This thesis focuses on the design, synthesis and development of dynamic multivalent nanostructures such as supramolecular dendrimers, liposomes and gold-functionalized nanostructures. These structures can be used for drug delivery and molecular sensing applications. This thesis is divided into three parts: In part one, a general introduction to self-assembly, dynamic systems, metalligand exchange, nanostructured dendritic scaffolds, liposomes and gold nanostructures is given. In part two, a microwave approach is presented as an efficient method for the regioselective deuteration of bipyridine scaffolds. Dynamic systems based on transition metal-bipyridine coordination complexes were investigated. The compositional self-adaptation and kinetics of these dynamic systems were successfully assessed by ESI-MS. Based on this amphiphilic dendrimers/metallodendrimers were also designed and synthesized via  a convergent strategy. Their ability to self-assemble into supramolecular assemblies and their controlled disassembly was effectively demonstrated. In part three, two types of drug delivery systems based on dynamic multivalent nanostructures of glycodendrimers/metalloglycodendrimers and drugpresenting liposomes were developed. The dynamic self-assembly of these architectures into supramolecular nanostructures with site-specific functionality through interacting carbohydrate or cholesterol moieties was assessed. The host-guest interaction/encapsulation and controlled release with external stimuli were studied using a fluorescent probe, as well as selected drug molecules. The antibacterial property of the drug delivery systems was also evaluated, demonstrating an enhanced bactericidal activity. A new, rapid and simple approach for the functionalization of plasmonic gold nanostructured surfaces was also developed. The optical performance and light-specific sensitivity of the fluorescent probe on the resulting nanostructures were also presented. / <p>QC 20151119</p>

Mechanisms of adsorption of alkaline copper quat (ACQ) components in wood were investigated with emphasis on: copper chemisorption, copper physisorption, and quat adsorption. Various factors were investigated that could affect the adsorption of individual ACQ components in red pine wood. Copper chemisorption in wood was affected by ligand types coordinating with Cu and the stability of the Cu-ligand complexes in solution. For Cu-monoethanolamine (Cu-Mea) system, the prevailing active solvent species at the solution pH, [Cu(Mea)2-H]+ complexes with wood acid sites and loses one Mea molecule through a ligand exchange reaction. The amount of adsorbed Cu was closely related to the cation exchange capacity of wood. An increase in Mea/Cu ratio increased the proportion of the uncharged Cu-Mea complex and resulted in decreased Cu chemisorption in wood. Copper precipitation is also an important Cu fixation mechanisms of Cu-amine treated wood. X-ray diffraction analysis revealed that in vitro precipitated Cu was a mixture of copper carbonates (azurite and malachite) and possibly Cu2O. Higher concentration Cu-amine solutions retarded the Cu precipitation to a lower pH because of higher free amine in the preservative-wood system. The changes in zeta potential of wood in relationship to the quaternary ammonium (alkyldimethylbenzylammonium chloride: ADBAC) adsorption isotherm showed two different adsorption mechanisms for quat in wood: ion exchange reaction at low concentration and additional aggregation form of adsorption by hydrophobic interaction at high concentration. Because of the aggregation effect, when wood was treated with ACQ, high amounts of ADBAC were concentrated near the surface creating a steep gradient with depth. This aggregated ADBAC was easily leached out while the ion exchanged ADBAC had high leaching resistance. Free Mea and Cu of ACQ components appeared to compete with ADBAC for the same bonding sites in wood.

