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Phoebe Allan PhD thesis PDF

292 Pages·2012·35.69 MB·English
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A STUDY OF METAL-ORGANIC FRAMEWORKS FOR THE STORAGE AND RELEASE OF MEDICAL GASES Phoebe Kate Allan A Thesis Submitted for the Degree of PhD at the University of St. Andrews 2012 Full metadata for this item is available in Research@StAndrews:FullText at: http://research-repository.st-andrews.ac.uk/ Please use this identifier to cite or link to this item: http://hdl.handle.net/10023/3198 This item is protected by original copyright AAAA SSSSttttuuuuddddyyyy ooooffff MMMMeeeettttaaaallll-OOOOOOrrrrrrggggggaaaaaannnnnniiiiiicccccc FFFFFFrrrrrraaaaaammmmmmeeeeeewwwwwwoooooorrrrrrkkkkkkssssss ffffffoooooorrrrrr tttttthhhhhheeeeee SSSSSSttttttoooooorrrrrraaaaaaggggggeeeeee aaaaannnnnddddd RRRRReeeeellllleeeeeaaaaassssseeeee ooooofffff MMMMMeeeeedddddiiiiicccccaaaaalllll GGGGGaaaaassssseeeeesssss PPPhhhoooeeebbbeee KKKaaattteee AAAllllllaaannn TTTTTTTTThhhhhhhhhiiiiiiiiisssssssss ttttttttthhhhhhhhheeeeeeeeesssssssssiiiiiiiiisssssssss iiiiiiiiisssssssss sssssssssuuuuuuuuubbbbbbbbbmmmmmmmmmiiiiiiiiitttttttttttttttttteeeeeeeeeddddddddd iiiiiiiiinnnnnnnnn pppppppppaaaaaaaaarrrrrrrrrtttttttttiiiiiiiiiaaaaaaaaalllllllll fffffffffuuuuuuuuulllllllllfffffffffiiiiiiiiilllllllllmmmmmmmmmeeeeeeeeennnnnnnnnttttttttt fffffffffooooooooorrrrrrrrr ttttttttthhhhhhhhheeeeeeeee dddddddddeeeeeeeeegggggggggrrrrrrrrreeeeeeeeeeeeeeeeee ooooooooofffffffff PPPPPPPPPhhhhhhhhhDDDDDDDDD aaaaattttt ttttthhhhheeeee UUUUUnnnnniiiiivvvvveeeeerrrrrsssssiiiiitttttyyyyy ooooofffff SSSSSttttt AAAAAnnnnndddddrrrrreeeeewwwwwsssss 7th June 22001122 I, Phoebe Kate Allan, hereby certify that this thesis, which is approximately 68000 words in length, has been written by me, that it is the record of work carried out by me and that it has not been submitted in any previous application for a higher degree. I was admitted as a research student in September 2008 and as a candidate for the degree of PhD in September 2009; the higher study for which this is a record was carried out in the University of St Andrews between 2008 and 2012. Date Signature of candidate I hereby certify that the candidate has fulfilled the conditions of the Resolution and Regulations appropriate for the degree of PhD in the University of St Andrews and that the candidate is qualified to submit this thesis in application for that degree. Date Signature of supervisor i In submitting this thesis to the University of St Andrews I understand that I am giving permission for it to be made available for use in accordance with the regulations of the University Library for the time being in force, subject to any copyright vested in the work not being affected thereby. I also understand that the title and the abstract will be published, and that a copy of the work may be made and supplied to any bona fide library or research worker, that my thesis will be electronically accessible for personal or research use unless exempt by award of an embargo as requested below, and that the library has the right to migrate my thesis into new electronic forms as required to ensure continued access to the thesis. I have obtained any third-party copyright permissions that may be required in order to allow such access and migration, or have requested the appropriate embargo below. The following is an agreed request by candidate and supervisor regarding the electronic publication of this thesis: Access to printed copy and electronic publication of thesis through the University of St Andrews. Date Signature of candidate Date Signature of supervisor Courses Attended The School of Chemistry at the University of St. Andrews requires that a postgraduate attend a number of taught courses. The courses attended were: Crystallography Frontiers in Main Group Chemistry EastChem Paper writing course EastChem Thesis writing course ii This thesis presents a study of the interaction of medical gases nitric oxide, carbon monoxide and hydrogen sulfide with metal-organic framework materials. Most analysis is performed via single-crystal X-ray diffraction and Rietveld and pair distribution function analysis of powder X-ray diffraction data. A background to the field and the experimental methods used are described in Chapters 1 and 3. The use of a specially designed static environmental gas cell to assess the role of coordinatively unsaturated metal sites in nitric oxide storage in Co-CPO-27 via in situ single-crystal structure determination is described in Chapter 4. Nitric oxide was shown to bind to the Co-centre of the material in a bent geometry in an approximately 1:1 Co:NO ratio. A multi-technique study was conducted on the framework Cu-SIP-3 in Chapters 5 and 6, utilising both single-crystal X-ray diffraction and pair distribution function analysis to obtain complementary information about atomic movements during a thermally active single-crystal to single-crystal transition. These techniques were further applied during in situ gas-loading experiments on the same framework. Application of the pair distribution function technique to metal-organic frameworks is described in Chapter 7, where refinements of both known and unknown metal-organic framework structures are presented. Partial PDFs are used to determine the secondary building block of a new metal-organic framework and verify the structural solution determined from powder X-ray diffraction data. Chapter 8 presents the study of the M-CPO-27 isostructural series for the adsorption and release of hydrogen sulfide and carbon monoxide. Gas adsorption isotherms and release measurements are correlated with the structure of the Ni-CPO-27 hydrogen sulfide-adduct