Digitized by Kansas Correctional Industries

This research focuses on how the structure of modified interfaces influence the behavior of the interface. Two groups of dialkyl sulfides are prepared and studied: a purely hydrocarbon dialkyl sulfide with the structure CH₃(CH₂)₁₇S(CH₂)_nCH₃, where n=7, 9, and 17, and a carboxylic acid containing dialkyl sulfide with the structure CH3₃(CH₂)₁₇S(CH₂)_mCOOH, where m=7, 10, and 15. The structure and the permeability of these monolayers are characterized by <i>ex situ</i> and <i>in situ</i> FTIR, contact angle measurements, and electrochemistry. It is found that the two groups of dialkyl sulfides have different surface structures and different monolayer-solution interfacial behaviors. The presence of a polar group, such as -COOH, within the monolayer structure is found to increase the charge transfer properties of the modified electrode by influencing the interfacial structure. The structure and permeability of monolayers prepared from 15-mercaptopentadecanoic acid, 16-mercaptohexadecanoic acid, and their corresponding ethyl esters are also studied. Infrared spectroscopy and electrochemical permeability measurements indicate that the ester monolayers are ordered and have few differences in their structural and physical properties. Monolayers prepared from 15-mercaptopentadecanoic acid and 16-mercaptohexadecanoic acid, however, are structurally and physically different from the esters and each other. The IR and contact angle results indicate that hydrogen bonding interactions between the terminal groups of the monolayers influence the structural organization and physical properties of the monolayer. The extent of the hydrogen bonding interactions within the ω-mercaptoalkanoic acid monolayers appear to be related to the structure of the interface, suggesting that the orientation of the terminal functional group influences its ability to interact within the monolayer. / Master of Science

Background: Biomonitoring of pesticides is an objective measure of short-term pesticide exposure as it measures possible exposure in the human body. Current evidence on the relationship between demographic, socio-economic and pesticide exposure risk factors and urinary levels of organophosphate (OP) pesticide metabolites among children is generally incomplete and conflicting in some cases. There is therefore a need for further research. Objectives: This study investigated the relationship between socio-economic, demographic and reported pesticide exposure related activities and characteristics in relation to urinary levels of three dialkyl phosphate (DAP) metabolites (diethyl phosphate (DEP), dimethyl phosphate (DMP) and dimethyl triphosphate (DMTP)) among boys living in the rural areas of the Western Cape, South Africa. Methods: This was an analysis of data collected during a cross- sectional study of 183 boys from three agricultural intense areas in the Western Cape of South Africa between April 2007 and March 2008. Measurements included a questionnaire on demographic, socio-economic and pesticide exposure risk factors and analysis of spot urine samples for DAP metabolites. Results: Most of the boys (70%) lived on farms with a median age of 12 years (range: 5.0 - 19.5 years). The median concentrations of DAP, DEP, DMP and DMTP were 68.3 ng/ml (IQR= 27.9; 129.5), 5.5 ng/ml, 32.6 ng/ml and 16.7 ng/ml, respectively. The sum of the three DAP levels wasinversely associated with age. Children older than 14 years had less DAP levels (β = -68.1; 95% CI: -136.8,0.6) than children 9 years and younger. DAP levels also varied significantly with residential area, with the levels highest in Grabouw (apple farming), followed by Hex River Valley (grape farming) (β= -52.1; 95% CI: -97.9, -6.3) then Piketberg (wheat farming) (β= -54.2; 95% CI:-98.8, -9.7). Other weaker and non-significant associations with increased DAP levels were found with increased household income, member of household work with pesticides, living on a farm, drinking water from an open water source and eating crops from the vineyard and or garden. Conclusion: The study found younger age and living in and around an apple and grape farms, to be associated with increased urinary DAP concentrations among the school children provide evidence that younger age and residential area can be associated with increased urinary DAP concentrations among boys. Additionally, there are other household and behavioural characteristics that are associated with elevated urinary DAP levels. Further studies with larger sample sizes and longitudinal designs to improve the statistical power and the associations found are recommended. The study provided more insight to incomplete and inconclusive evidence of previous studies.

