically viable the lipids have tobe isolated at extremely low cost. The large volumes of water associated with the biomassmean efficient solvent extraction is difficult to achieve. The most promising way to increasesolvent extraction efficiency is to break apart (disrupt or lyse) the cells to increase access of the solvent. While high-pressure homogenization is an effective method for disrupting cells,the energy requirements can be high, particularly for species of microalgae with tough cellwalls. This project will investigate a number of promising preconditioning methods aimed atweakening cells prior to homogenisation. Methods that will be considered include pH

adjustment, enzymatic treatment, and application of osmotic pressure. In addition the usemethanol to assist with weakening the cells prior to rupture and also assisting with theseparation of the TAGs due to their immiscibility may be investigated. The project will involveassessing the effect of preconditioning on both the physiological properties of the cell and therelative enhancement to subsequent disruption.

35. ** BIOENERGY PRODUCTION FROM MICROALGAE - THE INFLUENCEOF IMPURITIES ON BIODIESEL PRODUCTION FROMTRIGLYCERIDES

Project Supervisors: Sandra Kentish, Greg Martin, Ian OlmsteadLaboratory-based project



Background There is increasing interest in the possibility of large-scale cultivation of microalgae as asource of renewable liquid fuel. Microalgae offer numerous advantages over traditionalrenewable fuel crops (e.g. wheat, soy, corn, sugar, date palms etc.) including rapid, year-round, high-density production and the ability to be grown on non-arable land using saline or grey water sources. However, current production technologies are not economically viableand major advances need to be made. This project and the previous investigate the viability

and/or optimisation of various aspects of this process:Abstract/Project Description:

Biodiesel is traditionally produced from relatively pure oils sourced from vegetable or palmfeedstocks. While microalgae offer many potential advantages over conventional biodieselfeedstocks, isolation of pure TAGs from microalgae is difficult. The fatty acid methyl estersthat constitute biodiesel are produced from triacylglyercides (TAGs) by transesterificationreactions catalysed either by base or acid. While these reactions are known to bedetrimentally effected by the presence of contaminants such as free fatty acids, phospholipidsand water, the effects have not been thoroughly investigated in the context of microalgallipids. In particular, it would be advantageous to be able to effectively process TAG stream

that contain much higher quantities of water and phospholipids than are encountered usingtraditional feedstocks. This project will involve working with an industrial partner to develop


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transesterification methods that are effective on microalgal feedstocks and may include travelto their biodiesel processing facility in Laverton.

36. CO 2 CAPTURE USING POTASSIUM CARBONATE CRYSTALFORMATION

Project Supervisors: Clare Anderson, Wendy Tao and Geoff Stevens



The Cooperative Research Centre for Greenhouse Gas Technologies (CO2CRC) hasdeveloped a potassium carbonate solvent process that promises to provide a post-combustion carbon dioxide (CO 2) capture process that is lower in cost and energy demandwhen compared with other solvent processes.The CO2CRC solvent process (UNO Mk 3) uses a concentrated potassium carbonate(K2CO 3), which reacts with the CO 2 from the flue gas to produce potassium bicarbonate(KHCO3). A fraction of the KHCO 3 formed then precipitates from solution resulting in a slurrystream at the bottom of the absorber column.This research project aims to further understand the impact of process conditions(temperature, pressure, composition etc.) on the formation of the crystals (size, shape,particle distribution). The project will be based in the lab and will involve making andanalysing slurry samples.

37. INFLUENCE OF GELCASTING SYSTEM ON THE GREEN PROPERTIES OFCERAMIC PARTICLE STABILIZED FOAMS

Project Supervisors: Dr. Carolina Tallon, Muhamad Firdaus, A/Prof. George V. Franks

Experimental Project



Foams can be found in ordinary life. But are these soft and smooth substances ableto become a strong material to use them as a molten metal filter or in a rocket combustor,under extreme conditions? The answer is yes. If you are interested in discover how thistransition is done, this is your project.

