<p>Tetraazamacrocycles, such as cyclam (1,4,8,11-tetraazacyclotetradecane), are useful ancillary ligands in the formation of organometallic complexes. Coordination of a 3d metal can lead to the formation of square planar complexes, such as with Ni^II and Cu^II, or octahedral complexes upon coordination of additional ligands, such as with Co^II/III and Cr^II/III. Notably with Cr, a mixture of <i>cis-</i> and <i>trans-</i>octahedral complexes are formed, and the isomerism can be influenced through <i>C</i>-substitution of the cyclam macrocycle. Herein, Cr^III complexes featuring <i>C</i>-substituted cyclam derivatives and either redox-active ligands or alkynyl ligands are reported.</p> <p>Chapter 1 features an introduction to the photophysical processes of Cr(III), an overview of cyclam and its derivatives, and a brief review of Cr^III(cyclam/cyclam’) bis-alkynyl complexes for various applications. Chapter 2 discusses the structural, optical, electronic, and magnetic characterizations of <i>cis</i>-[Cr(HMC)catecholate]⁺ and <i>cis</i>-[Cr(HMC)semiquinonate]²⁺ complexes, which feature redox-active catecholate and semiquinonate ligands. Chapter 3 highlights a series of <i>trans</i>-[Cr(HMC)(C₂Ar)Cl]⁺ complexes, which expands upon prior research on bis-alkynyl complexes. Chapter 4 discusses how a different <i>C</i>-substituted cyclam derivative, MPC, is used to produce <i>trans</i>-[Cr(MPC)Cl₂]⁺ starting material in higher quantity than the HMC derivative. This allows for higher amounts of <i>trans</i>-[Cr(MPC)(C₂Ar)₂]⁺ complexes to be synthesized, making it a more practical macrocycle for the future pursuit of dissymmetric bis-alkynyl complexes.</p>

The fundamental knowledge of Cr(III) chemistry has been enhanced via detailed structural and spectroscopic studies of largely novel compounds that may potentially be active tri- and tetramerisation precursors. The compounds are based on various monodentate and bidentate nitrogen and phosphorus ligands which have been coordinated to [CrCl3 (thf) 3]. The few compounds that have been synthesised previously have in this study been made via novel synthetic routes and incorporate a combination of new and more detailed analysis than was carried out previously. The eight structures determined, in addition to offering novel crystallographic data, also provided insights into the synthetic pathways leading to compound formation. The isolation of monomeric structures suggests direct ligand substitution, while the cationic-anionic structures suggest the presence of dimeric intermediates which have been cleaved asymmetrically. Infrared and Raman spectra of these structures were able to add weight to these pathway proposals and, by means of vibrational comparisons, assisted in the general band assignments of the compounds' spectra where structures were not available. Vibrational shifts relative to the free ligands, as well as metal–ligand vibrations in the far infrared region, were also of significant value in terms of ligand coordination and geometry. Closely associated with the infrared and Raman spectra analysis was the generation of theoretical spectra using Density Functional Theory calculations. The excellent agreement between the calculated and experimental spectra confirmed the vibrational assignments. Also generated by computational means were the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of the compounds which indicated the sites of potential nucleophilic and electrophilic attack. 1H NMR spectroscopy is a technique normally avoided when studying paramagnetic materials. However, by employing a largely novel approach, information pertaining to both ligand coordination and reaction times was obtained. FAB-MS assisted in the confirmation that the single crystal determinations did indeed reflect the composition of the bulk precipitated samples. It also provided additional structural information through the identification of fragmentation patterns which could not be gained by techniques such as elemental analysis. / Thesis (PhD)--University of Pretoria, 2010. / Chemistry / unrestricted

