No description available.

Multiferroics and magnetic metal-organic complexes are candidates for sophisticated applications in the future. In thisthesis, the magnetism in BiFeO3 (a multiferroic material with an incommensurate spin cycloidal structure), copper guanidiniam formate (a multiferroic metal-organic complex with a one-dimensional magnetic structure) and CP -RE-COT (a series of \zero-dimensional" single molecule magnets) are discussed. A radio-frequency plasma sputtering thin lm deposition system and a ferroelectric characterisation system were developed for the study of BiFeO3 epitaxial thin lms. A large leakage current was observed in BiFeO3 thin lms, which hindered the investigations on the ferroelectric properties and magnetoelectric coupling in them. An evidence of the spin cycloid in a BiFeO3 thin lm was observed by grazing-incidence small angle neutron scattering. The magnetism of a multiferroic metal-organic complex with a one-dimensional magnetic chain, [C(NH2)3][Cu(HCOO)3], was studied by magnetometry and muon spin spectroscopy. A spin-canted antiferromagnetic order and critical phenomenon in this material were investigated. It was shown that this material possessed an 3D Heisenberg long-range order below 4.6K. The one-dimensional magnetic chain was also studied by muon spin spectroscopy. The correlation length was measured with a eld dependence of H 1. Magnetisation relaxations of a series of single molecule magnets CP -RE-COT (COT = C8H8- CP = C5Me, which show "zero-dimensional" magnetism, were studied using an AC magnetometer and muon spin spectroscopy. Three possible relaxation pathways, including a quantum tunnelling process and two Orbach relaxation processes, were suggested by the relaxation behaviour. The suppression of the quantum tunnelling effect resulting from the entanglement of the ground states, which probably arises from the exchange interactions in CP -RE-COT, was also observed with a 1000 Oe applied magnetic eld. Data that were consistent with long-range magnetic ordering was observed in CP -Dy-COT, which would be the fi rst ever report of long-range magnetic order in a single ion magnet.

Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: The availability of laser systems capable of generating ultrashort optical pulses in the visible spectral range have made it possible to study molecular species with a temporal resolution in the order of intra-molecular dynamics which previously were not accessible. Henceforth, in this study a popular pump-probe technique called ultrafast transient absorption spectroscopy (UTAS) is employed to study the initial photochromic reaction of metal complex, dithizonatophenylmercury (II) (DPM) under various conditions. These conditions include the use of different solvents and electronically altering DPM by the addition of substituents with specific electron affinity properties. For this study the photochromic behaviour of DPM dissolved in methanol is used as standard. Using this standard, the initial photochromic reaction after ultrafast excitation within less than 100 fs caused a radiationless photoreaction with a time constant of about 2 ps, which is interpreted as C=N isomerization along the twist coordinate. It is found that during this isomerization reaction an orthogonally twisted intermediate state was formed and observed through its excited-state absorption, which funnels through a conical intersection onto the ground state potential. Once here, bifurcation along pathways towards the ground states of the reactant and product configurations occurs. This was the first observation of photochromism for DPM in a strong polar solvent such as methanol. From the results of the test compound in methanol, comparisons to the photo-behaviour of DPM dissolved in deuterated methanol and dichloromethane are made. What is established is that changing the solvent resulted in slightly different decay times as well as spectral shifts in the absorption profile which suggested that the potential energy surface of the excited state is modified. This is similar to the results found from the electronically altered DPM species. Here the entire photoreaction is found to either be sped up (1 ps) or slowed down (4 ps) depending on the sample investigated. Previous studies on the