"Porous materials have been a focus of researchers for their applications as molecular storage, molecular sensing, catalysis, asymmetric synthesis and host materials. Metal-organic frameworks (MOFs) represent a promising new class of porous crystalline solids because they exhibit large pore volumes, high surface areas, permanent porosity, high thermal stability, and feature open channels with tunable dimensions and topology. We are currently investigating the design, synthesis, and structures of a new family of MOFs derived from transition metals complexes of 4-(imidazole-1-yl)benzoic acids. Here we present our effort in continuing design and synthesis MOFs composed of 4-(imidazole-1-yl)benzoic acids to expand our knowledge about 4-(imidazole-1-yl)benzoic acid MOF family. A series of ligands are synthesized and Cu MOF-3N, 4, 5 and Cd MOF-3 were synthesized, structure determination found out metal-ligand complex follows our proposal, while Cu MOF-4,5 exhibit porous framework structure via absolute structure determination. Sorption behavior is a key focus in MOF application because the great potential applications MOF bears. Here we carry out a fundamental study about MOF texture and selectivity on MOF-5 and Cd MOF-2. Non-polar polyaromatic hydrocarbons such as naphthalene, phenanthrene, and pyrene, polar molecules such as 2-naphthol, ibuprofen were selected to test our hypothesis that sorption is influenced by the degree of tight fitting, and guest-host interaction such as van der waals and hydrogen bonding. By determining Langmuir isotherms of selected guest molecules, we are able to demonstrate our hypothesis that tighter the fit of the guest molecule and the pores, the higher the amount it would sorb. The sorption difference of non-polar and polar molecules suggest hydrogen bonding is not involved in guest sorption and the dominating force of sorption is hydrophobic interaction. Polymorphism is an interesting phenomenon that bears great value in pharmaceutical industry. Here we report the first case for MOF to serve as a heterogeneous surface that induced nucleation of indomethacin. It is also a first report of this polymorph form of indomethacin. PXRD, DSC, TGA, NMR are conducted as our initial investigation effort. This polymorph exhibits exceptionally thermal stability and low solubility, indicating an unusual tight binding between indomethacin and ethanol solvate. "

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: The aim of this thesis was to study structure-property relationships in porous materials using various adapted analytical techniques and in-house instruments. The thesis is divided into two sections, and the first section of work constitutes the majority of the thesis. The first section of work deals with the theoretical versus experimental classification of sorption selectivity in porous compounds. A transiently porous metallocycle that can adsorb acetylene and carbon dioxide served as a model host for this experiment. A volumetric sorption instrument had to be constructed to carry out sorption with acetylene. Even though the metallocycle should theoretically be selective for acetylene over carbon dioxide based on single-gas sorption isotherms, this was not the case during the sorption of a mixture of the two gases. Furthermore, high-pressure single-crystal diffraction was carried out utilising an in-house environmental gas cell, and structural elucidation indicated that both acetylene and carbon dioxide coexist in a single cavity of the host. Additional complementary techniques are discussed that were used to confirm that both gases are present in a single host cavity. The techniques included infrared spectroscopy as well as high-pressure florescence and Raman spectroscopy, which had to be conducted with a specially designed pressure vessel and with adapted instrumentation. Finally, density functional theory calculations were employed to explain how host-guest and guest-guest interactions lead to the change in adsorption selectivity. It is concluded that researchers need to show experimentally that a compound is selective for the