Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: In this thesis we describe various attempts at incorporating macrocycles into dendritic architectures to form macrocycle-dendrimer conjugates with the aim of preparing materials that would exhibit properties that are more than the sum of the constituent parts, in this case macrocycles and dendrimers. A further aim was the synthesis and characterization of metallodendrimers based on such scaffolds and to test these as catalyst precursors in the catalytic oxidation of alcohols. The synthesis of two different types of conjugate systems was attempted; viz. dendrimers functionalized with macrocycles on the peripheries and dendrimers with macrocyclic cores. The synthesis of conjugate systems based on cyclam as the macrocycle was attempted. This required the mono functionalization of cyclam with a linker molecule capable of further reaction with the functional groups at the periphery of commercially available N,N,N,N-tetrakis(3-aminopropyl)-1,4-butanediamine dendrimer. Several approaches were taken in trying to make such conjugate systems but they were not entirely successful. One of the major issues was the final deprotection step, of the Boc-protected cyclam units which proved difficult in our hands. Another approach to prepare the target conjugates involved the use of click chemistry in order to synthesize a dendrimer with an aromatic core and cyclam peripheries. A dendrimer with Boc-protected cyclam peripheries that are bonded through triazole groups to the aromatic core was synthesized. However, subsequent attempts at de-protection of the cyclam functionalities of this conjugate failed to yield the pure de-protected dendrimer. Greater success was achieved with the preparation of a dendrimer with a macrocyclic core. A cyclam cored dendrimer with salicylaldimine peripheries was successfully synthesized and characterized. This dendritic ligand was complexed to Cu(II), Ni(II) and Zn(II) metal ions respectively to form a series of new metallodendrimers. These metallodendrimers were fully characterized using a range of analytical techniques including FT-IR spectroscopy, mass spectrometry, elemental analysis, thermogravimetric analysis, magnetic susceptibility measurements and NMR spectroscopy where appropriate. The Cu(II) and Ni(II) metallodendrimers were tested as catalyst precursors in the catalytic oxidation of benzyl alcohol to benzaldehyde. The catalytic system consisted of the appropriate metallodendrimer, the free radical, 2,2,6,6-tetramethylpiperidinyl- 1-oxyl (TEMPO) and O2 as the oxidant. The reaction parameters, namely the nature of the solvent, catalyst loading, substrate concentration and reaction temperature were sequentially optimized to achieve the best catalytic efficiency. The Cu(II) catalyst precursor exhibited relatively high catalytic activity and achieved TOF’s between 40 and 30 when operating under the optimized conditions, while the Ni(II) catalytic system showed very poor catalytic activity. / AFRIKAANSE OPSOMMING: In hierdie tesis beskryf ons pogings om makroringe in die dendritiese argitektuur te inkorporeer om makroring-dendrimeer gekonjugeerdes te vorm met die hoop dat sulke molekules eienskappe sal toon wat meer is as die somtotaal van die afsonderlike eenhede. ‘n Verdere doel was die sintese en karakterisering van metallodendrimere gebaseer op sulke draers sowel as die toetsing van hierdie molekules as pre-katalisore in die katalitiese oksidasie van alkohole. Pogings tot die sintese van twee verskillende tipes makroring-dendrimeer gekonjugeerdes word beskryf naamlik, dendritiese ligande met makroringe by die buiterand sowel as dendritiese ligande met ‘n makroring as kern word bespreek. Die sintese van makroring-dendrimeer gekonjugeerdes gebasseer op die makroring cyclam word beskryf. Hierdie sintese vereis die gebruik van ‘n monogefunksioneerde cyclam wat ‘n gepaste koppelingsgroep besit. Hierdie koppelingsgroep kan dan verder met funksionele groepe op die oppervlak van die kommersieel beskikbare DAB-dendrimeer reageer. Verskeie pogings is aangewend om sulke gekonjugeerde stelsels te sintetiseer maar hierdie pogings was nie volkome suksesvol nie. ‘n Groot uitdaging was die gebruik en gevolglike latere verwydering van beskermende groepe soos Boc. ‘n Ander benadering het gebruik gemaak van “click” chemie met die doel om ‘n dendrimeer bestaande uit ‘n aromatiese kern en cyclam periferie te vorm. ‘n Dendrimeer met Boc beskermde cyclam eenhede op die buiterand geheg aan ‘n aromatiese kern deur triasool groepe is gesintetiseer. Die verwydering van die beskermende groepe geheg aan die cyclam eenhede was egter weereens ‘n probleem en hierdie metode kon nie die suiwer dendrimeer lewer nie. Groter sukses is behaal met die sintese van ‘n dendrimeer met ‘n cyclam kern en salisielaldimien periferieë. Die dendritiese ligand is vervolgens met metaalsoute van Cu(II), Ni(II) en Zn(II) gereageer om verskeie multikern metaalkomplekse te vorm. Die metaalkomplekse is volledig gekarakteriseer deur verskeie analitiese tegnieke insluitende infrarooi spektroskopie, massa spektrometrie, termografiese analiese, mikroanaliese asook KMR spektroskopie waar moontlik. Die Cu(II) en Ni(II) metaalkomplekse is geëvalueer as pre-katalisatore in die katalitiese oksidasie van alkohole. Hierdie katalitiese sisteem bestaan uit die metaalkompleks, die radikaal TEMPO en molekulêre suurstof. Die invloed van verskeie reaksie- parameters soos die tipe oplosmiddel, die hoeveelheid katalisator, die konsentrasie van die alkohol asook die temperatuur is ondersoek. Gevolglik is die optimale kondisies bepaal om die hoogste opbrengs van bensaldehied te lewer. Die Cu(II) kompleks het ‘n relatief hoë omset van bensielalkohol na bensaldehied getoon met omset frekwensie waardes tussen 30 en 40 onder die optimale kondisies. Die Ni(II) kompleks het egter swak aktiwiteit getoon vir hierdie transformasie.