Amid a growing world population and diminishing living space, the discerning and beneficial use of steel plant slag as liming material in agriculture has become a viable option. However, until the potentially detrimental effect on human health and environmental quality of heavy metals contained within the matrixes of slag has been assessed, the use of slag in agriculture cannot be deemed sustainable. This study aims to correlate the mechanisms by which chromium(III) and nickel are sorbed in Eastern Highveld soils to easily classifiable soil constituents. In addition, the influence of an external source of silicon, as would be the case in dissolving slag, on Cr(III) and Ni mobility was investigated. The study consisted of an investigation into the mechanisms by which Cr(III) and Ni are sequestered in soil within a single wetting and drying cycle, as well as over a period of five rewetting and drying cycles. The effect of Si was observed for the latter and a detailed mineralogical study conducted as part of the former. Additionally, the reactivity of and heavy metal (Cr and Ni) release from two commercially available slag samples used as liming material in a highly buffered soil was investigated. Five main conclusions were drawn: (i) whereas Cr(III) is effectively sorbed (even at near water saturated conditions) and precipitation ascribed to bulk-solution saturation, Ni is not sequestered as effectively, and initially precipitates owing to the influence of soil mineralogy; (ii) conclusive evidence could not be gathered for the further immobilisation after sorption of Cr(III) and Ni over a short time period; (iii) both Cr(III) and Ni associate mainly with the amorphous Fe oxide mineral phase; (iv) an external source of Si renders Ni less mobile in soil that does not sequester the element effectively, but more mobile in soil that does tend to sequester the element to some degree; and (v) although neither Cr(III) nor Ni mobility could be explained using field classifiable soil characteristics (soil colour and texture), soil mineralogical and detailed surface charge characterisation did provide explanations for sorption behaviour. Copyright / Dissertation (MSc(Agric))--University of Pretoria, 2009. / Plant Production and Soil Science / unrestricted

No / (51)Cr-labeled, superparamagnetic, iron oxide nanoparticles ((51)Cr-SPIOs) and (65)Zn-labeled CdSe/CdS/ZnS-quantum dots ((65)Zn-Qdots) were prepared using an easy, on demand, exchange-labeling technique and their particokinetic parameters were studied in mice after intravenous injection. The results indicate that the application of these heterologous isotopes can be used to successfully mark the nanoparticles during initial distribution and organ uptake, although the (65)Zn-label appeared not to be fully stable. As the degradation of the nanoparticles takes place, the individual transport mechanisms for the different isotopes must be carefully taken into account. Although this variation in transport paths can bring new insights with regard to the respective trace element homeostasis, it can also limit the relevance of such trace material-based approaches in nanobioscience. By monitoring (51)Cr-SPIOs after oral gavage, the gastrointestinal non-absorption of intact SPIOs in a hydrophilic or lipophilic surrounding was measured in mice with such high sensitivity for the first time. After intravenous injection, polymer-coated, (65)Zn-Qdots were mainly taken up by the liver and spleen, which was different from that of ionic (65)ZnCl2. Following the label for 4 weeks, an indication of substantial degradation of the nanoparticles and the release of the label into the Zn pool was observed. Confocal microscopy of rat liver cryosections (prepared 2 h after intravenous injection of polymer-coated Qdots) revealed a colocalization with markers for Kupffer cells and liver sinusoidal endothelial cells (LSEC), but not with hepatocytes. In J774 macrophages, fluorescent Qdots were found colocalized with lysosomal markers. After 24 h, no signs of degradation could be detected. However, after 12 weeks, no fluorescent nanoparticles could be detected in the liver cryosections, which would confirm our (65)Zn data showing a substantial degradation of the polymer-coated CdSe/CdS/ZnS-Qdots in the liver.