photochromicity of DPM like systems concluded that apart from the photo-activated forward reaction, a back reaction occurs in the absence of light. Therefore a detailed look at the back reaction of DPM and its derivatives are also studied. This is done by temporally monitoring the absorption change of the photo-product as it converts back to the reactant. In doing so the lifetime of the photo-product is determined and found to differ greatly depending on the solvent and substituent used. Lastly, in assuming that the back reaction follows first order kinetics, an Arrhenius type measurement on the photo-product of DPM is conducted. The result of this measurement is that a potential energy barrier of 64.8 kJ/mol is overcome in the back reaction. The measurements performed and the results obtained from the photochromicity of DPM contribute to the understanding of photo-induced cis-trans isomerization reactions about a C=N double bond. / AFRIKAANSE OPSOMMING: Die beskikbaarheid van laser sisteme in staat om ultrakort optiese pulse te genereer in die sigbare spektrale gebied, het die studie van molekulˆere spesies met ’n tydresolusie in die orde van intra-molekulˆere dinamika wat voorheen nie toeganklik was nie. Voortaan, in hierdie studie word ’n populˆere aktiveer-interogeer tegniek genaamd ultravinnige tydafhanklike absorpsie spektroskopie (UTAS) aangewend om die aanvanklike fotochromiese reaksie van die metaal kompleks, ditisoonfenielkwik (II) (DFK) onder verskillende kondisies te bestudeer. Hierdie kondisies sluit in die gebruik van verskillende oplosmiddels en die elektroniese verstelling van DFK deur die toevoeging van substituente met spesifieke elektron affiniteit eienskappe. Vir hierdie studie word die fotochromiese gedrag van DFK, opgelos in metanol, as standaard gebruik. Met hierdie standaard, word gevind dat die aanvanklike fotochroom reaksie na ultravinnige opwekking binne minder as 100 fs, ’n stralingslose fotoreaksie met ’n tydkonstante van 2 ps veroorsaak. Hierdie fotoreaksie word verklaar as die C=N isomerisasie met betrekking tot die draai ko¨ordinaat. Daar is ook gevind dat gedurende hierdie isomerisasie reaksie, ’n ortogonaal verdraaide oorgangstoestand gevorm word wat waargeneem is deur sy absorpsie in die opgewekte toestand wat tregter deur ’n koniese kruispunt na die potensiaal van die grondtoestand. By hierdie punt vurk die proses na die grondtoestande van die reaktant en die produk vorme. Di´e was die eerste waarneming van fotochromisme van DFK opgelos in ’n sterk polˆere oplosmiddel soos metanol. Vanuit die resultate vir die toets mengsel in metanol word vergelykings getrek tot die fotogedrag van DFK opgelos in gedeureriese metanol en dichlorometaan. Wat hieruit vasgestel is, is dat die verandering in oplosmiddel wel die fotoreaksie be¨ınvloed deurdat verskillende vervaltye en spekrale verskuiwings in die apsorpsie profiel waargeneem word. Hierdie verskille dui aan dat die potensie¨ele energie oppervlakte van die opgewekte toestand wel gemodifiseer word. Dit is ook soortgelyk aan die resultate vir die elektronies verstelde BFK spesies. Hier is gevind dat die tempo van die totale fotoreaksie `of toeneem (1 ps) `of afneem (4 ps) afhanklik van die spesifieke spesie wat bestudeer word. Vorige studies van die fotochromiese gedrag van sisteme soortgelyk aan DFK het gevind dat behalwe vir die fotogeaktiveerde voorwaartse reaksie, daar ook ’n keersy reaksie plaasvind in die afwesigheid van lig. Dus word die keersy reaksie vir DFK en sy derivate ook in detial bestudeer. In hierdie studie word die absorpsie verskille van die fotoproduk tydelik waargeneem soos dit terugkeer na die reaktant. Op hierdie manier word die leeftyd van die fotoproduk bepaal en gevind dat dit grootliks afhang van die tipe oplosmiddel en tipe substituent wat gebruik word. Ten slote, wanneer daar aanvaar word dat di´e keersy reaksie eerste orde kinetika volg, word ’n Arrhenius tipe meting op die fotoproduk uitgevoer. Die resultaat van hierdie meting is dat ’n potensie¨ele enrgie versperring van 64.8 kJ/mol oorkom word in die keersy reaksie. Die metings wat uitgevoer is en die resultate wat verkry is van die fotochromiese gedrag van DFK dra by tot die verstandhouding van lig-ge¨ınduseerde cis-trans isomerisasie reaksies rondom ’n C=N dubbelbinding.

