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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
191

A comparative study of Hahnemannian and radionically prepared potencies of Natrum muriaticum using nuclear magnetic resonance spectroscopy

Allsopp, Clare January 2010 (has links)
Submitted in partial compliance with the requirements of the Master's Degree in Technology: Homoeopathy, Durban University of Technology, 2010. / The aim of this study was to compare the Nuclear Magnetic Resonance (NMR) spectra of homoeopathic potencies prepared according to the orthodox Hahnemannian method with those produced with Radionic instrumentation. Methodology The chemical shift values and relative integration values for the H2O, CH2, CH3 and OH peaks of the 6C, 12C and 30C potencies of Hahnemannian and Radionic Natrum muriaticum were compared. The orthodox Hahnemannian method of preparing potencies involves dilution of the crude substance followed by the dilution and succussion at each subsequent deconcentration (potency) level. The Hahnemannian potencies were prepared according to the German Homoeopathic Pharmacopoeia (GHP) and the potencies diluted using a 1:100 ratio and succussed ten times at each potency level. The Radionic group of potencies were prepared using the ‘Magnetogeometric Potency Simulator’ (a Radionic apparatus). NMR testing took place at the Chemistry Department at the University of KwaZulu Natal, Pietermaritzburg using a Bruker Avance lll NMR spectrometer 500MHz.The samples were dispensed into boro-silicate glass NMR tubes with a co-axial tube containing Dimethyl sulfoxide-d6 (DMSO-d6) which was used as a frequency lock around the tube. Three samples were drawn from each group, including the controls, and analysed using the NMR spectrometer. The NMR spectrometer information was received and the chemical shift and relative integration values of H2O, OH, CH2 and CH3 peaks on the NMR spectra recorded. All the data was entered into a Microsoft Excel© 2000 spreadsheet and then from there transferred into SPSS© software package for statistical analysis. The Kruskal-Wallis test was used to make a comparison between the eight unpaired groups. If a significant difference occurred between the groups iii individual comparisons between groups were made using the non-parametric Mann-Whitney test. The significant value was set at α= 0.05. Results The results of this study revealed significant differences between the Hahnemannian and Radionic samples. The chemical shift values of the parallel potencies showed significant differences for the H2O, CH2 and CH3 peaks. A significant difference for the OH peaks was observed between the 30C potencies. The relative integration values showed a significant difference for the OH and CH3 peaks between the parallel 12C and 30C potencies but not between the parallel 6C potencies. Conclusion From studying the results it can be concluded that the respective manufacture methods resulted in the NMR spectra of the parallel potencies being significantly different (exhibiting distinctive physico-chemical properties) thus confirming the hypotheses of the study. The standardisation of the process of preparing homoeopathic remedies is important as different methods produce potencies with distinct physico-chemical identities. Further studies into different methods should be researched in order to control and standardise the production of potencies.
192

Experimental supply demand analysis of yeast fermentative free energy metabolism : an in vivo and in situ investigation

Smith, Justin Alan 12 1900 (has links)
Thesis (MSc (Biochemistry))--University of Stellenbosch, 2010. / Please refer to full text for abstract
193

High resolution 195Pt and 119Sn NMR characterization of platinum(II)-tin(II) complexes

Barkhuysen, Shani 12 1900 (has links)
Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: See full text for abstract / AFRIKAANSE OPSOMMING: Sien volteks vir opsomming
194