xx, 134 p. : ill. (some col.) / Solar energy is a green alternative to fossil fuels but solar technologies to date have been plagued by low conversion efficiencies and high input costs making solar power inaccessible to much of the developing world. Semiconductor nanoparticles (NPs) may provide a route to efficient, economical solar devices through a phenomenon called multiple exciton generation (MEG). Through MEG, semiconductor NPs use a high-energy input photon to create more than one exciton (electron-hole pair) per photon absorbed, thereby exhibiting large photoconversion efficiencies. While MEG has been studied in many NP systems, and we understand some of the factors that affect MEG, a rigorous analysis of the NP-ligand interface with respect to MEG is missing. This dissertation describes how the NP ligand shell directly affects MEG and subsequent charge carrier recombination. Chapter I describes the motivation for studying MEG with respect to NP surface chemistry. Chapter II provides an in-depth overview of the transient absorption experiment used to measure MEG in the NP samples. Chapter III highlights the effect of oleic acid and sodium 2, 3-dimercaptopropane sulfonate on MEG in PbS NPs. The differences in carrier recombination were accounted for by two differences between these ligands: the coordinating atom and/or the secondary structure of the ligand. Because of these hypotheses, experiments were designed to elucidate the origin of these effects by controlling the NP ligand shell. Chapter IV details a viable synthetic route to thiol and amine-capped PbS NPs using sodium 3-mercaptopropane sulfonate as an intermediate ligand. With the versatile ligand exchange described in Chapter IV, the MEG yield and carrier recombination was investigated for ligands with varying headgroups but the same secondary structure. The correlation of ligand donor atom to MEG is outlined in Chapter V. Finally, Chapter VI discusses the conclusions and future outlook of the research reported in this dissertation. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Dr. Geraldine L. Richmond, Chairperson; Dr. David R. Tyler, Advisor; Dr. Mark C. Lonergan, Member; Dr. Catherine J. Page, Member; Dr. Hailin Wang, Outside Member

Cette thèse porte sur l’étude de nanocristaux semi-conducteurs ternaires, et leur application dansdes cellules solaires hybrides organiques/inorganiques. Les nanocristaux semi-conducteurs absorbentla lumière à des longueurs d’ondes déterminées par leur taille et leur composition, et conduisent lescharges électriques. Ils sont stables en solution, ce qui permet un dépôt de couches minces à bascout. Aujourd’hui les meilleurs rendements en cellules solaires hybrides sont obtenus à partir de nanocristauxbinaires contenant soit du plomb, soit du cadmium. Les nanocristaux ternaires conserventles propriétés particulières des nanocristaux binaires tout en permettant de s’affranchir des élémentstoxiques. Cependant, leur synthèse reste à optimiser pour contrôler de leur structure cristalline et leurcomposition.Nous avons réalisé, par voie chimique, la synthèse de nanocristaux de CuInS2 de taille et de compositioncontrôlées. En suivant in situ la synthèse de ces nanocristaux par diffraction des rayons X sous rayonnementsynchrotron nous avons trouvé que les précurseurs s’organisent avant nucléation sous forme deplans espacés par deux longueurs du ligand utilisé (ici dodécanethiol, DDT). Cela impacte nucléationet croissance des nanocristaux. Les ligands stabilisent les nanocristaux en solution colloïdale, maisleur caractère isolant peut inhiber le transfert et le transport de charges. Le remplacement du ligandd’origine (DDT) par un ligand plus court, l’éthylhexanethiol (EHT), modifie les niveaux d’énergie etpermet d’augmenter la conductivité des films de nanocristaux. Nous avons intégré des nanocristauxde CuInS2 entourés d’EHT dans des cellules hybrides constituées d’un polymère conjugué (P3HT) etd’un fullerène (PCBM). L’efficacité des cellules solaires contenant des nanocristaux entourés d’EHTest significativement améliorée par rapport à celle des cellules de P3HT :PCBM réalisées dans lesmêmes conditions. Le transfert et la mobilité des charges sont étudiés par RPE sous éclairement etphoto-CELIV respectivement. De ces études il ressort que l’amélioration des cellules provient d’unemeilleure génération et dissociation des charges. / This work is devoted to the study of ternary semiconductor nanocrystals, and their application inhybrid organic/inorganic solar cells. Semiconductor nanocrystals absorb light at controlled wavelength(depending on their size and composition) and are able to transport charges. They form a colloidalsolution in organic solvent compatible with low-cost deposition in thin films. Nowadays, the bestefficiency for such hybrid solar cells is obtained with binary nanocrystals containing lead or cadmium.Ternary nanocrystals preserve the opticla and electronic properties of binary nanocrystals withoutrelying on toxic elements, but it is still a challenge to control their composition and structure.In this thesis, CuInS2 nanocrystals of controlled size and composition were syntesized. A study ofnucleation and growth was carried out by following the synthesis in situ with X-ray radiation at thesynchrotron. This has shown that precursors’ organize themselves into plans of atoms separated by twotimes the length of the ligand (here dodecanethiol, DDT). Ligands stabilize the nanocrystals in colloidalsolution, but their insulating character inhibits efficient charge transfer and transport. Ligand exchangewith ethylhexanethiol (EHT) improves the conductivity of thin films and changethe energetic level ofthe nanocrystals.We studied an approach of hybrid solar cell design, consisting in a bulk heterojunctionof two semiconductor organic components (P3HT and PCBM) and CuInS2 nanocrystals. The efficencyof the cells where nanocrystals are added are better than the one with only P3HT:PCBM. The chargetransfer and mobility was studied by the mean of light induced ESR and CELIV respectively. It hasshown that the improvement of the solar cell efficiency is mainly related to an improvement of thecharge generation and dissociation in the ternary blend.

