As a first step to producing a shape selective catalysts or enzyme mimic, two preorganized host molecules were synthesized. Binding studies of the two hosts with a variety of guests in three solvents demonstrated that an important driving force in the association was the formation of C-H???X-R hydrogen bonds (X = halogen). A deuterated host was utilized to further examine the formation of the C-H???X-R hydrogen bonds. In an effort to place functionality in the hydrophobic pocket of these hosts, two methods were developed. The first utilized directed ortho metallation to place electrophiles above and/or directed into the cavity. Perlithiation of the host could lead to sixty-nine products but reaction conditions and host rigidity limited product formation. This reaction technique led to the placement of carboxylic acid groups onto the host and the isolation of twelve products. Two different positions of the carboxylic acids (endoand exo-) direct the orientation of the guest. 1D- and 2D-NMR were utilized to examine how the was orientated inside the host. The second method employed to place functionality on the host, sited a tripodal zinc binding ligand on the side of the hydrophobic pocket of the host. The synthesized host was able to bind zinc strongly and in a 1:1 manner.

Water-soluble deep-cavity cavitands provide a rare opportunity to study self-assembly driven by the hydrophobic effect. These molecular hosts dimerize in the presence of certain guest molecules to form water-soluble molecular capsules. These systems have given rise to numerous novel chemical phenomena and have potential use in drug delivery. The host octaacid (OA) has been particularly well-characterized, but studies are limited to basic pH because of limited host solubility. Herein we report an improved synthesis of OA and the syntheses of three new water-soluble deep-cavity cavitands. The new hosts are soluble at neutral pH, increasing relevance for biological studies. The new syntheses are versatile enough to apply to the synthesis of additional water- soluble cavitands in the future. We also describe preliminary characterization of the molecular recognition properties of the new hosts. Binding of organic guest molecules to form 1:1 host:guest complexes and 2:1 host:guest capsules was qualitatively similar to that of OA. However, binding of anions spanning the Hofmeister series revealed interesting new behavior. The new hosts bound a wider range of anions inside the hydrophobic pocket with much higher association constants. Moreover, external binding of several anions to the cavitand pendant feet was observed. Looking towards biological applications, we desired to learn how these molecules interact with phospholipid membranes. Six water-soluble cavitands were tested for their ability to permeabilize liposomal POPC membranes. One host showed very high potency in permeabilizing membranes, while three other hosts showed moderate activity. Host binding of POPC was found to be at least one factor in host-induced permeabilization. A requenching assay to determine leakage mechanism strongly supported all-or-none leakage, whereby some vesicles lose all contents while others lose none. These results suggest that these cavitands induce partial transient leakage of vesicles by the formation of transient membrane pores. These findings show potential for the use of these hosts as drug delivery carriers, antimicrobial compounds, and tools in membrane alteration studies.

As antocianinas compreendem o maior conjunto de pigmentos naturais do Reino Vegetal. São caracterizadas pelas colorações vermelha, roxa e azul de uma variedade de flores, frutas e folhas. A sua estabilidade é influenciada por diversos fatores como o pH local do meio, temperatura, luz ou copigmentos. A inclusão das antocianinas e análogos sintéticos, os sais de flavílio, dentro da cavidade da cucurbit[7]uril (CB[7]), sistema hóspede-hospedeiro, foi estudada a partir da espectroscopia de fluorescência. As antocianinas sintéticas utilizadas foram o cloreto de 7-hidroxi-4-metilflavílio (HMF) e o cloreto de 7-metoxi-4-metilflavílio (MMF) e as antocianinas naturais foram a cianindina-3-glicosídeo, cianidina-3,5-di-O-glicosídeo e antocianinas presentes no extrato