Existing commercially available microcarriers are very efficient at encouraging cell attachment and proliferation. However, recovery of the cells is problematic as it requires the use of proteolytic enzymes which are damaging to critical cell adhesion proteins. From this perspective, temperature responsive polymers appear to be a valid option. The current innovative study is to produce and engineer microcarriers in terms of particle size, surface coating and properties, as well as thermo-responsiveness for cell release. All these benefits are based on particle production by membrane emulsification to provide a highly controlled particle size. The polymer of choice is poly N-isopropylacrylamide (pNIPAM) because of the sharpness of its phase transition, biocompatibility and transition temperature close to the physiological value. These characteristics make pNIPAM a very attractive material for Tissue Engineering applications. Cells are cultured on the hydrophobic surface at 37??C and can be readily detached without using proteolytic enzymes from the surface by lowering the temperature to room temperature. The Dispersion Cell (MicroPore Technologies Ltd, UK) was successfully employed for the production of W/O emulsions. The generated monomer droplets were additionally solidified by applying a free radical polymerisation to manufacture solid pNIPAM microspheres. Additionally, calcium alginate particles were also generated and further functionalised with amine terminated pNIPAM to form temperature responsive core-shell particles by simply taking advantage of the electrostatic interactions between the carboxyl groups of the alginate and amino groups of the modified pNIPAM. Controlled particle production was achieved by varying process parameters and changing the recipe formulation (e.g. monomer concentration, surfactant concentration, pore size and inter-pore spacing, injection rate, shear stress applied at the membrane s surface). The manufactured particles were then analysed in terms of particle size and size distribution, chemical composition, surface analysis, shrinkage ratio and thermo-responsiveness and further sterilised and used for cell culture and release experiments. Swiss Albino 3T3 fibroblastic cells (ATCC, USA) were utilised to show proof-of-concept for this technology. Cell attachment and proliferation were assessed and successfully demonstrated qualitatively and quantitatively. pNIPAM solid particles, uncoated and with different protein coatings were shown to allow a limited degree of cell attachment and proliferation compared to a commercially available microcarrier. On a different approach, uncoated core-shell structures demonstrated improved capabilities for cell attachment and proliferation, similar to commercially available microcarriers. Having in mind the potential of temperature responsive polymers and the aim of this innovative study, cell detachment from the generated microcarriers was evaluated and compared to a commercially available temperature responsive surface. Necessary time for detachment was recorded and detached cells were recovered and reseeded onto tissue culture plastic surfaces in order to evaluate the replating and reattachment capabilities of the recovered cells. Successful cell detachment was achieved when using the core-shell structures as cell microcarriers, but the necessary time of detachment was of an order higher than that for the commercial temperature responsive surface.