The objectives were to investigate the effects of chromium (III) picolinate (CrPic; up to 2,000 ppb of Cr) on growing pigs subjected to a variety of stressors including thermal, immune, or dietary stress and to examine the effects of CrPic on steroidogenesis from adrenocortical cells. In the thermal stress study, high ambient temperature caused reduced weight gain and feed consumption (P andlt; 0.01), and low ambient temperature caused increased feed intake and feed:gain (P andlt; 0.01). However, these effects were not moderated by CrPic, and respiratory rate, plasma cortisol, or plasma glucose were unaffected by CrPic. In the immune stress study, pigs challenged with lipopolysaccharide (LPS) lost 951 g during 12 hours post injection, while the phosphate buffer saline (PBS) injected group gained 170 g (P andlt; 0.001). The LPS group showed higher rectal temperature (P andlt; 0.05), higher respiratory rate (P andlt; 0.05), greater plasma cortisol (P andlt; 0.001), and lower plasma glucose (P andlt; 0.05) than the PBS group. These effects were not ameliorated by CrPic. In the dietary stress study, pigs fed the high-fat diet (HFD) gained weight faster (P andlt; 0.05), consumed less feed (P andlt; 0.001), and had lower feed:gain (P andlt; 0.001). Plasma insulin concentration on d 14 decreased with CrPic (P andlt; 0.05) in a linear manner (P = 0.05). Consumption of the HFD resulted in increases of slaughter weight, perirenal fat, and back fat measurements (P andlt; 0.01). The CrPic resulted in linear reductions of carcass weight, last rib fat, last lumbar fat and average backfat (P andlt; 0.10). The effects of CrPic on carcass fat measurements were more significant in barrows than gilts. In the adrenocortical cell study, forskolin stimulated cortisol and DHEAs secretion from H295R cells. CrPic inhibited aspects of steroidogenesis in agonist-stimulated adrenocortical cells. Overall, dietary CrPic was unable to moderate the stress related effects due to high ambient temperature, low ambient temperature, or an endotoxin challenge. However, CrPic attenuated effects of HFD, mainly on body fat accretion of pigs, especially in barrows, and CrPic inhibited steroidogenesis in stimulated adrenocorticoid cells.

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-06-22T11:26:06Z No. of bitstreams: 1 2016 - B?rbara Magalh?es Neto.pdf: 3282939 bytes, checksum: a4ead0ff5e7307971c24940b1bea36a3 (MD5) / Made available in DSpace on 2017-06-22T11:26:06Z (GMT). No. of bitstreams: 1 2016 - B?rbara Magalh?es Neto.pdf: 3282939 bytes, checksum: a4ead0ff5e7307971c24940b1bea36a3 (MD5) Previous issue date: 2016-07-19 / Among the many existing methods for removing heavy metals off the effluents, the adsorption process stands out for being considered most effective, at lower cost. The phenomenon of adsorption consists in a process of the transfer of one or more constituents of a fluid phase to a surface of a solid phase. The adsorption process depends on physical and chemical characteristics, as: structural properties of the adsorbent (porosity, functional groups), adsorbate (ionic radius and coordination number), interaction between adsorbent and adsorbed. New technologies have emerged with focus returned to the use of biological materials with adsorbing properties for the treatment of effluents, in particular, removal and recovery of heavy metals, showing good performance. The main advantages of using natural adsorbents (biosorbents) in the process of sorption are: low waste generation, easy recovery of metals, the possibility of reuse of the adsorbent and lower operating costs, depending on the adsorbent material used in the process. From the foregoing this research used tablets of composite material, formed of recycled low density polyethylene (LDPErec) as polymer matrix and adsorbent materials (coconut fibber FC, chitosan Qui or clay B) and a comparative study using such tablets as adsorbents, to removal of the chromium (III), in order to determine which tablet has a better adsorption of chromium (III).To this end, there were realized three experimental design, where they were evaluated the influence of the size of coconut fibber particles, the composition of LDPErec/Fc, LDPErec/B, LDPErec/Qui, LDPErec/FC/Qui and LDPErec/B/Qui, the concentration of chromium (III) adsorbate and the exposure time of the tablets in the chromium (III) solution. With the results can conclude that the models used in the experimental design were valid for the evaluation of significant variables of this work, as the best chromium (III) removal conditions. That happened to the composition values of 40/60% to the tablets of LDPErec/FC1, LDPErec/FC3 and LDPErec/B. The particle size range of coconut fibber that proved more favourable was smaller particle size (100-120 mesh) in the composition of 40/60 %. The conductivity has been used to predict a chromium (III) sorption model but it