Porous ceramic materials have been prepared by different techniques 1. A new routeappeared in the last decade, combining surface chemistry with ceramic processing. Thecombination of these concepts, particle stabilized foam 2 and gelcasting 3,4,5 , allows to preparecomplex shape porous materials, controlling the degree of porosity, microstructure andproperties of the material 6,7 . Stable ceramic powders suspensions are the starting point. Thesurfaces of the ceramic particles in the suspension are rendered hydrophobic using surfactantmolecules. When the bubbles are introduced in the suspension, these particles move andattach to the interface of bubbles, stabilizing them. Then, the gelcasting process creates apolymeric network through the suspension, holding the particles and bubbles together toproduce the desired porous piece after drying. Further thermal treatment at high temperatureleads to the densification of the final product.

The gelcasting system plays a very important role, providing the necessary strengthto the material to be handled, shaped and in some cases, machined to obtain the requiredcomplex shape 3,4,5 . The aim of this project is to understand and identify the effect of differentgelcasting systems on the green properties of the ceramic foams: density, porosity and

mechanical strength. This project will comprise a comparison study of a thermal activatedgelcasting system (Polyvinyl Alcohol (PVA) as main polymer) and a chemically activated


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gelcasting system, (2-hydroxythethyl methacrylate (HEMA) as main monomer) and theevaluation of their performance in the preparation of ceramic foams.

1) A. R. Studart, U. T. Gonzenbach, E. Tervoort, and L. J. Gauckler, Processing Routes toMacroporous Ceramics: A Review, J. Am. Ceram. Soc. , 89 , [6] 17711789, (2006)2) T. N. Hunter , R. J. Pugh , G. V. Franks, G. J. Jameson, The role of particles in stabilising

foams and emulsions, Adv. Coll. Inter. Sci. 137 , 5781,(2008)3) O.O. Omatete , M.A. Janney , R.A. Strehlow, Gelcasting - A New Ceramic FormingProcess Am. Ceram. Soc. Bull ., 70 [10], 1641-1648 (1991)4) F. Chabert, D. E. Dunstan and G. V. Franks, Cross-linked Polyvinyl Alcohol as a Binder for Gelcasting and Green Machining, J. Am. Ceram. Soc ., 91 [10] 31383146 (2008)5) C. Talln, D. Jach, R. Moreno, M. I. Nieto, G. Rokicki and M. Szafran, GelcastingPerformance of Alumina Aqueous Suspensions with Glycerol Monoacrylate: A New Low-Toxicity Acrylic Monomer, J. Am. Ceram. Soc . 90 [5] 1386-1393 (2007)6) U. T. Gonzenbach, A. R. Studart, D. Steinlin, E. Tervoort, and L. J. Gauckler, Processingof Particle-Stabilized Wet Foams Into Porous Ceramics, J. Am. Ceram. Soc ., 90 [11] 34073414 (2007)7) H. Kim, S. Lee, Y. Han, J. Park , Control of pore size in ceramic foams: Influence of surfactant concentration, Mater. Chem. and Phys . 113 , 441444, (2009)

38. ** ANALYSIS OF PROTEIN INTERACTIONS DURING MILKCONCENTRATION

Project Supervisors: Greg Martin and Dave Dunstan



Spray-dried dairy powders are among the most important examples of value-added productsproduced by the Australian Dairy Industry. A key step in the production of these powders isthe concentration of milk by evaporation. Milk is complex biological system containing an oil-in-water emulsion of fat globules and a colloidal system of protein associations (caseinmicelles) suspended in an aqueous solution containing lactose, soluble proteins, mineralsand vitamins. The removal of water by evaporation alters the complex mineral equilibria andimposes inter-particle interactions. While there is some understanding of the macroscopiceffects of concentration on milk, less is understood about the changes occurring at thecolloidal scale. This project will begin with a thorough review of the literature pertaining to milkconcentration. A theoretical analysis considering spatial, biochemical and thermodynamicfactors will then be developed in order to predict the effect of concentration and heating onthe equilibria of the system. The knowledge and understanding gained from this analysis iscritical in the development of improved dairy processes.