Thesis (PhD (Chemistry and Polymer Science))--Stellenbosch University, 2008. / The successful preparation and structural characterization of a number of N,N-dialkyl-N’-benzoyl(thio)selenourea ligands is described; where the intermolecular interactions are characterized by the presence of Resonance Assisted Hydrogen Bonding (RAHB), π- π interactions between neighbouring benzene residues only being evident amongst the longer alkyl chain derivatives. The first structural characterization of an asymmetrically substituted N,N-dialkyl- N’-benzoylselenourea ligand reveals an increased stability of the Z isomer in the solid state, this being reflected by the sulfur analogue. Attempts to synthesise N,N-dicyclohexyl-N’-benzoylselenourea led to the isolation and structural characterization of a novel 1,3,5-oxaselenazine salt and dicyclohexylaminobenzoate. The first structural characterization of a “bipodal” N,N-dialkyl-N’-benzoylselenourea ligand, 3,3,3’,3’-tetrabutyl-1,1’- isophthaloylbis(selenourea), reveals RAHB in the crystal lattice similar to that exhibited by the “monopodal” analogue, N,N-dibutyl-N’-benzoylselenourea. The successful complexation of the N,N-dialkyl-N’-benzoyl(thio)selenourea ligands to a number of different transition metal ions is reported allowing the preparation of several potential single source precursors. Coordination through the O and Se/S donor atoms to Pd(II) results in the formation of square planar metal complexes, with a cis conformation, several of which could be structurally characterized. In particular, the first structural elucidation of an asymmetrically substituted N,N-dialkyl-N’-benzoylselenourea metal complex, cis-bis(N-benzyl-N-methyl-N’- benzoylselenoureato)palladium(II) indicates the increased stability of the EZ isomer in the solid state. Structural elucidation of the novel (N,N-diphenyl-N’-benzoylselenoureato)cadmium(II) reveals a bimetallic complex in the solid state, where the expected 2:1 ligand : metal ratio is maintained, and the two Cd(II) centres are 5 and 6 coordinated, with O and Se donor atoms. Multinuclear Nuclear Magnetic Resonance (NMR) Spectroscopy has been employed in the thorough characterisation of the potential single source precursors, 77Se NMR spectroscopy indicating a decreased shielding of the 77Se nucleus as the “hardness” of the central metal ion increases i.e. Pd(II) > Zn(II) > Cd(II). Use of 113Cd NMR spectroscopy indicates the preferential binding of N,N-diethyl-N’- benzoylselenourea to Cd(II) over that of its sulfur analogue, and initial studies suggest a form of chelate metathesis taking place in solution. 31P NMR spectroscopy is used to gain insight into the formation of cis-bis(N,N-diethyl-N’- benzoylselenoureato)Pt(II). Thermolysis of (N,N-diethyl-N’-benzoylselenoureato)cadmium(II) and its sulfur analogue led to the successful synthesis of CdSe and CdS quantum dots respectively, where thermolysis over a range of temperatures allows a degree of size control over the resulting nanoparticles. The effect of precursor alkyl chain length on nanoparticle morphology was investigated for both the N,N-dialkyl-N’-benzoylthio- and –selenoureas. A correlation between the two for the (N,N-dialkyl-N’-benzoylselenoureato)Cd(II) complexes is described and possible growth mechanisms are discussed. Preliminary investigations into the use of other N,N-dialkyl-N’-benzoyl(thio)selenourea metal complexes as single source precursors reveal that both (N,N-diethyl-N’-benzoylselenoureato)Zn(II) and its sulfur analogue show potential as single source precursors for the formation of ZnO and ZnS nanoparticles respectively. Initial studies into the use of N,N-dialkyl-N’-benzoyl(thio)selenourea metal complexes as single source precursors for the synthesis of core-shell nanoparticles is briefly described. The Aerosol Assisted Chemical Vapour Deposition (AACVD) of several N,N-dialkyl-N’-benzoyl(thio)selenourea metal complexes is reported, where both (N,N-diethyl-N’-benzoylselenoureato)Cd(II) and its sulfur analogue allow the deposition of crystalline CdSe and CdS respectively. The AACVD of (N,N-diethyl-N’- benzoylselenoureato)Zn(II) leads to the deposition of crystalline ZnSe, ZnS being deposited by (N,N-diethyl-N’-benzoylthioureato)Zn(II). The deposition of heazelwoodite (Ni3S2) with varying morphologies results from the AACVD of cis-bis(N,N-diethyl-N’-benzoylthioureato)Ni(II). Thermal annealing of the amorphous material deposited by the AACVD of cis-bis(N,N-diethyl-N’-benzoylthioureato)Pd(II), allows the formation of highly crystalline palladium. The deposition of metallic platinum using cis-bis(N,N-diethyl-N’-benzoylthioureato)Pt(II) is described as well as the deposition of crystalline Pd17Se15 from cis-bis(N,N-diethyl-N’-benzoylselenoureato)Pd(II). This, to the best of our knowledge, is the first time that AACVD has been performed, using the N,N-dialkyl-N’- benzoyl(thio)selenourea metal complexes as single source precursors, in addition, we believe it to be the first time that palladium selenide has been deposited using the AACVD technique.

