Zugl.: Regensburg, Universiẗat, Diss., 2008.

No description available.

Rotaxanes can be synthesized using a thermodynamically driven approach of self-assembly. The thermodynamically driven approach is an efficient method to provide a better controlled synthesis of specific structures. This synthetic approach takes advantage of a labile bond between the guest molecule and the end stopper group. The reversibility of this bond allows for threading by the host molecule via chemical equilibrium. Intramolecular interactions such as hydrogen bonding and π-π stacking facilitate threading to form the pseudorotaxane which is endcapped to form the thermodynamically stable rotaxane. In this work, the synthesis and characterization of rotaxanes using a thermodynamically driven approach is reported. New OH-functionalized secondary dibenzyl ammonium hexafluorophosphate and tetrafluoroborate salts were synthesized and complexed with dibenzo-24-crown-8. The complexation between the salts and dibenzo-24-crown-8 was observed using 1D and 2D ¹H NMR spectroscopy. An association constant of 110 M⁻¹ was determined by integration for the pseudorotaxane from the ammonium hexafluorophospate salt and dibenzo-24-crown-8. The new guest species were endcapped in situ as trityl ethers to form new thermodynamically stable rotaxanes. Further work to pursue would include synthesis of rotaxanes using functionalized crown ethers for polymerization to make polyrotaxanes and synthesis of self-assembled polymers using this synthetic method. / Master of Science

Based on the concept of covalent capture of supramolecular assemblies, the idea of mechanical encapsulation is exploited for the protection and delivery of peptidebased molecules. This thesis aims to establish a general method for the encapsulation of peptides within a rotaxane structure, as well as studying their mode of release under specific stimuli. The synthesis of such structures, relying on the elongation of short peptido[2]rotaxanes, is applied to the design of rotaxane peptide carriers whose function is to protect against biological degradation and release peptides under a biological stimulus. These molecules are composed of a rotaxane-encapsulated peptide bearing a biodegradable stopper, the enzyme-specific cleavage of which triggers peptide release, via ‘dethreading’. The synthesis and in vitro assessment of rotaxane carriers as agents for anti-cancer therapy will be described in detail. The future challenges and potential applications of the proposed systems will be addressed.

This thesis is concerned with the synthesis and study of novel anion templated rotaxanes and catenanes for electrochemical anion sensing, as well as interlocked structures that possess different anion binding properties, higher-order topologies and the ability to undergo molecular motion. Chapter One provides an introduction to anion recognition and the preparation of interlocked structures. A short summary of fundamental aspects of supramolecular chemistry is followed by detailed surveys of current approaches to anion binding and sensing, as well as the templated synthesis of rotaxanes and catenanes. Chapter Two describes the preparation of rotaxanes and catenanes appended with ferrocene to allow for electrochemical anion sensing. The anion recognition properties of a [2]rotaxane and a [2]catenane, as investigated by ¹H NMR spectroscopy and electrochemical methods, are presented. The utilization of a ferrocene-appended macrocycle in the construction of surface confined anion templated rotaxanes and catenanes is also discussed. Chapter Three reports the work carried out to achieve electrochemical anion sensing by the incorporation of redox-active groups into the integral structures of interlocked structures. The syntheses of a bis-stoppered 1, 2, 3, 4, 5-pentaphenylferrocene [2]rotaxane and a ferrocene containing [3]rotaxane are presented, along with their subsequent anion recognition studies. In addition, attempts to incorporate ferrocene into the macrocyclic components of rotaxanes and catenanes are outlined. Chapter Four details further investigations into the use of interlocked structures to achieve anion recognition. Doubly-charged [2]catenanes able to bind anions in aqueous solvent media, as well as the incorporation of alternative anion binding motifs into interlocked architectures are reported. The exploitation of anion templated synthesis to allow for the construction of higher order structures (including [3]catenanes, a “handcuff” catenane and a Janus [2]rotaxane), as well as a [2]catenane system with anion controlled molecular motion is also described. Chapter Five presents the experimental procedures and characterization data relating to the compounds prepared in Chapters Two, Three and Four. Chapter Six summarizes the main conclusions of the work contained within this thesis. Supplementary experimental information relating to titration protocols, investigations into self-assembled monolayers (SAMs) and crystallographic data are provided in Appendices I, II and III.

京都大学 / 0048 / 新制・課程博士 / 博士(薬科学) / 甲第19660号 / 薬科博第48号 / 新制||薬科||6(附属図書館) / 32696 / 京都大学大学院薬学研究科薬科学専攻 / (主査)教授 川端 猛夫, 教授 高須 清誠, 教授 竹本 佳司 / 学位規則第4条第1項該当 / Doctor of Pharmaceutical Sciences / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19734号 / 工博第4189号 / 新制||工||1646(附属図書館) / 32770 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 辻 康之, 教授 村田 靖次郎, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21116号 / 工博第4480号 / 新制||工||1696(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 辻 康之, 教授 大江 浩一, 教授 松田 建児 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

No description available.