M.Sc. (Chemistry) / In this dissertation the synthesis, characterization and the application of Ag, Au and Cu dendrimer encapsulated nanoparticles (DENs) in catalysis are described. Ag, Au and Cu-DENs were synthesized using G4-G6 PAMAM-OH and G4-G6 PAMAM-NH2 dendrimers as templates as well as stabilizers. NaBH4 was used as a reducing agent for the synthesis of DENs. Binding studies were carried out in order to determine the maximum capacity of the dendrimer to which the metal ions can be added. These binding studies were performed using UV-vis spectroscopy. The synthesis of these nanoparticles (NPs) was carried out at room temperature. For the synthesis of Ag and Au-DENs with PAMAM-NH2 dendrimers, the pH of the aqueous dendrimer solution was first adjusted to acidic condition (~pH 2) using HCl before the addition of the respective metal ion precursor to the dendrimer. This is done to avoid coordination of the metal ions to the primary amine groups on the periphery of the dendrimer, which might lead to particle agglomeration. These prepared DENs were characterized by UV-vis spectroscopy and high resolution transmission (HRTEM) microscopy. The synthesized DENs were evaluated as catalysts in the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. This reaction was monitored by UV-vis spectroscopy by following the absorbance at 400 nm These DENs were all found to be active catalysts for the afore-mentioned process. The rate constant for the reduction process was observed to decrease as the concentration of 4-nitrophenol increased. As the concentration of NaBH4 is increased, the rate constant was also found to increase, however this increase was only observed to a maximum concentration of NaBH4. The Au-DENs prepared using G4 PAMAM-NH2 dendrimers were subsequently immobilized onto a titania support via the sol-gel (Ti-Au-s) and wetness impregnation (Ti-Au-w) methods. The titania supported Au NPs were characterized using HRTEM, powder X-ray diffraction (PXRD), thermal gravimetric analysis (TGA), inductive coupled plasma-optical emission spectroscopy (ICP-OES) and Brunauer Emmett Teller (BET) surface area analysis. The dendrimer template was removed by calcining at 500 oC. The catalytic activity of these supported Au NPs was investigated in the oxidation of styrene using tert-butyl hydroperoxide (TBHP) as an oxidant. Benzaldehyde and styrene oxide were observed as the major products. The catalyst prepared by wetness impregnation method was found to give the highest styrene conversion as compared to the one prepared via sol-gel method. At 60 oC, the catalyst prepared by sol-gel method was found to selectively produce benzaldehyde while on the other hand, the catalyst prepared by wetness impregnation selectively produce styrene oxide. The highest conversion of styrene was observed at 70 oC for both catalysts. Ti-Au-w catalyst was generally found to give the highest styrene conversion.

by Mong Kwok Kong Tony. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2000. / Includes bibliographical references (p. 95-101). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