adsorption of a specific gas, because theoretical models are not always accurate. The second part of this work focuses on a fundamental study of the structure-property relationships in a porous hydrogen-bonded organic framework. The section starts off by exploring the activation conditions and thermal stability of the framework. This is followed by an exploration of a possible phase transformation or thermal expansion in the framework, but neither of these occurred. Thereafter, an extended study of the framework’s sorption behaviour with various gases is discussed. Then, a structural study of its solvated phase is used to explain the framework’s stability. Finally, a novel analytical method is introduced, and two examples are used to demonstrate why the instrument is useful in the field of supramolecular chemistry. The chapter is concluded by stating the importance these fundamental studies, as well the development of new analytical techniques. / AFRIKAANSE OPSOMMING: Die doel van hierdie tesis was om die struktuur-afhanklike eienskappe van poreuse materiale te ondersoek. Die studie het gebruik gemaak van verskeie aangepasde analitiese metodes asook instrumente wat spesifiek vir die studie gebou was. Die werk word in twee dele verdeel, en die meerderheid van die tesis word in die eerste deel bevat. In die eerste deel van die tesis word die validiteit van teoretiese- teen eksperimentele adsorpsie selektiwiteit opgeweeg. ʼn Gasheer wat bestaan uit ringvormige koördinasie-verbindings en wat asetileen asook koolstof dioksied kan adsorbeer, dien as ʼn model gasheer vir die studie. ʼn Volumetriese sorpsie instrument was spesiaal vir die studie gebou sodat asetileen sorpsie gedoen kon word. Volgens asetileen en koolstof dioksied se enkel-gas adsorpsie isoterme moet asetileen teoreties met voorkeur geadsorbeer word gedurende ʼn adsorpsie eksperiment waarin beide gasse teenwoordig is, maar eksperimenteel was dit bepaal dat dit nie so is nie, dus is daar ʼn verandering in die gasheer se adsorpsie selektiwiteit. Hierna word strukturele data van die gasheer, onder ʼn hoë druk van die gas mengsel, versamel deur gebruik te maak van enkel-kristal diffraksie en ʼn spesiaal-gemaakde gas sel. Die strukturele data toon dat beide asetileen en koolstof dioksied teenwoordig is binne elke porie van die gasheer. Daar word dan van addisionele analitiese metodes gebruik te maak om die observasie te bevestig. Die analitiese metodes sluit in infrarooi spektroskopie asook hoë-druk fluoressensie en Raman spektroskopie wat geëis het dat ʼn spesiale druk-bestande monster houer gebou moes word en dat analitiese instrumente gemodifiseer moet word. Ten slotte was daar van “density functional theory” gebruik gemaak om te verduidelik dat die interaksie tussen die gasheer en gas sowel as die interaksie tussen twee gasse lei tot die verandering in adsorpsie selektiwiteit. Uit hierdie bevinding word die gevolgtrekking gemaak dat navorsers met meer eksperimentele data vorendag sal moet kom voordat ʼn gevolgtrekking gemaak kan word dat ʼn raamwerk selektief een gas adsorbeer. Die tweede afdeling van die werk fokus op ʼn fundamentele studie van die struktuur-afhanklike eienskappe van ʼn poreuse waterstof-verbinde organies raamwerk. Die afdeling begin deur ʼn ondersoek van die aktivering kondisies sowel as die temperatuur-afhanklike stabiliteit van die raamwerk. Dit word gevolg deur te soek na moontlike fase veranderings of temperatuur-afhanklike uitsetting van die raamwerk, maar nie een van die twee eienskappe word waargeneem nie. Daarna word die deeglike ondersoek van die raamwerk se adsorpsie vermoë met verskeie gasse bespreek. Dit word gevolg deur ʼn strukturele studie van die solvaat van die raamwerk, wat dan gebruik word om die stabiliteit van die raamwerk te verduidelik. Ten slotte word ʼn analitiese metode bekend gestel, en twee voorbeelde word gebruik om te wys hoe nuttig die metode is om ʼn kombinasie van resultate te bekom. Die hoofstuk word saamgevat deur te verduidelik hoekom dit belangrik is om hierdie tipe fundamentele studies te doen asook waarom nuwe analitiese metodes ontwerp moet word.