do jambolão (Syzygium cumini). Os complexos de inclusão das antocianinas e os análogos sintéticos dentro da cavidade do CB[7] apresentaram uma estequiometria de inclusão do tipo 1:2, uma molécula hóspede e duas moléculas hospedeiras. A estequiometria de inclusão e as constantes de incorporação foram determinadas a partir de isotermas da inclusão pelo método de regressão não-linear. Para os íons flavílios, a determinação da estequiometria também foi comprovada pelo Método da Variação Contínua (MVC) ou método Job. A primeira constante de incorporação K11 obtida para as antocianinas e os íons flavílios foi da ordem de 105 - 106 M-1. Essa elevada constante de incorporação é devida à interação eletrostática entre as carbonilas do CB[7] e a carga positiva do anel pírilio das antocianinas. Entretanto, a segunda constante de incorporação, K12, apresenta um valor menor por causa da repulsão entre a primeira e a segunda molécula de CB[7]. A segunda constante de inclusão das antocianinas naturais apresentou um valor muito baixo em relação à segunda constante de incorporação do HMF e MMF. Essa diferença ocorreu pelo impedimento estérico provocado pelas unidades glicosídicas presentes nas antocianinas naturais. A hidratação das antocianinas do jambolão é uma reação muito rápida, ocorrendo em pH acima de 3,0. Quando o CB[7] foi adicionado às antocianinas em pH 4,62, a hidratação foi um pouco menor, mas mesmo assim a hidratação ocorreu. Após 24 horas, quando o equilíbrio das antocianinas do jambolão fosse deslocado na direção de formação das chalconas, o CB[7] foi adicionado ao meio, em elevadas concentrações. O equilíbrio de hidratação foi deslocado em direção ao cátion flavílio, indicando um aumento na estabilização desses compostos. / The anthocyanins, the largest group of natural plant pigments, are responsible for the red, purple and blue colors of a variety of flowers, fruit and leaves. Their stability is influenced by several factors, including the local pH of the medium, temperature, light and copigments. The inclusion of natural anthocyanins and their synthetic analogs, flavylium cations, in the cavity of cucurbit[7]uril, CB[7], to form host-guest complexes, was studied by fluorescence spectroscopy. The synthetic anthocyanin model compounds utilized were 7-hydroxy-4-methylalavylium (HMF) chloride and 7-methoxy-4-methylflavylium (MMF) chloride and the naturally-occurring anthocyanins were cyaniding-3-O-glucoside, cyaniding-3,5-di-O-glucoside and the anthocyanins extracted from jambolão (Syzygium cumini) fruit. The inclusion complexes of the anthocyanins and synthetic anthocyanin analogs with CB[7] presented a stoichiometry of 1:2, with one molecule of guest and two molecules of host. The stoichiometry of the inclusion and the incorporation equilibrium constants were determined from the binding isotherms by non-linear regression. For the synthetic flavylium ions, the stoichiometry was also verified using the method of continuous variations or Job plots. The first binding constant, K11, between the anthocyanins or flavylium ions and CB[7] was of the order of 105-106 M-1. This large equilibrium constant for incorporation reflects the electrostatic interaction between the carbonyl groups of CB[7] and the positive charge of the pyrilium ring of the anthocyanins. The binding constant for the second CB[7], K12, has a smaller value due to the repulsion between the first and second molecules of CB[7]. The second binding constant for the inclusion of the natural anthocyanins was much smaller than that of the synthetic anthocyanin analogs HMF and MMF. This difference was due to the steric hindrance afforded by the sugar residues present in the natural anthocyanins. The hydration of the anthocyanins of jambolão is very rapid above pH 3. When CB[7] was added to a mixture of jambolão anthocyanins at pH 4.62, the extent of hydration was diminished, but partial hydration did still occur. After equilibration at pH 4.62 for 24 hrs to form the chalcones, addition of high concentrations of CB[7] shifted the equilibrium back in the direction of the flavylium cation form of the anthocyanins, demonstrating the increase in the stabilization of this form upon host-guest complexation.

No description available.