[Alpha]-Amino ketones can serve as important intermediates for the synthesis of biologically active molecules, and making these precursors in a practical manner has long been a challenge for organic chemists. The oxygen-carbon-carbon-nitrogen (O-C-C-N) sequence is common in natural and synthetic compounds of biological interest, due in part to their relatedness to peptides. Because of the many known carbonyl transformations, [alpha]-amino ketones have the potential to form various amine derivatives. Herein we present our research endeavors which led to several novel methods of forming this type of functionality. These endeavors culminated with the development of a two-step hydrazidation/N-N bond cleavage technique for forming [alpha]-amino ketals--which can be readily hydrolyzed to [alpha]-amino ketones. / text

タンデトロン加速器質量分析計業績報告

The synthesis and reactions of hydrotris(pyrazolyl)borate, (TpR,R) supported ytterbium(II) borohydride and lanthanide(III) dialkyl (Ln = Yb, Lu) complexes were investigated. The lanthanide(III) dialkyl complexes were found to undergo both hydrogenolysis reaction and protonolysis reaction with terminal alkynes. Reaction of [(TptBu,Me)YbH]2 (1) with NH3BH3 and (TptBu,Me)YbI(THF) (2) with NaBH4 afforded the corresponding mono-ligand complexes, (TptBu,Me)Yb(BH4) (3) and (TptBu,Me)Yb(BH4)(THF) (4), respectively. Compounds 3 and 4 represent rare examples of lanthanide(II) tetrahydroborate complexes. IR spectroscopy data, in the B-H stretching region are consistent with the 3-BH4 bonding mode found in the solid state of compound 4 and the corresponding deuterium labelled BD4 analogue of 4 shows the expected IR isotope shifts. Mono-ligand lanthanide dialkyl complexes, (TpR,R)Ln(CH2SiMe2R)2(THF)0/1 (5-9) were synthesized from the homoleptic Ln(CH2SiMe2R)3(THF)2 (Ln = Yb, Lu; R = Me, Ph) complexes by two alternative and complementary methods: alkyl abstraction with the thallium salts of the ligands, TlTpR,R and protonolysis using the acid form of the ligands, HTpR,R. Hydrogenolysis of the dialkyl complexes (TpMe2)Ln(CH2SiMe3)2(THF) (7a, Yb; 8a, Lu) afforded the corresponding tetranuclear hydride complexes, [(TpMe2)LnH2]4 (11, Yb; 12, Lu). Similarly, hydrogenolysis of (Tp)Yb(CH2SiMe3)2(THF) (9) afforded the hexanuclear hydride [(Tp)YbH2]6 (13). When treated with a variety of terminal alkynes, the dialkyl complexes, (TpR,Me)Ln(CH2SiMe3)2(THF) (14a, Y; 8a, Lu), gave the corresponding bis-alkynide complexes, (TpR,Me)Ln(CCR)2 (15-27). The structures of the complexes depend on the steric size of both the alkyne substituents and the substituent on position 3 of the pyrazolyl ring. Except for the bulkiest substituents, the compounds are dimeric with two asymmetric 2-alkynide bridging groups and a coupled alkynide unit bridging the two lanthanide centers via an unusual enyne bonding motif. The synthesis of Lu(CH2Ph-4-R)3(THF)3 (R = H, 28a; R = Me, 28b) was achieved by salt metathesis reactions between KCH2Ph-4-R and LuCl3. Variable temperature NMR studies in THF shows that the formation of these complexes is accompanied by a small amount of the anionic ate K[Lu(CH2PH-4-R)4(THF)n] (30) complexes, which can be prepared independently by reaction of pure Lu(CH2Ph-4-R)3(THF)3 with one equiv. of KCH2Ph-4-R. One of the coordinated THF of 28a could be removed by trituration with toluene to give Lu(CH2Ph-4-R)3(THF)2 (29a). Protonolysis reaction with HTpR,R afforded the corresponding dibenzyl complexes, (TpR,R)Ln(CH2Ph-4-R)2(THF)n (31-33). X-ray crystal structures of complex 4, the dialkyl complexes 5b, 6b, 7 and 8; dihydride complexes 11, 12 and 13; bis-alkynide complexes 15, 16, 17, 21, 22 and 24 as well as the tribenzyl compounds 28a and 29a and dibenzyl complexes 31-33 were determined. The solution behaviour, solid state structures and structural diversity of these complexes are discussed.