Une étude théorique couplée à une partie expérimentale a été entreprise sur la dynamique de l'échange de ligand sur des surfaces de nanoclusters (GNC) dans le but de montrer qu'il était possible de contrôler les propriétés structurales et optiques de GNC à travers la composition de la couronne de ligand. Nos études de calcul ont été effectuées par la théorie fonctionnelle de la densité en chimie quantique (approche Kohn - Sham). Nous avons analysé les principales caractéristiques UV - Visible des spectres calculés par TD - DFT / niveau de CAMB3LYP pour les clusters métalliques Au13, Au25 et Au28 protégées par des ligands thiolate, chlorure, et phosphine. Nos résultats montrent qu'il est possible de régler l'énergie de la bande d'absorption la plus basse des clusters d'or par une répartition spécifique des ligands qui contrôle de fait la répartition des charges entre la couronne de ligand et le noyau métallique.En parallèle, nous avons synthétisé une série de clusters de composition Au25 (ATP)x (TP) 18 - x avec 4ATP (4 - aminothiophénol) et TP (thiophénol) par synthèse directe et par échange de ligands. Les mesures de spectroscopie de masse ESI - MS montrent que la nucléarité Au25 est préservée pour tous ces différents clusters. En revanche, l'échange de ligands TP par le DDT (1 - dodécanethiol) dans le mélange conduit à la formation de nanoparticules. Les mesures de spectroscopies IR confirment la présence de deux ligands différents sur la surface de l'or et les analyses SAXS montrent que nous avons une bonne corrélation entre la distance entre deux cœurs métalliques et la longueur du ligand de surface. / We performed a joint computational – experimental investigation of the dynamics of ligand exchange on gold nanoclusters (GNC) surface with the aim to understand how to control the structural and optical properties of GNC through the design of their ligand shell. Our computational studies were carried out in the framework of the Kohn – Sham implementation of density functional theory in quantum chemistry. We analyzed the main features of UV – Vis spectra computed at the TD – DFT / CAMB3LYP level for the Au13, Au25, and Au28 metallic cores protected by thiolate, chloride, and phosphine ligands. Our results show that it is possible to tune the energy of the lowest absorption band of gold clusters by ligand shell engineering in order to control the charge redistribution between ligand shell and metallic core.In parallel we synthesized a set of Au25(ATP)x(TP)18 – x clusters with different ATP/TP ratios using an adapted Demessence protocol by combining 4ATP (4 – aminothiophenol) and TP (thiophenol) ligands. ESI – MS measurements evidence that for these mixed ligand shells the Au25 nuclearity is preserved. However, the addition of the DDT (1 – dodecanethiol) ligand in the mixture leads to nanoparticle formation. FT – IR spectroscopy confirms the absorption of two different ligands on the gold surface and SAXS shows that we have a good correlation between the distance between two clusters and the length of the ligand protecting them.Finally, we carried out a comparison of the mode of binding and the structural and optical properties of the fully ligated PH3 and NHC GNC with metallic cores of different nuclearities.