39. CONTROLLED SYNTHESIS OF BLOCK COPOLYMER FOR PROTONEXCHANGE MEMBRANE APPLICATION

Project Supervisors: Zhao Shixiong, Dr. Paul Gurr, Prof. Greg Qiao

Number of Students 1student

Suitable for Minor RP(CHEN90026)? NO

Proton exchange membrane fuel cells

(PEMFCs), including Direct MethanolFuel Cells, have attracted increasingattention in recent years as alternative


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mobile and portable power sources owing to their outstanding advantages, such as highefficiency, high power density, low or zero emissions, and reliability. The key component of PEMFCs is the proton exchange membrane (PEM) which consists of a hydrophilic protonconductive phase and a hydrophobic non-conductive phase. These phases are usually distributedrandomly in the PEM. The hydrated hydrophilic phase forms tortuous channels in which protonscould be transported.

To enhance the conductivity of PEMs, researchers have attempted numerous methods tomodify the polymer [1] or optimise the method for membrane preparation [2]. But it is still aproblem to balance the membrane properties among transportation, selectivity and lifetime.

Controlled polymerization is a method which precisely controls polymer structures andarchitecture. This method will be applied to the development of well-defined PEMs withpredetermined structural compositions.

In this project the student will make a diblock or triblock copolymer by controlledpolymerization. The first block is hydrophilic, for proton conductivity, the second block ishydrophobic for phase separation and minimise solubility in water. The third block incorporates acrosslinking moiety which will enhance membrane strength and stability. However, the mostimportant advantage afforded by applying controlled polymerization into PEM synthesis, is thatwe will produce a precisely controlled material, which will self-assemble into a regular structurewith hydrophilic channels in the membrane trans-plane direction. In this way we will optimise the

proton exchange channels and improve PEM efficiency dramatically.Previous researchers have demonstrated that the block copolymers tend to self-assemble into

oriented structures, but only oriented in the in-plane direction [3]. This leads to a decrease in theconductivity in trans-plane direction. To overcome this some environmental stimulations such asnanotube templating or application of electric or magnetic fields are indented to be applied duringmembrane formation.References:[1] Kevork T. Adjemian, Raymond Dominey, Lakshmi Krishnan, etc Chem. Mater. 2006, 18,2238-2248[2] Hsiu-Li Lin, T. Leon Yu, and Fang-Hsin Han J. Polym. Research 2006, 13, 379385 [3] Emily M. W. Tsang, Zhaobin Zhang, Zhiqing Shi, etc J. Am. Chem. Soc. 2007, 129, 15106-15107

40. DUOLAYER FOR THE REDUCTION OF WATER EVAPORATION

Project Supervisors: Dr A Leung, Dr D Tran, Dr J Lim, Prof. G. Qiao, Prof. D.Solomon

Number of Students 3 (2 lab works and 1 literature review)

Suitable for Minor RP (CHEN90026)? YES (Lit. Review)

In excess of 40% of the water stored in dams and reservoirs across Australia is lost annuallythrough evaporation. A range of evaporation mitigation technologies are commercially

available for small storages (10ha, meaning thatalternative evaporation mitigation technologies are required. One such technology that isbeing investigated is the use of chemical monolayers: the application of a special amphiphilicchemical to the water surface which spreads effectively, providing a one molecule thick filmacross the water storage area (Figure 1). This film allows the transport of gases such asoxygen virtually unhindered, however it provides a barrier restricting the transfer of water tothe air, hence reducing evaporation.

Current research is focusing on producing improved duolayer materials with the addition of polymer which overcome the limitations of previously investigated compounds, such as lossof the monolayer itself to volatilization, and wind disruption. This project will investigatepotential new duolayer formulations. This may include testing of important properties such as

efficiency in forming a duolayer system on a turbulent water surface, capability to reducewater evaporation, volatilization and wind resistance.


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Figure 1: Schematic representation of a chemical monolayer on the water surface.

41. SYNTHESIS OF MONOLAYER-FORMING CHEMICALS FOREVAPORATION MITIGATION

Project Supervisors: Qiang Fu, Pejman Hojati Talemi and Greg Qiao




Water conservation has become a prevalent issue in the recent year duo to droughtconditions as well as concerns over the effect of climate change. In Australia, the loss of water by evaporation from agriculture dam can reach as high as 40% per year. Variousmethods to reduce water evaporation have been introduced, including the use of hoveringshade and floating covers. However, they are impractical and uneconomical to use on largewater bodies.

