Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / This study involved the preliminary investigation into the potential liquid-liquid extraction of Os(IV/III) from hydrochloric acid solutions with ligands of type N,N-dialkyl-N′-acyl(aroyl)thioureas (HL), and ultimate selective pre-concentration and separation of Os(IV/III) from the other platinum group metals. Investigations have also been focused towards understanding the speciation of Os(IV) in hydrochloric acid medium. A series of osmium complexes with ligands of type HL have been synthesised and characterised. This has been done with a view towards understanding the interaction of Os(IV/III) with the HL ligands, and what the resultant stereochemical influences would be on the solvent extraction capabilities of the ligands. The structures of two novel osmium-containing compounds have been verified by means of X-ray crytallography. Firstly, the ion pair OsCl6[(C4H9)4N]2 was obtained as a result of liquid-liquid extraction experiments. Secondly, the only known example (in our knowledge) of an Os(III) - N,N-dialkyl-N′- aroylthiourea complex, in this case tris(N,N-diethyl-N’-benzoylthioureato)osmium(III), was successfully synthesised and characterised. Lastly, preliminary studies into the substitution reactions of ruthenium-polypyridine complexes with N,N-dialkyl-N′-acyl(aroyl)thioureas were conducted. A series of cis-bis(2,2′-bipyridine)(N,N-dialkyl-N′-acyl(aroyl)thioureato)ruthenium(II) complexes have been successfully synthesised and characterised. The electronic absorption behaviour of the formed complexes have been investigated in detail via UV-Vis spectrophotometry.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / This work focuses on the biocatalytic production of coenzyme A (CoA) analogues with different tether lengths in its pantetheine moiety, and on analogues where the cysteamine moiety has been replaced with a range of other amines. An attempt was made to develop a simple biocatalytic method for the optimum production of such CoA analogues by chemo-enzymatic means. Pantothenic acid ethyl thioesters with different tether lengths were first synthesized as substrates of the CoA biosynthetic enzymes, CoaA, CoaD and CoaE. The acceptability of these compounds as substrates for the pantothenate kinase (CoaA) from prokaryotic and eukaryotic organisms was investigated through kinetic studies. These substrates were subsequently exposed to CoaA, CoaD and CoaE to produce various general CoA synthons (ethyl pre-CoAs). Finally aminolysis of these ethyl pre-CoAs by cysteamine and homocysteamine gave the various CoA analogues of different tether lengths in their pantetheine moiety. The identical production of a second type of CoA synthon (phenyl pre-CoA) from pantothenic acid phenyl thioesters was also investigated as a means to increase reactivity of the thioester substrates. Aminolysis of the phenyl pre-CoA produced the corresponding CoA derivative, but reactivity was lower than expected. A second strategy was also developed where the pantothenic acid phenyl thioesters were first aminolyzed, resulting in various pantothenamide intermediates. Aminolysis was attempted with thiol-bearing amines such as cysteamine and homocysteamine as well as with amines without sulfhydryl functionalities. These pantothenamide intermediates were then used in the biosynthesis of the corresponding CoA analogues by addition of CoaA, CoaD and CoaE. The ideal method of CoA analogue production will utilize a continuous bioreactor system in which these analogues can be prepared on large scale. However, to construct a bioreactor the enzymes involved need to be immobilized on a matrix in order to transform substrate to product. The enzymes CoaA, CoaD and CoaE can be immobilized on cellulose via a cellulose binding domain (CBD) affinity tag. Various types of CBDs were investigated and used in the construction of suitable expression vectors. Optimum expression conditions to obtain soluble CBD-fused enzymes were developed.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / Human African Trypanosomiasis (HAT) is a disease that threatens more then 60 million men, woman and children in Africa. It is known that the inhibition of the enzyme, ornithine decarboxylase (ODC) leads to cell arrest and subsequent death of Trypanosoma brucei, the parasite that causes the disease. The fluorinated ornithine analogue, DFMO (difluoromethylornithine or eflornithine) is a known inhibitor of ODC. Although various syntheses for DFMO exist they have some practical drawbacks which prevent the cost effective production of this compound as a drug for HAT treatment. This work focuses on the synthetic preparation of the fluorinated ornithine analogue DFMO as well as the fluorinated ornithine analogues 2-MFMO, 3-fluoro-ornithine and 3,3-difluoro-ornithine. Our chosen synthetic methodology focused on the introduction of the fluorine functionality using a simpler, safer and more convenient method than current direct fluorination techniques, or those that rely on the use of CFCs. Instead we decided to develop and optimise a fluorodehydroxylation method based on the transformation of hydroxylated ornithine analogues. The fluorodehydroxylation method substitutes a hydroxyl group to the corresponding fluorine and can also be used to transform an aldehyde or ketone to the corresponding difluoro group. Application of this fluorination method requires the synthesis of appropriate ...