by Chi-Wing Leung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (leaves 56-58). / Abstract also in Chinese. / Contents --- p.i / Acknowledgments --- p.ii / Abstract --- p.iii / Abbreviations --- p.v / Chapter Chapter I. --- Introduction / Chapter 1. --- Synthesis of Dendrimer --- p.2 / Chapter 2. --- The Ramberg-Backlund rearrangement --- p.9 / Chapter 3. --- Poly(phenylenevinylene) Dendrimer --- p.11 / Chapter Chapter II. --- "Synthesis, Results and Discussion" / Chapter 1. --- Synthesis --- p.15 / Chapter 2. --- Results and Discussion --- p.18 / Chapter Chapter III. --- Characterization / Chapter 1. --- Nuclear Magnetic Resonance Spectroscopy --- p.32 / Chapter 2. --- Ultra-Violet Spectroscopy --- p.36 / Chapter 3. --- Size Exclusion Chromatography --- p.36 / Chapter 4. --- Mass Spectrometry --- p.38 / Chapter Chapter IV. --- Conclusion --- p.40 / Chapter Chapter V. --- Experimental --- p.41 / References --- p.56 / Spectra --- p.59

Joseph Chung-Yin Lam. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2000. / Includes bibliographical references (leaves 62-64). / Abstracts in English and Chinese. / Contents --- p.i / Acknowledgements --- p.ii / Abstract --- p.iii / Abbreviations --- p.v / Chapter Chapter I. --- Introduction / Chapter (1) --- General background of dendrimers --- p.1 / Chapter (2) --- Electrochemically active dendrimers --- p.2 / Chapter (3) --- Electrochemically active dendrimers as models for studying the redox behaviour of complex proteins --- p.11 / Chapter Chapter II --- . Synthesis and Characterization / Chapter (1) --- Structure of the electrochemically active dendrimers --- p.16 / Chapter (2) --- Retrosynthetic analysis --- p.17 / Chapter (3) --- Synthesis --- p.18 / Chapter (4) --- Structural Characterization --- p.26 / Chapter (5) --- Conclusion --- p.33 / Chapter Chapter III. --- Physical and Electrochemical Properties / Chapter (1) --- Physical appearance and solubility properties --- p.34 / Chapter (2) --- Cyclic voltammetry studies --- p.34 / Chapter Chapter IV. --- Summary --- p.40 / Chapter Chapter V. --- Experimental --- p.41 / References --- p.62 / Spectra --- p.65

Wong Chun Ho. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (leaves 72-77). / Abstracts in English and Chinese. / Contents --- p.i / Acknowledgments --- p.iii / Abstract --- p.iv / Abbreviations and acronyms --- p.vi / Publications originated from the work of this thesis --- p.viii / Chapter Chapter 1 - --- Dendritic Macromolecules and Dendronized Polymers / Chapter 1.1 --- Introduction to Dendrimers and Dendronized Polymers --- p.1 / Chapter 1.2 --- Overview of the Synthesis of Dendronized Polymers --- p.4 / Chapter 1.2.1 --- Graft-from Approach --- p.4 / Chapter 1.2.2 --- Graft-to Approach --- p.5 / Chapter 1.2.3 --- Macromonomer Approach --- p.6 / Chapter 1.2.3.1 --- Step Growth Polymerization --- p.6 / Chapter 1.2.3.2 --- Chain Growth Polymerization --- p.8 / Chapter 1.2.3.3 --- Supramolecular Polymerization --- p.9 / Chapter Chapter 2 - --- En Route to Hydrogen Bond-Mediated. Supramolecular Dendronized Polymers / Chapter 2.1 --- Design of Supramolecular Dendronized Polymers --- p.15 / Chapter 2.1.1 --- Binding Modes in Supramolecular Polymers --- p.15 / Chapter 2.1.1.1 --- Hetero-Complementary Polymerization --- p.16 / Chapter 2.1.1.2 --- Self-Complementary Polymerization --- p.17 / Chapter 2.1.2 --- The Effect of Binding Constant on the Degrees of Polymerization --- p.18 / Chapter 2.1.3 --- The Effect of Dimerization Constant on the Molecular Weight Distribution --- p.21 / Chapter 2.1.4 --- The Dendritic Effect on the UPy Binding Behavior --- p.21 / Chapter 2.2 --- Summary --- p.24 / Chapter Chapter 3 - --- "Design, Synthesis, and Structural Characterization of