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La Province Volcanique du Rungwe (PVR) en Afrique de l’Est abrite diverses archives continentales (séquence de loess-paléosols, tourbières, lacs) permettant d’étudier les changements environnementaux passés des zones tropicales continentales. Ce travail s’est intéressé à l’applicabilité des alkyl tetraéthers de glycérol (tetraéthers) et des n-alcanes comme biomarqueurs de ces changements passés. Leur analyse le long de transects altitudinaux a permis de rendre compte de la capacité des tetraéthers à enregistrer de faibles changements de température de l’air dans la région. En conséquence, une calibration régionale a été établie afin d’améliorer les reconstructions de température de l’air en Afrique de l’Est. Au contraire, il est apparu que la composition isotopique de l’hydrogène des n-alcanes (δ²Hwax) était impactée par des paramètres physiques et biologiques supplémentaires ce qui complique son utilisation pour suivre les changements de température à l’échelle régionale. L’étude des variations de ces deux biomarqueurs le long d’une carotte de tourbe et d’une carotte de sédiment lacustre prélevées dans la PVR a révélé l’existence synchrone d’une période climatique plus chaude au cours de l’Holocène tardif. Par ailleurs, il a été observé dans la carotte de tourbe une transition d’un lac à une tourbière il y a ca. 2000 ans BP. Le présent travail démontre donc que les tetraéthers et les n-alcanes sont des biomarqueurs prometteurs, notamment parce qu’ils sont sensibles à de faibles variation climatiques ; cependant, afin de les interpréter correctement, il est nécessaire d’adopter une approche multi-marqueurs. / The Rungwe Volcanic Province (RVP) in East Africa offers a wide diversity of continental archives (loess-paleosols sequences, peatlands, lakes), allowing the investigation of past environmental changes in tropical continents. This work focused on the validation of glycerol dialkyl glycerol tetraether- (GDGT) and n-alkane-derived proxies. Analyses of these two biomarkers along altitudinal transects allowed assessing their ability to record temperature changes in the region. GDGTs were found to be robust temperature proxies in East Africa, and a regional calibration was established to improve temperature reconstructions from soil archives. In contrast, investigation of n-alkane hydrogen isotopic composition (δ²Hwax) in surface soils revealed that its variations seemed to be impacted by additional biological and physical parameters than temperature, preventing its generalization at a regional scale. Application of GDGT and n-alkane proxies to continental archives revealed past environmental changes over the Late Holocene in the RVP. A late Holocene synchronous temperature maximum was especially observed in a peat core and sediment core from two sites of the RVP. A multi-proxy approach was applied to the peat core, revealing that an ecosystem change from a lake to a peatland occurred ca. 2000 yrs BP ago. The present work showed that GDGTs and n-alkanes are promising biomarkers because of their sensitivity to slight climate variations, but that they need to be combined with other proxies to accurately reconstruct environmental changes.