Thesis (MSc)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: The determination of the concentrations of the transition metals Mn2 +, Cu2 + and Fe3 + in various types of pulps was carried out using a combination of chelation with Ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (S,SEDDS) and capillary zone electrophoresis (CZE) coupled with diode array uvdetection. The metals were found to be inhomogeneously distributed in the pulps, and therefore a relatively large (20 gms) pulp samples were taken for analysis. Heating the pulp samples at 45°C with stirring for three hours was used to leach the metals into an aqueous phase for complexation with the ligands. Leaching with EDTA enabled the quantitative determination of 0.0091,0.0048 and 0.0014 mM Cu2 + and 0.0088, 0.0012 and 0.0016 mM Mn2 + in the three types of pulps analyzed respectively while detection of Fe3 + was not possible using EDTA. The use of [S,S-EDDS] as the leaching agent on the other hand enabled the quantitative determination of 0.0041, 0.0036 and 0.0031 mM Cu2+ and 0.0024, 0.0018 and 0.0047 mM Fe3+ in the three types of pulps analyzed respectively while determination of Mn2 + was not possible using [S,S-EDDS] as the leaching agent. [S,S-EDDS] was generally better in complexing iron and copper than EDTA. The leaching procedure employed and the detectors response to specific analytes formed were found to be the most important factors in the analysis of the metals in pulp. / AFRIKAANSE OPSOMMING: Die konsentrasies van die oorgangsmetale Mn2 +, Cu2 + and Fe3 + in verskeie tipes pulp is bepaal met behulp van 'n kombinasie van kelasie met etileendiamientetra-asynsuur (EDTA) en etileendiamiendisuksiensuur (S,S-EDDS) en kapillêre elektroforese (CE) gekoppel met UV-deteksie. Daar is bevind dat die metale oneweredig versprei is in die pulp monsters, en gevolglik is relatiewe groot (20 g) monsters gebruik vir die analiese. Die metale is ge-ekstraeer deur kompleksasie met die kelasie-agente in die water-fase, deur die pulp monsters vir drie uur te roer by 45°C. Ekstraksie met EDT A is gebruik om 0.0091,0.0048 en 0.0014 mM Cu2 + en 0.0088,0.0012 and 0.0016 mM Mn2 + in drie tipes pulp te bepaal, terwyl Fe3 + nie waargeneem is met behulp van EDTA nie. Deur [S,S-EDDS] te gebruik as ekstraksie-agent, is 0.0041, 0.0036 en 0.0031 mM Cu2+ en 0.0024, 0.0018 en 0.0047 mM Fe3+ in die drie tipes pulp waargeneem. Die analise van Mn2 + was nie moontlik met die metode nie. Daar is gevind dat die keuse van ekstraksie metode en die detektor-sensitiwiteit vir spesifieke metale die mees bepalende faktore in die analise van metale in pulp monsters is. EDDS was 'n beter keiaat vir Fe3 + en Cu2 + as EDTA.