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: With a cure for HIV and AIDS still absent, non-nucleoside reverse transcriptase inhibitors (NNRTIs) play a major role in the current antiretroviral treatments used, which have shown to improve and prolong the lives of HIV patients significantly. However, with rapid mutations of the HI virus, the use of these drugs is becoming limited, thereby highlighting the need for the development of new NNRTIs. Previous work by our research team has led to the development of a cyclopropyl-containing indole-based compound with an inhibition activity (IC50 value) of 0.1 μM, as determined in an in vitro single-cycle, non-replicative phenotypic assay. Therefore, in this project, we focussed on enhancing the intermolecular interactions of our compound to three major areas in the NNRTI binding pocket, namely the Tyr181, the Val179, and the Lys101 binding pockets. Hereby we were able to obtain both improved and lower potencies, with our most active compound having an inhibition activity (IC50 value) of 1 nM. For the interaction to the Tyr181 binding pocket, we were thus unable to synthesise a heterocyclic ring system onto our molecule as opposed to the previously used phenyl ring. Secondly, for the interaction to the Lys101 binding pocket we were able to synthesise a tetrazole ring system and an amide functionality onto the 2-position of the indole. Lastly, in our quest to synthesise the cyclopropyl moiety onto our compound for the interaction in the Val179 binding pocket, we were able to investigate the full inhibition effect of this interaction by synthesising a similar compound with no interaction in this binding pocket. Moreover, we were able to synthesise a new compound with a methoxy moiety for this interaction with an inhibition activity (IC50 value) of 1 nM. With this compound only being submitted for efficacy evaluation as a racemic compound mixture, this opened a new door for research possibilities for our team. / AFRIKAANSE OPSOMMING: In die awesigheid van 'n geneesmiddel vir MIV en VIGS, speel nie-nukleosied omkeerbare transkripsie inhibitore ("NNRTIs")'n groot rol in die huidige antiretrovirale behandeling. Ongelukkig ondergaan die MI virus mutasies, wat dus die gebruik van hierdie antiretrovirale middels beperk. Hierdie beklemtoon dus die noodsaaklikheid vir die ontwikkeling van nuwe "NNRTIs". Vorige werk wat deur ons navorsings groep verrig is, het gelei tot die ontwikkeling van "n siklopropiel bevattende indol verbinding, met "n inhibisie aktiwiteit ("IC50" waarde) van 0.1 μM. Gevolglik, het ons in hierdie projek gefokus om die intermolekulêre interaksies van hierdie verbinding in drie hoof areas in die "NNRTI" bindings ruimte te verbeter, genaamd die Tyr181, die Val179, en die Lys101 bindings ruimtes. Hierdie projek het dus beide verbeterde en ook laer inhibisie aktiwiteits resultate gelewer, waar die mees aktiewe verbinding 'n inhibisie aktiwiteit ("IC50" waarde) van 1 nM behaal het. Vir die interaksie na die Tyr181 bindings ruimte, was ons dus onsuksesvol om 'n heteroaromatiese ring te sintetiseer as plaasvervanger vir die oorspronklike feniel ring. Tweedens, vir die interaksie na die Lys101 bindings ruimte, was ons in staat om 'n tetrazol ring en 'n amied funksionaliteit aan die 2-posisie van die indol te sintetiseer. In ons stryd om die siklopropiel ring aan ons verbinding te sintetiseer vir die interaksie in die Val179 bindings ruimte, was ons in staat om die volledige effek van hierdie interaksie te bepaal deur 'n soortgelykke verbinding te sintetiseer met geen interaksie in die Val179 bindings ruimte nie. Daarenbowe, het ons 'n verbining gesintetiseer met 'n inhibisie aktiwiet ("IC50" waarde) van 1 nM, waarvan die aktiwitiet van slegs die rasemiese mengsel van die verbinding bepaal is. Hierdie vinding het dus 'n nuwe navorsings deur vir ons groep geopen.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: The use of fluorine in medicinal chemistry has increased dramatically in the last 20 years. The addition of fluorine to a lead compound has various advantages such as the blocking of metabolic active sites, the increase of solubility and lipophilicity of a compound, acting as conformational probes for the active site of an enzyme, and influencing (in most cases increasing) the binding affinity of a compound to a target protein. Their use as mechanism based inhibitors is also well known. In this study we set out to synthesize hydroxyl- and fluorinated-amino acid analogues as potential inhibitors and probes towards the active site of various enzymes. The synthesis of the hydroxylamino acid analogues would precede the fluorinated analogues to serve as precursors with fuorination achieved via a fluoro-dehydroxylation reaction. These aims have successfully been achieved with the synthesis of the two enantiopure isomers of 3-fluoro-aspartic acid. The fluorinated aspartic acid analogues were subsequently used in a conformational analysis, with regards to substrate- and binding activity, which investigated the interaction of these compounds with aspartate decarboxylase (PanD). The synthesis of the 3- hydroxy-analogues of ornithine and diamino pimelic acid was also successfully achieved. These syntheses were done in a stereospecific manner to provide