NMR studies on the mechanism of iodine mediated polymerisation

Wright, Trevor 12 1900 (has links)
Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: In reverse iodine transfer polymerisation (RITP), chain transfer agents (CTAs) are generated in situ from the reaction between 2,2’-azobis(isobutyronitrile) (AIBN) and molecular iodine. This stage of RITP is the inhibition period, which ends when all iodine has been consumed. The evolution of CTAs was studied for the polymerisation reactions of n-butyl acrylate and styrene respectively. RITP of n-butyl acrylate was performed at 70 °C. In situ 1H nuclear magnetic resonance (NMR) experiments were carried out to study the evolution of CTAs during the inhibition period of n-butyl acrylate polymerisation and the structures A-I and A-Mn-I (where A represents the moiety originating from AIBN, M represents the monomer unit and n is the mean number degree of polymerisation) were observed. A polymer with the general structure A-Mm-I is formed. The molecular weight of poly(n-butyl acrylate) (PnBA) was evaluated with size exclusion chromatography (SEC) and NMR. Structural analysis of PnBA was done using NMR spectroscopy and matrix-assisted laser desorption/ionisation time-of-flight (MALDI-ToF) mass spectrometry. Similar conditions to those used for n-butyl acrylate polymerisation were used for RITP of styrene. The evolution of CTAs during the inhibition period of styrene polymerisation was studied using in situ 1H NMR. The inhibition period of styrene polymerised by RITP was much shorter than expected. This is due the consumption of iodine in the reaction between styrene and iodine which reversibly forms 1,2-diiodo-ethyl benzene. The CTAs A-I and A-Mn-I are formed, as well as 1-phenylethyl iodide (1-PEI). The molecular weight of polystyrene (PS) was determined using SEC and NMR and the functionality was evaluated using 1H NMR. The structure of PS was confirmed with 1H NMR and MALDI-ToF mass spectrometry. By increasing the temperature of the reaction, the inhibition period can be shortened. Both polymerisation systems retain control over molecular weight with an increase in temperature, however, n-butyl acrylate is limited due to the possible formation of mid-chain radicals. The formation of an A–Mm–A population (direct combination of the initiator and styrene) in RITP of styrene results in more initiator being consumed than for n-butyl acrylate, despite limited conversion of styrene to polymer. / AFRIKAANSE OPSOMMING: In omgekeerde-jodium-oordrag polimerisasie, is die kettingoordragagente gegenereer in situ van die reaksie tussen 2,2’-azobis(isobutironitriel) (AIBN) en molekulêre jodium. Hierdie fase van RITP is die inhibisie tydperk wat eindig wanneer alle jodium verbruik is. Die evolusie van kettingoordragagente is vir die polimerisasiereaksies van butielakrilaat en stireen onderskeidelik bestudeer. Omgekeerde-jodium-oordrag polimerisasie van butielakrilaat was uitgevoer by 70 °C. In situ 1H kernmagnetieseresonans (KMR) eksperimente is uitgevoer om die evolusie van die kettingoordragagente te bestudeer tydens die inhibisie van butielakrilaat polymerisasie en die strukture A-I en A-Mn-I (waar A die gedeelte voorstel wat afkomstig is van AIBN, M die monomeer-eenheid en n die gemiddelde aantal polymerisasiegraad verteenwoordig) is ge-identifiseer. 'n Polimeer met die algemene struktuur A-Mm-I is gevorm. Die molekulêre gewig van poli(butielakrilaat) (PnBA) was geëvalueer deur grootte-uitsluitings chromatografie en KMR spektroskopie. Strukturele ontleding van PnBA is gedoen deur die KMR spektroskopie en matriks ge-assisteerde laser desorpsie/ionisasie tyd-van-vlug massaspektroskopie. Soortgelyke kondisies as dié wat gebruik word vir butielakrilaat polymerisasie, is gebruik vir omgekeerde-jodium-oordrag polimerisasie van stireen. Die evolusie van die ketting oordrag agente gedurende die inhibisie periode van stireen polymerisasie is deur in situ 1H KMR bestudeer en die inhibisie periode is baie korter as verwag. Dit is as gevolg van die opname van jodium in die reaksie tussen stireen en jodium wat omkeerbare stireen-di-jodied tot gevolg hê. Die ketting oordrag agente A-I en A-Mn-I is gevorm, sowel as 1-feniel-etiel jodied. Die molekulêre massa van polistireen (PS) is bepaal met behulp van grootte-uitsluitings chromatografie en KMR spektroskopie en die funksioneering is geëvalueer met behulp van 1H KMR. Die struktuur van PS is bevestig deur 1H KMR en matriks ge-assisteerde laser desorpsie/ionisasie tyd-vanvlug massaspektroskopie. Deur die verhoging van die temperatuur van die reaksie, kan die inhibisie periode verkort word. Beide polimerisasie sisteme behou beheer oor die molekulêre massa met 'n toename in temperatuur, alhoewel butielakrilaat beperk word as gevolg van die moontlike vorming van middel kettingradikale. Die vorming van die A-Mm-A spesie (direkte kombinering van AIBN en stireen) in omgekeerdejodium- oordrag polimerisasie van stireen veroorsaak dat meer AIBN verbruik word as butielakrilaat, ten spyte van die beperkte omskakeling van stireen tot polimeer.
195