As antocianinas compreendem o maior conjunto de pigmentos naturais do Reino Vegetal. São caracterizadas pelas colorações vermelha, roxa e azul de uma variedade de flores, frutas e folhas. A sua estabilidade é influenciada por diversos fatores como o pH local do meio, temperatura, luz ou copigmentos. A inclusão das antocianinas e análogos sintéticos, os sais de flavílio, dentro da cavidade da cucurbit[7]uril (CB[7]), sistema hóspede-hospedeiro, foi estudada a partir da espectroscopia de fluorescência. As antocianinas sintéticas utilizadas foram o cloreto de 7-hidroxi-4-metilflavílio (HMF) e o cloreto de 7-metoxi-4-metilflavílio (MMF) e as antocianinas naturais foram a cianindina-3-glicosídeo, cianidina-3,5-di-O-glicosídeo e antocianinas presentes no extrato do jambolão (Syzygium cumini). Os complexos de inclusão das antocianinas e os análogos sintéticos dentro da cavidade do CB[7] apresentaram uma estequiometria de inclusão do tipo 1:2, uma molécula hóspede e duas moléculas hospedeiras. A estequiometria de inclusão e as constantes de incorporação foram determinadas a partir de isotermas da inclusão pelo método de regressão não-linear. Para os íons flavílios, a determinação da estequiometria também foi comprovada pelo Método da Variação Contínua (MVC) ou método Job. A primeira constante de incorporação K11 obtida para as antocianinas e os íons flavílios foi da ordem de 105 - 106 M-1. Essa elevada constante de incorporação é devida à interação eletrostática entre as carbonilas do CB[7] e a carga positiva do anel pírilio das antocianinas. Entretanto, a segunda constante de incorporação, K12, apresenta um valor menor por causa da repulsão entre a primeira e a segunda molécula de CB[7]. A segunda constante de inclusão das antocianinas naturais apresentou um valor muito baixo em relação à segunda constante de incorporação do HMF e MMF. Essa diferença ocorreu pelo impedimento estérico provocado pelas unidades glicosídicas presentes nas antocianinas naturais. A hidratação das antocianinas do jambolão é uma reação muito rápida, ocorrendo em pH acima de 3,0. Quando o CB[7] foi adicionado às antocianinas em pH 4,62, a hidratação foi um pouco menor, mas mesmo assim a hidratação ocorreu. Após 24 horas, quando o equilíbrio das antocianinas do jambolão fosse deslocado na direção de formação das chalconas, o CB[7] foi adicionado ao meio, em elevadas concentrações. O equilíbrio de hidratação foi deslocado em direção ao cátion flavílio, indicando um aumento na estabilização desses compostos. / The anthocyanins, the largest group of natural plant pigments, are responsible for the red, purple and blue colors of a variety of flowers, fruit and leaves. Their stability is influenced by several factors, including the local pH of the medium, temperature, light and copigments. The inclusion of natural anthocyanins and their synthetic analogs, flavylium cations, in the cavity of cucurbit[7]uril, CB[7], to form host-guest complexes, was studied by fluorescence spectroscopy. The synthetic anthocyanin model compounds utilized were 7-hydroxy-4-methylalavylium (HMF) chloride and 7-methoxy-4-methylflavylium (MMF) chloride and the naturally-occurring anthocyanins were cyaniding-3-O-glucoside, cyaniding-3,5-di-O-glucoside and the anthocyanins extracted from jambolão (Syzygium cumini) fruit. The inclusion complexes of the anthocyanins and synthetic anthocyanin analogs with CB[7] presented a stoichiometry of 1:2, with one molecule of guest and two molecules of host. The stoichiometry of the inclusion and the incorporation equilibrium constants were determined from the binding isotherms by non-linear regression. For the synthetic flavylium ions, the stoichiometry was also verified using the method of continuous variations or Job plots. The first binding constant, K11, between the anthocyanins or flavylium ions and CB[7] was of the order of 105-106 M-1. This large equilibrium constant for incorporation reflects the electrostatic interaction between the carbonyl groups of CB[7] and the positive charge of the pyrilium ring of the anthocyanins. The binding constant for the second CB[7], K12, has a smaller value due to the repulsion between the first and second molecules of CB[7]. The second binding constant for the inclusion of the natural anthocyanins was much smaller than that of the synthetic anthocyanin analogs HMF and MMF. This difference was due to the steric hindrance afforded by the sugar residues present in the natural anthocyanins. The hydration of the anthocyanins of jambolão is very rapid above pH 3. When CB[7] was added to a mixture of jambolão anthocyanins at pH 4.62, the extent of hydration was diminished, but partial hydration did still occur. After equilibration at pH 4.62 for 24 hrs to form the chalcones, addition of high concentrations of CB[7] shifted the equilibrium back in the direction of the flavylium cation form of the anthocyanins, demonstrating the increase in the stabilization of this form upon host-guest complexation.