Thesis (PhD)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: The synthesis of structured nanoparticles, in particular core/shells, IS of great technological and economical importance to modem materials science. One of the advantages of structured particles is that they can be synthesized with either a solid core (albeit soft or hard) or a liquid core (of varying viscosity). This adds to the versatility of structured particles and their relevance to a majority of industrial and commercial endapplications. The synthesis of core/shell particles with liquid cores was investigated for the effective impact modification of glassy amorphous polymers. Polybutyl acrylate was chosen as the shell due to its rubbery nature. Hexadecane functioned as the core oil and facilitated osmotic stability by being a suitable hydrophobe for the miniemulsion synthesis. Polymer synthesis was preceded by the prediction of particle morphology by using thermodynamic prediction models. Core/shell particles with liquid cores were synthesized via miniemulsion polymerization. This resulted in the direct introduction of core-oil and monomer into the miniemulsion droplets. Polymerization was achieved in situ, resulting in the formation of particles with the desired morphology. For additional strength, stability and matrix mixing capabilities, methyl methacrylate (MMA) was grafted onto the initial core/shell particles. The obtained morphology was in contradiction with the predicted morphology, thus pointing to strong kinetic influences during the polymerization process. These influences could be attributed to surface anchoring of polymer chains due to the initiator (KPS) used, the establishment of the polymerization locus as well as the increase in viscosity at the polymerization locus. To test these influences a surface-inactive initiating species (AIBN) and an interfacial redox initiating species (cumyl hydroperoxide/Fe/") were used. Use of the former resulted in the formation of solid polymer particles due to homogeneous polymerization throughout the droplet, thus leading to an inverse core/shell morphology as a result of thermodynamic considerations. The redox initiator promoted kinetic influences as a result of fast polymerization kinetics at the droplet/water interface. This, as well as the increase in viscosity, facilitated the production of core/shell particles. To obtain core/shell particles with the desired size, the influence of surfactant concentration was investigated. Capillary hydrodynamic fractionation (CHDF) was used to determine the particle size of the initial core/shell particles as well as the size of the MMA-grafted core/shell particles. The area stabilized per surfactant molecule was calculated stoichiometrically and compared to "classical" miniemulsion results, i.e. data generated from the synthesis of polymeric latexes in the presence of a hydrophobe, but at a much lower hydrophobe:monomer ratio than was used here. The influence of methanol as well as the possibility of scaling-up the process was also investigated. The study was further expanded to the investigation of living miniemulsion polymerization techniques to control the molecular architecture of synthesized core/shell latexes. The influence of different RAFT agents, initiators and monomers were investigated on the core/shell formation properties of the investigated systems. The combined effects of establishing the polymerization locus as well as increased polymerization kinetics, thus increasing the viscosity at the polymerization locus, lead to the successful formation of liquid- filled core/shell particles. To conclude, the ability of the synthesized core/shell particles to induce impact modification in glassy amorphous polymers was investigated. Results showed that incorporation of these particles could effectively modify the intrinsic properties of the investigated polymers, resulting in a brittle-to-ductile transition. Improved impact results of the investigated glassy matrix were obtained. Keywords: core/shell, liquid-filled, RAFT, miniemulsion, impact modification / AFRIKAANSE OPSOMMING: Die sintese van gestruktureerde nano-partikels, meer spesifiek kern/skil partikels, is van onskatbare tegnologiese en ekonomiese belang vir moderne materiaalkunde. Een van die voordele van hierdie tipe partikels is dat sintese kan geskied met 'n soliede kern (hard of sag) of vloeistofkern (met wisselende viskositeit). Dit