Chemical monolayers have the potential to be the method of choice for reducing evaporation

from large water bodies. As they do not require complex mechanical structures, monolayerscan be used at a relatively lower price compared to the physical covers. In this project, avariety of chemicals will be designed, synthesized, characterized and applied in evaporationmitigation.

The student involved in this project will investigate the synthesis and characterization of monolayer-forming chemicals. He will also learn the skills of organic synthesis, purificationand analysis.

42. NANOSTRUCTURED COMPOSITE MEMBRANE FOR CARBONDIOXIDE SEPARATION

Project Supervisors: Andri Halim, Dr. Paul Gurr, Prof. Greg Qiao




Global warming is arguably the greatest environmental problem facing the world today. Agreat deal of effort is being undertaken to reduce CO 2 gas emissions through technologicalinnovation. The use of membranes for gas separation has been studied for more than 150years. There are two main criteria for membrane selection; these are high gas permeation flux(permeability) and ability to separate the gas of interest from other gases (selectivity).

Water

Hydrophilic head

Hydrophobic tail Air


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Polymeric membranes suffer from a typical upper performance limit as membranes that havehigh permeability tend to have low selectivity and vice-versa [1].

Figure 1 shows the Robesons trade-off curve for carbon dioxide and methane gas pairs [1]

Membranes specifically designed for CO 2 separation with increased permeability andselectivity are required to reduce capture costs and increase efficiencies. When compared toother polymers, polyimide is considered as a high performance polymer as its permeabilityand selectivity approaches the present upper bound.Molecular modification of polyimide membrane can be regarded as a viable approach tofabricating a membrane with superior separation characteristics. One of the approaches toincrease CO 2 permeability is to fabricate composite membrane that incorporatespoly(ethylene oxide) (PEO). PEO is considered as an attractive candidate as it has a strongaffinity for CO 2 molecules. Additionally, membranes containing PEO are relatively easy tofabricate, however, PEO tends to crystallize [2]. This research project will involve a literaturereview on the molecular architecture and separation performance of polyimide membranesthat incorporate PEO. The student will make recommendations as to the future direction for the fabrication of novel PEO-composite membranes.References :

1. Robeson, L.M., Correlation of separation factor versus permeability for polymeric membranes . Journal of Membrane Science, 1991. 62 (2): p. 165-185

2. Lin, H. and Freeman, B.D., Materials selection guidelines for membranes that removeCO2 from gas mixture . Journal of Molecular Structure, 2005. 739 (1-3): p. 57-74

43. PH-RESPONSIVE NANOGELS: COMBINATION OF ROMP AND THIOL-ENE

Project Supervisors: Jason Xu, Greg Qiao




Aim and Backgroud Nanogels consist of crosslinked nano-sized particles or fibers made of hydrophilic

polymers. They are soluble in water, but have properties different from linear macromoleculesof similar molecular weight. They have the ability to encapsulate lipophilic (or hydrophobic)guest molecules (e.g. some anti-cancer drugs). 1


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Nanogels are generally prepared by microemulsion or inverse microemulsion methods. 2,3 However, these methods are relatively complex and require multiple purification steps toremove unreacted monomers and surfactants that are used as emulsion stabilizers.In this proposal, we will employ linear amphiphilic diblock copolymers to generate nano-sizedmicelles with thin corona, following by appropriate crosslinking of the core. Subsequenthydrophilic modification of the core to be primary amine functionalities will give crosslinked

water soluble nanoparticles (that is, nanogel). This amphiphilic diblock copolymers will bemade by ring-opening methathesis polymerization, 4,5 which provides controlled molecular weight and low polydispersity, and olefin backbone. Olefin backbone can be directly utilized tobe crosslinking sites for the nanoparticles by thiol-ene chemistry. This would be a facilemethod to make well-defined nanogels as drug delivery vehicles.