one enantiomer of the L-amino acid analogue. However, our efforts toward the synthesis of the other enantiomer of hydroxy analogues as well as our attempts at the conversion of the hydroxyl group to a fluorine were unsuccessful to date. Nevertheless, these results gave us a new direction towards the synthesis of the desired compounds and have led us to new strategies and ideas. Hopefully, the work done in this study will be part of the ground work towards new methodologies for the synthesis of desired halogenated amino acid analogues as small molecule inhibitors. / AFRIKAANSE OPSOMMING: The use of fluorine in medicinal chemistry has increased dramatically in the last 20 years. The addition of fluorine to a lead compound has various advantages such as the blocking of metabolic active sites, the increase of solubility and lipophilicity of a compound, acting as conformational probes for the active site of an enzyme, and influencing (in most cases increasing) the binding affinity of a compound to a target protein. Their use as mechanism based inhibitors is also well known. In this study we set out to synthesize hydroxyl- and fluorinated-amino acid analogues as potential inhibitors and probes towards the active site of various enzymes. The synthesis of the hydroxylamino acid analogues would precede the fluorinated analogues to serve as precursors with fuorination achieved via a fluoro-dehydroxylation reaction. These aims have successfully been achieved with the synthesis of the two enantiopure isomers of 3-fluoro-aspartic acid. The fluorinated aspartic acid analogues were subsequently used in a conformational analysis, with regards to substrate- and binding activity, which investigated the interaction of these compounds with aspartate decarboxylase (PanD). The synthesis of the 3- hydroxy-analogues of ornithine and diamino pimelic acid was also successfully achieved. These syntheses were done in a stereospecific manner to provide one enantiomer of the L-amino acid analogue. However, our efforts toward the synthesis of the other enantiomer of hydroxy analogues as well as our attempts at the conversion of the hydroxyl group to a fluorine were unsuccessful to date. Nevertheless, these results gave us a new direction towards the synthesis of the desired compounds and have led us to new strategies and ideas. Hopefully, the work done in this study will be part of the ground work towards new methodologies for the synthesis of desired halogenated amino acid analogues as small molecule inhibitors.

Thesis (PhD)--Stellenbosch University, 2008. / ENGLISH ABSTRACT: Electrospinning is a simple yet versatile method used for producing nanofibers from various materials, including natural and synthetic polymers, polymer blends, ceramics and metals. The high specific surface areas, high aspect ratios (length/diameter), and the biomimicking nature of nanofibers make them ideally suited for application in diverse areas, including high-performance filtration, biomedical materials for tissue engineering scaffolds, wound dressings and controlled drug release, fiber-reinforced composites and highly sensitive nano-sensors. Two of the main requirements that need to be met for electrospun nanofiber materials to become commercially viable are: (1) a process for manufacturing continuous aligned nanofiber yarns, and (2) a drastic increase in the fiber production rate of the electrospinning process. The objectives of this study were to develop a scalable process for making continuous yarns of aligned electrospun nanofibers, and to develop a needleless electrospinning method for the high-throughput production of nanofibers. Three novel processes were developed while exploring innovative ways for making yarns from electrospun fibers. Finally, a fourth process, the so-called the NanoCaterpillar process, was developed. This process can be used as a scalable method for obtaining continuous yarns of aligned nanofibers. Advantages of the process include the requirement for relatively simple equipment, the simple process variations required for obtaining yarns of different linear densities, and the fact that, as a 'dry' process, it can be used to manufacture yarns from most materials that can be electrospun. The second goal of this study was to develop a needle-less electrospinning process, capable of making nanofibers at commercially viable throughput rates. The phenomenon of bubble electrospinning was discovered and developed further. Initial exploratory studies showed that bubble electrospinning could be employed to produce nanofibers from polymers in aqueous as well as organic solutions, and that the process follows similar trends to classic electrospinning such as the dependence of fiber diameter on polymer solution concentration and the possibility of including substances in the formed fibers by including them in the spin solution. A second, more in-depth study of the bubble electrospinning process revealed that fibers could be produced at very high rates with estimates, under ideal spinning conditions, reaching 5 kg/h per square meter of bubble bath surface. Furthermore it was found that fiber yield did not depend on the size or the lifetime per bubble. Investigations into several interesting aspects of bubble and jet behaviour during