Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: The distribution of different free chemical functional groups on wood and pulp fibres was determined by means of atomic force microscopy (AFM) with chemically modified tips. Because these functional groups show a higher affinity to similar groups on the substrate surface during scanning, AFM images were recorded using an additional digital pulsed-force mode (DPFM) controller. This allowed the distribution of the chemical components to be imaged and to a degree, also to be quantified. The investigated tip coatings showed different sensitivities towards the major chemical components present in wood fibres. These components were determined on spin-coated films as well as wood fibres. It was possible to make a clear distinction between cellulose and lignin in both cases. This technique could therefore be used to differentiate between cellulose and lignin present on pulp fibre surfaces and to confirm the successful removal of lignin by pulping. The chemical composition of wood fibres and fibre surfaces of several acacia and eucalyptus species, and hybrids originating from various growth sites in South Africa, are compared. The objective was to determine the differences in chemical surface composition due to genetics or site. The motivation for this was to eventually facilitate a tailor-made supply of wood for pulping which results in an optimal blend of fibres that can be pulped together with similar yields. This, however, first requires a sound knowledge of the fibre properties. The surface functionality on the single fibre level is a key property because it determines how good inter-fibre bonding will be when paper is formed, which in turn depends to a large degree on the amount of free hydroxyl groups that are available and therefore on the cellulose content on the fibre surface. The cellulose and lignin contents on the fibre surface were determined with chemical force microscopy (CFM), a variation of AFM. CFM involves the use of chemically modified tip using selected functional groups. Since, the general bulk composition of the fibre and the surface composition differ, both parameters were determined. Significant differences in the cellulose and lignin content on fibre surfaces were found, with regard to genotype and site, respectively. In some, but not all, cases the surface composition of wood fibres followed the bulk composition and differences were generally more pronounced. Differences due to genotype were significant, especially with regards to the surface lignin content - but variation due to site was also distinctly recognisable. This variation in surface functionality could be the reason why some pulpwood blends result in a lower pulp yield and different quality. / AFRIKAANSE OPSOMMING: Die verspreiding van verskillende vrye chemiese funksionele groepe op hout en pulpvesels is bepaal deur middel van atoomkragmikroskopie (AFM), met chemies-gemodifiseerde punte (tips). Omdat hierdie funksionele groepe 'n hoër verwantskap tot soortgelyke groepe op die substraat se oppervlak gedurende skandering toon, kan AFM-beelde wat met 'n addisionele digitalepulskragmodusbeheerstel bepaal word dit moontlik maak om die verspreiding van die chemiese komponente uit te beeld en tot op ‘n sekere vlak te kwantifiseer. Die ondersoekte punt-oppervlakmiddels het verskillende sensitiwiteite teenoor die hoof chemiese komponente in die houtvesels en spin-bestrykte films getoon. 'n Duidelike onderskeid kon in beide gevalle tussen sellulose en lignien gemaak word. Hierdie tegniek kon dus gebruik word om te onderskei tussen sellulose en lignien wat op die pulpveseloppervlak teenwoordig was en om die suksesvolle verwydering van lignien gedurende die pulpproses (pulping) te bevestig. In hierdie studie is die chemiese samestelling van houtvesels en die veseloppervlaktes van verskeie akasia en eucalyptus spesies, asook dié van gekruisde spesies wat van verskeie werfliggings in Suid-Afrika afkomstig is, vergelyk. Die doel was om te toets vir verskille in chemiese oppervlaksamestellings, wat veroorsaak kan word deur genetika of werf verskille, met die uiteindelike mikpunt om ‘n spesiaal-gemaakte voorraad van hout vir pulping te fasiliteer, wat kan lei tot 'n optimale mengsel van vesels wat saam gepulp kan word met soortgelyke opbrengs. Dit vereis natuurlik 'n goeie kennis van die veseleienskappe. Die oppervlakfunksionering van enkel vesels is ‘n kritiese eienskap omdat dit bepaal hoe goed interveselverbindings sal wees wanneer papier gevorm word. Dit hang tot ‘n groot mate af van die hoeveelheid vry hydroksielgroepe wat beskikbaar is en dus ook van die sellulose inhoud op die veseloppervlak. Die sellulose- en lignieninhoud op die veseloppervlak is bepaal met chemiese kragmikroskopie – 'n variasie van atoomkragmikroskopie. Omdat die algemene grootmaat samestelling van die vesel en die oppervlaksamestelling mag verskil, is altwee parameters bepaal. Beduidende verskille in die sellulose- en lignieninhoud, met betrekking tot genotipe en werfligging, op veseloppervlaktes is gevind. In sommige, maar nie alle, gevalle het die oppervlaksamestelling van houtvesels ooreengestem met die grootmaatsamestelling, en verskille was oor die algemeen meer beduidend. Verskille as gevolg van genotipe was beduidend, veral met betrekking tot die oppervlak lignieninhoud, maar variasie as gevolg van werfligging was ook duidelik herkenbaar. Hierdie variasie in oppervlakfunksionering kan die rede wees hoekom sommige pulp–hout mengsels lei tot 'n laer pulpopbrengs en verskille in kwaliteit.