dra by tot die veelsydigheid van gestruktureerde partikels en dus tot grootskaalse aanwending in industriële en kommersiële toepassings. Die sintese van kern/skiI partikels met vloeistofkerne is ondersoek met die oog op effektiewe slagsterkte modifikasie van glasagtige amorfe polimere. Polibutielakrilaat is gekies as skil-polimeer op grond van sy rubberige voorkoms. Heksadekaan moes funksioneer as die kern-olie, maar het ook bykomende osmotiese stabiliteit verleen tydens die miniemulsie-polimerisasie proses. Dit is as gevolg van die gepaste hidrofobiese eienskappe van heksadekaan. Polimeer sintese is voorafgegaan deur die voorspelling van partikel morfologie met behulp van termodinamies gebaseerde voorspellingsmodelle. Kern/skil partikels is gesintetiseer deur middel van 'n miniemulsie-polimerisasie reaksie wat die direkte inkorporering van kern-olie en monomeer in die miniemulsiedruppel teweeg bring. Polimerisasie vind in situ (lat. vir in die oorspronklike plek, m.a.w. binne-in die druppel) plaas en lei tot die vorming van partikels met die gewenste morfologie. Metielmetakrilaat is ge-ent op die oorspronklike kern/skil partikels om addisionele sterkte, stabiliteit en vermenging met die matriks polimeer te bewerkstellig. Die verkrygde morfologie is teenstrydig met die voorspelde morfologie, wat dus die teenwoordigheid van sterk kinetiese invloede aandui. Hierdie invloede kan toegeskryf word aan die oppervlak-aktiewe afsetter (KPS, kaliumpersulfaat) wat gebruik is, die daarstelling van die polimerisasie lokus asook die toename in viskositeit by die lokus van polimerisasie. Om hierdie invloede te toets is 'n oppervlak-onaktiewe afsetter (AIBN, asobisisobutironitriel) en intervlak redoks-afsetter (kumielhidroperoksied/Pe'") gebruik. Gebruik van eersgenoemde het die vorming van soliede partikels teweeg gebring. Dit is as gevolg van homogene polimerisasie in die druppel en dus die ontstaan van omgekeerde kern/skiI partikels weens termodinamiese oorwegings. Die redoks-afsetter het egter die kinetiese oorwegings bevoordeel as gevolg van vinnige polimerisasiekinetika by die druppel/water intervlak. Dit, tesame met die toename in viskositeit, maak die produksie van kern/skil partikels moontlik. Vir die verkryging van kern/skiI partikels met die gewenste partikelgrootte is die invloed van die seep konsentrasie ondersoek. CHDF (eng. capillary hydrodynamic fractionation) is gebruik om die partikelgrootte van die oorspronklike kern/skiI partikels, sowel as dié ge-ent met metielmetakrilaat, te bepaal. Die area gestabiliseer per seepmolekule is bereken d.m.v. stoichiometrie en vergelyk met "klassieke" miniemuisie data, d.i. data verkry deur die sintese van latekse in die teenwoordigheid van 'n hidrofoob, maar teen 'n baie laer hidrofoob:monomeer-verhouding as wat hier gebruik is. Die invloed van metanol, asook die moontlikheid om die reaksie op te skaal, is ondersoek. Die studie is verder uitgebrei om die invloed van lewende miniemulsie-polimerisasie tegnieke in te sluit, om sodoende beheer uit te oefen oor die molekulêre argitektuur van die gesintetiseerde latekse. Die invloed van verskeie RAFT (eng. reversible additionfragmentation chain transfer) agente, afsetters en monomere op die kern/skiI vormingsmoontlikhede van die bestudeerde stelsels, is ondersoek. Die gesamentlike effek van die daarstelling van die polimerisasie lokus en dus die verhoging van die viskositeit by die lokus, lei tot die suksesvolle vorming van vloeistof-gevulde kern/skiI partikels. Laastens is die invloed van die gesintetiseerde kern/skil partikels op die slagsterkte van glasagtige amorfe polimere ondersoek. Resultate dui daarop dat die insluiting van hierdie partikels kan lei tot die effektiewe verandering van die intrinsieke eienskappe van die bestudeerde polimere, en dus 'n oorgang van bros na rekbaar kan veroorsaak. 'n Verbetering in die slagsterkte resultate van die bestudeerde glasagtigte matriks is ook waargeneem.