Thesis (MSc)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: Capillary electrophoresis (CE) has recently attracted considerable attention as a promising analytical technique for the separation of cations and anions in complex matrices. Determination of ions in aqueous samples using capillary electrophoresis can be accomplished with indirect UV detection. Most inorganic ions have weak absorption profiles in the UV-Vis wavelength range. These mostly non-absorbing species are commonly detected by indirect UV absorbance through addition of an absorbing co-ion (chromophore) into the electrolyte. Inorganic cations most often require an additional complexing agent to selectively alter their similar mobilities and proper separation. For optimal determination of alkali, alkaline, and transition metal ions, several electrolytes systems were studied. These include pyridine, imidazole and 4- aminopyridine as UV-absorbing species and glycolic acid, a-hydroxyisobutyric acid and their mixture were used as complexing reagents. A mixture of 10 metal ions (K+, Na+,Ca2+, Mg2+, Mn2+, Fe2+, Cd2+, Pb2+, Ni2+and Zn2+) was successfully separated. Detectionwas performed at 210,214 and 254 nm. In the anion determination chromate and 2, 6 pyridine dicarboxylic acids (PDC) were used as back ground electrolytes for inorganic ions (F-, CI- en SO₄² ̄ ) and organic acids (tartaric acid, malic acid, succinic acid and citric acid) separations respectively. Electroosmotic flow (EOF) was reversed in the direction of the anode by adding Cetyltrimethylammonium bromide (CTAB) to the electrolyte. Highly alkaline conditions were used to confer a negative charge on inorganic and organic anions to promote their migration towards the anode. The detection wavelength was 200 nm. All peaks were completely resolved and well separated. The limit of detection (LOD) of cations and anions were in the range of 0.5 - 3 ppm and 2 - 3.5 ppm respectively. The described methods were used successfully in routine analysis of real samples. This includes the qualitative and quantitative analysis of an environmental water samples from the areas surrounding Stellenbosch, beverages and orange juice. / AFRIKAANSE OPSOMMING: Kapillêre Elektroforese (CE) het in die onlangse verlede heelwat aandag getrek as "n belowende analitiese tegniek vir die skeiding van katione en anione in komplekse monsters. Die bepaling van ione in waterige medium met kapillêre elektroforese word gedoen deur indirekte Ultraviolet (UV) deteksie aangesien meeste anorganiese ione swak absorbsie in die die sigbare UV (UV-Vis) golflengtegebied toon. Deteksie van hierdie meestal nie-absorberende spesies word algemeen gedoen deur indirekte UV absorbansie deur die byvoeging van "n ko-ioon (chromofoor) tot die elektroliet. Anorganiese katione benodig dikwels "n addisionele komplekserings reagens om selektief hulle eenderse mobiliteite te verander en sodoende goeie skeiding te bewerkstellig. Vir die optimale bepaling van alkali-, alkali-aard- en oorgansmetaal ione is verskeie elektrolietsisteme bestudeer. Hierdie sluit in piridien, imidasool en 4-aminopiridien as UV absorberende spesies en glikoliensuur, a-hydroksie-isobottersuur asook "n mengsel van die twee as komplekserings reagense. "n Mengsel van 10 metaalione (K+, Na+, Ca2+, Mg2+, Mn2+, Fe2+, Cd2+, Pb2+, Ni2+ en Zn2+) is sukselvol op hierdie wyse geskei. Deteksie is gedoen by golflengtes van 210, 214 en 254 nm. Vir die anioon bepaling is chromaat en 2,6-piridiendikarboksielsuur gebruik as agtergrond elektroliete vir die skeiding van anorganiese anione (F-, CI- en SO₄² ̄ ) en organiese sure (tartaarsuur, malonsuur, suksiensuur en sitroensuur), onderskeidelik. Elektroosmotiese vloei (EOF) is omgekeer na die rigting van die anode deur byvoeging van setieltrimetielammoniumbromied (CTAB) by die elektroliet. Sterk alkaliese kondisies is gebruik om 'n negatiewe lading op die anorganiese en organiese anione te konsentreer en sodoende hul migrasie na die anode te bevorder. Die deteksiegolftengte hier gebruik was 200 nm. Volkome resolusie en goeie skeiding is gerealiseer vir al die pieke. Die deteksielimiete (LOD) vir die katione en die anione was 0.5 - 3 ppm en 2 - 3.5 ppm, onderskeidelik. Die metodes wat beskryf word is suksesvol aangewend vir roetiene analise van werklike monsters. Dit sluit in kwalitatiewe sowel as kwantitatiewe analise van omgewingswater monsters uit die Stellenbosch area, koeldranke en lemoensap.

