Gold nanoparticles have received significant interest recently due to their utility in biomedical imaging and therapy. Nanoparticles which exhibit intense extinction in the near infrared (NIR) region, where blood and tissue absorb light weakly, are of great interest as contrast agents for biomedical imaging applications. While strong NIR extinction often requires sizes greater than ~20-30 nm, effective clearance from the body to avoid toxic accumulation necessitates sizes below ~6 nm. Moreover, effective clearance depends upon lack of adsorption of serum proteins in the bloodstream onto the particles. Herein, this conflict is addressed by assembling sub-5 nm gold nanoparticles into clusters with controlled size and morphology, in order to provide intense NIR extinction. Furthermore, the surfaces of the primary gold nanoparticles are designed such that the particles avoid the adsorption of any serum proteins. Binary ligand monolayers of anionic citrate and appropriate amounts of either cationic lysine or zwitterionic cysteine are synthesized to completely prevent serum protein adsorption from undiluted fetal bovine serum. A mechanism is proposed whereby the zwitterionic tips which are present on both the lysine and cysteine ligands limit the interactions between serum proteins and the "buried" charges on the nanoparticle surfaces. These primary nanoparticles are subsequently assembled into biodegradable nanoclusters via "quenched assembly", wherein nanoclusters are assembled and subsequently quenched by the adsorption of a biodegradable polymer on the cluster surface. The sizes of completely reversible "quenched equilibrium" nanoclusters formed from gold nanoparticles coated with a mixture of lysine and citrate are tuned from 20 nm to 40 nm, and nanocluster size is semi-quantitatively predicted by a free-energy model. Additional control over nanocluster size and extinction is demonstrated by adding NaCl, which is shown to decrease the polymer adsorption on the clusters and thus decrease polymer bridging interactions. This nanocluster formation platform is extended to nanospheres capped with citrate and the thiolated, zwitterionic cysteine ligand. A general paradigm is presented whereby the sizes and optical properties of biodegradable gold nanoclusters formed from nanospheres which do not adsorb any serum proteins are tuned via control over van der Waals, electrostatic, depletion, and polymer bridging colloidal interactions. / text

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This thesis reports research to investigate the mechanical, thermal and acoustic properties of biodegradable foams in block forms based on wheat starch and developed at Brunel University's School of Engineering & Design, in order to exploit the potential environmental benefits of this renewable and biodegradable class of materials. Two emergent novel technologies have been developed based on a combination of the extrusion foaming of starch in conjunction with the natural adhesive characteristics of moistened starch to produce block foams. Regular Packing & Stacking (RPS), and Compression Bonded Loosefill (CBL), are foam fabrication technologies which have both demonstrated the potential to produce bulk foams based on wheat starch with unique structures and properties - a new class of foam materials in the form of macro-composites reinforced by a network of high-density bonding interfaces. This thesis, as part of a Department of Trade & Industry/Technology Strategy Board funded project, reports an investigation into the following areas to address the scientific and technical issues involved in the further development of the materials and their applications. - The basic properties of the raw materials used in the manufacture of CBL and RPS foams are outlined and the fabrication and preparation of these starch-based foams are described. The limitations of these production techniques are discussed with preliminary work and suggestions made for their enhancement. - Research into the mechanical properties of the CBL and RPS foams includes compression, tensile, creep and dynamic impact tests, whilst the mechanical behaviour of the foams subject to high temperature and high humidity conditions is also reported. - Research into the thermal properties of CBL and high density RPS foams includes testing of the material's thermal conductivity. This aspect of the research also involved a case study detailing the use of RPS in a commercial thermal insulation application. - Research into the acoustic properties of CBL and RPS foams includes tests for sound absorption coefficient and sound transmission loss. - Data obtained from these tests are benchmarked against data pertaining to the mechanical, thermal and acoustic properties of conventional polymer foams in order to provide a basis on which to identify the potential cushioning, thermal insulation and acoustic insulation applications of the starch-based materials. The research has demonstrated the following: - Potential cushioning applications include those limited to the range of static loads within the capabilities of the materials, taking into account the resilience of CBL and RPS which is likely to be compromised by successive impacts. - Tensile forces tend to exploit weaknesses in the macrostructure of these materials. By implication the behaviour of the materials under shear forces would be expected to be similarly compromised. - CBL and RPS exhibited dimensional shrinkage, density increase and significantly reduced mechanical properties under conditions of high temperature and humidity. This suggests that neither CBL nor RPS foams would be suitable for applications in regions where tropical conditions may be encountered unless used in conjunction with other protective materials which would not acutely increase the environmental burden of the products. - Low-density RPS and CBL foams exhibit lower thermal conductivities and hence higher thermal insulation properties compared to many commercially available polymer foams of similar densities. As such these foams have the potential to be used in applications in which a measure of thermal insulation is required. A case study based on an existing commercial application in which the temperature of chilled products must be maintained over a 24 hour period reinforced these findings. - The performance of CBL and RPS starch foams would not provide sufficient functionality to be employed in applications in which dedicated acoustic performance is required, although their sound absorption capabilities may facilitate overall marketability for applications in which a degree of acoustic performance is required if used in conjunction with other materials which demonstrate good acoustic performance. It is anticipated that this work will make significant contributions toward advances in the development of these novel technologies, specifically in terms of establishing an understanding of the properties of the starch-based materials and in identifying potential applications. The research results should thus provide a fundamental element in the basis for the industrial development of these renewable and biodegradable materials.