Biomolecular receptors can catalyse reactions, alter their geometry, and inhibit their activity in response to molecules binding around their periphery. Synthetic receptors that can mimic this allosteric binding behaviour extend the potential applications of host-guest chemistry to programmable molecular systems. Modulating the degree and magnitude of interaction between components within these systems enables the design of chemical behaviour akin to biological complexity. With a view to developing artificial guest-binding regulation systems, a series of metal-organic cages capable of both the peripheral and internal encapsulation of guests are presented: octahedra capable of accommodating two guests in different locations simultaneously; cuboctahedral receptors that bind fullerenes with all-or-nothing positive cooperativity and assemble supramolecular entities internally; a heteroleptic triangular prism capable of recognising steroids and enantiopure natural products; and a tetrahedron that binds fullerene clusters. Each of these architectures employs one or more binding site to either: a) template specific products; b) regulate the cooperativity of binding of large anionic guests; c) assemble coordination complexes and interlocked species inside their cavities; d) alter their morphology in well-defined ways; or e) form assemblies with new electronic and electrochemical functionality. In all cases, chemical systems that respond to multiple stimuli simultaneously are explored, and new applications for bringing multiple species into proximity are detailed. The allosteric binding motifs described herein can be extended to sort reaction mixtures, generate specific isomeric forms, stabilise labile species and promote tuneable modes of intermolecular cooperativity.

No description available.

Les systèmes moléculaires de taille nanométrique sont impliqués dans une grande variété de procédés et de fonctions biologiques. La compréhension des mécanismes permettant le contrôle de leur structure à plusieurs échelles présente un grand intérêt. Par exemple, malgré le défi que cela représente, il n'existe actuellement aucun système synthétique permettant la formation d'objets fibrillaires de diamètre monodisperse et modulable en milieu aqueux. L'objectif de ce travail est de développer une boite à outils moléculaires de cyclodextrines (CDs) sélectivement di-fonctionnalisées de façon à pouvoir s'auto-assembler sous forme de fibres pouvant ensuite s'associer pour former des assemblages hiérarchiques via des interactions secondaires. L'étude de la formation du premier niveau d'assemblage de ces composés par viscosimétrie, ITC et SANS a montré que l'utilisation de CDs pontées permet de favoriser la polymérisation de ces composés en supprimant le phénomène d'auto-inclusion. Cette étude a permis de développer deux polymères supramoléculaires (PSM) cationiques à base de ?-CDs fonctionnalisées possédant un degré de polymérisation plus élevé que ceux existant actuellement. Leur capacité à former des PSM hiérarchiques en présence de polyanions rigides a ensuite été évaluée par analyses DLS, spectroscopie et cryo-MET. Dans des conditions de concentration en CDs et de rapport en charges optimisées, trois différents assemblages hiérarchiques solubles dans l'eau ont été formés. Nous avons montré que le premier niveau d'association ainsi que la directionnalité des interactions secondaires étaient des paramètres clés pour la formation d'assemblages hiérarchiques stables et de morphologies bien définies. Ces structures modulables nous serviront donc de plateformes pour étudier et mieux comprendre les mécanismes impliqués dans la formation des assemblages hiérarchiques. / Molecular systems with nanometer-sized dimensions are involved in a wide variety of processes and biological functions. Understanding the mechanisms controlling their multi-lengthscale structure presents a major interest. For instance, despite this challenge, there is so far no reliable synthetic system forming well-defined tunable fibrillar objects with a monodisperse diameter in aqueous solution. The aim of this work is to develop a tool box of di-functionalized cyclodextrins (CDs) specifically designed to self-assemble into supramolecular rods that could then reach higher levels of hierarchy via interactions mediated by the secondary functionalization. The study of the first level of association of these compounds by viscosimetry, ITC and SANS showed that the use of bridged CDs allows the polymerization by suppressing the self-inclusion phenomenon. As a result, we developed two tunable cationic supramolecular polymers (SMP) based on functionalized β-CD with relatively high polymerization degrees. Their ability to form hierarchical SMP with rigid polyanionic species was then assessed by DLS, spectroscopy and cryo-TEM. In optimized concentration and charge ratio conditions, three different water-soluble hierarchical assemblies were formed. We showed that the first level of association and the high directionality of the secondary interactions are key parameters to achieve these stable, well-defined, hierarchical assemblies. These tunable structures will be therefore used as a platform to get greater insight into hierarchical assembling processes.

