Thesis (PhD)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Synthetic polymers are complex compounds that have multiple distributions with regard to molar mass, chemical composition, functionality and molecular architecture. Therefore, the molecular complexity of these compounds can only be analysed using a combination of analytical techniques. Well-defined complex polymers can be prepared by different types of living radical polymerisation, including reversible addition–fragmentation chain transfer polymerisation (RAFT) and reverse iodine transfer polymerisation (RITP). Using these techniques, several different homopolymers and copolymers have been prepared. However, there is still space for some more extended research. Many different types of multifunctional RAFT agents have been reported in literature. A tetrafunctional RAFT agent was prepared in our laboratory and used for the first time in the polymerisation of styrene. The polymerisation reaction was followed using in situ 1H nuclear magnetic resonance (NMR) and the molar masses of the resultant polymers were determined using size exclusion chromatography (SEC). The molar masses of the star-shaped polystyrenes (PS) were found to be less than the theoretical molar masses. This was due to the fact that SEC was calibrated with linear PS standards, while the samples under investigation are branched. Linear and branched polymers have different hydrodynamic volumes at similar molar masses. In order to prove that the star-shaped polymers were in fact four-armed, the samples were cleaved by aminolysis to yield the linear PS arms. The molar masses of the arms were in agreement with the theoretical arm molar masses based in the fourarmed structure. RITP is a relatively new living radical polymerisation technique. Various monomers have been prepared using RITP, including acrylates, methacrylates and styrene. The polymers formed using this technique have been characterised by techniques such as SEC, NMR and mass spectrometry (MS). However, very little advanced characterisation work has been done on polymers synthesised via RITP. Polystyrene-block-poly(n-butyl acrylate) (PS-b-PBA) block copolymers were prepared via RITP and the microstructure analysed by in situ NMR and other advanced analytical techniques. The chromatograms from gradient HPLC of the PS-b-PBA block copolymers showed a separation based on chemical composition. The preparation of deuterated polymers via RITP has not been reported in literature. Hydrogenous-polystyrene-block-deuterated-polystyrene (hPS-b-dPS) was synthesised via RITP and analysed using liquid chromatography at critical conditions. An isotopic separation was achieved when critical conditions were established for hydrogenous PS (h-PS). A separation of the block copolymer from the first block was also achieved under chromatographic conditions where the block copolymer eluted in SEC mode while the first block eluted in LAC mode. The separation according to the block structure was confirmed by two-dimensional liquid chromatography. / AFRIKAANSE OPSOMMING: Sintetiese polimere is komplekse verbindings wat meervoudige verspreidings ten opsigte van molêre massa, chemiese samestelling, funksionaliteit en molekulêre argitektuur. Daarom kan die molekulêre kompleksiteit van hierdie verbindings net ontleed word met behulp van 'n kombinasie van analitiese tegnieke. Goed-gedefinieerde komplekse polimere kan voorberei word deur verskillende soorte lewende radikaal polimerisasie, insluitend omkeerbare addisie-fragmentasie kettingoordrag polimerisasie (OAFO) en omgekeerde jodium oordrag polimerisasie (OJOP). Met behulp van hierdie tegnieke, was verskeie homopolimere en kopolimeer opgestel. Maar daar is nog plek vir nog uitgebreide navorsing. Baie verskillende tipes multifunksionele OAFO agente is aangemeld in die letterkunde. Ons het 'n nuwe vier-armige OAFO agent in ons laboratorium voorberei en dit was vir die eerste keer in die polimerisasie van stireen gebruik. Die polimerisasie reaksie is gevolg met behulp van in situ 1H kernmagnetieseresonans (KMR) en die molêre massas van die gevolglike polimere was bepaal deur grootteuitsluitings chromatografie (SEC). Die molêre massas van die ster-polistireen (PS) is bevind as minder as teoretiese molêre massas. Dit is omdat SEC instrumente gekalibreer