Cette thèse est divisée en trois parties. La première traite la synthèse de la polyaniline (PANI), un polymère conducteur de trou, utilisé dans plusieurs applications. En variant les quantités du monomère et de l'oxydant tout en fixant leur rapport molaire à 1:1,25, et en ajoutant de l'oxyde de magnésium, des aiguilles et des nouvelles structures semblables aux échinides sont formées. Le mécanisme de formation des structures unidimensionnelles est expliqué à l'aide de la théorie des multicouches. La deuxième partie est consacrée à la fabrication des monocouches photovoltaïques à faible coût en se basant sur le principe de fonctionnement des cellules à pigment photosensible (en anglais DSSC, Dye-Sensitized Solar Cell). En 1991, Grätzel a réintroduit l'effet photo-électrochimique en développant la première DSSC, une des cellules solaire troisième génération, formée d'un film de TiO2 (photo-anode) pigmenté à l'aide d'un colorant et d'un électrolyte qui sert à régénérer le pigment oxydé. Malgré leur faible coût, les DSSCs font face à de nombreux problèmes tels que le coût élevé du pigment, la fuite de l'électrolyte, la sublimation du couple I-/I3- à travers I2, etc. Afin de résoudre ces problèmes, des monocouches photovoltaïques ont été développées. Des composites formés de PANI et TiO2 sont la base de ces dispositifs nouvelle génération. La polymérisation in-situ de l'aniline en présence des nanoparticules de TiO2 conduit à une forte interaction entre la PANI et les particules de TiO2 où une structure " core (TiO2)/shell (PANI) " existe dans le composite. Dans le dispositif photovoltaïque basé sur le composite PANI-TiO2, PANI est considérée comme pigment à la photo-anode et comme poly-électrolyte plus profondément dans le composite. En plus, des textiles fabriqués utilisant ces composites photo-génèrent une tension de 0,6 V et un courant de 1 A/m2 lorsque l'éthanol est injecté dans le dispositif. Une nouvelle architecture a été développée qui sert à améliorer la performance de la cellule et en même temps stocker l'énergie pour des utilisations ultérieures. La dernière partie est consacrée à la fabrication des DSSCs basées sur les pigments naturels. L'anthocyane, un pigment naturel halochromique responsable de la couleur rouge dans les plantes, a été extrait du chou rouge et utilisé pour pigmenter les films de TiO2. Cette propriété se traduit par la fabrication des DSSCs de différentes couleurs et comportement photovoltaïque. Avec un pH égal à 0, une Vco et une Jcc de 520 mV et 185 μA/cm2 sont respectivement obtenues prouvant la possibilité d'utiliser le chou rouge comme source de pigment à très faible coût des DSSCs.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Thesis presented in partial fulfilment of the requirements for the degree of Master of Science (polymer science) at the University of Stellenbosch / Embargo date 2010-03-31 plt 2010 / ENGLISH ABSTRACT: A novel method, herein referred to as ‘solvent facilitated coaxial electrospinning’, was used to produce reversibly thermochromic core-shell fibres with poly(methyl methacrylate) (PMMA) as shell and a thermochromic dye composite as core. The thermochromic dye composite consisted of combinations of 1-dodecanol, bisphenol A (BPA) and crystal violet lactone (CVL). In the ‘solvent facilitated coaxial electrospinning’ method, the thermochromic dye composite was dissolved in a suitable ‘facilitating solvent’ prior to spinning, instead of being spun into the fibres from the melt as previously described in literature. A low interfacial tension between the core and shell liquids, which is beneficial to effective core entrainment, was achieved by using a correctly chosen core ‘facilitating solvent’. The PMMA was dissolved to form the shell spinning liquid and by selecting the correct core and shell solvents, spinneret blockage and precipitation due to core and shell liquid interactions were eliminated. High molar mass PMMA was used to produce fibres with diameters in the range of 3–10 μm (larger than typical electrospun fibres) in order to minimize light scattering and subsequently allow visual observation of the thermochromic transitions, unlike the fibres that were produced in literature. The fibres were analyzed using SEM, TEM, TGA and DSC to investigate fibre morphology, dye composite thermal transition and fibre composition. Physical