bubble electrospinning, such as child bubble formation and jet-splitting, led to predictive multiple linear regression models being fitted to the experimental data to describe process variables like yield per bubble, number of jets per bubble and fiber diameters. / AFRIKAANSE OPSOMMING: Die elektrospintegniek is 'n eenvoudige, dog veelsydige metode wat gebruik word om nanovesels van verskeie materiale, insluitend natuurlike en sintetiese polimere, polimeermengsels, keramieke, en ook metale te vervaardig. Die hoë spesifieke oppervlakareas, hoë lengte tot deursnee verhoudings en bio-naboodsende eienskappe van nanovesels maak hulle ideaalgeskik vir toepassing in uiteenlopende velde soos filtrasie, biomediese materiale vir weefselingenieurswese, wondbedekkings en beheerde vrystelling van geneesmiddels, veselversterkte saamgestelde materiale en hoogs-sensitiewe nanosensors. Twee van die hoofvereistes waaraan voldoen moet word, voordat elektrogespinde nanovesels kommersieël-lewensvatbaar kan word, is: (1) 'n proses vir die vervaardiging van kontinuë garings van gerigte nanovesels, en (2) 'n drastiese toename in die vervaardigingstempo van die elektrospinproses. Die doelwitte van hierdie studie was om 'n skalleerbare proses te ontwikkel vir die vervaardiging van kontinuë garings van gerigte nanovesels, en om 'n naaldlose elektrospinmetode te ontwikkel vir die hoë-uitset vervaardiging van nanovesels. Drie nuwe prosesse is ontwikkel tydens ondersoeke na innoverende maniere om garings van elektrogespinde nanovesels te vervaardig. Laastelik is 'n vierde proses, die sogenaamde NanoCaterpillar proses ontwikkel. Hierdie proses kan gebruik word as 'n skalleerbare metode vir die vervaardiging van kontinuë garings van gerigte nanovesels. Voordele van die proses sluit in dat relatief eenvoudige toerusting benodig word om die konsep toe te pas, dat slegs eenvoudige veranderinge aan die proses benodig word om garings van verskillende liniêre digthede te verkry, en dat die proses, synde 'n 'droë' proses, gebruik kan word om garings te maak van meeste materiale wat gespin kan word met die elektrospintegniek. Die tweede doelwit van hierdie studie was om 'n naaldlose elektrospinproses te ontwikkel wat nanovesels kon vervaardig teen kommersieël-lewensvatbare tempo's. Die borrelelektrospin verskynsel is ontdek en verder ontwikkel. Aanvanklike ondersoeke het getoon dat die borrelelektrospinproses gebruik kon word om nanovesels te vervaardig van polimere in water- sowel as organiese oplossings. Dit het ook getoon dat die proses soortgelyke tendense toon as die klassieke elektrospintegniek, soos die afhanklikheid van veseldeursnee aan polimeeroplossingkonsentrasie en die moontlikheid om ander stowwe in die gevormde vesels in te sluit deur dit aanvanklik in die spinoplossing in te sluit. 'n Verdere indiepte ondersoek van die borrelelektrospinproses het onthul dat vesels, onder geïdealiseerde omstandighede, vervaardig kon word teen baie hoë tempo's, na beraming 5 kg/h per vierkante meter borrelbadoppervlakarea. Verder is bevind dat die veselopbrengs nie afhanklik was van die borrelgrootte of -lewensduur nie. Ondersoeke na verskillende aspekte van die borrel- en polimeerstraalgedrag tydens die borrelelektrospinproses, soos die vorming van kind-borrels en polimeerstraalsplitsing, het gelei tot die passing van voorspellende meerfoudige liniêre regressiemodelle op die eksperimentele data, ten einde prosesveranderlikes soos opbrengs per borrel, aantal polimeerstrale, en vesels deursnee te kan beskryf.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Thesis presented in partial fulfilment of the requirements for the degree of Master of Science (polymer science) at the University of Stellenbosch / Embargo date 2010-03-31 plt 2010 / ENGLISH ABSTRACT: A novel method, herein referred to as ‘solvent facilitated coaxial electrospinning’, was used to produce reversibly thermochromic core-shell fibres with poly(methyl methacrylate) (PMMA) as shell and a thermochromic dye composite as core. The thermochromic dye composite consisted of combinations of 1-dodecanol, bisphenol A (BPA) and crystal violet lactone (CVL). In the ‘solvent facilitated coaxial electrospinning’ method, the thermochromic dye composite was dissolved in a suitable ‘facilitating solvent’ prior to spinning, instead of being spun into the fibres from the melt as previously described in literature. A low interfacial tension between the core and shell liquids, which is beneficial to effective core entrainment, was achieved by using a correctly chosen core ‘facilitating solvent’. The PMMA was dissolved to form the shell spinning liquid and by selecting the correct core and shell solvents, spinneret blockage and precipitation due to core and shell liquid interactions were eliminated. High molar mass PMMA was used to produce fibres with diameters in the range of 3–10 μm (larger than typical electrospun fibres) in order to minimize light scattering and subsequently allow visual observation of the thermochromic transitions, unlike the fibres that were produced in literature. The fibres were analyzed using SEM, TEM, TGA and DSC to investigate fibre morphology, dye composite thermal transition and fibre composition. Physical and chemical interactions between the thermochromic dye composite