Dendronized Dimers" / Chapter 3.1 --- Design of Dendronized Dimers --- p.25 / Chapter 3.1.1 --- The Nature of R and R on the Dimerization Behavior --- p.25 / Chapter 3.1.2 --- Selection of Dendrons --- p.26 / Chapter 3.1.3 --- Positioning of Dendrons and the Synthetic Feasibility --- p.27 / Chapter 3.2 --- Synthesis of Dendronized Dimers --- p.28 / Chapter 3.3 --- Characterizations of the Intermediates and Target Dimers --- p.31 / Chapter 3.3.1 --- 1H NMR Spectroscopy --- p.31 / Chapter 3.3.2 --- 13C NMR Spectroscopy --- p.38 / Chapter 3.3.3 --- Mass Spectrometry --- p.41 / Chapter 3.3.4 --- Vapor Pressure Osmometry --- p.43 / Chapter 3.3.5 --- Infrared Spectroscopy --- p.43 / Chapter 3.3.6 --- Gel Permeation Chromatography --- p.44 / Chapter 3.4 --- Conclusions --- p.46 / Chapter Chapter 4 - --- Determination of Dimerization Constants / Chapter 4.1 --- Overview of the Self-Assembling Process in UPy System --- p.47 / Chapter 4.2 --- Determination of the Dimerization Constants (Kdim*) --- p.49 / Chapter 4.2.1 --- Dimerization Constants in CDCl3 at 25 °C --- p.50 / Chapter 4.2.2 --- Dimerization Constants in 10% (v/v) DMSO-d6/CDCl3 at 25 °C --- p.53 / Chapter 4.2.3 --- Dimerization Constants in CDCl3 at 50 °C --- p.56 / Chapter 4.3 --- Heterodimerization Experiment --- p.56 / Chapter 4.4 --- Conclusions --- p.57 / Chapter Chapter 5 - --- Experimental Procedures / Chapter 5.1 --- General Information --- p.60 / Chapter 5.2 --- General Synthetic Procedures --- p.61 / Chapter 5.3 --- Experimental Procedures --- p.62 / References --- p.72 / Appendix / NMR Spectra --- p.78 / GPC results --- p.119

by Chi-wai Wan. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (p. 129-136). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

本論文敘述了 III-B類輪烷樹狀物的人工合成及其表徵。透過重覆(1) 經改良的 銅(I) 催化炔烴 -疊氮偶極環加成反應 (2) 生成醯胺鍵以及最後 (3) 格拉澤 -希偶聯反應合成第一代 (G1) 及第二初代 (G2 ’)IIIB類輪烷樹狀物。 銨鹽啞及冠醚被採用來組合成分支結構的偽輪烷。 III B類輪烷樹狀物被核磁共振波譜法及電噴霧離子化法－質譜所表徵。這項研究為 III-B類輪烷樹狀物合成研究提供不可或缺的雛型 。這項研究為超分子及高化學家開拓新的領域，給予他們研究III-B類輪烷樹狀物的特性及其生醫學和電子應用機會。 / In this thesis, the syntheses and characterizations of a series of Type III-B Rotaxane Dendrimers are described. First generation (G1) and prototypical second generation (G2’) Type IIIB Rotaxane Dendrimer, which incorporate rotaxane features as the branching units, were synthesized by employing consecutive (1) modified Copper-Catalyzed Alkyne-Azide Cycloaddition (CuAAC), (2) amide formation through stopper molecule and pseudorotaxanes, and (3) GlaserHay’s acetylene homo-coupling reaction. Pseudorotaxanes with ammonium thread and crown ether macrocycle were employed. The Type III-B Rotaxane Dendrimers were characterized by nuclear magnetic resonance (NMR) spectroscopy, electrospray ionisationmass spectrometry (ESI-MS). This study provides an indispensable prototype to the synthesis of novel Type III-B Rotaxane Dendrimer. It opened up great opportunity for supramolecular and polymer chemists to further explore the properties and biomedical and electronic application of the novel dendrimers. / Detailed summary in vernacular field only. / Ho, Kwok Wai. / "October 2012." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 49-51). / Abstracts also in Chinese. / Contents --- p.i / Acknowledgments --- p.ii / Abstract --- p.iii / Abbreviations and Acronyms --- p.v / Synthetic Studies Towards Type III-B Rotaxane Dendrimer / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Classification of Rotaxane Dendrimers --- p.2 / Chapter 1.2 --- Type II-B Rotaxane Dendrimer --- p.5 / Chapter 1.3 --- Application of Copper Catalyzed Alkyne Azide Cycloaddtion(CuAAC) in Rotaxane Synthesis --- p.8 / Chapter 1.4 --- Potential Application of Type III-B Rotaxane Dendrimer --- p.12 / Chapter 1.5 --- Aim of Project --- p.14 / Chapter Chapter 2 --- Synthetic Studies Towards of Type III-B Rotaxane Dendrimer / Chapter 2.1 --- Design and Synthesis of Type III-B Rotaxane Dendrimer --- p.15 / Chapter 2.2 --- Characterization of G1 and G2’ Type III-B Rotaxane Dendron/Dendrimer --- p.27 / Chapter 2.2.1 --- ¹H NMR Spectroscopy --- p.27 / Chapter 2.2.2 --- ¹³C NMR Spectroscopy --- p.32 / Chapter 2.2.3 --- Mass Spectrometry --- p.32 / Chapter 2.3 --- Conclusion --- p.38 / Chapter Chapter 3 --- Experimental Procedures / Chapter 3.1 --- General Information --- p.39 / Chapter 3.2 --- Experimental Procedures --- p.40 / References / Appendix / List of Spectra --- p.A1

本論文論述了一系列包含疏水性樹枝狀烷烴基團的兩親性分子的合成和表徵、在水溶液中的自組裝性質及其對小分子客體的增溶能力的研究。第一部分為第一至第三代兩親性“樹枝直鏈雜化物“[Gn]-OEG₈ 128-130, 該類雜化物含有的樹枝狀烷烴基團以醯胺鍵在其核心連接親水性八聚乙二醇基團。這些兩親性分子在水溶液中自組裝形成膠束結構。此外我們還製備了烷烴雙鏈[Dn]-OEG₈及烷烴單鏈[Ln]-OEG₈同分異構體，並研究其疏水基團的支化程度對自組裝性質的影響。第二部分,我們通過銅()催化-疊氮-端基炔的環加成反應（CuAAC）對第〇代至第二代樹枝狀烷烴聚合物OEG-[Gn]-dendrimer 171-173進行表面修飾，製備了具有親水性四聚乙二醇外殼的樹枝狀兩親性分子，並研究其疏水基團大小對自組裝性質及對小分子客體增溶能力的影響。 / 所有化合物的結構均通過核磁共振氫譜、碳譜、質譜和凝膠排阻色譜進行表徵。其自組裝性質如臨界膠束/聚集濃度（CMC/CAC）、微環境極性、粒子尺寸分佈和藥物承載能力的大小則通過熒光光譜、紫外可見光譜和光散射等方法進行研究。實驗結果表明：（一）臨界膠束/聚集濃度隨著疏水基團的增大而減小；（二）臨界膠束/聚集濃度隨著疏水基團的支化程度的提高而增加（即直鏈<雙鏈<樹枝狀）；（三）支化程度較高的兩親性分子會形成較為鬆散的膠束結構，其核心的極性也會相應提高；（四）膠束核心的極性隨著樹枝狀聚合物的代數增加而降低。這些結論均與疏水烷烴基團的尺寸（即長度或代數）及結構（即支化程度）相關聯，並與文獻中的計算擬合結果相符。 / 同時本工作也發現了一些與文獻的擬合結果不吻合的實驗結果：（一）由於長鏈烷烴的自卷現象，烷烴單鏈[L2]-OEG₈比其雙鏈[D2]-OEG₈異構體具有更高的臨界膠束濃度；（二）基於光散射實驗結果，具有“單分子膠束“結構的樹枝狀烷烴聚合物OEG-[Gn]-dendrimer 171-173能夠形成大型膠束聚集體；（三）這些樹枝狀烷烴聚合物的增溶能力與其疏水內核的大小並不相關。後兩個結果反映出由於大型兩親性分子具有多種自組裝方式，其膠束性質及增溶能力具有相當的複雜性和不確定性。 / 在此之前，相關研究工作主要集中在理論計算和電腦模擬部分，本論文首次以實驗手段研究具有不同支化程度的疏水樹枝狀烷烴基團的兩親性分子及其自組裝性質。我們的大部分結果證實了文獻報導的結論，並指出了一些模擬計算忽略的問題，為以後的相關工作提供重要的數據支援。 / This thesis described the synthesis, self-assembling and/or encapsulation properties of two different classes of amphiphilic dendritic compounds. The first set of amphiphilic dendrons [Gn]-OEG₈ 128-130 (n = 1-3) are dendritic-linear hybrid molecules that have a hydrophobic hydrocarbon (HC) dendron connected to a hydrophilic octa(ethylene glycol) chain. The effect of the branching architecture on their self-assembling properties was then compared to that of their doubly branched [Dn]-OEG₈ and linear [Ln]-OEG₈ analogs, which were also prepared in this study. The second set of compounds are a series of amphiphilic dendrimers OEG-[Gn]-dendrimer 171-173 (n = 0-2) decorated with surface tetra(ethylene glycol) chains on the periphery of a HC dendrimer. The size effect of the HC sector on their self-assembling and drug encapsulation properties with indomethacin was examined. / The structures of all compounds were characterized by ¹H and ¹³C NMR spectroscopy, mass spectrometry, and gel permeation chromatography. Their self-assembling and host-guest complexation properties, such as critical micellar/association concentrations (CMC/CAC), micro-environmental polarity, particle size distributions and drug loading capacity were investigated by various physical techniques such as UV and fluorescent spectroscopy, as well as static and dynamic laser light scattering. Based on our experimental findings, we were able to confirm the