Thesis (MSc)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: Please see fulltext for abstract / AFRIKAANSE OPSOMMING: Sien asb volteks vir opsomming

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Due to numerous accidents involving munitions, recent interest has focused on the development and use of insensitive munitions (IM). Polymeric materials are used in insensitive munitions as binders or plasticizers. Most of the polymeric binders used are based on polycondensation reaction via using urethane linkages. The main aim of this study was the synthesis and characterization of selected energetic thermoplastic elastomers binder based on utilizing controlled free radical polymerization. This was achieved by using hydroxyl terminated poly (epichlorohydrin) (PECH-diol) and hydroxyl terminated glycidyl azide polymer (GAP-diol) as starting materials, and the subsequent synthesis of different macroinitiators. These macro-initiators were used to polymerize methyl methacrylate (MMA) to obtain thermoplastic elastomers. PECH-diol was prepared by cationic ring-opening polymerization (CROP) based on using borontrifluoride etherate (BF3-etherate) as catalyst and a low molecular weight diol as initiator. GAP-diol was synthesized by the reaction of PECH-diol with sodium azide in organic solvent.. Poly(epichlorohydrin-methyl methacrylate) (PECH-PMMA) and poly(glycidyl azidemethyl methacrylate) (GAP-PMMA) block copolymers were prepared by free radical polymerization of MMA monomer in presence of PECH and GAP macro-azoinitiator (MAI). The MAIs were prepared by the polycondensation reaction of hydroxyl terminated groups of elastomer with 4,4' azobis (4-cyanopentanoyl chloride) (ACPC). The phase behavior of blends of amorphous PMMA/PECH-diol and PMMA/GAP-diol was also investigated. Poly(epichlorohydrin-methyl methacrylate) (PECH-PMMA) and poly(glycidyl azidemethyl methacrylate) (GAP-PMMA) graft copolymers were synthesized by photopolymerization of MMA in presence of PECH and GAP with pendant N,Ndiethyldithiocarbamate groups as macro-photoiniferters. . Photopolymerization of MMA proceeded in a controlled fashion. A macro RAFT agent, based on the reaction of PECH with pendent dithiobenzoate was prepared. The macro-RAFT agent was used in the controlled thermal bulk polymerization of methyl methacrylate. Finally, living/controlled radical polymerization of MMA with four different photoiniferters, namely benzyl diethyl dithiocarbamate (BDC), 2-(N,N-diethyldithiocarbamyl) propionic acid (PDC), 2-(N,Ndiethyldithiocarbamyl) isobutyric acid (DTCA), and diethyl dithiocarbamateepichlorohydrin was achieved.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / This study describes the development of simplified analytical methods for the analysis of trace quantities of selected naturally occurring target compounds in complex biological matrices by stir bar sorptive extraction (SBSE) and gas chromatography/mass spectrometry (GC/MS). SBSE facilitates the direct extraction of organic compounds from aqueous samples by allowing the solutes to partition between the aqueous phase and a glass stir bar that is coated with a layer of polydimethylsiloxane (PDMS). The partitioning of polar compounds into the PDMS coating was enhanced by using different derivatization techniques in combination with SBSE. The derivatization of polar functional groups was performed with ethyl chloroformate, acetic acid anhydride, and O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine directly in the aqueous samples. Headspace derivatization of compounds containing a secondary alcohol group was performed directly on the stir bar coating in the presence of acetic acid anhydride vapors. The derivatized compounds were thermally desorbed (TD) and analyzed on-line by GC/MS. A number of experimental parameters, including salt addition, temperature and time were optimized to improve the recovery of the derivatized compounds by SBSE. The optimized methods were validated in terms of linearity, precision, and detection and quantitation limits prior to performing the quantification. Trace levels of tuberculostearic acid, a marker of tuberculosis, was detected in sputum samples that were decontaminated and concentrated