Synthetic polymers intended for use in biomedical applications require the additional criteria of biocompatibility and sometimes biodegradability included within the design parameters along with mechanical properties, manufacturability, and other properties depending on the specific application in mind. The composition of the monomer and the type of linker within the main chain polymer as well as the chemical reactivity of these chemical entities will define the degradation rates and the conditions under which degradation will or will not occur. However, biocompatibility is usually a built-in characteristic related to the polymer (and monomer) composition and is not easily engineered into an existing polymer by conversion from a non-biocompatible to a biocompatible polymer. Consequently, a majority of the biocompatible polymers used in medical devices or evaluated for biomedical uses are composed of substances that are natural metabolites or known to be biocompatible and nontoxic. Using this design principle, a number of successful examples of biocompatible polymers have been reported such as poly(lactic acid), poly(glycolic acid), and their copolymers, and today, all of these polymers are used in US and EU approved devices. For similar reasons, glycerol-based polymers are attracting increasingly more attention for both fundamental studies and practical applications. Various glycerol polymer architectures from linear to dendritic have been reported for pure polyglycerol ethers and carbonates as well as copolymers with hydroxyacids, for example, to give polyether esters or polycarbonate esters. Herein, the design and synthesis of glycerol-based polycarbonates via copolymerization of epoxide and carbon dioxide is described. The underlying chemistry that affords these glycerol-based polycarbonates will be discussed. Their structural characteristics, their chemical, physical, and rheological properties, and as well as their applications with a focus on drug carrier will also be covered.

Low cost, light weight, recyclability, and high specific strength of natural fibres make them a good replacement for synthetic fibre such as glass in fibre reinforced plastics (FRP). Green and ecofriendly source of these fibres offer less reliance on oil sources. However, their moisture uptake ability, low thermal stability and quality variations are some disadvantages that restrict their use. Biodegradable polymers or biopolymers such as polylactic acid polymers (PLA) are polyesters of lactic acid, and originally made from renewable agricultural raw materials e.g. corn starch. Development of new composite products from the existing renewable resources has a strong potential to bring a new biodegradable composite material suitable for the automotive and packaging industry to replace non-renewable petroleum based plastics. These biodegradable composites could degrade completely in soil or by composting process and do not emit any toxic or harmful components. The purpose of this work is to investigate the effects of increasing natural fibre content, and also adding Biomax modifier on the mechanical properties of poly lactic acid. PLA was reinforced with two different kinds of sustainable natural fibres, cotton, and jute fibres respectively. Biomax strong 120 was used as modifier for PLA/natural fibre composites in order to improve the impact strength and toughness properties. Mixtures of different fibre mass proportions as reinforcement, and PLA as a base resin with modifier additive were compounded in a twin-screw extruder. The extruded materials were processed in a novel compression moulding system to produce test samples. Composites without any modifier content were also produced under the same conditions and used as reference materials. iv Addition of plant fibres to the PLA reduces the composites flexural strength, while improves the elastic modulus significantly, compared to neat PLA. PLA 3001D based composites containing 40% jute fibre exhibited the highest stiffness (5.9 GPa) amongst the composites. Investigation of the impact properties of the composites showed that increasing fibre mass proportion leads to an increase in the impact strength of the composites. The impact strength of the PLA/cotton composite is more promising than PLA/Jute composites. The most significant result is that addition of even 3% Biomax Strong 120 had a positive effect on the impact properties of the specimens. Analysis of the rheological properties of the composites demonstrates that the cotton fibre reinforced PLA has higher complex viscosity than Jute fibre reinforced PLA composites. The DSC results explain that the crystallization temperature increases with increasing the jute fibre content. Furthermore composite‟s microstructure was monitored using Scanning Electron Microscope (SEM). A better adhesion between the cotton fibres and the PLA matrix than jute fibres and PLA was observed in the SEM images. / UOIT