word met lineêre PS standaarde, terwyl die monsters wat tans ondersoek word vertakte polimere is. Lineêre en vertakte polimere het verskillende hidrodinamiese volumes by soortgelyke molêre massas. Ten einde te bewys dat die ster polimere in werklikheid vier-armig is, is die monsters gesny deur ‘n aminolisasiereaksie om die lineêre PS arms te lewer. Die molêre massas van die arms was ooreenkomstig met die teoretiese arm molêre massas gebaseer op die vier-armige struktuur. OJOP is 'n relatiewe nuuts lewende radikaal polimerisasie tegniek. Verskeie monomere is opgestel deur OJOP, insluitend akrilate, metakrilate en stireen. Die polimere wat gevorm is deur middel van die tegniek is al gekenmerk deur tegnieke soos SEC, KMR en massaspektrometrie (MS). Tog is daar baie min gevorderde karakterisering werk gedoen oor polimere gesintetiseer deur middel van OJOP. Polistireen-blok-poli(n-butylacrylaat) (PS-b-PBA) blokkopolimere was voorberei deur middel van OJOP en die mikrostruktuur ontleed met behulp van gevorderde analitiese tegnieke. Die chromatogramme van gradiënt HPLC van die PS-b-PBA blokkopolimere het 'n skeiding ondergaan gebaseer op die chemiese samestelling. Die voorbereiding van gedeutereerde polimere deur middel van OJOP word nie in die letterkunde gevind nie. Gehidrogeneerde-polistireen-blok-gedeutereerde-polistireen (hPS-b-dPS) is gesintetiseer deur middel van OJOP en ontleed met behulp van vloeistofchromatografie onder kritiese kondisies. 'n Isotopiese skeiding was bereik wanneer kritiese kondisies gestig is vir gehidrogeneerde PS (h-PS).'n Skeiding van die blok kopolimeer van die eerste blok was ook bereik onder chromatografiese omstandighede waar die blok kopolimeer elueer in SEC terwyl die eerste blok elueer in LAC. Die skeiding volgens die blok struktuur was bevestig deur twee-dimensionele vloeistofchromatografie.

Thesis (MSc)--Stellenbosch University, 2002. / Please refer to fulltext for abstract / Verwys asb na volteks vir opsomming

Thesis (MSc)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: There is limited experimental and computational information available on the structures of compounds of the form R2GeX2, where X is a halogen and R an alkyl group. Gas phase electron diffraction studies of the dihalo(dimethyl)germanes (R=Me)consistently give C-Ge-C angles in the range of 120-125°, about 10° larger than the corresponding C-C-C angles in the 2,2-dihalopropanes. However, in dimethylgermane, where the halogen atoms are substituted by hydrogen, the value of the C-Ge-C is very similar to the corresponding C-C-C angle in propane and deviates little from the tetrahedral value of 109.47°. The unusually large influence of atomic substituents on the value of the valence angles in these compounds introduces a serious challenge to the development of empirical force fields, where the size of an angle is traditionally determined only by the atoms directly involved in the formation of the angle and not by the other substituents attached to the central atom. Unfortunately, the large experimental errors in the gas phase electron diffraction studies and the lack of representative crystalline compounds in the Cambridge Structural Database make it impossible to establish conclusively whether these large valence angles are significant or just statistical anomalies. A systematic ab initio study of a number of compounds of the general form Me2AX2with A=C, Si or Ge and X=H, F, Cl, Br or I has been initiated to verify the experimental results and to try to explain this observed deviation in valence angle in terms of electronic effects and existing theories of structure and bonding. The carbon and silicon analogs of the dimethylated germanes were included in the calculations to ascertain whether the observed effect is an anomaly or merely a periodic trend in the group IVelements. To obtain a clearer overall view, identical calculations were also performed on compounds of the form AHnX4-n,MeAH2X, MeAHX2and Me2AHX,where Aand X have the same meaning as before. The ab initio calculations confirmed that there is in fact a significant increase in the C-A-C angle from A=C to A=Ge in the compounds Me2AX2,although the calculated increase is smaller than the experimentally determined increase by a few degrees. Together with this observed increase in the C-A-C angle