before being analyzed by SBSE-TD-GC/MS. The method is sufficiently sensitive to detect the marker without the need to culture the organisms, namely M. Tuberculosis. The analysis of 4-hydroxynonenal has also been demonstrated by detecting trace levels of this oxidative stress marker in urine samples obtained from healthy volunteers. Furthermore, abnormally low testosterone/epitestosterone ratios were detected in a group of HIV positive patients by means of SBSE-TD-GC/MS. Further research is required to determine the clinical significance of this finding in the context of HIV infection. Finally, the excessive urinary excretion of estrone and 17β-estradiol following the administration of a high dose of the conjugated equine estrogens to a female volunteer has also been demonstrated.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch,2005. / This study comprises the preparation and full characterisation of new carbene complexes of group 10 metals (Ni, Pd or Pt), the group 9 metal, rhodium, as well as group 6 metals (Cr and/or W). N-heterocyclic carbene (NHC) complexes of nickel and palladium were prepared via oxidative addition of the corresponding carbene precursors imidazolium-, imidazolinium-, pyridinium- and quinolinium chloride salts, to M(PPh3)4 (M = Ni or Pd). Three types of carbene complexes, namely the standard five-membered two-N carbene complexes, new six-membered NHC complexes and novel six-membered rNHC complexes received attention. In the rNHC complexes the heteroatom (N) is removed from the carbene carbon. These new square planar carbene complexes of the general formula trans-[(PPh3)2MCl(L)]X (M = Ni or Pd; X = BF4 or PF6) L = 1,3-dimethyl-2,3-dihydro-1Himidazol- 2-ylidene, 1,3-dimethyl-2,3,4,5-tetrahydro-1H-imidazol-2-ylidene, 1-methyl-1,2-dihydropyridin- 2-ylidene, 1-methyl-1,2-dihydro-quinolin-2-ylidene, 1,4-dimethyl-1,2-dihydro-quinolin-2- ylidene, 2-methoxy-1-methyl-1,4-dihydro-quinolin-4-ylidene, 1-methyl-1,4-dihydro-pyridin-4- ylidene) have been isolated and characterised. The preparation of the corresponding carbene complexes of platinum was complicated by the formation of [PtCl(PPh3)3]BF4 and the desired carbene complexes could not be isolated in pure form. The investigation of rNHC complexes was extended to include the synthesis of (CO)5M{CSC(CNCMe2CH2O)CHCH} (M = Cr and W). The molecular and crystal structures of thirteen of the new carbene complexes including the structures of both cis- (only formed below –20°C) and trans-chloro(1-methyl-1,2-dihydro-quinolin- 2-ylidene)bis(triphenylphosphine)palladium(II) tetrafluoroborate were determined. The metalcarbene bond distances in both the palladium and nickel carbene families do not differ significantly. The carbene ligands can be arranged in a series of increasing trans-influence, using the metalchloride bond distance as a guideline, as follows: 1,3-dimethyl-2,3-dihydro-1H-imidazol-2-ylidene and 1,3-dimethyl-2,3,4,5-tetrahydro-1H-imidazol-2-ylidene < 1-methyl-1,2-dihydro-pyridin-2- ylidene < 2-methoxy-1-methyl-1,4-dihydro-quinolin-4-ylidene, 1-methyl-1,4-dihydro-pyridin-4- ylidene. The crystal and molecular structures of two platinum compounds, cis-chloro(2-methoxy-1- methyl-1,4-dihydro-quinolin-4-ylidene)bis(triphenylphosphine)platinum(II) tetrafluoroborate and the byproduct [PtCl(PPh3)3]BF4 were also determined. Trans-chloro(2-methoxy-1-methyl-1,4-dihydro-quinolin-4-ylidene)bis(triphenylphosphine) palladium(II) tetrafluoroborate was found to be a very active catalyst, compared to simpler palladium carbene and phosphine complexes, in the Mizoroki-Heck and Suzuki-Miyaura coupling reactions. Quantum mechanical calculations indicated that the rNHC ligand in this complex is bound stronger to the palladium than a standard imidazole-derived NHC ligand. Further calculations suggested that the remote heteroatom carbene (rNHC) complexes of nickel(II) are significantly more stable when compared to the normal carbene (NHC) complexes. Energy decomposition analysis suggested that the rNHC ligands are strong s-donors and weak -acceptors. Unsymmetrical imidazolium-derived bis(carbene) complexes, [Rh(NHC)2COD]Br, bromomono( carbene) complexes, Rh(Br)COD(NHC), and chloro-mono(carbene) complexes, Rh(Cl)COD(NHC) where