The environmental menace associated with the existing eco-unfriendly conventional plastics prompted the exploration of natural polymers such as starch for the development of biodegradable plastics. These efforts have seen starch used in various ways, one of which is in the processing of thermoplastic starch (TPS). Thermoplastic starch (also known as plasticized starch) is the product of the interaction between starch and a plasticizer in the presence of thermomechanical energy. While starch blends with conventional plastics only yield products that biofragment, thermoplastic starch (TPS) offers a completely biodegradable option. However, it is limited in application due to its weak mechanical strength and poor moisture resistance. To this end, the objective of this study was to determine the effects of incorporating polycaprolactone (PCL) and flax fiber into glycerol-plasticized pea starch. The effects of processing moisture content on the physical properties of glycerol-plasticized pea starch were also evaluated. The physical properties investigated included morphology, tensile properties, moisture absorption, and thermal properties.<p> Accordingly, two thermoplastic pea starch mixtures containing 9.3 and 20% processing moisture contents were prepared while maintaining starch (pea starch) and glycerol in ratio 7:3 by weight (dry basis). Polycaprolactone was then compounded at 0, 10, 20, 30, and 40% by weight in the solid phase with the TPS mixtures to determine the effects of processing moisture content and PCL incorporation on the physical properties of glycerol-plasticized pea starch. This experiment was structured as a 2 x 5 factorial completely randomized design at 5% level of significance. Subsequently, PCL and flax fiber were compounded with the TPS mixture containing 20% processing moisture to determine the effects of PCL (0, 20, and 40% wt) and flax fiber (0, 5, 10, and 15% wt) incorporation on the physical properties of glycerol-plasticized pea starch. This was structured as a 3 x 4 factorial completely randomized design at 5% level of significance. All the samples were compressed at 140°C for 45 min under 25000-kg load. The compression-molded samples were characterized using scanning electron microscopy (SEM), tensile test, moisture absorption test, and differential scanning calorimetry (DSC) techniques.<p> The tensile fracture surfaces showed a moisture-induced fundamental morphological difference between the two TPSs. The TPS prepared at 20% processing moisture content revealed complete starch gelatinization, thus, exhibiting a rather continuous phase whereas the TPS prepared at 9.3% processing moisture content revealed instances of ungelatinized and partly gelatinized pea starch granules. Consequently, the tensile strength, yield strength, Youngs modulus, and elongation at break increased by 208.6, 602.6, 208.5, and 292.0%, respectively at 20% processing moisture content. The incorporation of PCL reduced the degree of starch gelatinization by interfering with moisture migration during compression molding due to its (PCL) hydrophobicity. At both processing moisture levels of 9.3 and 20%, PCL incorporation had significant impacts on the tensile properties of the plasticized pea starch. Flax fiber incorporation also increased the tensile strength, yield strength, and Youngs modulus while concomitantly reducing the elongation at break of the plasticized pea starch. In the TPS/PCL/flax fiber ternary composites, both PCL and flax fiber improved the tensile strength by acting as independent reinforcing materials as no PCL-fiber interfacial bonding was observed. Maximum tensile strength of 11.55 MPa was reached at 10% flax fiber and 40% PCL reinforcement. While the PCL-TPS interfacial interaction was poor, some degree of TPS-flax fiber interfacial bonding was noticed due to their chemical similarity.<p> TPS prepared at 20% moisture showed more moisture affinity than that prepared at 9.3% moisture. The moisture absorption of TPS dropped progressively with the addition of hydrophobic PCL. Fiber incorporation also reduced moisture absorption by the plasticized pea starch. PCL-fiber incorporation also yielded improved moisture resistance vis-à-vis pure TPS. Finally, the TPS processed at 9.3% moisture exhibited higher thermal stability than that processed at 20%. Individual components of the composites retained their respective thermal properties, thus, implying thermodynamic immiscibility.