and the PMMA shell were identified as possible causes of differences between the thermochromic transition temperatures of the core-shell fibres and the bulk dyes, as well as of the instability of the colour developed state of certain thermochromic fibres. The spatial confinement of the dye composite inside the fibres and the extensive volume reduction (from bulk dye to small volume inside the fibres) affected the thermochromic behaviour of the thermochromic composite once it was entrained in the fibres. An excess BPA was used in the dye composition to allow the production of reversibly thermochromic fibres with a stable colour developed state. / AFRIKAANSE OPSOMMING: A nuwe metode, hierin beskryf as ‘oplosmiddel gefasiliteerde koaksiale elektrospinnery’, is gebruik om omkeerbare termochromiese kern-skil vesels met polie(metiel metakrilaat) (PMMA) as skil en ‘n saamgestelde termochromiese kleurmiddel as kern te vervaardig. Die saamgestelde termochromiese kleurmiddel het bestaan uit kombinasies van 1-dodekanol, bisfenol A (BPA) en kristal violet laktoon (CVL). Vir die ‘oplosmiddel gefasiliteerde koaksiale elektrospin’-metode, is die saamgestelde termochromiese kleurmiddel opgelos in ‘n gepaste ‘fasiliterende oplosmiddel’ voordat dit geëlektrospin is, eerder as om dit te smelt om dit sodoende in vesels te kan inspin soos beskryf in die literatuur. ‘n Lae raakvlakspanning tussen die kern- en skilspinvloeistowwe, wat voordelig is vir doeltreffende kern insluiting, is bereik deur gebruik te maak van sorgvuldig verkose ‘fasiliterende oplosmiddels’ vir die kern. Die PMMA is opgelos om die skilspinoplossing te vorm en, deur die keuse van die korrekte kern- en skiloplosmiddels, kon spinneret blokkasie en neerslag van die polimeer as gevolg van kern- en skilvloeistofinteraksies elimineer word. Hoë molekulêre massa PMMA is gebruik om vesels te vervaardig met deursnee in die omtrek van 3–10 μm (groter as tipiese elektrogespinde vesels) om sodoende lig-verstrooiing te verminder en daardeur visuele waarneming van die termochromiese oorgange moontlik te maak, in teenstelling met die vesels wat in die literatuur gevorm is. Die vesels is ge-analiseer met SEM, TEM, TGA en DSC om veselmorfologie, termiese omskakelinge van saamgestelde kleurmiddels en veselsamestelling te bestudeer. Fisiese en chemiese interaksies tussen die saamgestelde termochromiese kleurmiddel kern en die PMMA skil is geïdentifiseer as moontlike oorsake van verskille tussen die termochromiese oorgangstemperature van die kern-skil vesels en die kleurmiddels in grootmaat, asook van die onstabiliteit van die gekleurde toestand van sommige termochromiese vesels. Die ruimtelike inperking van die saamgestelde kleurmiddel binne in die vesels asook die beduidende volume verkleining (van grootmaat kleurmiddel tot klein volume binne in die vesels) het die termochromiese gedrag van die saamgestelde kleurmiddel binne die vesels beïnvloed. ‘n Oormaat BPA is in die saamgestelde termochromiese kleurmiddel gebruik om die produksie van omkeerbaar termochromiese vesels met ‘n stabiele gekleurde toestand toe te laat.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / Two cationic polymerizable surfactants (surfmers), (11-acryloyloxyundecyl)dimethyl-(2-hydroxyethyl)ammonium bromide (Ethanol surfmer) and (11-acryloyloxyundecyl)-dimethylethylammonium bromide (Ethyl surfmer) were synthesized and characterized. Characterization was done using, conductivity, Fourier transform infra-red spectroscopy (FT-IR), electrospray mass spectrometry (ESMS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), small angle X-ray scattering (SAXS) and polarized light microscopy with a heating stage. These surfmers and the commercial surfactant cetyltrimethylammonium bromide (CTAB) were used for functionalization of sodium montmorillonite (Na+-MMT), thereby forming organophilic MMT. The functionalization of MMT dispersions was carried out by ion exchange of the sodium ions in Na+-MMT by surfactants in aqueous media. Organophilic MMT clays were then dispersed in styrene and subsequently polymerized by a free radical reaction to yield polystyrene-clay nanocomposites. This in-situ intercalative polymerization process resulted in an exfoliated structure for Ethyl surfmer modified clay, a partially exfoliated structure for Ethanol surfmer modified clay and an intercalated structure for CTAB modified clay. These nanocomposite structures were confirmed by SAXS and transmission electron microscopy (TEM). The nanocomposites exhibited enhanced thermal stability. All the nanocomposites exhibited an inferior storage modulus (GI) at low clay contents relative to polystyrene. At higher clay loadings there was an increase in GI which was dependent on the level of clay dispersion and the clay content. All the nanocomposites showed an increase in glass transition temperature (Tg), regardless of the amount of clay and the level of clay dispersion. There was a shift towards higher temperatures and broadening of the tan δ peak, which was in turn dependent on the amount of clay and level of clay dispersion. Molecular masses of polystyrene-clay nanocomposites were in the range 105 g/mol for bulk polymerization relative to 103 g/mol for solution polymerization as revealed by gel permeation chromatography (GPC).