Understanding glycolysis in Escherichia coli : a systems approach using nuclear magnetic resonance spectroscopy

Eicher, Johann Josef 12 1900 (has links)
Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: This dissertation explores the behaviour and regulation of central carbon metabolism in Escherichia coli K12 W3110 under fermentative microaerobic conditions. To achieve this, an integrative systems modelling approach was adopted, which is introduced in Chapter 1 along with a review of metabolism in E. coli. An open-source software suite NMRPy, developed using the Python programming language, is presented in Chapter 2. NMRPy provides a host functions for basic processing, analysis and visualisation of Nuclear Magnetic Resonance (NMR) spectroscopy data. In addition to this, NMRPy offers specialised functions for the deconvolution of arrayed reaction time series, which proved indispensable to the research presented in this dissertation. NMRPy presents an easy to use, extensible tool for both routine and advanced use. In Chapter 3, a novel methodology is presented which was developed for the effective and comprehensive determination of enzyme kinetic parameters for systems biology using NMR. In contrast to traditional enzyme kinetic assay methods, this new methodology is less labour-intensive and yields significantly more information per experiment. By fitting kinetic equations to real time NMR data, dynamic changes in substrates, products and allosteric modifiers are quantified and allowed to inform the parameter fitting procedure. These data contain information on cooperative substrate binding, reversibility, product inhibition and allosteric effects. The proposed methodology is applied to the study of the first two enzymes of the glycolytic pathway. In Chapter 4, the construction, parameterisation and validation of a number of kinetic models of glycolysis in E. coli under microaerobic conditions is detailed. To model the lower half of glycolysis, a similar technique was adopted as in Chapter 3, in which models representing the reactions from triosephosphate isomerase to pyruvate kinase were parameterised by fitting them to a collection of 31P NMR reaction time series. This approach extends the methodology to enzyme sub-networks, yielding data that encompass the full complexity of the network regulatory interactions. The verified kinetic models were subjected to scrutiny, the results of which are presented in Chapter 5. The value of the modelling approach is demonstrated by the ease with which cumbersome in vivo experiments can be performed in silico. A structural analysis of the model topology was conducted, elucidating the elementary flux modes of fermentative glycolysis in E. coli, and identifying a futile cycle around PEP carboxylase and PEP carboxykinase. Model steady-state behaviour and control properties were explored in silico under various degrees of ATP demand and oxygen availability and a number of hypotheses are presented, explaining the regulation of free energy in E. coli, and the metabolic responses of E. coli to changing redox demands. Amongst other things, the results demonstrated that the glucose importing phosphoenolpyruvate: phosphotransferase pathway controlled glycolytic flux, and that under microaerobic conditions E. coli is able to regulate redox balance not only by balancing flux between acetate and ethanol, but also by altering the balance of flux between acetate and lactate at the pyruvate formate lyase/lactate dehydrogenase branch point. This study demonstrates the value of an integrated computational and experimental systems