Thesis (MSc)--Stellenbosch University, 2012. / AFRIKAANSE OPSOMMING: Berekeninge met Density Functional Theory (DFT) is ’n nuttige tegniek om die dinamika van molekules op potensiële energievlakke te verstaan. Beginnende met ’n prototipe molekuul formaldimien, wat die kern vorm van die groter fotochromiese molekuul dithizonatophenyl kwik (DPM), word die modellering van die molekuul meer ingewikkeld tot laasgenoemde bestudeer kan word asook sy fotochromiese afgeleides wat vervanging van elektronryk en elektronarm radikale by orto, meta en para posisies van die phenyl ringe insluit. DFT berekeninge word met spektra van Absorpsiespektroskopie met UV en sigbare lig asook tyd opgeloste spektra, verkry dmv femtosekondespektroskopie, vergelyk. In pol^ere aprotiese, pol^ere protiese en nie-pol^ere oplosmiddels, isomeriseer die molekuul om die C=N dubbelbinding. Daar kan tussen die twee isomere onderskei word deur dat die een in oplossing in sy grondtoestand blou en die ander een oranje voorkom. Die isomerisering is’n fotogeinduseerde proses. Die optimering van die molekul^ere struktuur, absorpsiespektra, oplosmiddel-afhanklikheid, en potensiële energievlak metings van die molekuul word bestudeer. Die sterk/swak wisselwerking wat in pol^ere protiese/aprotiese oplosmiddels verskyn word geopenbaar deur die hoe/lae absorpsie van die sekond^ere bande van die molekules. Daar is gevind dat die absorpsiespektra van DPM bathochromies in oplosmiddels met hoë diëlektriese konstantes is. Vir die potensiële energievlak berekeninge van die grondtoestand word rigiede en ontspanne metodes gebruik waar laasgenoemde met gebroke simmetrie berekeninge verkry word. Van alle metodes wat vir berekeninge gebruik was, gee die B3LYP/CEP-31G metode die beste benadering aan eksperimentele data. Alle berekeninge word gedoen met twee bekende sagteware pakkette; Amsterdam Density Functional (ADF) en Gaussian, wat op twee verskillende DFT metodes gebaseer is. / ENGLISH ABSTRACT: Density functional theory is a useful computational tool in the understanding of molecular dynamics on potential energy surfaces. Starting with a prototype molecule formaldimine, the photochromic molecule dithizonatophenylmercury II (DPM) and a set of its photochromic derivatives, (involving substitutions of electron donating and electron withdrawing substituents at ortho, meta and para positions of the dithizonato phenyl rings), are studied through density functional calculation in comparison with steady state absorption spectra obtained from UV-Visible and femto second spectroscopy experiments. In polar aprotic, polar protic and non-polar solvents these molecules isomerise around C=N double bond chromophore, from orange electronic ground states to blue electronic ground states upon photo-excitation. We investigate the structural optimisations, the absorption spectra, the solvent dependence and the potential energy surface (PES) of these molecules. The strong (weak) interactions exhibited by the polar protic (aprotic) solvents used are revealed through high (low) absorbance in the secondary bands of these molecules. The absorption spectra of DPM are found to be bathochromic in solvents with high dielectric constants. For the ground state PES calculation we make use of rigid and relaxed methods, and the latter is obtained through broken symmetry calculation. Of all the methods used in calculation, B3LYP/CEP-31G method gives the best approximation to the experimental data. All calculations are done using the two renown software, Amsterdam Density Functional (ADF) and Gaussian, availing their different density functional methods.

Ce projet de thèse vise à étudier les processus géochimiques de l'aluminium dans les sols acides à sulfates. Les résultats obtenus avec le dispositif de dialyse de Donnan montrent que l'aluminium dans la solution du sol est presque exclusivement (> 98%) présent sous forme de complexes de charge négative, vraisemblablement des organo-complexes d'aluminium. Les concentrations d'aluminium isotopiquement échangeables (valeurs-E) et les concentrations obtenues par extractions chimiques révèlent qu'une solution de 1 M KCl sous-estime systématiquement les valeurs E. Une méthode d'extraction séquentielle a révélé qu'une quantité importante de minéraux primaires (initialement présents dans les sols) a déjà été dissoute, comme en témoignent les concentrations élevées d'aluminium présentes en tant que minéraux secondaires d'aluminium. Ces études permettent de mieux comprendre la géochimie de l'aluminium dans les sols CLASS et de pouvoir intégrer ces connaissances dans la gestion des sols. / The aim of this thesis was to further understanding on Al geochemistry in coastal lowland acid sulfate soils (CLASS). It was observed that Al was present almost solely (> 98%) as negatively charged complexes in CLASS pore-waters, presumably with natural organic matter. Isotopically exchangeable concentrations (E-values) of Al and extraction solutions used to estimate the exchangeable pool showed that 1 M KCl always underestimated isotopically exchangeable Al concentrations in these soils and that 0.2 M CuCl2 improved agreement between both methodologies but sometimes overestimated corresponding E values. A sequential extraction procedure showed that substantial amounts of Al have already been dissolved from primary aluminosilicates initially present in the soils and remain in the soils mostly as reactive secondary Al minerals. The outcomes of this thesis significantly further our understanding of Al geochemistry in CLASS environments and how this knowledge can be incorporated into land management practices.