there is a corresponding decrease in the X-A-X angle. Calculation of the electron density of three representative compounds revealed a significant difference in electron distribution between the germanium compounds and their carbon analogs, suggesting that the ionicity of the bonds and the electronegativity of the substituents may playa role in the size of the C-A-C angle in compounds of this form. This is supported by a statistical analysis of compounds in the Cambridge Structural Database containing a C2GeYZ fragment, where Y and Z may be any elements except carbon, which showed that the average C-Ge-C angle in compounds where Y and Z are electronegative is approximately 7° larger than in compounds where Y and Z are electropositive. The qualitative trends in the C-A-C and X-A-X angles have also been discussed in terms of three different bonding models. To verify the results of the ab initio calculations experimentally, a representative compound, dichlorobis(phenethyl)germane, has been synthesized and its crystal structure determined by X-ray diffraction. The C-Ge-C angle was found to be 121.2°, which is in good agreement with both the ab initio and the gas phase electron diffraction results. Furthermore, a force field for halogenated organic carbon, silicon and germanium compounds has also been developed based on the structural and vibrational data obtained from the ab initio calculations. Molecules of the form AHnX4-nand Me2AX2with A=C, Si, Ge and X=H, F, Cl and Br were used in the training set and the bond lengths, bond angles and vibrational frequencies were used to optimize the force field. Calculations performed with the force field reproduce the C-A-C angles to within 1° of the observed values and the reproducibility for the rest of the experimental data is also good. Force fields have been developed for some of the simpler molecules in our training set and where this is the case, the force field parameters have been compared to the previously determined values. / AFRIKAANSE OPSOMMING: Sien volteks vir opsomming

Thesis (MSc)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: Please refer to fulltext for abstract. / AFRIKAANSE OPSOMMING: Sien volteks vir opsomming

Thesis (MSc)--Stellenbosch University, 2003. / ENGLISCH ABSTRACT: Please refer to fulltext for abstract / AFRIKAANSE OPSOMMING: Sien volteks vir opsomming

Thesis (MSc)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: In this study, a number of mono- and di-substituted acyl(aroyl)thioureas were investigated for potential application as specific carriers (ionophores) for the transport and extraction of Ag(l) from a mixture of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(lI) ions. The experimental arrangement for the transport experiments employed a liquid membrane set up involving a 3-phase system - 2 aqueous phases (source and receiving phase) separated by a chloroform membrane incorporating the ligand. Competitive metal ion transport experiments were conducted using the liquid membrane set up. The aqueous source and receiving phases were analyzed using Atomic Absorption Spectroscopy (AAS) and results were confirmed by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICPOES). The transport results show that the N,N-dialkyl-substituted-N'-acyl(aroyl) (HL) thioureas studied, with the exception of the N,N-di-(2-hydroxyethyl)-N'-benzoylthiourea (HL3 ) and N-piperidyl-N'-4-nitrobenzoylthiourea (HL9 ), were efficient and selective for Ag(I). HL9 was also selective for Ag(l) but not efficient. HL3 was selective for Cu(II). Under the experimental conditions employed, 13% Cu(lI) was transported by HL3 . Among the N,Ndialkyl- N'-aroylthioureas, maximum Ag(l) transport was obtained by using N,N-diethyl-N'-4- chlorobenzoylthiourea (HL5 ) and N,N-di-n-butyl-N'-benzoylthiourea (HL \ Under the experimental conditions employed, the percentages of Ag(l) transported by HL5 and HL 1 were 48% and 42% respectively. The transport selectivity and efficiency of 3,3,3' ,3'-tetraethyl-1 ,1'-isophthaloylbisthiourea (H2L12 ) and N,N-diethyl-N'-camphanoylthiourea (HL13)for Ag(l) were also studied. We were particularly interested, in comparing the Ag(l) transport and extraction efficiency of these ligands with that of the HL and H2L ligands. The experimental results reveal that, of all the