and chemical interactions between the thermochromic dye composite and the PMMA shell were identified as possible causes of differences between the thermochromic transition temperatures of the core-shell fibres and the bulk dyes, as well as of the instability of the colour developed state of certain thermochromic fibres. The spatial confinement of the dye composite inside the fibres and the extensive volume reduction (from bulk dye to small volume inside the fibres) affected the thermochromic behaviour of the thermochromic composite once it was entrained in the fibres. An excess BPA was used in the dye composition to allow the production of reversibly thermochromic fibres with a stable colour developed state. / AFRIKAANSE OPSOMMING: A nuwe metode, hierin beskryf as ‘oplosmiddel gefasiliteerde koaksiale elektrospinnery’, is gebruik om omkeerbare termochromiese kern-skil vesels met polie(metiel metakrilaat) (PMMA) as skil en ‘n saamgestelde termochromiese kleurmiddel as kern te vervaardig. Die saamgestelde termochromiese kleurmiddel het bestaan uit kombinasies van 1-dodekanol, bisfenol A (BPA) en kristal violet laktoon (CVL). Vir die ‘oplosmiddel gefasiliteerde koaksiale elektrospin’-metode, is die saamgestelde termochromiese kleurmiddel opgelos in ‘n gepaste ‘fasiliterende oplosmiddel’ voordat dit geëlektrospin is, eerder as om dit te smelt om dit sodoende in vesels te kan inspin soos beskryf in die literatuur. ‘n Lae raakvlakspanning tussen die kern- en skilspinvloeistowwe, wat voordelig is vir doeltreffende kern insluiting, is bereik deur gebruik te maak van sorgvuldig verkose ‘fasiliterende oplosmiddels’ vir die kern. Die PMMA is opgelos om die skilspinoplossing te vorm en, deur die keuse van die korrekte kern- en skiloplosmiddels, kon spinneret blokkasie en neerslag van die polimeer as gevolg van kern- en skilvloeistofinteraksies elimineer word. Hoë molekulêre massa PMMA is gebruik om vesels te vervaardig met deursnee in die omtrek van 3–10 μm (groter as tipiese elektrogespinde vesels) om sodoende lig-verstrooiing te verminder en daardeur visuele waarneming van die termochromiese oorgange moontlik te maak, in teenstelling met die vesels wat in die literatuur gevorm is. Die vesels is ge-analiseer met SEM, TEM, TGA en DSC om veselmorfologie, termiese omskakelinge van saamgestelde kleurmiddels en veselsamestelling te bestudeer. Fisiese en chemiese interaksies tussen die saamgestelde termochromiese kleurmiddel kern en die PMMA skil is geïdentifiseer as moontlike oorsake van verskille tussen die termochromiese oorgangstemperature van die kern-skil vesels en die kleurmiddels in grootmaat, asook van die onstabiliteit van die gekleurde toestand van sommige termochromiese vesels. Die ruimtelike inperking van die saamgestelde kleurmiddel binne in die vesels asook die beduidende volume verkleining (van grootmaat kleurmiddel tot klein volume binne in die vesels) het die termochromiese gedrag van die saamgestelde kleurmiddel binne die vesels beïnvloed. ‘n Oormaat BPA is in die saamgestelde termochromiese kleurmiddel gebruik om die produksie van omkeerbaar termochromiese vesels met ‘n stabiele gekleurde toestand toe te laat.

© Springer Science+Business Media Dordrecht 2016 / Reducing AgNO3 by glucose at basic pH coated the surface of silica spheres with a high density of hemispherical silver nanoparticles (average diameter 3.2±1 nm). A much lower silver concentration than is standard favored heterogeneous nucleation of silver on the silica surface at the expense of homogeneous nucleation in solution. The slow growth rate of the nuclei promoted the formation of discrete silver particles rather than a continuous shell. Based on scanning electron microscopy and transmission electron microscopy, the surface coverage of silver seed particles was as high as 25% at 10 °C without prior functionalization of the silica. The particles were composed of metallic silver based on x-ray photoelectron spectroscopy. There was a sharp increase in the silver surface coverage and decrease in the particle size when the temperature was raised from 5 °C to 10 °C and the amount of silica was decreased from 0.2 to 0.025 V/V. The size was controlled by the diffusion barrier through the ion shell surrounding the silica spheres and by maintaining reaction conditions where the particles on the surface compete for silver.