Made available in DSpace on 2014-06-11T19:30:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2004-09-10Bitstream added on 2014-06-13T20:00:32Z : No. of bitstreams: 1 lima_ev_dr_botfca.pdf: 664587 bytes, checksum: fcb3616f07a9c17f7f9f145d54e6987b (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Atualmente vem existindo interesse na calagem superficial, sem prévia incorporação, para implantação do sistema de plantio direto (SPD). Dessa forma, objetivou-se avaliar a quantidade, a qualidade e os efeitos de resíduos de diferentes plantas de cobertura, com e sem calagem superficial, sobre os atributos químicos no perfil do solo e as respostas do milho e da soja, no SPD em fase de implantação em região de inverno seco. O experimento foi realizado nos anos agrícolas de 1999/00, 2000/01 e 2001/02 na FCA/UNESP-Botucatu (SP), em Nitossolo Vermelho Distroférrico. O delineamento experimental foi em blocos ao acaso, com parcelas subdivididas e quatro repetições. As parcelas foram constituídas pelos tratamentos de cobertura vegetal, sendo: 1-sorgo de Guiné vermelho, 2-sorgo de Guiné branco/preto, 3-milheto, 4-painço, 5-vegetação espontânea e 6-sem vegetação. Nas subparcelas foram admitidos dois níveis de saturação por bases: A- a original do solo e B- visando a elevação da V% a 70 (recebendo inicialmente uma aplicação superficial de calcário e posterior reaplicação). Foi utilizado um calcário dolomítico faixa D (filler). As coberturas vegetais foram dessecadas aos 53, 56 e 50 dias após a emergência... / Interest has been on the rise toward surface liming, without previous incorporation, during no-till system implementation. The objective was thus to evaluate the amount, quality, and effects of residues of different ground cover plants, either with or without surface liming, on the soil profile's chemical attributes, and the responses of corn and soybean, under no-till system at the implementation stage in a dry-winter region. The experiment was conducted during the 1999/00, 2000/01, and 2001/02 cropping seasons at FCA/UNESP-Botucatu (SP), on a Red Nitosol (Alfisol). The experimental design was organized as random blocks, with split-plots and four replicates. Plots consisted of ground cover plant treatments, as follows: 1-red broomcorn millet, 2- white/black broomcorn millet, 3- millet, 4- fall panicum, 5-spontaneous vegetation, and 6-no vegetation. Two base saturation levels were admitted in the subplots: A- the soil's original value, and B- a value that would raise V% to 70 (initially receiving one surface lime application and a later reapplication). Ground cover plants were desiccated at 53, 56, and 50 days after emergence, in the three cropping years... (Complete abstract, click electronic address below)

This work is concerned with the design and synthesis of the cheap, late first row transition metal complexes of Schiff base ligand systems. The prepared complexes readily afford systematic variation in order to probe potency and understand the role of metal, chelating ligands and anionic ligands when carrying out their cytotoxic effect. This study has lead to a better understanding of the action of these classes of complex and will be used to direct the design of new anti-cancer metallopharmaceuticals going forward. This thesis details the synthesis of a library of Schiff base macroacyclic ligands and their novel late first row transition metal complexes with varying anionic counterparts. The creation of a library with several degrees of variability provides a wide array of parameters to afford subtle variation in structure and chemistry e.g. denticity, co-ordination mode, chelate hole size, metal centred redox potentials, hydrolysis rates, co-ordinative saturation, lipophilicity, solubility and more. Complexation of the ligands was carried out by the free ligand and a novel macroacyclic metal template approach using the cheap late first row transition metal salts of Cobalt (II), Nickel (II), Copper (II) and Zinc (II) plus one Ru (III) complex. Structural studies of the 80 generated complexes was carried out by vibrational spectroscopy, elemental analysis, mass spectrometry, magnetic susceptibility and NMR. Single crystal X-ray structures have been determined with 20 reported in this thesis. All ligands act as tridentate ligands in all except one case to form monomeric distorted trigonal-bipyramidal, square-pyramidal or octahedral structures. In the case of zinc nitrate, the ligand L2PhMe acts as a tetradentate ligand to give a distorted octahedral structure. Paramagnetic NMR and solution magnetic susceptibility of paramagnetic complexes was achieved by the Evans NMR method and analysis of the solution NMR showed