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Towards molecular machine functionalised biological and biomimetic systems

Maclean, Catherine Elaine (2012) Towards molecular machine functionalised biological and biomimetic systems. PhD thesis, University of Glasgow.

Due to Embargo and/or Third Party Copyright restrictions, this thesis is not available in this service.

Abstract

Overall this thesis describes the study of the ability of the tetracationic cyclophane CBPQT4+ to form inclusion complexes with electron-rich moieties such as tetrathiafulvalene (TTF) and dioxynaphthalene. These complexes are strengthened by π-stacking and charge transfer interactions, which give rise to coloured complexes. The complexes are fully reversible and can be decomplexed by the addition of a stimulus that can be chemical, electrochemical, and thermal. In addition we have exploited the ability of ferrocene to form inclusion complexes with cyclodextrins in aqueous media. The host-guest interactions that occur between these molecules were investigated using a number of techniques such as UV-Vis, fluorescence, NMR spectroscopy and cyclic voltammetry. Isothermal titration calorimetery (ITC) was also be used to measure the Ka of the complexes. Chapter two describes the synthesis of naphthalene and ferrocene functionalised dihydroimidazophenanthridines (DIPs). These materials were synthesised in order to create DNA intercalating agents that could undergo further host-guest interactions with either CBPQT4+ or β-cyclodextrin. These interactions were studied using ITC in a number of aqueous buffers with calf thymus DNA and the synthetic Dickerson dodecamer D-DNA. Additionally, the host-guest interactions for the naphthalene functionalised DIP with CBPQT4+ were studied using UV-Vis, fluorescence and NMR spectroscopy. The cytotoxic nature of the functionalised DIPs were investigated using MDCK epithelial cell culture experiments. Chapter three describes the synthesis and analysis of silane and disulfides modified with chosen electron rich substrates for the production of functionalised surfaces where self-assembled monolayers were produced on either glass or gold surfaces. These functionalised surfaces were then utilised in cell adhesion experiments with MDCK cells where the modulation of adhesion was attempted by the formation of pseudorotaxanes with either CBPQT4+ or β-cyclodextrin and by changing the oxidation state of the functional group in the case of ferrocene. Chapter four describes the synthesis of functionalised diacetylenes for the formation of polydiacetylene liposomes in aqueous conditions. The liposomes successfully formed were analysed by DLS. UV-Vis spectroscopy and cyclic voltammetry were used to investigate the dual response chromophoric sensing applications of these materials. Chapter five describes the synthesis of functionalised surfactant compounds for the formation of mixed micelles in aqueous conditions with sodium dodecyl sulfate (SDS). The interactions between the surfactant and CBPQT4+ were measured by ITC, NMR, UV-Vis, and fluorescence spectroscopy. Chapter six describes the modification of the protein BSA with a naphthalene functionalised chloroacetate. The modified protein was analysed by ITC, MALDI TOF, UV-Vis, and fluorescence spectroscopy in order to identify the degree of functionalisation that had occurred and whether complexation was possible with CBPQT4+. Chapter seven describes the synthesis of a naphthalene, and two ferrocene functionalised biotin conjugates with a view to investigate the interactions with avidin proteins. The interactions were measured by ITC and UV-Vis spectroscopy. The effect of changing the chain length on binding to neutravidin and β-cyclodextrin was studied in the ferrocene biotin conjugates where the interactions were assessed using ITC, cyclic voltammetry, and NMR spectroscopy. The interactions between the naphthalene based conjugate and CBPQT4+ was measured by UV-Vis and fluorescence spectroscopy.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Supramolecular chemistry, CBPQT4+, naphthalene, ferrocene, TTF, Isothermal titration calorimetry ITC, UV-Vis, Fluorescence, Host-guest Interactions,
Subjects: Q Science > QD Chemistry
Colleges/Schools: College of Science and Engineering > School of Chemistry
Supervisor's Name: Cooke, Prof. Graeme and Cooper, Prof. Alan and Riehle, Dr. Mathis and Smith, Dr. Brian O.
Date of Award: 2012
Embargo Date: 7 May 2016
Depositing User: Miss Catherine Elaine Maclean
Unique ID: glathesis:2012-3277
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 26 Mar 2012
Last Modified: 07 May 2013 14:36
URI: http://theses.gla.ac.uk/id/eprint/3277

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