Ce travail développe une nouvelle approche de la catalyse biphasique aqueuse qui repose sur la construction de micelles réticulées à partir de polymères de type cœur-coquille. Le catalyseur (Rh) doit être incorporé sur les ligands du polymère dans la couche interne lipophile et la coquille hydrophile externe permettra de le séparer aisément du milieu réactionnel organique (oct-1-ène, nonanal, pour la réaction modèle d'hydroformylation choisie). La première partie du projet a donc consisté à préparer ces polymères à couche périphérique hydrophile assurant leur confinement en phase aqueuse et une partie interne lipophile contenant les sites actifs pour la réaction. Deux stratégies ont été explorées avec succès pour aboutir à ces structures en s'appuyant sur la polymérisation radicalaire par transfert d'atome. La première, dite « convergente », met en jeu la réticulation des copolymères linéaires fonctionnalisés préformés en présence de monomères divinyliques. La préparation des macroamorceurs linéaires fonctionnalisés a permis d'effectuer en parallèle une optimisation des conditions d'introduction d'un monomère fonctionnalisé par une phosphine qui servira par la suite de ligand pour le métal. Cette voie d'assemblage s'est avérée inefficace car un résidu des chaines linéaires non-incorporées accompagnait les produit de réticulation. Sa contrepartie, l'approche dite « divergente », a été abordée à partir de l'extension de chaines provenant d'un cœur réticulé. Les structures cœur-coquille fonctionnalisées ainsi obtenues ont des distributions de taille très homogènes. Dans le but d'évaluer leur potentiel catalytique, les copolymères fonctionnalisés, linéaires et réticulés, ont été utilisés comme ligands pour l'hydroformylation de l'oct-1-ène catalysée par le rhodium en phase homogène. Le confinement du complexe au sein des polymères a entraîné une amélioration de la régiosélectivité ainsi qu'une diminution de l'activité avec les deux types de polymères utilisés par rapport au ligand PPh3. Grace au caractère vivant de la polymérisation qui permet l'association des étapes synthétiques en séquence, il a été possible d'introduire des blocs de type PtB(M)A comme précurseurs pour l'obtention d'un bloc externe hydrophile de type P(M)AA. Les résultats préliminaires d'hydrosolubilisation des nanoréacteurs sont aussi présentés. / The current project is focused on the development of a new tool for the rhodium-catalyzed aqueous biphasic hydroformylation based on the construction of crosslinked micelles from core-shell polymers. The first goal of the project was the preparation of polymers having an hydrophilic shell that insures solubility and total confinement in the aqueous phase and a lipophilic inner shell acting as a support of active catalytic sites. Two strategies were explored to achieve such structures based on atom transfer radical polymerization. The first one, known as “arm-first”, involved the crosslinking of preformed functionalized linear copolymers in the presence of divinyl monomers. The preparation of functionalized linear macroinitiators allowed at the same time the optimization of the conditions for the introduction of a functionalized phosphine monomer that will ultimately serve as a ligand for the metal. This assembly pathway was ineffective because some residual dead chains accompanied the crosslinking product of the reaction. Its counterpart, the approach called "core-first", is based on the extension of chains from a crosslinked core. From this second approach, functionalized core-shell structures with very uniform size distributions were obtained. Both linear and cross-linked copolymers were used as ligands for the rhodium catalyzed hydroformylation of 1-octene under homogeneous conditions in order to test their catalytic performance. Because of the confinement of the ligand inside the polymer coils, a selectivity improvement as well as the slowdown of the reaction rate was observed relative to PPh3 ligand. The living character of the synthesis technique allowed the introduction of external PtB(M)A blocks: precursors to obtain a hydrophilic outer shell P(M)AA. Preliminary hydrosolubilization results of the nanoreactors will be presented in the last part of the manuscript.

Master of Science / Department of Chemistry / Emily McLaurin / Cu-doped ZnSe/CdSe core/shell nanocrystals were synthesized using the growth doping method. Upon shell growth, the nanocrystals exhibit dual emission. The green luminescence peak is assigned as band edge emission and the broad, lower energy red peak is due to Cu dopant. Although, the oxidation state of Cu in the nanocrystals is debated, the emission is explained as recombination of a hole related to Cu²⁺ with an electron from the conduction band. The emission changed in the presence of dodecanethiol. Generally, the band edge emission intensity decreases and the Cu emission intensity increases. One explanation is the thiol acts as a hole trap, preventing hole transfer to the conduction band. Samples were obtained with varying amounts of Cd²⁺. In the presence of larger amounts of Cd²⁺, the nanocrystals had “thicker shells”, and both the band edge and Cu emission were less sensitive to thiol. The sensitivity likely decreased because the shelled, larger nanocrystals have fewer surface defects resulting in more available electrons.