We report a rapid additive-free synthesis of nanocrystals (NCs) of RHO-type ZIF-71 (1) of composition [Zn(dcim)₂] (dcim = 4,5-dichloroimidazolate) in 1-propanol as solvent at room temperature. NC-1 has a size of 30–60 nm and exhibits permanent microporosity with a surface area (SBET = 970 m² g−¹) comparable to that of microcrystalline material. When kept under the mother solution NC-1 undergoes transformation into a novel SOD-type polymorph (2), which in turn converts into known ZIF-72 (3) with lcs topology. It is shown that microcrystals (MCs) of 2 can be favourably synthesised using 1-methylimidazole as a coordination modulator. NC-2 with size <200 nm was prepared using NC-ZIF-8 as a template with SOD topology in a solvent assisted ligand exchange-related process. DFT-assisted Rietveld analysis of powder XRD data revealed that novel polymorph 2 possesses an unusual SOD framework conformation. 2 was further characterised with regard to microporosity (SBET = 597 m² g−¹) and thermal as well as chemical stability. DFT calculations were performed to search for further potentially existing but not-yet synthesised polymorphs in the [Zn(dcim)₂] system.

No description available.

We report on a novel and simple approach to surface ligand design of CdSe-based nanocrystals (NCs) with biocompatible, heterobifunctional polyethylene glycol (PEG) molecules. This method provides high transfer yields of the NCs into aqueous media with preservation of the narrow and symmetric emission bands of the initial organic-capped NCs regardless of their interior crystal structure and surface chemistry. The PEG-functionalized NCs show small sizes, high photoluminescence quantum yields of up to 75%, as well as impressive optical and colloidal stability. This universal approach is applied to different fluorescent nanomaterials (CdSe/CdS, CdSe/CdSCdxZn1–xS, and CdSe/CdS/ZnS), extending the great potential of organic-capped NCs for biological applications.

<p> The development of high-quality screening assays for the identification of biologically active ligands is critical in drug discovery. This thesis is aimed at developing new advances m capillary electrophoresis (CE) for the characterization of the conformational stability and enzymatic activity of protein targets with small molecules. CE provides a convenient platform for unbiased assessment of multiple thermodynamic and kinetic parameters associated with biomolecular interactions involving regulatory protein or isomerase enzymes, where various sample pretreatment steps can be integrated directly in-capillary during analysis. The first two chapters of the thesis (Chapters II, III) outline the development of dynamic ligand exchange-affinity capillary electrophoresis (DLEACE) as a novel strategy for the screening of allosteric ligands based on the differential stability of urea-induced unfolding of various apolholo-protein states of cAMP receptor protein constructs. This work introduced a label-free and multivariate approach for ligand selection based on complementary thermodynamic parameters that allowed for determination of the dissociation constant of protein-ligand interactions over a wide dynamic range (> 10^4, Kd = nM-mM). The subsequent two chapters of the thesis (Chapters IV, V) describe the development of a novel kinetic assay for unbiased characterization of isomerase activity associated with D/L-amino acid metabolism using hydroxyproline epimerase as a model system. Stereoselective resolution of various hydroxyproline isomers was accomplished via off-line or on-line chemical derivatization with dynamic complexation usmg chiral selector(s) in order to screen potential inhibitors for putative epimerase and racemase activity. The integration of both thermodynamic and kinetic strategies for differentiation of mutant from wild-type enzymes was important for revealing the function of a catalytic acid/base cysteine pair in the epimerase active site. Overall, this thesis outlines an integrative framework based on CE for high-quality screening, which is relevant in reducing the high attrition rate of lead candidates in drug development. </p> / Thesis / Doctor of Philosophy (PhD)

The work presented in the thesis is focused on the synthesis of diverse colloidal semiconductor NCs in organic media, their surface design with tiny inorganic and hybrid capping species in solution phase, and subsequent assembling of these NC building units into two-dimensional close-packed thin-films and three-dimensional non-ordered porous superstructures.