ligands we investigated in this study, HL 13 was the most efficient and selective carrier for Ag(l) transport. The interesting result is that, depending on the ligand concentration used, HL 13 transported 71-81% of Ag(I). Competitive two-phase metal ion solvent extraction experiments were also performed under conditions similar to the transport studies. The results show that by varying the ligand concentration in the membrane phase, up to 100% Ag(l) can be selectively and efficiently extracted from the mixture of the seven metal ions. Finally, the N,N-di-(n)-butyl-N'-benzoylthiourea (HL1) ligand and its complex with Ag(l) were synthesized. Single crystals of the complex were grown for X-ray crystallography and the crystal and molecular structure of the complex was determined. The crystal structure showed that Ag(l) is bonded to the deprotonated ligand through the S,O atoms forming interesting cluster [Ag (L - S, 0)] 4 in the solid state. This structure is monoclinic and crystallizes in the space group P21!c with a = 17.805 (4) A, b = 21.759 (4) A, c = 36.438 (7) A, f3= 96.34(3)°, Z = 8 and a final R-factor of 5.4%. / AFRIKAANSE OPSOMMING: In hierdie proefskrif is 'n aantal mono- en di-gesubstitueerde asiel(ariel) tioureums ondersoek vir moontlike gebruik as ionofore (spesifieke draers) vir die transportasie en ekstraksie van Ag(l) vanuit 'n mengsel van Co(ll), Ni(II), Cu(II), Zn(II), Cd(II), Ag(l) en Pb(lI) ione. 'n Drie-fase selsisteem is gebruik vir die transportasie eksperimente, twee waterige fases (bron- en ontvang-fase) wat geskei is met die chloroform membraan fase wat die ligande bevat. Kompeterende metaalioon transportasie eksperimente is uitgevoer met behulp van hierdie vloeistof membraan stelsel. Die twee waterige fases is deur middel van Atoomabsorpsie Spektroskopie (AAS) ge-analiseer en resultate is bevestig met gebruik van Induktief-gekoppelde Plasma-Optiese Emissie Spektroskopie (IGP-OES). Die resultate het getoon dat elkeen van die N,N-dialkiel-gesubstitueerde-N'-asiel(ariel) (HL) tioureums, met uitsondering van N,N-di(2-hidroksie-etiel)-N'-benzieltioureum(HL 3) en Npiperidiel- N'-4-nitrobenzieltioureum(HL9 ), doeltreffend en selektief was vir Ag(l) transportasie. HL9 was selektief vir Ag(I), maar die transportasie waarde was nie hoog nie, dws. dit was nie doeltreffend nie. HL3 was selektief vir Cu(II). Met gebruik van ons eksperimentele kondisies is 13% Cu(lI) getransporteer deur HL 3. Van die N,N-dialkiel-N'- ariel tioureums, is maksimum transportasie van Ag(l) verkry met gebruik van N,N-dietiel- N'-4-chlorobenzieltioureum (HL5) en N,N-di-n-butiel-N'-benzieltioureum (HL1). Met gebruik van ons eksperimentele kondisies was die persentasie transportasie van Ag(l) deur HL5 en HL 1 48% en 42% onderskeidelik. Die selektiwiteit en doeltreffendheid van 3,3,3' ,3'-tetra-etiel-1 ,t-isoftaltelblstioureumtl+L 12) en N,N-di-etiel-N'-kamfonieltioureum (HL13) vir Ag(l) transportasie is ook onderneem. Ons was besonder ge-interesseerd om die Ag(l) transportasie en ekstraksie van hierdie ligande te vergelyk met dié van die HL en H2L tipe ligande. Die eksperimentele resultate het getoon dat van al die ligande wat bestudeer is, HL 13 die doeltreffendste en mees selektiewe ionofoor was. Van besondere, belang was dat, afhangend van die ligand konsentrasie wat gebruik is, HL13 71-81% Ag(l) getransporteer het. Kompeterende twee-fase metaalioon vloeistof-vloeistof ekstraksie eksperimente is ook uitgevoer onder toestande soortgelyk aan dié van die transportasie eksperimente. Die resultate toon dat met varierende ligand konsentrasie, tot soveel as 100% Ag(l) selektief en doeltreffend geëkstrakeer word vanuit 'n mengsel van die sewe metaal ione. N,N-di-n-butiel-N'-benzieltioureum (HL1 ) ligande en die kompleks daarvan met Ag(l) is ook gesintetiseer. Enkel-kristalle van die kompleks is verkry en X-straal kristallografiese analiese is onderneem. Die kristalstruktuur toon hoedat Ag(l) gebind is aan die gedeprotoneerde ligand deur die S en Q atome en toon ook interessante [Ag(L-S,Q)]4 groepe in die vaste toestand. Hierdie struktuur is monoklinies en kristaliseer in die ruimtegroep P21!c met a = 17.805(4) Á, b = 21.759(4)Á, c = 36.438(7)Á, P = 96.34(3t, z = 8 en 'n finale R-faktor van 5.4%.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Master / Master of Philosophy