NHC = 1-R-3-methyl-2,3-dihydro-1H-imidazol-2-ylidene (R = ethyl, propyl or butyl), were formed in each reaction of the corresponding free carbene ligand with [Rh(Cl)COD]2. [Rh(Br)COD(NHC)] formed as a result of substitution of a chloride ligand by a Br-- anion. The carbonyl complexes, cis-[Rh(CO)2X(NHC)] (X = Br or Cl; NHC = 1-ethyl-3-methyl- 2,3-dihydro-1H-imidazol-2-ylidene) were isolated after the substitution of the COD ligand in Rh(X)COD(NHC) (X = Br or Cl) with CO. Isomerisation of these cis-carbonyl complexes to the trans isomers was observed. Cis-[(h4-1,5-cyclooctadiene)bis(1-butyl-3-methyl-2,3-dihydro-1H-imidazol-2-ylidene)rhodium(I)] bromide, bromo(h4-1,5-cyclooctadiene)(1-methyl-3-propyl-2,3-dihydro-1H-imidazol-2-ylidene) rhodium(I) and cis-[(h4-1,5-cyclooctadiene)bis(1-butyl-3-methyl-2,3-dihydro-1H-imidazol-2- ylidene)rhodium(I)]bromide were also characterised by single crystal X-ray diffraction. The synthesis and structural characterisation of a series of acyclic and heterometallacyclic Fischertype carbene complexes in which a soft donor atom (P) attached to the carbene side chain is either uncoordinated, (CO)5M=C(NMe2)CH2PPh2 (M = Cr or W), bonded to the original central metals (Cr or W) in four-membered chelates, (CO)4M=C(NMe2)CH2PPh2, or coordinated to a second M(CO)5 unit (only isolated for chromium) (CO)5Cr=C(NMe2)CH2P(Ph2)Cr(CO)5, were carried out. These compounds were produced by the reaction of the anionic Fischer-type aminocarbene complexes, [(CO)5Cr=C(NMe2)CH2]Li (M = Cr or W), with ClPPh2. The formation of the four-membered chelates, via cyclisation, occurs much faster for Cr than for W. The aminocarbene-phosphine chelates represent the first examples of structurally characterised, four-membered C,P-chelate carbene complexes.

Thesis(PhD)--Stellenbosch University, 2008. / ENGLISH ABSTRACT: Aminopolycarboxylic acids (APCAs) are chelating agents widely used to inactivate various metal ions by complex formation in industrial and household applications. Ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) are the widely used agents. Their use is under scrutiny due to their persistence in the environment because they cannot readily biodegrade. This led to the introduction of readily biodegradable agents namely ethylenediaminedisuccinic acid (EDDS) and iminodisuccinic acid (IDS) as alternatives especially to EDTA. Therefore, there was an interest to study the separation of EDDS, IDS and other APCAs using a simple, quick and accurate method. Capillary electrophoresis was used to determine the separation and speciation of iminodisuccinic acid with various metal ions at various pH levels. Speciation modelling was also utilized to compare and validate the presence and distribution of metal-ligand species. The obtained CE results were compared with speciation profiles and a reasonable agreement was obtained. The degradation studies at various time intervals for the metal-ligand (ML) complexes of DTPA, S,S-EDDS, IDS and R,S-IDS with various metal ions (Cd2+, Cr3+, Cu2+, Fe3+, Mn2+, Pb2+ and Zn2+) at pH 7 and 9 was evaluated using CE. New peaks were observed in some ML complexes when the pH was changed from pH 9 to 7. Sharp peaks were seen for CuL (L = DTPA, S,S-EDDS, IDS and R,S-IDS), FeDTPA and FeEDDS at both pH s. While small broad peaks were observed for FeIDS, CrL and MnL complexes. CuDTPA and CuEDDS complexes showed a greater stability over some considerable time as compared to CuIDS, CuR,S-IDS and other metal complexes at pH 9. This work also investigated the effect of various cationic electroosmotic flow (EOF) modifiers and counter anions on the CE separation of EDTA, EDDS and IDS as Cu(II) complexes. The performance of the modifiers was evaluated in terms of migration times, resolution and plate numbers. The best results were observed when Tetradecyltrimethylammonium bromide (TTAB) and Cetyltrimethylammonium bromide (CTAB) was used as modifiers in order to reverse the EOF in the fused silica capillary. This resulted in short analysis time and better peak shapes. The effect of different counteranions attached to EOF modifiers on the separation was also shown. It was also found that the counter anions of EOF modifiers used influences the