proved not to be good parameter / Entre os muitos m?todos existentes para a remo??o de metais pesados em efluentes, o processo de adsor??o destaca-se por ser considerado um dos mais efetivos, com menor custo. O fen?meno da adsor??o consiste em um processo de transfer?ncia de um ou mais constituintes de uma fase fluida para a superf?cie de uma fase s?lida. O processo de adsor??o depende de caracter?sticas f?sicas e qu?micas, como: propriedades estruturais do adsorvente (porosidade, grupos funcionais), do adsorvato (raio i?nico, n?mero de coordena??o) e intera??es entre o adsorvente e o adsorvato. Novas tecnologias t?m surgido com o foco voltado para a utiliza??o de materiais biol?gicos com propriedades adsorventes para tratamento de efluentes, e particularmente, na remo??o e recupera??o de metais pesados, apresentando bom desempenho. As principais vantagens de utiliza??o de adsorventes naturais (biossorventes) no processo de sor??o s?o: baixa gera??o de res?duos, f?cil recupera??o dos metais, a possibilidade de reutiliza??o do adsorvente e menor custo operacional, dependendo do material adsorvente que ? utilizado no processo. A partir do exposto essa pesquisa utilizou pastilhas de materiais comp?sitos, formadas por polietileno de baixa densidade reciclado (PEBDrec) como matriz polim?rica e materiais adsorventes (fibra de coco-FC, quitosana-Qui ou argila-B) e realizar um estudo comparativo utilizando essas pastilhas como adsorventes, na remo??o de cromo (III), a fim de determinar qual apresenta uma melhor adsor??o de cromo. Com esta finalidade, foram realizados tr?s planejamentos experimentais, onde foram avaliadas a influ?ncia da granulometria das part?culas de fibra de coco, a composi??o das pastilhas de PEBDrec/FC, PEBDrec/B, PEBDrec/Qui, PEBDrec/FC/Qui e PEBDrec/B/Qui, a concentra??o do adsorvato de cromo (III) e o tempo de exposi??o das pastilhas a solu??o de cromo (III). Com os resultados p?de-se concluir que os modelos usados nos planejamentos experimentais foram v?lidos para a avalia??o da signific?ncia dessas vari?veis, como para as melhores condi??es de remo??o do cromo (III), as quais aconteceram nos valores de composi??o de 40/60% das pastilhas de PEBDrec/FC1, PEBDrec/FC3 e PEBDrec/B. A faixa granulom?trica da fibra de coco que se mostrou mais favor?vel foi de menor granulometria (100-120 mesh) na composi??o de 40/60%. Utilizou-se a t?cnica de condutividade para predizer um modelo de sor??o de cromo (III), por?m nas condi??es do estudo, a condutividade n?o demonstrou ser um bom par?metro

An innovative sampling technique employing extractant impregnated membranes is presented for the selective sorption and stabilization of specific oxidation states of chromium. Polymer-based selective ion traps employing the extractants tricaprylmethylammonium chloride (Aliquat-336) and di-(2-ethylhexyl) phosphoric acid (DEHPA) were used for the selective removal and enrichment of the anionic forms of Cr(VI) and cationic forms of Cr(III), respectively. Results show Aliquat-336 and DEHPA effectively remove Cr(VI) and Cr(III) from aqueous solutions. Extraction efficiency is independent of source concentration from 1-50 ppm but is dependent upon time, pH of the source, ionic strength, extractant concentration, composition of source phase, and choice of stripping agent and stripping agent concentration. Optimum conditions for Cr(VI) and Cr(III) were determined to be 1 v/v% Aliquat-336 and 30 v/v% DEHPA; an extraction time of at least 3-5 days; source phase pH between 3-5; and 1 M NaOH/ 0.5 M HNO3 as stripping agent for Cr(VI) and Cr(III) species, respectively. Batch extraction efficiencies of 97 +/- 3 % were obtained for the optimal conditions. Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) was used for total chromium determination. UV-VIS spectrometry was used for Cr(VI) determination. Scanning Electron Microscopy revealed the physical structure of the polymeric supports and subsequent impregnation was evidenced by the SEM images. X-ray photoelectron spectroscopic results provided the elemental composition of the Versapor-450 membrane to be 71. 5% C, 7.0% O, 9.5% Cl and 12.0% N. The Whatman PP membrane was and 100.0 % C. Elemental composition of 1 v/v% Aliquat-336 on Versapor-450 and Whatman PP membrane was 92.3% C, 0.8% O, 3.6% N, and 3.3% Cl and 94.3% C, 3.3% N, and 2.4% Cl, respectively. Elemental composition of 30 v/v% DEHPA on Versapor-450 and Whatman PP membranes were 78.8% C, 3.4% P, 17.8% O and 76.3% C, 19.3% O, 4.4% P, respectively. Column studies under simulated groundwater conditions utilizing the extractant impregnated membranes showed no statistical difference in Cr(VI) recoveries from those obtained in batch experiments. Cr(III) extraction revealed a statistical difference in analyte recovery vs. batch experiments. This is attributed to the lowered pH and cationic interferences present in simulated groundwater. / Ph. D.