Doctor of Philosophy / Department of Chemistry / Jun Li / Solar energy as a sustainable resource is a promising alternative to fossil fuels to solve the tremendous global energy crisis. Development of three generation of solar cells has promoted the best sunlight to electricity conversion efficiency above 40%. However, the most efficient solar cells rely on expensive nonsustainable raw materials in device fabrication. There is a trend to develop cost-effective biophotovoltaics that combines natural photosynthetic systems into artificial energy conversion devices such as dye sensitized solar cells (DSSCs). In this research, a model system employs natural extract light-harvesting complex II (LHCII) as a light-absorbing sensitizer to interface with semiconductive TiO₂ and plasmonic nanoparticles in DSSCs. The goal of this research is to understand the fundamental photon capture, energy transfer and charge separation processes of photosynthetic pigment-protein complexes along with improving biophotovoltaic performance based on this model system through tailoring engineering of TiO₂ nanostructures, attaching of the complexes, and incorporating plasmonic enhancement. The first study reports a novel approach to linking the spectroscopic properties of nanostructured LHCII with the photovoltaic performance of LHCII-sensitized solar cells (LSSCs). The aggregation allowed reorganization between individual trimers which dramatically increased the photocurrent, correlating well with the formation of charge-transfer (CT) states observed by absorption and fluorescence spectroscopy. The assembled solar cells demonstrated remarkable stability in both aqueous buffer and acetonitrile electrolytes over 30 days after LHCII being electrostatically immobilized on amine-functionalized TiO₂ surface. The motivation of the second study is to get insights into the plasmonic effects on the nature of energy/charge transfer processes at the interface of photosynthetic protein complexes and artificial photovoltaic materials. Three types of core-shell (metal@TiO₂) plasmonic nanoparticles (PNPs) were conjugated with LHCII trimers to form hybrid systems and incorporated into a DSSC platform built on a unique open three-dimensional (3D) photoanode consisting of TiO₂ nanotrees. Enhanced photon harvesting capability, more efficient energy transfer and charge separation at the LHCII/TiO₂ interface were confirmed in the LHCII-PNP hybrids, as revealed by spectroscopic and photovoltaic measurements, demonstrating that interfacing photosynthesis systems with specific artificial materials is a promising approach for high-performance biosolar cells. Furthermore, the final study reveals the mechanism of hot electron injection by employing a mesoporous core-shell (Au@TiO₂) network as a bridge material on a micro-gap electrode to conduct electricity under illumination and comparing the photoconductance to the photovolatic properties of the same material as photoanodes in DSSCs. Based on the correlation of the enhancements in photoconductance and photovoltaics, the contribution of hot electrons was deconvoluted from the plasmonic near-field effects.