approach to exploring biological phenomena. / AFRIKAANSE OPSOMMING: In hierdie proefskrif word die gedrag en regulering van die sentrale koolstofmetabolisme in Escherichia coli K12 W3110 onder fermenterende mikro-a¨erobiese toestande ondersoek. Dit is moontlik gemaak deur ’n ge¨ıntegreerde stelsel-modelleringsbenadering, wat in Hoofstuk 1 bekendgestel word. D´ıe hoofstuk verskaf ook ’n oorsig van die metabolisme in E. coli. ’n Oopbron-kodepakket NMRPy, wat in die programmeringstaal Python ontwikkel is, word in Hoofstuk 2 beskryf. NMRPy verskaf ’n aantal funksies vir die basiese verwerking, analise en visualisering van Kern-Magnetiese Resonansie (KMR) spektroskopiese data, sowel as gespesialiseerde funksies vir die dekonvolusie van opeenvolgende reaksie-tydreekse. Hierdie funksionaliteit was onontbeerlik vir die verdere navorsing in hierdie proefskrif. Hoofstuk 3 beskryf die ontwikkeling van ’n nuwe metodiek vir die omvangryke bepaling van ensiem-kinetiese parameters vir sisteembiologie, deur van KMR gebruik te maak. In teenstelling tot tradisionele ensiem-kinetiese essai-metodes, is hierdie nuwe metodologie minder arbeidsintensief en lewer dit beduidend meer inligting per eksperiment. Deur die kinetiese vergelykings op tydsafhanklike KMR data te pas, word dinamiese veranderinge in substrate, produkte en allosteriese effektors gekwantifiseer en hierdie inligting gebruik in die passingsprosedure. Die data bevat inligting oor ko¨operatiewe substraatbinding, omkeerbaarheid, produkinhibisie en allosteriese effekte. Die voorgestelde metodologie word toegepas op die karakterisering van die eerste twee glikolitiese ensieme. In Hoofstuk 4 word die konstruksie, parameterisering en validering van ’n aantal kinetiese modelle van glikolise in E. coli onder mikro-a¨erobiese toestande uiteengesit. Die waarde van die modelleringsbenadering lˆe in die gemak waarmee omslagtige in vivo eksperimente in silico uitgevoer kan word. Om die onderste helfte van die glikolitiese pad te modelleer word ’n soortgelyke tegniek as in Hoofstuk 3 gebruik. Modelle van die reaksies vanaf triosefosfaat-isomerase tot by pirovaat-kinase is geparameteriseer deur dit op ’n versameling 31P KMR-tydreekse te pas. Hierdie benadering brei bostaande metodologie uit tot ensiem-subnetwerke en genereer data wat die volle kompleksiteit van regulerende interaksies in die netwerk insluit. Die geverifieerde modelle word in Hoofstuk 5 noukeurig ondersoek. ’n Strukturele analise van die modeltopologie word onderneem om die elementˆere fluksie-modes van fermentatiewe glikolise in E. coli te verklaar, sowel as om ’n futiele siklus rondom fosfo¨enolpirovaat karboksilase en fosfo¨enolpirovaat karboksikinase te identifiseer. Die bestendige-toestandsgedrag en kontrole-eienskappe word in silico ondersoek onder toestande van verskeie ATP beladings en suurstofbeskikbaarheid. ’n Aantal hipoteses word voorgelˆe, wat die regulering van vry energie in E. coli, sowel as die metaboliese reaksies van E. coli onder veranderende redoks-vereistes kan verklaar. Onder andere dui die resultate daarop dat die fosfo¨enolpirovaat:fosfotransferase sisteem (wat verantwoordelik is vir glukose-opname in die sel) die glikolitiese fluksie beheer en dat E. coli onder mikro-a¨erobiese toestande die redoksbalans nie net tussen asetaat en etanol kan reguleer nie, maar ook die deur wysiging van die fluksie-balans tussen asetaat en laktaat rondom die pirovaat-formiaat-liase/laktaatdehidrogenase vertakkingspunt. Hierdie studie toon die waarde van ’n ge¨ıntegreerde rekenaarmatige en eksperimentele sisteembenadering om biologiese verskynsels te ondersoek.
196