Thesis (MSc (Chemistry and Polymer Science))--Stellenbosch University, 2008. / The competitive transport, extraction, and coordination chemistry for a series of N- (thio)phosphorylated (thio)amide and N-(thio)phosphorylated (thio)urea ligands were investigated with the seven transition and post-transition metal ions Co(II), Ni(II), Cu(II), Zn(II), Ag(I), Cd(II) and Pb(II). Three N-benzylated derivatives of 1,4,7,10- tetraazacyclododecane (cyclen) were synthesized and a similar study carried out with the same metal ions and the deprotonated precursors. The ligands were all potential specific carriers (ionophores) in the organic phase. The seven metal ions had equal concentrations in the source phase. The experimental arrangement for the transport studies employed a set-up involving three phases: a source phase and a receiving phase (both aqueous), separated by a chloroform membrane (organic phase). Competitive metal ion solvent extraction involved two phases: an aqueous phase and an organic phase. Similar conditions were used in transport and extraction studies. The metal ion concentrations in the aqueous phases were analyzed by atomic absorption spectroscopy (AAS). The transport results of deprotonated N-(thio)phosphorylated (thio)amides and N- (thio)phosphoryated (thio)ureas showed that PhC(S)NPO(OPri)2 (L1), BrPhC(S)NPO-(OPri)2 (L11) and PriNHC(S)NPO(OPri)2 (L16) transported Ag(I) into the receiving phase. Under these experimental conditions, L1 had the highest Ag(I) transport efficiency, at 36.3%, while L11 only transported one metal ion, viz. Ag(I). With NH2C(S)NP(S)(OPri)2 (L4), 94.6% of Ag(I) remained in the membrane phase. Thus L4 appeared to have the highest formation constant with Ag(I). A small amount of Cu(II) was also transported by L1, NH2C(S)NP(O)(OPri)2 (L9), L16 and ButNHC(S)-NPO(OPri)2 (L20). L20 had the highest selectivity for Cu(II). Results of competitive metal ion extraction studies revealed that most ligands extracted up to 100% Ag(I), except L1 and morpholine substituted ligands (L7, L17) . The formation constant of L1 effects a subtle balance between metal uptake and metal loss into and out of the respective membrane phase. HL7 and HL17 had low solubility in chloroform. L4 extracted the highest percentage of Cu(II) (49%). Two neutral ligands, PhCONHPO(OPri)2 (1) and BrPhCONHPO(OPri)2 (2) were isolated and their molecular structure determined. They had monoclinic unit cells in the space groups C2/c and P21/n, respectively. An unprecedented octanuclear [Ag(I)(L4-S,N)]8 (3) complex was also crystallized. The extended structure showed three different cavities alternating with two unique 16-membered rings, creating a novel AgS2N2 cage. Two polynuclear Cu(I) chelates with deprotonated L4 and L6 (tBuNHC(S)NP(S)(OPri)2) were isolated by the same crystallization method. The complex [Cu(I)(L4–S,S)]9 (4) consisted of a hexagonal-prismatic hexamer, which exhibited an unusual and unprecedented supramolecular “honeycomb” packing. The trinuclear [Cu(I)(L6–S,S)]3 (5) consisted of a 6-membered Cu3S3 ring attached to a hydroxy tetrahydrofuran molecule. Di-, tri- and tetra-benzyl-1,4,7,10-tetraazacyclododecane (cyclen) was synthesized, and characterized. None of these compounds was effective in metal transport under these experimental conditions. Nevertheless, Tetra-benzyl cyclen showed the highest extraction efficiency for Ag(I), at 100%, and the highest selectivity for Ag(I) extraction, compared to Cu(II). An intermediate of dibenzyl cyclen compound dibenzylated dioxocyclen (6) was crystallized and found a host THF molecule in the lattice. The crystal and molecular structure confirmed the cis-configuration. The X-ray structure of the Cu(II) complex with dibenzylated cyclen (7) was determined for the first time. It was found to have an ideal square pyramidal coordination geometry around the central metal ion. A serendipitous organic compound of isopropylammonium(isopropylamino)- oxoacetate mono-hydrate (8) was crystallized. The crystal was held together by inter-molecular hydrogen bonds, which lead to two-dimensional layers with hydrophobic interactions.

Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: Water-borne coatings often contain multiple additives including pigments, dispersing agents, rheology modifiers, UV stabilizers and biocides. Due to their low molar mass and endocrinedisrupting properties, many of these additives, upon leaching from the substrate film, with time pollute water systems and become hazardous to the environment and to human health. In this study, I aimed to develop a facile method for the production of a polymeric biocide to serve as alternative to low molar mass biocides used in water-borne coatings. A secondary aim was to show that, without additional modification, the polymeric species can be used in surfactant-free ab initio emulsion polymerizations. Using a two-step process, I modified a commercially available copolymer, poly(styrene-alt-maleic anhydride) (SMA 1000), with mixed amines in order to obtain latexes with inherent antimicrobial activity. In the first step, I reacted SMA 1000 with 3-dimethylamino-1-propylamine and aqueous ammonia to confer antimicrobial activity and water-solubility to the SMA copolymer. In the second step, the copolymer was incorporated into a film-forming styrene-butyl acrylate (STY/BuA) latex. The modified SMA was incorporated into a latex in two ways: (1) post-added to the latex, and (2) used as stabilizer in emulsion polymerization. In both cases, the latex remained stable for up to 11 months, and stability was probably due to steric stabilization of the polymer particles. Antimicrobial activity of the latex film was achieved with both methods. When the modified SMA was post-added, antimicrobial activity was restricted to specific areas on the eventual polymer film, and when modified SMA was used as stabilizer, antimicrobial activity was evenly distributed throughout the polymer film. Fluorescence microscopy showed homogeneous distribution of antimicrobial activity upon inoculation in Gram positive bacteria dispersions when the modified copolymer was used as polymeric stabilizer for the synthesis of STY/BuA latexes. No antimicrobial activity against Gram negative bacteria was achieved. The homogeneous distribution of antimicrobial activity throughout the film was a result of adsorption of polymeric biocide/stabilizer to each individual latex particle. With further commercial development, high molar mass copolymers modified for antimicrobial activity may be a feasible, environmentally-friendly and healthy alternative to be used as stabilizers in emulsion polymerizations to produce water-borne coatings. / AFRIKAANSE OPSOMMING: Waterverf bestaan gewoonlik uit ‘n verskeidenheid bestandele, onder andere: pigmente, verspreiding middels, reologie modifiseerders, UV stabiliseerders en biologies aktiewe verbindings. As gevolg van die lae molêre massa en die endokrien ontwrigtende vermoë van baie van die bestandele hou hulle ‘n bedreiging in vir die omgewing in terme van waterbesoedeling en menslike gesondheid, soos hulle die film oor tyd verlaat. In hierdie studie het ek beoog om ‘n eenvoudige metode vir die vervaardiging van ‘n polimeries biologies aktiewe verbindings daar te stel om sodoende as ‘n alternatief vir die lae molêre massa biologies aktiewe verbindings, wat tans in waterverf gebruik word, te dien. ‘n Sekondêre uitkoms van die studie was om te wys dat, sonder enige adissionele omskakelings, dieselfde polimeer gebruik kan word in seep-vrye emulsie polimerisasie. Deur gebruik te maak van ‘n proses, wat uit twee stappe bestaan, het ek ‘n kommersieel beskikbare kopolimeer, poly(stireen-alt-maleinesuuranhidried) (SMA 1000), met gemengde amiene reageer om ‘n sintetiese lateks van stireen en butiel akrilaat (STY/BuA) met inherente antibakteriële aktiwiteit te verkry. In die eerste stap is SMA 1000 met 3-dimetielamien-1-propielamien en waterige ammoniak reageer om ‘n water oplosbare kopolimeer met inherente anti-bakteriële aktiwiteit te verkry. In die tweede stap is hierdie kopolimeer by ‘n sintetiese lateks gevoeg op twee maniere: (1) deur dit nadat die lateks geproduseer is by te voeg, en (2) deur die kopolimeer as stabiliseerder te gebruik in die vervaardiging van die lateks. In albei gevalle is stabiele latekse verkry vir ‘n tydperk van tot 11 maande. Die stabilisering was van steriese geaardheid. Albei die latekse het gevolglik antibakteriële eienskappe getoon. Daar was nie homogene verspreiding van die aktiwiteit in die geval waar