Ethyl iodide and ethyl chloride have been used as reactants to produce ethyl fragments on the stoichiometric α-Cr₂O₃ (1012) surface by means of thermal dissociation. Ethyl iodide is dissociated giving iodine adatoms and ethyl fragments bound to surface Cr cation sites, while ethyl chloride is dissociated giving chlorine adatoms and ethyl fragments. No oxygenated products are observed in thermal desorption, suggesting the 3-coordinate lattice oxygen on the stoichiometric α-Cr₂O₃ (1012) surface is very stable, and no nucleophilic attack occurs at the carbon atoms on surface ethyl fragments. For both reactants, the only reaction products observed are ethylene gas (CH₂=CH₂), ethane gas (CH₃-CH₃), hydrogen gas (H₂) and halogen adatoms (Cl_ads or I_ads). In thermal desorption experiments, all the gas phase products from ethyl chloride are produced in a reaction-limited, high temperature desorption feature attributed to a rate limiting β-hydride elimination from surface ethyl fragments. Similar product desorption features are observed for the reaction of ethyl iodide. However, the reaction of ethyl iodide also produces ethylene and ethane via a low temperature, desorption-limited reaction channel. It is postulated that I adatoms produced in the reaction of ethyl iodide thermal desorption might somehow promote a low temperature route to products that Cl adatoms do not. / Master of Science

A sampler has been fabricated to facilitate the in-situ speciation of Cr. Teflon® was selected as the material for the samplers because of its inert chemical nature. The design of the sampler is based on the Supported Liquid Membrane (SLM) extraction technique, which utilizes charged organic carrier molecules loaded onto a polymeric (Teflon®) support membrane and the principles of electrostatics to selectively transport Cr ions through an ion-pairing mechanism. Cr ions in the feed solution that have an opposite charge from the carrier molecule form an ion-pair with the carrier and are transported through the membrane and deposited into a second aqueous phase referred to as the acceptor phase. A counter-ion from the acceptor phase is exchanged for the Cr ion to complete the extraction process. Since the acceptor phase is contained in a Teflon® bottle, the SLM sampler is capable of speciation and storage of Cr ions, which is a major advantage over current speciation techniques. A food coloring test was used to check the samplers for leaks. A plastic barrier was used in place of the polymeric membrane and the acceptor phase bottle was filled with DI water. The sampler was submerged in a beaker containing food coloring and DI water. The bottle contents were checked for the presence of food coloring using UV-vis spectroscopy. The sampler was determined to be leak-free if the bottle did not contain food coloring. All systems prepared were validated upon the initial test and required no further manipulation to ensure structural soundness. The SLM extraction technique involves two liquid-liquid extractions (LLEs). Before the samplers could be evaluated for their performance and stability in Cr speciation applications, liquid-liquid extraction studies were conducted on both systems (Cr (III) and Cr (VI)) to determine the optimal operating parameters (carrier concentration, decanol concentration, and acceptor phase concentration) of the SLM system. The selectivity of each system was also evaluated to validate proper SLM function. The performance of the samplers was evaluated in a series of tank studies that focused on the uptake of Cr into the acceptor phase as well as the depletion of Cr ion from this phase. The goal of the performance studies was to determine the mechanical and chemical stability of the SLM samplers. As part of the validation process, selectivity studies and studies without the carrier molecule were conducted to ensure that the systems were functioning according to SLM theory. Tank studies that simulated natural sampling condition were also conducted. The results of the tests conducted in the laboratory indicate that the SLM samplers are a stable, reliable, and viable method for Cr speciation. Future directions of this project will include the incorporation of the SLM sampler into the existing Multi-layer Sampler (MLS) technology as well as the analysis of the stability and performance of the incorporated systems in the ""in-situ speciation application. / Ph. D.

