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dc.contributor.advisorMorris, Russell Edward
dc.contributor.authorVornholt, Simon Maximilian
dc.coverage.spatialxvii, 280 p.en_US
dc.date.accessioned2021-07-14T15:27:20Z
dc.date.available2021-07-14T15:27:20Z
dc.date.issued2021-06-30
dc.identifier.urihttp://hdl.handle.net/10023/23566
dc.description.abstractThe research presented in this thesis aimed to develop new metal-organic framework (MOF) materials and MOF composites for biomedical applications. New synthesis methods of CPO-27-M (M = Co, Mg, Ni, Zn) were explored with particular focus on the formation of single crystals. Low temperature syntheses showed formation of crystalline CPO-27-Zn down to 195 K. Single crystals of CPO-27-Mg and -Zn were afforded from a modulated solvothermal synthesis using salicylic acid, and an isomorph called UTSA-74 was obtained when benzoic acid was used. All three materials proved suitable for structural analysis through in-house single crystal X-ray diffraction (SXRD). The concept of modulation chemistry was employed to control the crystallite size and a novel mixed-linker synthesis approach yielded large single crystals of CPO-27-Ni. All materials displayed phase pure through PXRD, compositional analysis, TGA, and electron microscopy methods. Large single crystals of CPO-27-Ni were used in synchrotron based in situ gas cell experiments to probe the adsorption of nitric oxide (NO). An efficient activation protocol was developed leading to a dehydrated structure after just 4 h. For the first time, single crystal structure models of CPO-27-Ni were presented of the as-synthesised, dehydrated, and subsequently NO loaded conformation. A multifaceted study of the interactions between CPO-27-Ni and polyurethane (PU) was conducted to rationalise the NO release performance of composite films used as proxy for antibacterial coatings. From a range of MOF loadings (5, 10, 20, and 40 wt%) an optimal MOF loading of 10 wt% was identified, where highest amounts of NO with a potent bactericidal efficacy are released. Molecular dynamics simulations and FIB-SEM techniques revealed an excellent compatibility and connectivity between the MOF/PU interface. Reconstruction of the microstructure of a high MOF loading composite (40 wt%) showed that the MOF exhibits a highly connected network, which was proposed to contribute to a more tortuous gas transport. This also may be the reason for reduced NO efficiencies and tensile strengths seen in high MOF loading composites (20−40 wt%). The Kolbe-Schmitt reaction was utilised for the synthesis of new functional linkers. Two methylated 4,6-dihydroxyisophthalic acids were obtained and used to generate new MOF materials for storage and release of NO. The 2,3-dihydroxyterephthalic acid linker was used to synthesise a new MOF system that has properties of isoreticular chemistry and is systematically named SIMOF-0, 1, 2, and 3 (St Andrews Isoreticular MOF). All four phases were characterised through SXRD. SIMOF-3 displayed an interesting, pillared crystal structure with indication of flexibility. A drug loading study using flutamide showed a prolonged release of the drug over the course of 72 h and solid-state NMR indicated that the drug may be adsorbed in the pore system of the MOF. SIMOF-1 was used as a precursor for other materials. In a ‘regeneration’ synthesis approach, a sample of SIMOF-1 was transformed to phase pure SIMOF-3.en_US
dc.description.sponsorship"[T]his work was supported by the EPSRC (grant number EP/K005499/1) and the ERC (grant number 787073)." -- Acknowledgementsen
dc.language.isoenen_US
dc.publisherUniversity of St Andrews
dc.relationSynthesis and characterisation of metal-organic frameworks and composites for biomedical applications (thesis data) Vornholt, S.M., University of St Andrews. DOI: https://doi.org/10.17630/d7c4899f-f50a-4bf9-8530-007f5bbb3395en
dc.relation.urihttps://doi.org/10.17630/d7c4899f-f50a-4bf9-8530-007f5bbb3395
dc.rightsCreative Commons Attribution-NonCommercial-NoDerivatives 4.0 International*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectMetal-organic frameworken_US
dc.subjectMOFsen_US
dc.subjectSingle crystalen_US
dc.subjectX-ray diffractionen_US
dc.subjectBiomedical applicationsen_US
dc.subjectSEMen_US
dc.subjectFIB-SEMen_US
dc.subject3D reconstructionen_US
dc.subjectModulated synthesisen_US
dc.subjectCompositesen_US
dc.subjectPolymer formulationsen_US
dc.subject.lccQD411.V7
dc.subject.lcshMetal-organic frameworksen
dc.subject.lcshPolymersen
dc.titleNovel metal-organic frameworks and polymer formulations for biomedical applicationsen_US
dc.typeThesisen_US
dc.contributor.sponsorEuropean Research Council (ERC)en_US
dc.contributor.sponsorEngineering and Physical Sciences Research Council (EPSRC)en_US
dc.type.qualificationlevelDoctoralen_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US
dc.rights.embargodate2023-06-03
dc.rights.embargoreasonThesis restricted in accordance with University regulations. Print and electronic copy restricted until 3rd June 2023en
dc.identifier.doihttps://doi.org/10.17630/sta/112
dc.identifier.grantnumber787073en_US
dc.identifier.grantnumberEP/K005499/1en_US


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