A modular approach for the synthesis of highly ordered porous and chiral auxiliary (Evans auxiliary) decorated metal–organic frameworks is developed. Our synthesis strategy, which uses known porous structures as model materials for incorporation of chirality via linker modification, can provide access to a wide range of porous materials suitable for enantioselective separation and catalysis. Chiral analogues of UMCM-1 have been synthesized and investigated for the enantioseparation of chiral compounds in the liquid phase and first promising results are reported. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Le greffage radio-induit de polymères fonctionnels, tels que le poly(acide acrylique) (PAA), la poly(4-vinyl pyridine) (P4VP) et le poly(bis[2-(methacryloyloxy)ethyl] phosphate (B2MP), dans la structure nanoporeuse de membranes en poly(fluorure de vinylidène) (PVDF) à traces attaquées est ici rapporté, l’objectif étant la pré-concentration sélective des ions Pb(II), Hg(II) et U(VI) en solution dans l’eau. Les membranes en PVDF à traces attaquées sont fabriquées par irradiation aux ions lourds rapides suivie par la révélation chimique des traces. Les membranes nanoporeuses en PVDF ainsi créées sont ensuite fonctionnalisées dans la porosité grâce à la présence de radicaux résiduels à la paroi des nanopores. La spectroscopie RPE a été utilisée pour déterminer la quantité et la réactivité des radicaux piégés, notamment dans le cas d’une fonctionnalité nouvelle comme le B2MP. Il a été montré que ces radicaux, alkyles et peroxyles, étaient en quantité suffisante pour initier une polymérisation radicalaire en présence des trois monomères étudiés. Le FESEM, le FTIR et une méthode moins conventionnelle comme le potentiel Zeta ont permis la caractérisation des groupes fonctionnels. Dans le cas du greffage de la P4VP dans les nanopores, la mesure des états de charges à la surface des nanopores versus le pH a montré que le greffage était uniforme et relativement dense tout au long des canaux poreux. L’objectif de ce travail étant de développer des capteurs électrochimiques innovants pour la détection des métaux toxiques, une étude en adsorption a confirmé des capacités de sorption très efficaces des membranes à traces en PVDF greffées dont les groupes fonctionnels facilitent les réactions de coordination partant d’une interaction électrostatique pure inhérente au PAA à la complexation chélatante avec la P4VP en passant par celle du B2MP. L’effet complexant modéré du B2MP dans le cas de l’adsorption de l’U(VI) est dû à la co-existence de groupements échangeurs d’ions et chélatants dans la structure du B2MP. Pour la détection électrochimique, les membranes en PVDF nanoporeuses radio-greffées sont converties en électrodes. La pré-concentration de métaux toxiques adsorbés dans la nanoporosité permet de diminuer la limite de sensibilité de la voltammétrie à redissolution à des concentrations sub-ppb (μg/L). Les données acquises en photoluminescence résolue en temps (TRPL) et en XPS ont approfondi la compréhension du mécanisme de coordination du complexe U(VI)-B2MP. / Present work reports on radiation grafting of poly(acrylic acid) (PAA), poly(4-vinyl pyridine) (P4VP) and bis[2-(methacryloyloxy)ethyl] phosphate (B2MP) functional polymers inside nanoporous structure of track-etched poly(vinylidene fluoride) (PVDF) membranes for selective pre-concentration of Pb(II), Hg(II) and U(VI) from aqueous solutions. Track-etched PVDF membranes were made by means of swift heavy ion (SHI) irradiation followed by ion track revealing. The resulting nanoporous PVDF membranes were then functionalized through remained radicals at the nanopore walls. EPR spectroscopy was used to examine the amount and reactivity of the trapped radicals, notably towards a novel functionality inside the etched tracks, namely B2MP. It was found that these radicals, alkyl and peroxy ones, were sufficient to initiate free-radical polymerization in presence of the three studied vinyl monomers. FESEM, FTIR and a less conventional zeta-potential measurements were utilized for examination of functional group presence. In case of P4VP grafting, the measured nanopore surface charge versus pH demonstrated uniform and relatively dense grafting all along the nanopore channels. As the objective of this work is to develop innovative electrochemical sensors for toxic metal determination in water, adsorption experiments were performed confirming that efficient uptakes of the grafted track-etched PVDF membranes are due to the presence of functional groups that facilitate coordination reactions from pure inherent to PAA electrostatic interaction to chelating complexation with P4VP and B2MP complexation in between. The moderate interaction effect in case of U(VI) adsorption by B2MP is due to the co-existence of ion-exchange and chelating groups in B2MP. For electrochemical sensoring, membranes functionalized with abovementioned chelate polymers were converted into electrodes. The pre-concentration of toxic metal adsorbed inside the nanoporosity permit to below stripping voltammetry sensitivity limits to sub-ppb (μg/L) level. Time-resolved photoluminescence (TRPL) measurements accompanied with XPS were performed on uranyl adsorbed B2MP-g-PVDF membranes in order to understand deeper the U(VI)-B2MP coordination mechanism.