[pt] Metais pesados contidos em efluentes industriais são fontes de grande potencial de degradação ambiental; visto que eles produzem alterações físicoquímicas na qualidade da água. Estas alterações têm um impacto direto na mortandade da flora e fauna afetando indiretamente a saúde dos seres humanos. Esta dissertação refere-se ao estudo dos aspectos cinéticos da remoção de cromo (III) por flotação de precipitados a partir de cloreto de cromo hexahidratado, utilizando dodecilsulfato de sódio (DSS) como coletor aniônico. Para este estudo, foram realizadas medidas de potencial zeta, bem como ensaios de flotação do cromo (III) para determinar os parâmetros adequados de operação: vazão de ar, concentração de coletor e concentração de espumante. Medições de potencial zeta das partículas de hidróxido de cromo na presença de eletrólito indiferente KCl, indicaram ponto isoelétrico (PIE) em pH em torno de 8,5. A presença do coletor aniônico (DSS) no sistema hidróxido de cromo-água indicou uma redução do potencial zeta, para os três níveis de concentrações investigados. Havendo um deslocamento do PIE na direção de valores de pH mais inferiores, atribuindo tal comportamento à adsorção do coletor sobre o Cr(OH)3 através de interação eletrostática. Com relação aos resultados dos ensaios de flotação de precipitados do cromo (III), obtiveram-se remoções de aproximadamente 96,2%, conseguindo-se chegar a valores inferiores ao estabelecido pela norma do CONAMA (20/86), ou seja, [Cr3+]£0,5 mg/L. O estudo da cinética da flotação mediante as análises integral e diferencial evidenciaram que o processo de remoção do precipitado de hidróxido de cromo segue um modelo de primeira ordem. / [en] Heavy metals contained in industrial effluents are sources of great potential environmental degradation, since their presence produce physicochemical alterations harming in the quality of the water. These alterations have a direct impact in the mortality of the flora and fauna affecting indirectly the human health. This dissertation refers to the study of the kinetic aspects of chromium (III)removal by precipitate flotation from chromium chloride (CrCl3.6H2O), using sodium dodecylsulfate (SDS) as anionic collector. For this study, measurements of zeta potential were accomplished as well as chromium (III) tests of flotation to determine the appropriate parameters operation: gas flow rate, concentration of collector and frother. Measurements of zeta potential of the particles of chromium (III) hydroxide in the presence of indifferent electrolyte KCl, indicated an isoelectric point (PIE)in pH around 8,5. The particles of chromium (III) hydroxide in the presence of anionic collector (SDS) showed a decrease in module of the zeta potential, for the three levels of concentrations investigated, as well as a displacement of the PIE in the direction of the more inferior pH values. This behavior can be attributed to the adsorption of the anionic collector on Cr(OH)3 due to the electrostatic attraction. Chromium (III) removals of 96,2% were obtained by precipitate flotation. Residual values of chromium reached are lower than the standards values established by the CONAMA (20/86), that mean [Cr3+]£0,5 mg/L. The kinetic flotation study showed that the removal of chromium (III)hydroxide precipitates followed a first order model.