Approach and MethodsThe approach is shown in Scheme 1.1) Synthesis of block copolymer. It will be provided by Dr Jiangtao Xu.2) Self-assembly of amphiphilic block copolymer. The polymer will be dissolved in co-

solvent THF and then dialyze against water.3) Core-crosslinking of the prepared micelles. Appropriate amount of crosslinker

pentaerythritol tetra(3-mercaptopropionate) (PETMP) and photoinitiator Lucirin TPO dissolved

in THF is added into micelle aqueous solution and stirred overnight, followed by dialyzeagainst water again to remove THF.

4) Deprotection of Boc-groups in the core. TFA will be added to the aqueous solution toremove Boc-protecting groups and release primary amine functionalities convertinghydrophobic core to be hydrophilic. The nanogel will be obtained after dialysis again water toremove byproducts. The sizes of this nanogel will be dependent to pH value.

Scheme 1. Designed routes for the preparation of pH-responsive nanogels in this proposal.

Selected References(1) Ryu, J.-H.; Chako, R. T.; Jiwpanich, S.; Bickerton, S.; Babu, R. P.; Thayumanavan, S. J.

Am. Chem. Soc. 2010 , 132 , 17227-17235.(2) Bachelder, E. M.; Beaudette, T. T.; Broaders, K. E.; Dashe, J.; Frechet, J. M. J. J. Am.

Chem. Soc. 2008 , 130 , 1049410495.(3) Oh, J. K.; Siegwart, D. J.; Lee, H.-i.; Sherwood, G.; Peteanu, L.; Hollinger, J. O.; Kataoka,

K.; Matyjaszewski, K. J. Am. Chem. Soc. 2007 , 129 , 59395945.(4) Xia, Y.; Olsen, B. D.; Kornfield, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2009 , 131 ,1852518532.


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(5) Conrad, R. M.; Grubbs, R. H. Angew. Chem., Int. Ed. 2009 , 48 , 83288330.

44. LITERATURE REVIEW OF ULTRA-THIN POLYIMIDE FILM FOR CO 2 GAS SEPARATION

Project Supervisors: Qiang Fu, Greg Qiao




A large component of global warming or anthropogenic climate change is driven by increasingatmospheric carbon dioxide (CO 2) levels caused bythe worlds dependence on fossil fuels. Currently,there is significant effort being directed towardstechnologies that will reduce CO 2 emissions into theatmosphere. In particular, the capture of carbondioxide from large point sources, such as power plants, is recognized as a viable option, since itallows storage opportunities, such as geo-sequestration. The energy efficiency and simplicity of membrane gas separation makes it extremelyattractive for such CO 2 capture. Gas separationmembranes are already used commercially for theproduction of oxygen-enriched air, the separation of CO 2 from natural gas, and the dehydration of other gases. Two characteristics dictate membraneperformance: permeability (that is the flux of aspecific gas through the membrane) and selectivity (the preference of the membrane to allowpassage of one gas species and not another). However, these two criteria usually run counter to each other. Increasing the permeability of a membrane tends to decrease its selectivity (asit tends to increase in permeability for all gases). Likewise, increasing the selectivity of themembrane for a targeted gas over another gas tends to decrease its permeability to the targetgases.

We will focus on a membrane structure with an ultra-thin nanometer scale polyimidefilm. Polyimides combine excellent thermal and chemical stability for gas separationmembranes, and importantly they possess very high CO 2 permeability and selectivity,significantly greater than currently employed commercial membranes. As the flux of a gas isproportional to the thickness of the film, an increase in permeability will be achieved whilst stillmaintaining the selectivity characteristic of the proposed polyimide copolymers.

The student involved in this project will review the literature about the synthesis of ultra-thinpolymeric film. The student will also learn the knowledge in the following fields, such as gasseparation and polymer synthesis.

45. THE INVESTIGATION OF THE FORMATION OF HIGHLY ORDEREDPOROUS POLYMERIC FILMS WITH SELF-ASSEMBLEDHONEYCOMB STRUCTURE VIA BREATH FIGURE TECHNIQUE

Project Supervisors: Zhou Zhang, Dr. Paul Gurr, Prof. Greg Qiao



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To achieve this amazingly highly orderedporous films in LESS than 1min viasimple Breath Figure technique.