Synthesis and characterization of multiphase copolymers

Elhrari, Wael K. S. 12 1900 (has links)
Thesis (PhD)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: Multiphase copolymers generally consist of copolymers where the disparate natures of each of the segments results in complex phase-segregated morphologies in the solid state. The outstanding properties and wide range of applications of multiphase copolymers has led to the need for more sophisticated synthesis methods to produce copolymers with controlled structures. Associated with developments in synthetic methods is the need to develop suitable techniques to characterize these materials in order to obtain a better understanding of their structure–property relationships. The synthesis of multiphase copolymers presents many challenges. These are related to the nature of the molecular requirements, were the monomers of each of the different components may not be polymerized by all available polymerization techniques. This has led to the need to combine different polymerization techniques to overcome such limitations. The focus of this study is the combination of living controlled polymerization techniques, namely anionic polymerization and RAFT polymerization, with hydroboration/autoxidation, to produce non-polyolefin block and graft copolymers. Block copolymers were synthesized by coupling anionic polymerization and hydroboration/autoxidation reactions. The first block segment was prepared via anionic polymerization, and then end-functionalized with a suitable functional group (e.g. an allyl group). A hydroboration/autoxidation reaction was then used to initiate the polymerization of the second block by the slow addition of oxygen at room temperature. Graft copolymers were synthesized using the 'grafting from' technique, by coupling RAFT copolymerization with hydroboration/autoxidation reactions. The backbone polymer was synthesized via RAFT copolymerization of symmetric and asymmetric monomer, after which a hydroboration/autoxidation reaction was carried out to produce graft copolymers. The hydroboration/hydroxylation reaction could also be used to modify an unsaturated polymer chain. The EPDM rubber chain was modified by transforming the double bond into an hydroxyl group, which could undergo an esterification reaction with an acid chloride RAFT agent to produce the multifunctional RAFT polymer. This was used for the controlled living free radical polymerization of the graft chains. Significant amounts of homopolymerization in addition to graft formation were obtained. Solid state NMR (SS NMR) and positron annihilation lifetime spectroscopy were used to determine the compositional phase segregation point in the graft copolymers. The spin diffusion data from the SS NMR provided insight into the seemingly anomalous positron data at the phase segregation point. It is demonstrated how these two techniques can provide complimentary data on the solid state morphology of these multiphase materials. / AFRIKAANSE OPSOMMING: In die algemeen bestaan multifase kopolimere uit segmente van verskillende aard wat komplekse fase-geskeide-morfologie in die vastetoestand tot gevolg het. Die uitstekende eienskappe en wye reeks toepassings van multifase kopolimere het daartoe gelei dat meer gesofistikeerde sintesemetodes vir die bereiding van kopolimere met gekontrolleerde strukture nodig was. Gepaardgaande met verwante ontwikkelings op die gebied van sintesemetodes was dit nodig om gepaste analitiese tegnieke te ontwikkel vir die karakterisering van hierdie verbindings, ten einde die struktuur–eienskap verwantskap van hierdie materiale beter te verstaan. Daar is egter baie uitdagings m.b.t. die sintese van hierdie multifase kopolimere. Dit is afhanklik van die aard van die molekulêre vereistes waar die monomere van elk van die verskillende komponente nie deur alle beskikbare polimerisasietegnieke gepolimeriseer kan word nie. Dit het daartoe gelei dat verskillende polimerasietegnieke gekombineer is ten einde hierdie beperkinge te oorbrug. Die fokus van hierdie studie is die kombinering van lewende vry-radikaal gekontrolleerde polimerisasietegnieke, naamlik anioniese polimerisasie en RAFTpolimerisasie, met hidroborering/outoksidasie, om nie-olefiniese blok- en entkopolimere te berei. Blok-kopolimere is berei deur die koppeling van anioniese polimerisasie en hidroborering/outoksidasie reaksies. Die eerste bloksegment is berei via anioniese polimerisasie en daarna is endfunksionering met 'n geskikte funksionele groep (bv. 'n allielgroep) bewerkstellig. Daarna is 'n hidroborering/outoksidasie reaksie gebruik om die polimerisasie van die tweede blok te inisieer d.m.v. die stadige toevoeging van suurstof by kamertemperatuur. Entkopolimere is berei deur gebruik te maak van die 'ent-vanaf' tegniek, d.m.v. die koppeling van RAFT-kopolimerisasie met hidroborering/outoksidasie reaksies. Die rugraatpolimeer is berei d.m.v. kopolimerisasie van simmetriese en nie-simmetriese monomere waarna die hidroborering/outoksidasie reaksie uitgevoer is om sodoende entkopolimere te vorm. Die hidroborering/hidroksilasie reaksie kon ook gebruik word om 'n onversadigde polimeerketting te wysig. Die EPDM rubberketting is gewysig deur die omskakeling van die dubbelbinding in 'n hidroksielgroep, wat dan 'n esterifikasie reaskie kon ondergaan met 'n suurchloried-RAFT verbinding, om sodoende die multifunksionele RAFT-polimeer te vorm. Dit is gebruik vir die gekontrolleerde lewende vry-radikaalpolimerisasie van die entkettings. Behalwe entvorming is 'n hoë mate van homopolimerisasie waargeneem. Vastetoestand KMR (VS KMR) en positronvernietigingsleeftydspektroskopie is gebruik om die saamgestelde faseskeidingspunt in die entkopolimere te bepaal. Die spindifffusie data van VS KMR het insig verleen aan die oënskynlik onreëlmatige positrondata by die faseskeidingspunt. In die studie is bewys hoe hierdie twee tegnieke komplimentêre data kan lewer m.b.t. die vastetoestandmorfologie van hierdie multifase materiale.
197