Supramolecular systems comprised of non-covalent interactions are reversible in nature. This intrinsic reversibility of these systems is essential in achieving several functions, making it crucial to understand the dynamics of supramolecular systems. However, studies on the dynamics of supramolecular systems have always lagged behind structural and thermodynamic characterization of innumerable supramolecular systems developed. The first objective of this work was to understand the dynamics leading to a shift in the acidity constant (pKa) for 2-aminoanthracenium cation (AH+) upon binding with cucurbit[7]uril (CB[7]) host molecule. The adiabatic deprotonation of free AH+ in water was found to be inhibited in the complex with CB[7]. Different spectral characteristics for the protonated and deprotonated form of the guest molecule were used to understand the mechanism of this pKa shift associated with the binding to CB[7]. The results suggested that the pKa shift upon binding with CB[7] is a result of the slowing down of the deprotonation step in the complex, whereas the association rate constant did not change very much. The second objective of this work was to understand the role of cations on the binding dynamics of the N-phenyl-2-naphthyl amine (Ph-A-Np) binding to CB[7]. Ph-A-Np has two binding sites, which can lead to 1:1 and 2:1 host-guest complexes. The results indicate a switch in the binding mechanism for Ph-A-Np at low and high concentration regimes of sodium ions. Sodium ion was found to reduce the binding affinity of the naphthyl group to CB[7] whereas the complex formed by the phenyl group with CB[7] bound to one sodium ion was found to be stabilized. The final objective of this work was to study how structural changes to a guest molecule can affect the binding dynamics for the formation of a 2:1 “capsule” like complex with octa acid (OA). The dissociation for the OA capsule with pyrene (Py) as the encapsulated guest was shown to happen in 2.7 s previously. Two pyrene derivatives, 1-methylpyrene (MePy) and 1-pyrenemethanol (PyMeOH) were chosen as guest molecules to study the effect of these substituents on pyrene on the capsule dissociation dynamics. The results show that the residence time for the guests in the OA capsule depends on the substituents. For PyMeOH and MePy a shorter and longer residence time respectively in the capsule was observed when compared to Py. / Graduate / 2019-09-30

A series of five linked β-cyclodextrin (βCD) dimers N,N-bis(6 [superscript]A-deoxy-6[superscript]A-β-cyclodextrinyl)-succinamide, 66βCD₂su, N-((2[superscript]A S,3 [superscript]A S)-3 [superscript]A-deoxy-3 [superscript]A-β-cyclodextrinyl)-N’-(6 [superscript]A-deoxy-6 [superscript]A -β-cyclodextrinyl)-urea, 36βCD₂su, N,N-bis((2 [superscript]A S,3 [superscript]A S)-3 [superscript]A -deoxy-3 [superscript]A-β-cyclodextrinyl)-succinamide, 33βCD₂su, N,N-bis(6[superscript]A-deoxy-6[superscript]A-β-cyclodextrinyl)-urea, 66βCD₂ur, and N-((2 [superscript]A S,3 [superscript]A S)-3 [superscript]A-deoxy-3 [superscript]A-β-cyclodextrinyl)-N’-(6 [superscript]A -deoxy-6 [superscript]A -β-cyclodextrinyl)urea, 36βCD₂ur, has been prepared. The complexation of 6-(4’-(toluidinyl)naphthalene-2-sulphonate, TNS⁻, by βCD and the five linked βCD dimers was characterized by UV, fluorescence and 2D ¹H ROESY NMR spectroscopy. In aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm⁻³ and 298.2 K, TNS⁻ forms host-guest complexes with βCD of stoichiometry βCD.TNS⁻ (K₁ = 3020 and 3320 dm³ mol⁻¹) and βCD₂.TNS⁻ (K₂ = 57 and 11 dm³ mol⁻¹) where the first and second values were determined in UV and