Breath figures are arrays of liquid dropsformed during vapor condensation onto asurface [1]-[4]. This technique has manyadvantages over other processes: it issimple, cheap, and the structure is easilycontrolled by changing the castingconditions. These films have been producedfrom a range of polymeric materials, for

example: rod-coil block copolymers, blockcopolymers, amphiphilic copolymers, star polymers, and core crosslinked star (CCS)polymers.

Plenty of applications: catalysis, microreactors, photonics, chromatography, sensors, andbiosensors.

The student on this project will be involved in the optimization of the optimal cast conditionsfor honeycomb films based on a library of PMMA CCS polymers with different number of armsand core size and characterization of honeycomb films. Moreover, the student will work onscaling up honeycomb films by using static casting system. The student will also have theopportunity to synthesize basic core cross-linked star polymers using PMMA via AtomTransfer Radical Polymerization (ATRP). The student will learn analysis techniques including:Scanning Electronic Microscopy (SEM), Microscopy, Gel Permeation Chromatography (GPC),Gas Chromatography Mass Spectrometry (GC-MS), and Nuclear Resonance Spectrometry(NMR)

[1] J. Aitken, Nature 1911, 86, 516.[2] L. Rayleigh, Nature 1912, 90, 436.[3] a) C. M. Knobler, D. Beysens, Europhys.Lett. 1998, 6, 707. b) A. Steyer, P.Guenoun, D. Beysens, C. M. Knobler Phys. Rev. B: Condens. Matter Mater. Phys.1990, 42, 1086.[4] G. Widawski, M. Rawiso, B. Francois,Nature 1994, 369, 387.

.

46. COMPOSITE MEMBRANE: A ROUTE TO FABRICATING MEMBRANEWITH SUPERIOR SEPARATION CHARACTERISTICS

Project Supervisors: Andri Halim, Dr. Paul Gurr, Prof. Greg Qiao


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Abstract/Project Description :

Global warming is arguably the most environmental problem facing the world today. A greatdeal of effort is being undertaken to reduce CO 2 gas emissions through technologicalinnovation. Membranes have been used commercially for gas separation purposes. However membranes specifically designed for CO 2 separation with increased permeability andselectivity are required to reduce capture costs and increase efficiencies. One approach toincrease CO 2 permeability is to introduce functional moeities that increase CO 2 affinity for theresultant polymer. A good example is a system consisting of a hard block from a well-packedand rigid glassy polymer, and a soft block based on flexible rubbery polymers [1]. However,hard and soft blocks do not mix well as these two components have low mixing entropy andtherefore tend to phase separate [2].

This research project will involve the synthesis of composite membranes and investigate theeffect of varying block length and soft polymer content on polymer morphology and gastransport properties. Their separation characteristics will be analyzed using a constantvolume, variable pressure (CVVP) rig. The student will also use various analytical techniquessuch as nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) anddynamic light scattering (DLS) to analyze intermediates, and resulting membranes. Thefabrication of these composite membranes will utilize a co-solvent system, in which onesolvent solubilizes the soft block polymer and the other solubilizes the hard polymer matrix, toevenly distribute the soft domains within the glassy polymer matrix.

Figure 1 shows the domains formed by soft polymer content within the hard polymer matrix

References :1. Powell, C.E. and Qiao, G.G., Polymeric CO 2 /N 2 gas separation membranes for the

capture of carbon dioxide from power plant flue gases . Journal of Membrane Science,2006. 279 (1-2): p. 1-49.

2. Ku, C-K. and Lee, Y-D., Microphase separation in amorphous poly(imide siloxane)segmented copolymers . Polymer, 2007. 739 (1-3): p. 57-74.