results obtained from earlier theoretical simulations. First, for both series of dendritic amphiphiles, their CMC/CAC values decreased with increasing size of the hydrophobic segment. Second, with the same molecular formula and hydrophobic/lipophilic balance (HLB), amphiphiles containing a hydrophobic segment of a higher branching degree possessed a higher CMC/CAC value. Third, the micellar core of amphiphiles with a dendritic hydrophobic sector was more polar than that of non-dendritic amphiphiles having the same molecular formula. Fourth, the micellar core of a dendritic amphiphile of a higher generation was more non-polar than that of the lower generation analogues. All the findings could be correlated to the size (i.e. length or generation) and the architecture (i.e. branching pattern) of the hydrophobic HC sector. / Three unusual findings that deviated from previous theoretical simulations were noted. First, the doubly branched [D2]-OEG₈ 132 was found to have a lower CMC value than the linear [L2]-OEG₈ 134. This anomaly could be rectified if backfolding of the linear HC chain is taken into consideration. Second, based on DLS study, it was noted that the ‘unimolecular’ OEG-[Gn]-dendrimers 171-173 were capable of forming ‘giant’ aggregates in aqueous solutions. Third, their drug loading capacity did not correlate to the size of the hydrophobic HC sector. The latter two findings revealed the complexity in dealing with the understanding of the self assembling and host-guest complexation processes of these large amphiphile dendrimers. Prior to our work, only theoretical calculations had been carried out. The work described in this thesis serves to provide solid experimental evidence in support of the theoretical simulations and offer additional insights that were previously neglected in this subject area. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Liang, Yuting. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 149-156). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Contents --- p.i / Acknowledgments --- p.vi / Abstract --- p.vii / Abbreviations --- p.xi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- General --- p.1 / Chapter 1.2 --- Construction of Dendrimers --- p.2 / Chapter 1.2.1 --- The Divergent Approach --- p.2 / Chapter 1.2.2 --- Convergent Approach --- p.3 / Chapter 1.2.3 --- Modification --- p.4 / Chapter 1.2.3.1 --- Modification at the Focal Point --- p.5 / Chapter 1.2.3.2 --- Modification on the Periphery --- p.6 / Chapter 1.2.4 --- CuAAC ‘Click’ Reaction in Dendrimer Synthesis --- p.8 / Chapter 1.3 --- Physical Properties of Dendrimers --- p.13 / Chapter 1.3.1 --- Location of End Groups --- p.13 / Chapter 1.3.2 --- Comparison of Dendritic -- Linear Analogs --- p.15 / Chapter 1.3.3 --- Generation Dependence -- Dendritic Effect --- p.16 / Chapter 1.4 --- Dendritic Amphiphiles --- p.18 / Chapter 1.4.1 --- Amphiphiles and their aggregations --- p.18 / Chapter 1.4.2 --- Dendritic Amphiphiles --- p.20 / Chapter 1.4.2.1 --- Unimolecular Micelles --- p.20 / Chapter 1.4.2.2 --- Bolaamphiphiles --- p.22 / Chapter 1.4.2.3 --- Amphiphilic dendritic-linear polymer hybrids --- p.23 / Chapter 1.4.2.4 --- Facially amphiphilic dendrimers --- p.25 / Chapter 1.5 --- Applications of Dendritic Amphiphiles --- p.27 / Chapter 1.5.1 --- Drug Delivery --- p.27 / Chapter 1.5.1.1 --- Encapsulation via Non-Covalent Interactions --- p.27 / Chapter 1.5.1.2 --- Covalent