A modular approach for the synthesis of highly ordered porous and chiral auxiliary (Evans auxiliary) decorated metal–organic frameworks is developed. Our synthesis strategy, which uses known porous structures as model materials for incorporation of chirality via linker modification, can provide access to a wide range of porous materials suitable for enantioselective separation and catalysis. Chiral analogues of UMCM-1 have been synthesized and investigated for the enantioseparation of chiral compounds in the liquid phase and first promising results are reported. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Maîtrise internationale bi-diplômante conjointe avec l'Université Toulouse III - Paul Sabatier et l'Université de Montréal, Maîtrise en co-tutelle / Le traitement de différents polymères issus de sources renouvelables est, depuis relativement récemment, un domaine de très fort intérêt dans les communautés scientifiques. Ce travail aborde le traitement de mousses de microfibrille de cellulose, issues de biomasses forestières, dans des décharges à barrière diélectrique dans l’hélium à la pression atmosphérique. Lorsque la mousse occupe l’entièreté de l’espace inter-électrodes, nous avons montré que la décharge s’amorce et se propage à travers la mousse. L’effet de dégazer la mousse avant le traitement par plasma s’avère aussi bénéfique à la production de décharge de type « homogène ». En effet, en situation dégazée, la décharge à 60 kHz révèle une caractéristique « homogène » tandis qu’à 10 kHz elle devient filamentaire. Toutefois, nettement moins de dommage sont observés sur la mousse sujette à une décharge à 10 kHz par rapport à celle à 60 kHz. En situations non dégazées, le relâchement d’espèces issues de l’air ambiant lors de l’enclenchement de la décharge augmente considérablement la puissance injectée et dissipée dans le plasma, générant plus de dommage qu’en conditions dégazées. Ces connaissances ont ensuite été appliquées à la modification des mousses à l’aide d’un précurseur d’hexaméthyldisiloxane pour ajuster leurs mouillabilités à l’eau et à l’huile. Lorsque la mousse occupait tout l’espace inter-électrodes, le régime de décharge filamentaire produit des dépôts très inhomogènes, bien souvent localisés au voisinage des régions endommagées. Au contraire, lorsque la mousse n’occupe qu’une partie du volume inter-électrodes, une décharge homogène a été observée, induisant une défibrillation des fibres cellulosiques. Ces conditions mènent néanmoins à des surfaces hydrophobes sur les surfaces supérieure et inférieure des mousses, tout en maintenant leur caractéristique oléophile. Ces travaux semblent donc prometteurs pour la séparation efficace d’huile des eaux usées à partir de matériaux verts, biodégradables, et renouvelables. / The treatment of different polymers issued from renewable sources has recently become of high interest in today’s scientific community. This work focused on the treatment of microfibrillated cellulosic foams, issued from wood biomass, in an atmospheric pressure dielectric barrier discharge in helium. When foams occupied all of gas gap volume, we demonstrated that the discharge ignites and propagates through the foams. The act of outgassing before plasma treatment has also been shown to be highly beneficial to the production of homogeneous glow-like discharges. Indeed, it was found that, in outgassed conditions, discharges occurring at a frequency of 60 kHz were glow-like, while those at 10 kHz were filamentary. However, significantly less damage was observed on the foams subjected to a 10 kHz discharge as opposed to those subjected to a 60 kHz discharge. In non-outgassed situations, we have also shown that the release of oxidising species originating from ambient air upon plasma ignition considerably increased injected and dissipated power in the plasma, in turn producing more damage than in outgassed conditions. This knowledge was then applied to the modification of these foams using a hexamethyldisiloxane precursor for plasma deposition to adjust their wettability to water and to oil. When foams occupied all of gas gap volume, the discharge regime was filamentary, and produced inhomogeneous coating, often very localised around damaged regions. When foams took up only a portion of gas gap volume, a homogeneous glow-like discharge was observed, inducing defibrillation of the cellulosic fibers. These conditions produced hydrophobicity on both the top and bottom surfaces of the foams, all while maintaining the foam’s characteristic oleophilicity. This supports the idea of selective adsorption of oily wastewater using a green, biodegradable, and renewable cellulosic product.