determined by both powder X-ray diffraction and differential pair distribution function methods which reveal the open-metal site as the primary adsorption interaction in the material. The hydrogen sulfide released from Zn-CPO-27 is determined to be biologically active through vasodilatation experiments. iii Declarations i Abstract iii Acknowledgements v List of abbreviations vii Publications arising from this work ix 1 Introduction 1 1.1 Gaseous signalling molecules 1 1.2 Structure and chemistry of NO, CO and H S 3 2 1.3 Endogenous production of NO, CO and H S 8 2 1.4 Biological actions of NO, CO and H S 13 2 1.5 Potential of gasotransmitters as therapeutics 18 1.6 Metal-organic frameworks 21 1.7 Gas storage in porous materials 23 1.8 MOFs for biological applications 29 1.9 References 40 2 Aims 53 3 Experimental Methods 55 3.1 Solvothermal Synthesis 55 3.2 The crystalline state 56 3.3 X-ray diffraction 59 3.4 X-ray generation and synchrotrons 66 3.5 Single-crystal X-ray diffraction (SCXRD) 68 3.6 Powder X-ray diffraction 79 3.7 Pair Distribution Function (PDF) analysis 84 3.8 Gas adsorption and release measurements 97 3.9 References 103 xi 4 Development of an environmental gas cell for single-crystal studies 107 4.1 Declaration 107 4.2 Introduction 107 4.3 Aims 115 4.4 Synthesis of Co-CPO-27 115 4.5 General experimental procedures 116 4.6 Dehydration studies 119 4.7 Gas-loading studies 123 4.8 Discussion 134 4.9 Conclusions and Further Work 135 4.10 Key to data sets given in Appendix B 137 4.11 References 138 5 In situ single-crystal diffraction studies on copper-sulfosiophthalate 141 5.1 Introduction and aims 141 5.2 Structure of copper sulfoisophthalate (Cu-SIP-3) 142 5.3 Experimental details 149 5.4 Variable temperature single-crystal studies 151 5.5 Where does the Bragg diffraction go? 169 5.6 Nitric oxide adsorption in Cu-SIP-3 170 5.7 Conclusions and further work 173 5.8 References 174 6 Pair distribution function analysis of copper-sulfoisophthalate 175 6.1 Motivation 175 6.2 Aims 176 6.3 Experimental details 176 6.4 Results 180 6.5 Gas-loading experiments 204 6.6 Discussion 206 6.7 Conclusions and Further Work 210 6.8 References 213 xii 7 Application of pair distribution function analysis to metal-organic 215 frameworks for gas storage 7.1 Introduction 215 7.2 Aims 217 7.3 Experimental methods 217 7.4 Pair distribution function analysis of M-CPO-27 220 7.5 PDF as a fingerprinting methods for gas adsorption 233 7.6 Application of PDF analysis to unknown framework STAM-2 236 7.7 Conclusions and Further Work 251 7.8 References 253 8 Towards the use of MOFs for storage and release of hydrogen sulfide and 255 carbon monoxide: the isostructural series M-CPO-27 8.1 Motivation 255 8.2 Aims 256 8.3 Synthetic details 257 8.4 Experimental details 257 8.5 Hydrogen sulfide adsorption and release 260 8.6 The structure of the H S-adduct of Ni-CPO-27 266 2 8.7 Preliminary biological experiments using H S-Zn-CPO-27 274 2 8.8 Carbon monoxide adsorption and release 276 8.9 Discussion and Conclusions 280 8.10 References 281 9 General implications and Future Directions 283 xiii This thesis examines the interaction of the medical gases nitric oxide (NO), carbon monoxide (CO) and hydrogen sulfide (H S) with metal-organic frameworks. In the 2 following introduction the chemistry, endogenous production and biological actions of these gases are reviewed, and current technologies for implementing their use in medicine are presented. Subsequently, a background to the field of metal-organic frameworks is presented with consideration of why these materials present a promising technology for storing and delivering biological gases. Finally, the importance of crystallographic studies in revealing the structural details associated with gas adsorption in materials is discussed and previous studies in this area are described. 1.1 Gaseous Signalling Molecules Cells signal to each other in order to coordinate cellular actions. This intercellular signalling takes place through the use of neurotransmitters. Chemicals traditionally recognised as neurotransmitters are compounds produced by neurons and stored in vesicles until stimulation of the neurons trigger their release (Figure 1-1a). They bind to specific membrane receptors in a neighbouring cell to produce a physiological effect. ‘Gasotransmitters’ are a group of small gaseous molecules that exhibit a similar signalling function in the body but through a different mechanism. They function without receptors because they are freely permeable to cell membranes (Figure 1-1b).1 The term gasotransmitter was first used in a paper by Rui Wang in 2002,2 in order to distinguish the receptor-independent signalling nature of these molecules from that of traditional neurotransmitters. Wang suggested that for a molecule to be considered a gasotransmitter, a number of criteria must be met (Table 1).1 Most importantly, the molecule must be produced endogenously (within the body) for a specific biological function. The term gasotransmitter additionally serves to recognise the similarities between signalling methods employed by each of the gasotransmitter molecules and to group the molecules together. The similarities and differences between the actions of each gasotransmitter are discussed in section 1.4.3. To date, three gasotransmitter molecules have been proposed; nitric oxide, carbon monoxide and hydrogen sulfide. 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http://research-repository.st-andrews.ac.uk/. Please use this identifier monoxide and hydrogen sulfide with metal-organic framework materials. This chapter aims to collect and process total scattering data for known and novel.
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