die kopolimeer na die tyd bygevoeg is nie en het veroorsaak dat daar sekere areas van die finale film was wat geen aktiwiteit getoon het nie. Fluoresensie mikroskopie het egter homegene verspreiding van die anti-bakteriële aktiwiteit reg deur die film getoon, na inokulasie met Gram positiewe bakterië suspensies wanneer die kopolimeer as polimerisasie stabiliseerder gebruik was. Geen aktiwiteit teen Gram negatiewe bakterië was egter verkry nie. Die homogene verspreiding was as gevolg van die feit dat die kopolimeer sterk adsorbeer op elke individuele lateks partikel wanneer dit as stabiliseerder gebruik word. Verdere ontwikkeling op ‘n kommersiële basis kan daartoe lei dat polimeries biologies aktiewe verbindings as ‘n lewensvatbare en omgewingsvriendelike alternatief vir heidige stabiliseerders in emulsies vir waterverf gebruik kan word.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Please refer to full text for abstract. Abstract contains special characters.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: In this study, a functional styrene – maleic anhydride copolymer (SMA) was synthesized via reversible addition-fragmentation chain transfer mediated polymerization (RAFT). The obtained copolymer had an alternating structure with well controlled molecular weight. The structure of the copolymer was found to alternating when characterized by NMR and MALDI-Tof-MS. SMA copolymer is functional polymer due to the presence of reactive maleic anhydride moiety in its backbone. The SMA copolymer was used as a starting material for synthesis of other three copolymers with potential anti-viral activity. These three copolymers are referred to as SMA copolymer derivatives because they were synthesized by reacting either maleic anhydride or styrene moieties with certain chemical compounds. The three derived copolymers are; styrene-maleimde copolymer (SMI), styrene sulfonate-maleic anhydride copolymer (SSMA) and styrene sulfonate– maleimide copolymer (SSMI). SMI was synthesized by reacting 4-aminomethylbenzene sulfonamide compound with maleic anhydride moieties on the backbone of SMA copolymer. The reaction proceeded in the presence of co-catalysts triethylamine and dimethylamino pyridine to from amide linkages. The copolymer was characterized by NMR spectroscopy, SEC and FTIR spectroscopy. SSMA copolymer was successfully synthesized by reacting styrene moieties of the SMA copolymers with chlorosulfonic acid. The SSMA copolymer was further reacted with amine compound to synthesize SSMI copolymer. The synthesis of SSMI was achieved by reacting the maleic anhydride moieties in the backbone of the SSMA copolymer with N1,N1- dimethylpropane-1,3-diamine. Both copolymers were successfully characterized by FTIR spectroscopy. / AFRIKAANSE OPSOMMING: 'n Funksionele stireen-maleïensuuranhidried (SMA) kopolimeer is berei d.m.v. omkeerbare addisie-fragmentasie ketting-oordrag-beheerde (OAFO) polimerisasie. Die polimere het 'n wissellende struktuur en goed beheerde molekulêre massa gehad. Die wisselende struktuur is bevestig d.m.v. KMR en MALDI-ToF analise. Die SMA kopolimeer is funksioneel a.g.v. die teenwoordigheid van reaktiewe anhidriedgroepe in die polimeerrugraat. Hierdie SMA kopolimeer is gebruik as uitgangstof vir die bereiding van drie ander kopolimere met potensiele teenvirale-aktiwiteit: stireenmaleïimied kopolimeer (SMI), stireensulfonaat-maleïensuuranhidried kopolimeer (SSMA) en stireensulfonaat-maleïimied kopolimeer (SSMI). Hiedie kopolimere staan bekend as SMA-kopolimeerderivate omdat hulle berei is deur d.m.v. die reaksie van of maleïensuuranhidried of stireengroepe. SMI is suksesvol berei d.m.v. die reaksie van 4-aminobenseensulfonamied met maleïensuuranhidriedeenhede op die polimeerruggraat in die teenwoordigheid van die kokataliste trietielamien of dimetielaminopiridien, om sodoende amiedbindings te vorm. Die kopolimere is gekarakteriseer m.b.v. grootte-uitsluitings-chromatografie (SEC), KMR en FTIR. Die SMMA kopolimeer is suksesvol gesintetiseer d.m.v. die reaksie van die stireeneenhede van die SMMA kopolimeer met chlorosulfoonsuur. Die SSMA kopolimeer is verder gereageer met amienverbindings om die SSMI kopolimeer te lewer. SMMI kopolimere is berei d.m.v. die reaksie van die maleïensuuranhidriedgroepe in die ruggraat van die SSMA kopolimeer met N',N'-dimetielpropaan-1,3-diamien. Albei kopolimere is suksesvol gekarakteriseer m.b.v. KMR en FTIR.