Novel α-olefin polymer systems

Siphuma, Lufuno 03 1900 (has links)
Thesis (PhD)--Stellenbosch University, 2005. / ENGLISH ABSTRACT: See fulltext for abstract / AFRIKAANSE OPSOMMING: Sien volteks vir opsomming
198

A multinuclear (1H, 13C, 31P and 195Pt) magnetic resonance spectroscopy study of mixed ligand platinum(II) complexes with new N,N-dialkyl-N'-acyl(aroyl)thioureas as ligands

Mtongana, Sibusiso 12 1900 (has links)
Thesis (MSc)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: Please refer to fulltext for abstract / AFRIKAANSE OPSOMMING: Sien asb volteks vir opsomming
199

A study of isotope-effects in the high-resolution 195Pt NMR spectra of octahedral complexes of the type [PtCl6-n(OH)n]2-, n = 0-6, in water

Engelbrecht, Leon de Villiers 03 1900 (has links)
Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The high-resolution 195Pt NMR signals (128.8 MHz) of most of the octahedral mixed-ligand Pt(IV) complexes in the series [PtCl6-n(OH)n]2-, n = 0-6, have been recorded in aqueous solutions at 293 K. These signals show characteristic 35/37Cl isotope-induced fine structure that results from the presence of several isotopologues in samples with a natural chlorine isotope distribution; each 37Cl isotope incorporated into the Pt coordination sphere of one of these complexes affords a fixed upfield (low frequency) isotope shift of between 0.17 and 0.22 ppm, depending on the particular complex. This assignment is confirmed by the excellent agreement between the natural abundances of the various isotopologues and the relative contributions of the corresponding signals to the overall area of the experimental spectrum of the particular isotoplogue set, obtained by a non-linear least-squares line fitting procedure. These results confirm that the 195Pt magnetic shielding in isotopomers differing only in the combination of the two chlorine isotopes coordinated in sites trans to hydroxido-ligands are indistinguishable under these experimental conditions, unlike those of similar isotopomers in the related series of aqua-complexes [PtCln(H2O)6-n]4-n, n = 3-5, as reported by Koch and co-workers. Moreover, the order of 195Pt shielding for the members of all stereoisomer pairs in the series of hydroxido-complexes is the reverse of that reported for the corresponding pairs in the aqua-series. These and other observations are interpreted qualitatively in terms of the relative strengths of the trans-influences of aqua-, hydroxido- and chlorido-ligands and the effect of these on bond displacements in these complexes. The 195Pt NMR spectra of especially the complexes cis-[PtCl2(OH)4]2- and [PtCl(OH)5]2- show remarkable fine structure in a ca. 45 % 18O-enriched aqueous solution; apart from additional signals resulting from 18O-containing isotopologues, the resonance signals of isotopomers differing in the combination of 16/18O isotopes in sites trans to chlorido-ligands are partially resolved. The effect of temperature on the 35/37Cl isotope-induced fine structure in the 195Pt signals of [PtCl6]2- and [PtCl(OH)5]2- was investigated in the range 283-308 K; some interesting differences are observed. 