separation of the complexes. The EOF modifiers namely Cetyltrimethylammonium chloride (CTAC) and Tetradecyltrimethylammonium chloride (TTAC) were further utilized for the determination of EDTA in South African river waters and industrial effluents. A method for the simultaneous separation of Fe (III) complexed with EDTA, S,S -EDDS and IDS was developed by CE and high-performance liquid chromatography (HPLC). The recalcitrant EDTA is used in combination with readily biodegradable analogues like EDDS and IDS in many commercial products. The methodology performance was evaluated in terms of linearity, limit of detection (LOD), limit of quantitation (LOQ) and reproducibility for both CE and HPLC methods. The LOD values obtained from HPLC were low when compared with CE. The applicability of both methods was demonstrated for the analysis of cosmetic products such as foam bath and shower cream. The results obtained by both CE and HPLC were found to be comparable and are in good agreement. / AFRIKAANSE OPSOMMING: Aminopolikarboksiel sure (APCAs) is komplekseer middels wat algemeen gebruik word om verskillende metaal ione te deaktifeer deur kompleks vorming in industriële en huishoudige toepassings. Etileendiamientetraasynsuur (EDTA) en dietileentriamienpentaasyn suur (DTPA) is die mees algemene APCA s. Hul gebruik word deesdae noukerig ondersoek as gevolg van hul volharding in die omgewing. Daar is n intense soektog na bio-afbreekbare agente soos etieleendiamiendisuksien suur (EDDS) and iminodisuksien suur (IDS) wat as plaasvervangers kan dien vir nieafbreekbare EDTA. Daar is dus n behoefte om te kyk na eenvoudige, vinnige en noukeurige metodes vir die bepaling van EDTA, EDTA , IDS en ander APCA s. Kapillere elektroforese (CE) was gebruik vir die skeiding en spesiering van iminodisuksien suur met verskillende metale by verskillende pH s. Spesiasie modellering was ook gebruik om die teenwoordigheid en verspreiding van metaal- spesies te vergelyk. Die CE uitslae was met die spesiasie profiele vergelyk en n redelike ooreenkoms was gevind. Die degraderings studies as n funksie van tyd was met CE bestudeer vir verskillende metal-ligand (ML) samestellings van DTPA, S,S-EDDS, IDS en R,S-IDS met verskillende metal ione (Cd2+, Cr3+, Cu2+, Fe3+, Mn2+, Pb2+ en Zn2+) by pH 7 en 9. Nuwe pieke was opgemerk in sommige ML samestellings wanneer die pH van pH 9 na 7 verander. Hoë pieke was vir CuL (L = DTPA, S,S-EDDS, IDS and R,S-IDS), FeEDTA en FeEDDS by alle pH s gevind. Lae, breë pieke was vir FeIDS, CrL en MnL komplekse gevind. CuDTPA en CuEDDS komplekse het n goeie stabiliteit gewys oor ʼn redelike tyd as dit met CuIDS, CuR,S-IDS en ander metal komplekses by pH 9 vergelyk word. In hierdie werk was die effek van verskillende kationiese elektro-osmotiese stroom (EOF) modifiseerders ook ondersoek. Veral die effek wat teen ioone op die CE skeidings het van EDTA, EDDS en IDS asook Cu(II) komplekse was ondersoek. Die effek van die modifiseerders was ondersoek en ge-evalueer in terme van migrasie tye, resolusie en plaat getalle. Die beste skeidingskondisies was bereik wanneer tetradesieltrimetielammonium bromied (TTAB) and setieltrimetielammonium bromied (CTAB) as modifiseerders gebruik word. Hierdie kondisies het ook aanleiding gegee tot korter ondersoek tye en beter piekvorme. Die effek van verskillende teen ioone wat aan die EOF modifiseerders gekoppel was het ook interresante resultate opgelewer. Die EOF modifiseerders setieltrimetielammonium chloried (CTAC) en tetradesieltrimetielammonium chloried (TTAC) was ook gebruik vir die bepaling van EDTA in Suid Afrikaanse rivier waters en industrieel afloop. ʼn Metode vir die gelyktydige skeiding van Fe(III) met EDTA, S,S’-EDDS en IDS was met behulp van CE en hoedruk vloeistof chromatography (HPLC) ontwikkel. Die metodologie was ondersoek ingevolge lineariteit, limiet van deteksie (LOD), limiet van kwantifisering (LOQ) en die herhaalbaarheid van CE en die HPLC metodes. Die LOD waardes verkry vanaf HPLC was swakker vergeleke met die verkry deur CE. Die toepaslikheid van al die metodes was vir die ontleding van kosmetiese produkte soos bad skuim en stortbad room getoets. Die uitslae deur CE en HPLC was vergelykbaar en ʼn goeie ooreenkoms was gevind.