that L2R and L3R ligands display 2-fold symmetry and are likely either tetradentate in solution or a fast exchange between imine N-donar sites is occurring even down to -65°C. The majority of the resulting complexes of L1R were screened against a panel of three cancer cell lines. Several categories of complex were able to afford structure activity relationships. It was discovered that the ligand is indeed essential for activity of the metal salts against the panel of cell lines and it was largely discovered that the variation in 'tail group' and anionic coordinating ligands played little role in providing a dramatic variation in activity of the metal salt. In general all L1R complexes displayed moderate cytotoxicity showing a trend in activity with respect to the metal in the order RuIII≈CoII>CuII≈ZnII>NiII, over a 6 day exposure to the three cell panel RuIII was shown to be the most potent metal of the L1R series providing IC50 values of 4.6 (0.7) and 7.5 (1.2) μM against the DLD-1 and H460 cell lines respectively, which is Ca. 4.6 and 15 times less potent than cisplatin to the same cell panel respectively. RuIII was also discovered to be the only metal to provide an IC50 value from a 1 hour exposure to the DLD-1 cell panel. The value of 20.4 (3.5) μM is a moderate figure but again Ca. 10 fold less potent than cisplatin for the same test. The L2R and L3R complexes could not be screened by the same comprehension due to their low solubilities. However the lone screen that was possible from the very sparingly soluble complex [CuCl2(L3Bui)] gave the most exciting result and most potent complex of this thesis. After a 6 day exposure, [CuCl2(L3Bui)] gave IC50 values of 4.3 (0.1) and 2.9 (0.1) μM against the DLD-1 and H460 cell lines respectively. These values are merely 4 and 6 fold more than Cisplatin to the same cell lines respectively and demonstrates the potential of this class of complex as cytostatic agents. Further studies utilising a semi-quantitative DNA damaging assay, demonstrated that all first row complexes can damage DNA when in the presence of hydrogen peroxide, with the exception of ZnII complexes. CoII appeared to afford the greatest DNA damage with the most intsense bands for double strand breaks and the CuII complex of the ligand L3Bui also demonstrated a greater DNA damage as opposed to its L1Bui analogue.

Orientador: Carlos Alexandre Costa Crusciol / Banca: Dirceu Maximino Fernandes / Banca: Luis Reynaldo F. Alleoni / Banca: Edson Lazarini / Banca: Julio Cezar F. dos Santos / Resumo: Atualmente vem existindo interesse na calagem superficial, sem prévia incorporação, para implantação do sistema de plantio direto (SPD). Dessa forma, objetivou-se avaliar a quantidade, a qualidade e os efeitos de resíduos de diferentes plantas de cobertura, com e sem calagem superficial, sobre os atributos químicos no perfil do solo e as respostas do milho e da soja, no SPD em fase de implantação em região de inverno seco. O experimento foi realizado nos anos agrícolas de 1999/00, 2000/01 e 2001/02 na FCA/UNESP-Botucatu (SP), em Nitossolo Vermelho Distroférrico. O delineamento experimental foi em blocos ao acaso, com parcelas subdivididas e quatro repetições. As parcelas foram constituídas pelos tratamentos de cobertura vegetal, sendo: 1-sorgo de Guiné vermelho, 2-sorgo de Guiné branco/preto, 3-milheto, 4-painço, 5-vegetação espontânea e 6-sem vegetação. Nas subparcelas foram admitidos dois níveis de saturação por bases: A- a original do solo e B- visando a elevação da V% a 70 (recebendo inicialmente uma aplicação superficial de calcário e posterior reaplicação). Foi utilizado um calcário dolomítico faixa D (filler). As coberturas vegetais foram dessecadas aos 53, 56 e 50 dias após a emergência... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Interest has been on the rise toward surface liming, without previous incorporation, during no-till system implementation. The objective was thus to evaluate the amount, quality, and effects of residues of different ground cover plants, either with or without surface liming, on the soil profile's chemical attributes, and the responses of corn and soybean, under no-till system at the implementation stage in a dry-winter region. The experiment was conducted during the 1999/00, 2000/01, and 2001/02 cropping seasons at FCA/UNESP-Botucatu (SP), on a Red Nitosol (Alfisol). The experimental design was organized as random blocks, with split-plots and four replicates. Plots consisted of ground cover plant treatments, as follows: 1-red broomcorn millet, 2- white/black broomcorn millet, 3- millet, 4- fall panicum, 5-spontaneous vegetation, and 6-no vegetation. Two base saturation levels were admitted in the subplots: A- the soil's original value, and B- a value that would raise V% to 70 (initially receiving one surface lime application and a later reapplication). Ground cover plants were desiccated at 53, 56, and 50 days after emergence, in the three cropping years... (Complete abstract, click electronic address below) / Doutor