The environmental menace associated with the existing eco-unfriendly conventional plastics prompted the exploration of natural polymers such as starch for the development of biodegradable plastics. These efforts have seen starch used in various ways, one of which is in the processing of thermoplastic starch (TPS). Thermoplastic starch (also known as plasticized starch) is the product of the interaction between starch and a plasticizer in the presence of thermomechanical energy. While starch blends with conventional plastics only yield products that biofragment, thermoplastic starch (TPS) offers a completely biodegradable option. However, it is limited in application due to its weak mechanical strength and poor moisture resistance. To this end, the objective of this study was to determine the effects of incorporating polycaprolactone (PCL) and flax fiber into glycerol-plasticized pea starch. The effects of processing moisture content on the physical properties of glycerol-plasticized pea starch were also evaluated. The physical properties investigated included morphology, tensile properties, moisture absorption, and thermal properties.<p> Accordingly, two thermoplastic pea starch mixtures containing 9.3 and 20% processing moisture contents were prepared while maintaining starch (pea starch) and glycerol in ratio 7:3 by weight (dry basis). Polycaprolactone was then compounded at 0, 10, 20, 30, and 40% by weight in the solid phase with the TPS mixtures to determine the effects of processing moisture content and PCL incorporation on the physical properties of glycerol-plasticized pea starch. This experiment was structured as a 2 x 5 factorial completely randomized design at 5% level of significance. Subsequently, PCL and flax fiber were compounded with the TPS mixture containing 20% processing moisture to determine the effects of PCL (0, 20, and 40% wt) and flax fiber (0, 5, 10, and 15% wt) incorporation on the physical properties of glycerol-plasticized pea starch. This was structured as a 3 x 4 factorial completely randomized design at 5% level of significance. All the samples were compressed at 140°C for 45 min under 25000-kg load. The compression-molded samples were characterized using scanning electron microscopy (SEM), tensile test, moisture absorption test, and differential scanning calorimetry (DSC) techniques.<p> The tensile fracture surfaces showed a moisture-induced fundamental morphological difference between the two TPSs. The TPS prepared at 20% processing moisture content revealed complete starch gelatinization, thus, exhibiting a rather continuous phase whereas the TPS prepared at 9.3% processing moisture content revealed instances of ungelatinized and partly gelatinized pea starch granules. Consequently, the tensile strength, yield strength, Youngs modulus, and elongation at break increased by 208.6, 602.6, 208.5, and 292.0%, respectively at 20% processing moisture content. The incorporation of PCL reduced the degree of starch gelatinization by interfering with moisture migration during compression molding due to its (PCL) hydrophobicity. At both processing moisture levels of 9.3 and 20%, PCL incorporation had significant impacts on the tensile properties of the plasticized pea starch. Flax fiber incorporation also increased the tensile strength, yield strength, and Youngs modulus while concomitantly reducing the elongation at break of the plasticized pea starch. In the TPS/PCL/flax fiber ternary composites, both PCL and flax fiber improved the tensile strength by acting as independent reinforcing materials as no PCL-fiber interfacial bonding was observed. Maximum tensile strength of 11.55 MPa was reached at 10% flax fiber and 40% PCL reinforcement. While the PCL-TPS interfacial interaction was poor, some degree of TPS-flax fiber interfacial bonding was noticed due to their chemical similarity.<p> TPS prepared at 20% moisture showed more moisture affinity than that prepared at 9.3% moisture. The moisture absorption of TPS dropped progressively with the addition of hydrophobic PCL. Fiber incorporation also reduced moisture absorption by the plasticized pea starch. PCL-fiber incorporation also yielded improved moisture resistance vis-à-vis pure TPS. Finally, the TPS processed at 9.3% moisture exhibited higher thermal stability than that processed at 20%. Individual components of the composites retained their respective thermal properties, thus, implying thermodynamic immiscibility.