Bonded Dendrimer -- Drug Conjugates --- p.29 / Chapter 1.5.2 --- Biomimetics --- p.30 / Chapter Chapter 2 --- Architecture and Generation Effects on the Self-Assembly of Amphiphilic Dendritic-Linear Polymer Hybrids --- p.33 / Chapter 2.1 --- Packing Parameters --- p.33 / Chapter 2.2 --- Computer Simulations --- p.35 / Chapter 2.3 --- Experimental studies --- p.38 / Chapter 2.4 --- Methods --- p.40 / Chapter 2.4.1 --- Fluorescence Studies --- p.41 / Chapter 2.4.2 --- Laser Light Scattering --- p.42 / Chapter 2.4.3 --- Electron Microscopy --- p.42 / Chapter 2.5 --- Research Objectives --- p.43 / Chapter Chapter 3 --- Design, Synthesis and Characterization of Novel Amphiphilic Dendritic-Linear Polymer Hybrids --- p.44 / Chapter 3.1 --- Design --- p.45 / Chapter 3.1.1 --- Dendritic-Linear Polymer Hybrids: Hydrocarbon Dendrons (Gn) and Their Linear (Ln) and Doubly Branched (Dn) Analogs --- p.45 / Chapter 3.1.2 --- Selection of Hydrophilic Block: Oligo(Ethylene Glycol) Chains --- p.47 / Chapter 3.2 --- Synthesis --- p.48 / Chapter 3.2.1 --- Preparation of Amino- and Azido- Functionalized Oligoethylene Glycols --- p.48 / Chapter 3.2.2 --- Preparation of [Gn]-COOH, [Dn]-COOH and [Ln]-COOH --- p.49 / Chapter 3.2.3 --- Preparation of [Gn]-OEG₈, [Dn]-OEG₈ and [Ln]-OEG₈ --- p.52 / Chapter 3.3 --- Characterization --- p.53 / Chapter 3.3.1 --- ¹H NMR Spectroscopy --- p.53 / Chapter 3.3.2 --- ¹³3C NMR spectroscopy --- p.55 / Chapter 3.3.3 --- Mass Spectrometry --- p.56 / Chapter 3.3.4 --- Gel Permeation Chromatography --- p.57 / Chapter 3.3.5 --- Physical Appearance and Melting Point --- p.59 / Chapter 3.4 --- Self-assembly Behavior of [Gn]-OEG₈, [Dn]-OEG₈ and [Ln]-OEG₈ in Water --- p.60 / Chapter 3.4.1 --- Critical Micellar Concentration (CMC) --- p.60 / Chapter 3.4.1.1 --- Effect of the size of hydrophobic sector --- p.63 / Chapter 3.4.1.2 --- Effect of Branching on Micelle Formation --- p.64 / Chapter 3.4.2 --- Microenvironment Polarity inside the Micelles --- p.67 / Chapter 3.4.3 --- Hydrodynamic Radius (R[subscript h]) --- p.71 / Chapter 3.5 --- Summary --- p.73 / Chapter Chapter 4 --- Amphiphilic Unimolecular Micelles: Multiple Surface Functionalized Hydrocarbon-Based Dendrimers --- p.75 / Chapter 4.1 --- Design --- p.75 / Chapter 4.1.1 --- The Surface Acetonide-Protected Hydrocarbon Dendrons --- p.76 / Chapter 4.1.2 --- Peripheral Post-Modification via CuAAC ‘click’ chemistry --- p.77 / Chapter 4.2 --- Synthesis --- p.78 / Chapter 4.2.1 --- Preparation of Amphiphilic HC Dendrimers with a Peripheral Acetylene Layer --- p.78 / Chapter 4.2.1.1 --- Preparation of Amphiphilic Dendrimers via CuAAC ‘click’ reaction --- p.83 / Chapter 4.3 --- Characterization --- p.85 / Chapter 4.3.1 --- ¹H NMR Spectroscopy --- p.85 / Chapter 4.3.1.1 --- Dendrons/Dendrimers with Acetonide-Protected or Polyol Surface --- p.86 / Chapter 4.3.1.2 --- Dendrons/Dendrimers with Multiple Acetylene Functionalized Surface --- p.87 / Chapter 4.3.1.3 --- Amphiphilic Dendrimers with Triazolo OEG Surface --- p.89 / Chapter 4.3.2 --- ¹³C NMR spectroscopy --- p.90 / Chapter 4.3.2.1 --- Dendrons/Dendrimers with Acetonide-Protected or Polyol Surface --- p.90 / Chapter 4.3.2.2 --- Dendrons/Dendrimers with Multiple Acetylene Surface --- p.91 / Chapter 4.3.2.3 --- Amphiphilic Dendrimers with Triazolo OEG Surface Groups --- p.93 / Chapter 4.3.3 --- Mass Spectrometry --- p.94 / Chapter 4.3.4 --- Gel Permeation Chromatography --- p.98 / Chapter 4.4 --- Micellar Properties of Amphiphilic OEG-[Gn]-Dendrimers 171-173 --- p.101 / Chapter 4.4.1 --- Critical Micellar Concentration (CMC) --- p.101 / Chapter 4.4.2 --- Particle Size Distribution and Aggregation Number --- p.105 / Chapter 4.5 --- Encapsulation with Hydrophobic Guest Molecule -- Indomethacin --- p.107 / Chapter 4.5.1 --- Hydrodynamic Radius of IMC Loaded Particles --- p.107 / Chapter 4.5.2 --- Loading Efficiency --- p.109 / Chapter 4.5.2.1 --- Effect of Amphiphile Concentration on Loading Efficiency --- p.109 / Chapter 4.5.3 --- Release Profile --- p.113 / Chapter 4.6 --- Summary --- p.113 / Chapter Chapter 5 --- Conclusions --- p.115 / Chapter Chapter 6 --- Experimental --- p.117 / Chapter 6.1 --- General Methods --- p.117 / Chapter 6.2 --- Synthesis --- p.118 / Chapter 6.3 --- Characterization of Micellar Properties --- p.143 / Chapter 6.3.1 --- Preparation of Micellar Solutions --- p.143 / Chapter 6.3.2 --- Preparation of Pyrene Loaded Samples --- p.143 / Chapter 6.3.3 --- Determination of CMCs from Fluorescence Probe Method --- p.143 / Chapter 6.3.4 --- Laser Light Scattering --- p.146 / Chapter 6.3.5 --- Transmission Electron Microscopy --- p.147 / Chapter 6.4 --- Drug Encapsulation and Release Study --- p.147 / Chapter 6.4.1 --- Preparation of Indomethacin (IMC) Loaded Samples --- p.147 / Chapter 6.4.2 --- Determination of IMC Loading Amount --- p.147 / Chapter 6.4.3 --- In vitro Drug Release Profile --- p.148 / Reference --- p.149 / Chapter Appendix --- List of Spectra --- p.Ai

Abstract not available

This dissertation investigates the synthesis, characterization and electrochemical properties of viologen-containing dendrimers. Additionally, the self-assembled system of resorcinarenes was investigated with paramagnetic guests using EPR and 1H NMR techniques. Chapter one is a brief introduction to the dendrimers and describes its evolution, structural features, synthetic methods and emerging applications to various fields of research such as catalysis, material science, drug delivery and medicine. Chapter two describes the synthesis, characterization and electrochemical properties of a new series of dendrimers. These dendrimers have a viologen unit at the core surrounded by Newkome and Fr¨¦chet dendrons. The potentials of two consecutive one-electron reductions of the viologen core were determined by cyclic voltammetry. The electrochemistry of viologen unit showed a distinct and obvious trend. Newkome and Frechet dendrons having different functional groups as repeating units has opposite effect on the half-wave potentials. The overall effect of these two dendrons is reflected by the corresponding reduction potentials. The redox site encapsulation by the Frechet and Newkome dendrons is indicated by the attenuation in heterogeneous electron transfer rate constants. Chapter three describes the probing of self-assembled capsule of resorcinarenes with 4-amino tempo and 4-trimethyl-ammonium tempo derivative. EPR spectroscopy and 1H NMR spectroscopy were used to investigate the nature of complexations involved in these systems. We observed a subsequent change in their spectroscopic parameters. Careful investigation of rotational correlation times and NMR line-widths at half height revealed that 4-trimethyl-ammonium tempo has stronger binding affinity with these capsules compared to 4-amino tempo due to favorable cation -pi interactions.