This work is concerned with the design and synthesis of the cheap, late first row transition metal complexes of Schiff base ligand systems. The prepared complexes readily afford systematic variation in order to probe potency and understand the role of metal, chelating ligands and anionic ligands when carrying out their cytotoxic effect. This study has lead to a better understanding of the action of these classes of complex and will be used to direct the design of new anti-cancer metallopharmaceuticals going forward. This thesis details the synthesis of a library of Schiff base macroacyclic ligands and their novel late first row transition metal complexes with varying anionic counterparts. The creation of a library with several degrees of variability provides a wide array of parameters to afford subtle variation in structure and chemistry e.g. denticity, co-ordination mode, chelate hole size, metal centred redox potentials, hydrolysis rates, co-ordinative saturation, lipophilicity, solubility and more. Complexation of the ligands was carried out by the free ligand and a novel macroacyclic metal template approach using the cheap late first row transition metal salts of Cobalt (II), Nickel (II), Copper (II) and Zinc (II) plus one Ru (III) complex. Structural studies of the 80 generated complexes was carried out by vibrational spectroscopy, elemental analysis, mass spectrometry, magnetic susceptibility and NMR. Single crystal X-ray structures have been determined with 20 reported in this thesis. All ligands act as tridentate ligands in all except one case to form monomeric distorted trigonal-bipyramidal, square-pyramidal or octahedral structures. In the case of zinc nitrate, the ligand L2PhMe acts as a tetradentate ligand to give a distorted octahedral structure. Paramagnetic NMR and solution magnetic susceptibility of paramagnetic complexes was achieved by the Evans NMR method and analysis of the solution NMR showed that L2R and L3R ligands display 2-fold symmetry and are likely either tetradentate in solution or a fast exchange between imine N-donar sites is occurring even down to -65°C. The majority of the resulting complexes of L1R were screened against a panel of three cancer cell lines. Several categories of complex were able to afford structure activity relationships. It was discovered that the ligand is indeed essential for activity of the metal salts against the panel of cell lines and it was largely discovered that the variation in ¿tail group¿ and anionic coordinating ligands played little role in providing a dramatic variation in activity of the metal salt. In general all L1R complexes displayed moderate cytotoxicity showing a trend in activity with respect to the metal in the order RuIII¿CoII>CuII¿ZnII>NiII, over a 6 day exposure to the three cell panel RuIII was shown to be the most potent metal of the L1R series providing IC50 values of 4.6 (0.7) and 7.5 (1.2) ¿M against the DLD-1 and H460 cell lines respectively, which is Ca. 4.6 and 15 iii times less potent than cisplatin to the same cell panel respectively. RuIII was also discovered to be the only metal to provide an IC50 value from a 1 hour exposure to the DLD-1 cell panel. The value of 20.4 (3.5) ¿M is a moderate figure but again Ca. 10 fold less potent than cisplatin for the same test. The L2R and L3R complexes could not be screened by the same comprehension due to their low solubilities. However the lone screen that was possible from the very sparingly soluble complex [CuCl2(L3Bui)] gave the most exciting result and most potent complex of this thesis. After a 6 day exposure, [CuCl2(L3Bui)] gave IC50 values of 4.3 (0.1) and 2.9 (0.1) ¿M against the DLD-1 and H460 cell lines respectively. These values are merely 4 and 6 fold more than Cisplatin to the same cell lines respectively and demonstrates the potential of this class of complex as cytostatic agents. Further studies utilising a semi-quantitative DNA damaging assay, demonstrated that all first row complexes can damage DNA when in the presence of hydrogen peroxide, with the exception of ZnII complexes. CoII appeared to afford the greatest DNA damage with the most intsense bands for double strand breaks and the CuII complex of the ligand L3Bui also demonstrated a greater DNA damage as opposed to its L1Bui analogue.

No description available.