D. Tech. Polymer Technology. / Objectives of this work were to develop PLA/PBSA-based hybrid materials with better barrier properties, thermal stability, impact strength and at the same time, have relatively good strength and modulus. The specific objectives were: 1) To optimise PLA/PBSA blend composition for the desired blend properties. This entailed understanding of the role of specific interfacial area obtained from the morphologies of the blends in controlling the properties of the same and relate qualitatively, the phase morphologies to the properties of the PLA/PBSA blends. 2) To study the effect of annealing on the properties of PLA/PBSA blends. 3) To study the effect of organic modifiers on clay surfaces and the interlayer d-spacing of the clay on the morphology and properties of PLA/PBSA-clay composites 4) To study clay dispersion at various loadings and how it affects the crystallization of PLA and PBSA components in the blend.5) To study clay loading effect on the thermal and mechanical properties of the PLA/PBSA-clay composites. 6) To optimise the processing parameters, vis-a-vis: reaction time, coupling agent content, PLA/PBSA composition and processing sequence during in-situ reactive compatibilization of PLA/PBSA blends. 7) To improve the thermal stability and barrier properties through reactive processing of PLA/PBSA, in the presence of organoclays and a coupling agent. 8) To study the rheological properties of the blends prepared, as a function of clay content in the physically and reactively compatibilized PLA/PBSA blends.

In recent years, magnesium and magnesium alloys have received much attention as a new biomaterial in orthopaedic applications due to their biodegradability, biocompatibility, and their mechanical properties that are similar to natural bone tissue. The most common problem associated with magnesium as a biomaterial is low corrosion resistance in physiological solutions. This decreases the mechanical integrity of the implants in the early stages of healing and has a negative impact on the overall biocompatibility. The main goal of this study was to create a multi-layered coating consisting of a silica sol-gel under-layer to protect the substrate from corrosion in body fluids and a mesoporous silica top-layer to enhance the bioactivity of the coated implant material. The results indicate that the deposited multi-layered coating enhances both the bioactivity and the corrosion resistance of the material.

The racemic (±)-2,4-di-tert-butyl-6-(((2-(dimethylamino)cyclohexyl)(methyl) amino)methyl)phenol ((±)-(NNMeOtBu)H), (±)-2,4-di-tert-butyl-6-((2-(dimethylamino) cyclohexylamino)methyl)phenol ((±)-(NNHOtBu)H), and (±)-2-(((2-(dimethylamino) cyclohexyl)(methyl)amino) methyl)phenol ((±)-(NNMeOH)H) are chiral ancillary NNO proligands, which synthesis was adapted from a published procedure. Reaction of (±)-(NNMeOtBu)H ((±)-2), (±)-(NNMeOH)H ((±)-3) and (±)-(NNHOtBu)H ((±)-1) with ZnEt2 successfully yielded the corresponding zinc ethyl complexes (±)-5, (±)-6 and (±)-7 respectively; the enantiomerically pure (R,R)-5 was synthesized from (R,R)-2. NMR spectroscopy experiments and X-ray crystallography allowed identification of two stereoisomers for (±)-5, which were observed in solution and in the solid state. The two stereoisomers, 5-α and 5-β, are in equilibrium in solution, with 5-β being thermodynamically favored. The zinc ethyl complexes were found to be unreactive towards weakly acidic alcohols (methanol, ethanol, isopropanol). However, the zinc chloride complex (±)-(NNMeOtBu)ZnCl ((±)-8) and the zinc phenoxide (NNMeOtBu)ZnOPh ((±)-9 and (R,R)-9) could be isolated and characterized. Comparison of the reactivity of both (±)-5 and the reported L₁ZnEt (L₁ = 2,4-di-tert-butyl-6- {[(2'-dimethylaminoethyl) methylamino]methyl}phenolate) in presence of pyridine led to the proposal of a dissociative mechanism explaining the fundamental difference between the two zinc ethyl species. Polymerization of rac-lactide catalyzed by 9 showed that the complex, in its racemic or enantiomerically pure version, has a slow activity and is not stereoselective.