47. QUANTITATIVE SYNTHESIS OF DEGRADABLE CORE CROSS-LINKED STAR (CCS) POLYMERS

Project Supervisors: Jing Ming Ren, Prof. Greg Qiao




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Core cross-linked star (CCS) polymers possess a unique 3-D architecture, which consists of across-linked core surrounded by a number of radiating arms. CCS polymers can possess highmolecular weights whilst still maintaining good solubility and low viscosities. 1 Recently anumber of potential applications of CCS polymers have arisen including in drug delivery,

cascade reaction catalysis, membrane formation and paint additives.2

Recent advance in thedesign of CCS polymers via the arm first approach through ring opening polymerization 3 (ROP) of cyclic esters endows the resultant CCS polymers with degradability, and makesthem suitable candidates for in vivo drug delivery devices. 4 However, the previous reportedsynthetic protocols via ROP suffer from low yields, and often require tedious and costlypurification processes to isolate the CCS polymers product due to low arm-to-star conversions. 4,5 Therefore, large scale synthesis of these CCS polymers is infeasible. This interm creates a shortage of materials in research and development of the polyester-baseddegradable CCS polymer and prevents them from potential commercialization.

Scheme 1 . Synthesis of polyester-based degradable CCS polymers via the arm firstapproach through ROP.

The students involve in this project will investigate the synthesis of degradable CCS polymersvia ROP using the robust catalyst system 6 i.e. stannous triflate (Sn(OTf) 2) and to optimize thereaction condition with the aim to achieve quantitative CCS polymer yields.

1. Blencowe, A.; Tan, J. F.; Goh, T. K.; Qiao, G. G. Polymer 2009 , 50 , 5.2. Ren, J. M.; Wiltshire, J. T.; Blencowe, A.; Qiao, G. G. Macromolecules 2011 , in press.3. Albertsson, A.-C.; Varma, I. K. Biomacromolecules 2003 , 4 , 1466.4. Wiltshire, J. T.; Qiao, G. G. Aust. J. Chem . 2007 , 60 , 699.5. Wiltshire, J. T.; Qiao, G. G. Macromolecules 2006 , 39 , 4282.6. Mller, M.; Knge, R.; Hedrick, J. L. J. Polym. Sci. Part A: Polym. Chem. 2000 , 38 , 2067.

48. HISTORY AND PROJECTIONS FOR THE SUPPLY OF MATERIALSProject Supervisors: Dr Shane Usher, Prof Peter Scales


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This project is for Minor RP (CHEN90026) only


The 20 th Century involved exponential increases in the exploitation of natural resources for the global supply of materials. How long can this growth continue and what are likelyprojections for the 21st century? The answers to these questions depend on the size andquality of the available resources combined with the cost of extraction and purification of thematerial and the associated environmental footprint of processing. In this project, eachstudent will investigate a significant material considering resources, production, demand,processes and costs of production through the 20 th Century and develop informed projectionsfor the 21 st Century. Projections will seek to highlight the technical challenges and requiredresearch directions for sustainable production of this material.

Topics include:

A) Water (2 students)With rapidly expanding populations and industries sourcing fresh water from rivers, lakesand storage dams, the availability and quality of these sources are in rapid decline. As aresult, increased processing is required to improve quality, while more collection andstorage capacity is being developed to meet increasing demand. Sources of water andmethods of producing water for domestic, industrial and recreational use include;- Rainfall collection and storage (rivers, lakes, storage dams, rainwater tanks,

stormwater collection etc.)- Treatment and Re-use (traditional wastewater treatment and desalination of domestic

wastewaters & industrial liquors)- Recovery (dewatering processes including sedimentation, centrifugation and filtration

of particulate suspensions such as mineral tailings)- Production Technologies (desalination of seawater, dehumidification, mist capture)

B) Rare Earth Elements (2 students)These transition elements including all of the lanthanoids, plus scandium and yttrium areabundant in the earths crust, but only produced in small quantities because of thecomplex extraction processes required. However, prices have recently skyrocketed dueto use in green technologies such electric motors, wind turbines, hybrid electric vehicles,photovoltaics, computer monitors and the list goes on. World production is currentlydominated by China. The Chinese government is currently reducing export quotas tosupply domestic demand and also to enable restructuring of the industry to improve poor environmental performance attributed to the presence of rogue processing operations.The price hike has spurred interest in developing processes outside China to meet thedemand. A number of orebodies have been identified around the world in Australia, TheUnited States, Canada, Brazil, South Africa and even Greenland and extractionprocesses are being developed to come online this decade.