195Pt relaxation time measurements for [PtCl6]2- in this temperature range reveal that line-broadening is at least partially responsible for the loss of resolution between the signals of isotopologues of this complex as the temperature is increased, possibly due to the spin-rotation relaxation mechanism. The temperature coefficient of 195Pt shielding and the magnitude of isotope shifts in the spectra of the complexes in this series show interesting correlations with the 195Pt shielding itself; an interpretation of these observations is presented. / AFRIKAANSE OPSOMMING: Die hoëresolusie 195Pt NMR seine (128.8 MHz) van die oktaëdriese gemengde-ligand Pt(IV) komplekse in die reeks [PtCl6-n(OH)n]2- is waargeneem in waterige oplossing by ʼn temperatuur van 293 K. Hierdie seine toon ʼn karakteristieke 35/37Cl isotoop-geïnduseerde fynstruktuur as gevolg van die teenwoordigheid van verskeie isotopoloë in monsters met ʼn natuurlike chloor isotoopverspreiding. Die verplasing van ʼn 35Cl isotoop deur ʼn 37Cl isotoop in die Pt koördinasiesfeer van hierdie komplekse lei tot ʼn laefrekwensie isotoopverskuiwing van die 195Pt resonansiesein van tussen 0.17 en 0.22 ppm, afhangend van die spesifieke kompleks. Die toekenning van resonansieseine in hierdie spektra word ondersteun deur die goeie ooreenstemming tussen die berekende natuurlike verspreiding van isotopoloë en die persentasie area bydrae van die ooreenstemmende pieke tot die area van volledige stel seine van die chemiese spesie, soos bepaal deur ʼn nie-linieêre kleinste-kwadrate passingsmetode. Hierdie resultate bevestig dat vir isotopomere waarvan slegs die kombinasie van chloorisotope wat in posisies trans tot hidroksido-ligande gekoördineer is ʼn ononderskeibare 195Pt magnetiese skerming waargeneem word, m.a.w. ʼn enkele resonansiesein word vir hierdie isotopomere gemeet, anders as gerapporteer deur Koch en medewerkers vir die verwante aqua-komplekse [PtCln(H2O)6-n]4-n waar n = 3-5. Verder is die order van 195Pt magnetiese skerming vir stereoisomere in hierdie hidroksido-komplekse in elke stereoisomer paar die teenoorgestelde van dit waargeneem vir die ooreenstemmende aqua-komplekse. Hierdie waarnemings word kwalitatief geïnterpreteer in terme van die verskillende trans-invloede van die chlorido-, aqua- en hidroksido-ligande en die effekte daarvan op bindingslengtes in die komplekse. In ʼn ongeveer 45 % 18O-verrykte monster toon die 195Pt seine van veral die komplekse cis-[PtCl2(OH)4]2- en [PtCl(OH)5]2- uitsonderlike fynstruktuur vanweë die addisionele seine van 18O-bevattende isotopoloë en die parsiële resolusie van die seine van isotopomere wat verskil in die kombinasie van 16/18O isotope wat trans tot chlorido-ligande gekoördineer is. ʼn Studie is gemaak van die uitwerking van temperatuur op die 35/37Cl isotoop-geïnduseerde fynstruktuur in die 195Pt seine van die komplekse [PtCl6]2- en [PtCl(OH)5]2- in die gebied 283-308 K; interessante verskille is waargeneem. 195Pt magnetiese relaksasietyd metings vir die kompleks [PtCl6]2- in waterige oplossing in hierdie temperatuurgebied toon dat verbreeding van resonansieseine ten minste gedeeltelik verantwoordelik is vir die waargenome verlies aan resolusie tussen die seine van isotopoloë namate die temperatuur styg; die verbreeding van seine kan waarskynlik aan die spin-rotasie relaksasiemeganisme toegeskryf word. Die temperatuurkoëffisiënt van 195Pt magnetiese skerming en die grootheid van isotoopverskuiwings in die spektra van die hidroksido-komplekse in hierdie reeks toon interessante korrelasies tot die 195Pt magnetiese skerming; ʼn interpretasie van hierdie waarnemings word voorgestel.
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A kinetic and thermodynamic study of procyanidin oligomer conformation by 1H NMR and DFT

O'Kennedy, Sean James 12 1900 (has links)
Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Please refer to full text for abstract / AFRIKAANSE OPSOMMING: Sien asb volteks vir opsomming

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