The mechanism by which chiral selectivity takes place is complicated by the surface morphology, the possible involvement of the solvent, and the characteristics of the chiral molecules at the surface. My goal is to model and understand the factors which lead to significant discrimination in the case of three closely related chiral stationary phases: N-(1-phenylethyl)-N’-[3-(triethoxysilyl)propyl]-urea (PEPU), [(3,5-dinitrobenzoyl)-amino]-N-[3-(triethoxysilyl)propyl]-2-phenylacetamide (DNB-phenyglycine), and [(3,5-dinitrobenzoyl)amino]-N-[3-(triethoxysilyl)propyl]-4-methylpentanamide (DNB-leucine). Ab initio calculations are used to develop molecular models of these chiral selectors. These models are employed in molecular dynamics (MD) simulations, which provide the theoretical framework for modelling chiral interfaces in different solvent mixtures. The MD simulations of PEPU interfaces show that, in alcohol/water mixtures, the alcohols form domains at the interface with the hydrophobic portions of the molecule tending to orient towards the surface. This disrupts the water hydrogen bonding networks at the interface and leads to the exclusion of water from the surface region relative to the bulk. The MD simulations of DNB-phenylglycine and DNB-leucine selectors in hexane/2-propanol mixtures demonstrate that the interfaces are distinct both in terms of the selector orientations at the surface and in the number of hydrogen bonds formed with 2-propanol. This occurs despite the structural similarity between these two selectors. The interfaces are also prepared experimentally by attaching the chiral selectors onto oxidized Si(111) samples and AFM tips. In particular, for DNB-phenylglycine and DNB-leucine samples, two synthetic routes have been explored. Using AFM, the morphologies of the resulting chiral interfaces are obtained. X-ray photoelectron spectroscopy and refraction-absorption infrared spectroscopy provide information regarding the relative distribution of the compounds on the surface. Using chemical force microscopy (CFM) measurements, chiral self-selectivity is examined in various solvent mixtures. For PEPU interfaces, the extent of hydrogen bonding at the surface is the dominant contributor to the measured forces. In the case of DNB-phenylglycine and DNB-leucine, CFM measurements of the chiral self-selectivity in 2-propanol demonstrate that chiral discrimination is present in both systems, but larger forces are observed for DNB-phenylglycine, consistent with the molecular dynamics study that shows much weaker solvent interactions with this species. / Thesis (Ph.D, Chemistry) -- Queen's University, 2008-08-14 11:26:37.436

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Made available in DSpace on 2016-06-02T19:19:55Z (GMT). No. of bitstreams: 1 AMARANTE_Adriano_2013.pdf: 11925080 bytes, checksum: 6de5e4ba7ae233d30b78c7f1d927740a (MD5) Previous issue date: 2013-03-19 / Universidade Federal de Sao Carlos / In this work was developed a prototype of a new nanobiosensor with molecular specificity through a study of theoretical models of Chemical Force Microscope. For the sensing were used molecular modeling techniques as well as experimental models of the functionalized Atomic Force Microscope tip with the Acetil co-A Carboxylase (ACC) attached. Specific and non-specific inhibitors were used to evaluate substrate-enzyme interactions. The nanobiosensor investigates specific enzymatic inhibition characteristics of the ACC enzyme through the herbicide Diclofop by reversing this process applying a force in a determined direction. The force is theoretically calculated by using molecular dynamic techniques associated to the adhesion force experimentally obtained. Theoretical and experimental questions involving nanobiosensors of AFM tips still obscure until now, such as, the number of functional enzymes attached on the AFM tip, the number of the active sites available to interact after immobilization process, the consequences of the enzyme immobilization as well as the substrate and theoretical adhesion between AFM tip and substrate were analyzed here. / Este trabalho teve como objetivo principal desenvolver o protótipo de um novo nanobiossensor de alta especificidade por intermédio do estudo e desenvolvimento de modelos teóricos específicos para a Microscopia de Força Química (MFQ). Para o sensoriamento foram utilizadas técnicas de Modelagem Molecular Computacional (MMC) e resultados experimentais de MFQ, do qual a ponta do Microscópio de Força Atômica (AFM, do inglês Atomic Force Microscopy) foi funcionalizada com enzimas Acetil-coA Carboxilase (ACC). O nanobiossensor foi utilizado para detectar especificamente substratos de herbicidas específicos e não-específicos. O nanobiossensor explora as características de inibição enzimática específica da enzima ACC pelo herbicida Diclofop revertendo esse processo aplicando-se uma força numa determinada direção. Essa força foi calculada teoricamente por intermédio de cálculos de técnicas de Dinâmica Molecular e associada à força de adesão experimental. Os resultados experimentais validaram os modelos teóricos de forma inequívoca. Questões teóricas e experimentais envolvendo nanobiossensores de ponta de AFM não respondidas até o momento (número de enzimas úteis na ponta do AFM que podem interagir com o substrato, o número de sítios ativos disponíveis, consequências da imobilização das enzimas e do substrato, força de adesão teórica entre a ponta do AFM e o substrato de herbicidas, etc.) foram solucionadas neste trabalho.