49. HISTORY AND PROJECTIONS FOR THE SUPPLY OF ENERGY

Project Supervisors: Dr Shane Usher, Prof Peter Scales


This project is for Minor RP (CHEN90026) only



31/50

The 20 th Century involved exponential increases in the exploitation of natural resources toprovide for an energy hungry world. How long can this growth continue and what are likelyprojections for the 21 st Century? The answers to these questions depend on the size andquality of the resources being utilised combined with the cost of production, ease of use andthe associated environmental footprint of producing that energy. In this project, each studentwill investigate a significant aspect of energy production considering resource availability,

energy production, demand, processes, capital costs and ongoing costs of production throughthe 20 th Century and develop informed projections for the 21 st Century. Projections will seekto highlight what the industry will look like at the end of the century, the costs and benefits tosociety, the technical challenges and required research directions to enable sustainability inthis area of energy production.

Topics include:

A) Electricity Production: (4 students)- Coal & Gas Power Stations- Nuclear Power Stations- Hydro-electric, Tidal, Wind and Geothermal Power - Solar Energy (photovoltaics, solar concentrators, solar towers)

B) Energy Storage: (1 student)- Electrical- Thermal- Chemical- Mechanical

50. LAYER-BY-LAYER CAPSULES: TOWARDS VERSATILE POLYMERICCARRIERS

Project Supervisors: Dr Georgina Such and Prof. Frank Caruso




Polymer capsules formed by electrostatic or H-bonds interaction are very promisingarchitectures for applications in the biomedical field, such as for sensors or therapeuticdelivery. In this project, we aim to design new bio-responsive capsules made of polymers thatshows responsiveness around physiological pH enabling tissue-specific behaviour.

The robustness of the system needs to be evaluated, tuned and bio-functionalised (addition of cell-targeting/bio-fouling properties). More specifically, the use of biodegradable cross-linkersto stabilise capsules or to graft surface modifying agents will be investigated. Physico-chemical characterisation of the protein capsules will be carried out with numerousinstruments of microscopy and spectroscopy available in our laboratory, includingfluorescence, various light-based microscopy techniques, Quartz Crystal Microbalance(QCM), Atomic Force (AFM) and Electronic (TEM/SEM) Microscopes, and UV/VIS, Infra-Red(FTIR), Optical Waveguide (OWLS) spectrophotometers. Cell assays may also be conducted.

51. REPLICA PARTICLES FROM NON-COVALENT POLYMERS FORDRUG DELIVERY PURPOSES

Project Supervisors: Dr Henk Dam and Prof. Frank Caruso


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Drug delivery is aimed at the transport of a drug in the body and its controlled release at aspecific site. 1 One of the most promising approaches to deliver a drug is via its encapsulationwithin a nanocarrier; in this way the drug can be shielded from the immune system and it alsooffers the possibility of tailoring the outside of the capsule with receptors for targeting specificsites in the body. Once delivered, the drug must be released from the nanocarrier which canbe accomplished by disassembling the capsule.

The Caruso research group recently started working with non-covalent polymers(polyrotaxanes) 2 as building blocks for the preparation of nanocarriers. These polymers arehighly tunable, degradable, easy to prepare and consist of the non-toxic components a-cyclodextrins 3 and poly(ethylene glycol) 4. Therefore, it is expected that nanocarrierscomposed of them will have tunable and bio-friendly properties as well. In this project thestudent will used mesoporous silica particles 5 as a template for the formation of replica

particles consisting of polyrotaxanes. Click chemistry will be used for their preparation (seeRef. 6 for papers already published by our group in which click chemistry is used). 6 The firstgoal of this project will be the formation of stable replica particles; when successful their degradation and drug-loading capabilities will be studied.

The student will be using Atomic Force Microscopy and Fluorescence Microscopy for the characterization of the formed replica particles, and for the study of their degradationbehavior Flow cytometry will be used.

1 Shi, J.; Votruba, A. R.; Farokhzad, O. C.; Langer, R. Nanoletters 2010, 10 , 3223.2 Harada, A.; Hashidzume, A.; Yamaguchi, H.; Takashim

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