fluorescence studies, respectively. For 66βCD₂su, 36βCD₂su, 33βCD₂su, 66βCD₂ur and 36βCD₂ur, the analogous K₁ = 16100, 10900, 10700, 55100 and 18300 dm³ mol⁻¹ and K₁ = 12500, 8700, 9600, 38000 and 9800 dm³ mol⁻¹(fluorimetric studies), respectively. ¹H 2D ROESY NMR studies provided evidence for variation of the mode of complexation of the TNS⁻ guest as the βCD host is changed. The factors affecting complexation are discussed. UV and ¹H NMR studies showed that 6-(4’-(t-butyl)-phenyl)naphthalene-2-sulphonate, BNS⁻, and its dimer, (BNS⁻)₂, form host-guest complexes with βCD of the stoichiometry βCD.BNS⁻ (K₁ = 5.54 × 10⁴ dm³ mol⁻¹ ) and βCD.BNS₂ ²⁻(K₂ = 3.07 × 10² dm³ mol⁻¹ ) where the complexation constant K₁ = [βCD.BNS⁻]/([βCD][BNS⁻] and K₂ = [βCD.(BNS⁻)₂]/([βCD.BNS⁻][BNS⁻]) in aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm⁻³ and 298.2 K. For 66βCD₂su, 36βCD₂su, 33βCD₂su, 66βCD₂ur and 36βCD₂ur the analogous K₁ = 125, 74, 10.2, 364 and 16.1 (× 10⁴ dm³ mol⁻¹ ) and K₂ = 25.7, 2.30, 2.57, 17.6 and 17.2 (× 10² dm³ mol⁻¹ ), respectively. For the dimerisation of BNS⁻ K[subscript]d = 2.63 × 10² dm³ mol⁻¹ . Fluorimetric studies showed that the complexation stability for βCD.BNS⁻, forms βCD. BNS⁻, 66βCD₂su.BNS⁻, 36βCD₂su.BNS⁻, 33βCD₂su. BNS⁻, 66βCD₂ur.BNS⁻ and 36βCD₂ur. BNS⁻ characterized by K₁ = 4.67, 330, 101, 11.0, 435 and 29.6 (× 10⁴ dm³ mol⁻¹ ), respectively. The factors affecting the variations in these data are discussed. The enantioselectivity of substituted βCDs 6 [superscript]A -[bis (carboxylatomethyl)amino]-6 [superscript]A -deoxy-β-cyclodextrin (6βCDidaH₂) and (2 [superscript]A S,3 [superscript]A S)-3 [superscript]A -[bis(carboxylatomethyl)amino]-3[superscript]A -deoxy-β-cyclodextrin (3βCDidaH₂) and 6 [superscript]A -[tris(carboxylatomethyl)(2- aminoethyl)amino]-6 [superscript]A -deoxy-β-cyclodextrin (6βCDedtaH₃) and their Eu³ ⁺ complexes in forming host-guest complexes with six enantiomeric guests in D₂O was studied by 1D and 2D ¹H NMR (600 MHz) spectroscopy. The guests are D/L-tryptophanate (Trp⁻), 4-hydroxyl-D/L-phenylglycinate (4HOPhg⁻), D/L-histidinate (His⁻), D/L-pheniramine (Phm), D/L-phenylglycinate (Phg⁻) and (D/L)-β-phenylserinate (βPhs⁻). Enantioselective host-guest complexation was observed between the [Eu(6βCDida)]⁺ , [Eu(3βCDida)]⁺ and [Eu(6βCDedta)] complexes and Trp⁻, [Eu(6βCDida)]⁺ and [Eu(3βCDida)]⁺ and 4HOPhg⁻, and βCD, 6βCDida²⁻, 3βCDida²⁻, 6βCDedta³⁻ and the Eu³⁺complexes of the three substituted βCDs and Phm. The His⁻, Phg⁻ and βPhs⁻ enantiomers showed no evidence for selective host-guest complexation. The preparation of 3βCDidaH₂ and 6βCDedtaH₃ and the determination of their pK[subscript]a s are also reported. In collaboration with the research group of Prof. Matthew A. Tarr, (University of New Orleans, USA), the 6βCDida²⁻ and the 6βCDedta³⁻ has been utilized to improve Fenton oxidation of aromatic pollutants. To further support to this work, the binary complexation of Fe² ⁺ by 6βCDida²⁻ has been studied by potentiometric titrations. A series of six modified poly(acrylic acid)s 3% substituted with either βCD or the adamantyl moiety with different length of substituent chain was synthesised. To advance the understanding and control of aqueous supramolecular assembly, the host-guest interactions between the βCD substituted poly(acrylic acid)s and adamantane-1-carboxylic; adamantyl substituted poly(acrylic acid)s with βCD and linked βCD dimers; and between both βCD and adamantyl substituted poly(acrylic acid)s have been studied. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1311237 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008