The objective of this Ph.D. study is to explore an important and fertile research topic on the methods for synthesis of nanomaterials by homogeneous nonaqueous solution phase reaction. Research in this work focuses on synthesizing several kinds of nanomaterials in different environments and structure, including spherical nanoparticles, nanowires and core-shell structure composites We first synthesized metallic nanomaterials in this system, such as ~10 nm Fe nanoparticles, ~6 nm Au nanoparticles, and ~100 nm Bi nanoparticles, this system are the preparation for the following studies. Secondly, we synthesized bimetallic nanomaterials in this system, such as Fe50Co50 alloy and Bi doped with Mn. For FeCo alloy, after annealing at 500 °C, a pure phase of Fe50Co50 was obtained. And we first synthesized the nanowires of bismuth doped with manganese. By studying intermediates at different temperatures during the growth process of nanowires, the evolution of the crystallization of metallic products and the mechanism of the formation of the nanowires are investigated. Thirdly, we synthesized core-shell structure nanocomposites, including either gold as the shell or polymer as the shell. Au-coated magnetic Fe nanoparticles have been successfully synthesized by partial replacement reaction in a polar aprotic solvent with about 11 nm core of Fe and about 2.5 nm shell of Au. HRTEM images show clear core-shell structure with different crystal lattices from Fe and Au. SQUID magnetometry reveals that particle magnetic properties are not significantly affected by the overlayer of a moderately thick Au shell. The Aucoated particles exhibit a surface plasmon resonance peak that red-shifts from 520 to 680 nm. And Poly (Vinyl Pyrolidone) (PVP) coated iron nanoparticles also have been successfully synthesized in a polar aprotic solvent, which shows the welldefined core-shell structures. In this approach, Poly (Vinyl Pyrolidone) (PVP) was employed as the coating polymer directly coated on metallic core (iron) nanoparticles. In this work, a combination of TEM (transmission electron microscopy), EDS (Energy disperse X-ray spectroscopy), XRD (X-ray powder diffractometry), ICP (inductively-coupled plasma spectrometer), TGA (Thermogravimetric analysis), UV-visible absorption spectroscopy, IR (infrared) spectroscopy and SQUID magnetometry (Superconducting Quantum Interference Device) were employed to characterize the morphology, structure, composition and magnetic properties of the products. In summary, this Ph.D. study successfully and systematically synthesized several kinds of nanocomposites in a system. The synthetic procedure is simple, economic and easily scaled-up for further applications. And many techniques were employed to characterize the products.

La manipulation des propriétés physiques des nanostructures, telles que leur forme ou leur composition, suscite de plus en plus l’intérêt des recherches à cause des propriétés exceptionnelles des matériaux à cette échelle. L’ingénierie des contraintes a pour objet d’utiliser la déformation pour contrôler les propriétés. Cela est particulièrement intéressant dans les nano-objets car ils peuvent supporter des déformations élastiques élevées. Dans ce travail, nous étudions la déformation et l’influence de la température dans des nanofils uniques de type coeur/coquille. Ceci est possible en utilisant la diffraction cohérente des rayons X (CDI) en condition de Bragg, une technique d’imagerie qui remplace les lentilles optiques par des algorithmes d’inversion capables de reconstruire l’amplitude (densité électronique) et la phase (projection du champ de déplacement atomique) de l’échantillon à partir des clichés de diffraction. Cette méthode a également été appliquée à des particules facettées de platine qui ont des propriétés catalytiques exceptionnelles. Des expériences CDI in situ ont permis d’étudier l’évolution du champ de déformation dans les particules pendant des réactions chimiques et donc de progresser vers le découplage entre leur déformation intrinsèque et leur activité chimique. / Manipulating the physical and chemical properties of nanostructures by changing their characteristics (such as shape, strain or composition) is a vivid field of research spurred by the numerous applications that may take advantage of the unique properties that materials offer at this scale.Strain engineering aims to tune the strain in order to control the properties of materials. This is particularly interesting in nano-objects because they can sustain much higher elastic strains before the occurrence of defects. In this work, we study the strain and the influence of temperature in single core/shell nanowires. This is possible thanks to X-ray coherent diffraction (CDI) in Bragg condition, an imaging technique that replaces the optical lenses by inversion algorithms that are able to reconstruct the amplitude (electronic density) and the phase (projection of the atomic displacement field) of the sample from the experimental diffraction patterns. In addition to nanowires, the method is applied to metallic particles of platinum with exceptional catalyticproperties. In situ CDI experiments allowed to study the strain evolution within particles during chemical reactions, thereby moving forward in the understanding of important relationships such as the intrinsic strain and chemical activity of the nanoparticles.