<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>

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.

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

[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.

Submitted by Silvana Teresinha Dornelles Studzinski (sstudzinski) on 2015-07-01T13:48:29Z No. of bitstreams: 1 MarieleLunkes.pdf: 2185395 bytes, checksum: 0e139b106b90af719386462d648c9ec7 (MD5) / Made available in DSpace on 2015-07-01T13:48:29Z (GMT). No. of bitstreams: 1 MarieleLunkes.pdf: 2185395 bytes, checksum: 0e139b106b90af719386462d648c9ec7 (MD5) Previous issue date: 2013-03 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / CNPQ – Conselho Nacional de Desenvolvimento Científico e Tecnológico / FAPERGS - Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul / FINEP - Financiadora de Estudos e Projetos / A utilização de resíduos perigosos em produtos construtivos, técnica denominada estabilização por solidificação (E/S), requer um conhecimento aprofundado de sua composição, viabilidade técnica e econômica, além de uma avaliação ambiental ao longo do uso e pós-uso do produto. Quando se trata da avaliação de um produto da E/S durante a fase de uso, o Brasil não dispõe de um procedimento adequado que considere a integridade física da amostra e as características do cenário onde o resíduo encapsulado se encontra. O objetivo geral desta pesquisa é avaliar a lixiviação de cromo total em monólitos de cerâmica vermelha durante a fase de uso, por imersão e irrigação. Foram confeccionados corpos de prova com adição de 0,05% de óxido de cromo III (Cr2O3), além de corpos de provas referência (sem adição Cr2O3). Com base no regime pluviométrico da região metropolitana de Porto Alegre/RS desenvolveram-se dois testes de lixiviação para a avaliação da efetividade da E/S: imersão e irrigação. O primeiro com o propósito de simular um ambiente hostil em situação de prolongado contato da cerâmica com o lixiviante e o segundo para uma condição de exposição à chuva ácida ou ciclos de molhagem e secagem, possibilitando a avaliação do desempenho ambiental do material. A E/S do Cr na cerâmica vermelha foi acima de 99,90%. Nos corpos de prova com Cr2O3 a concentração de Cr lixiviado foi de 0,1243 ppm no teste de imersão, 0,01183ppm no teste de irrigação e 0,023 ppm no teste de lixiviação da norma ambiental brasileira para resíduos sólidos. As duas formas de avaliação da lixiviação de cromo total em monólitos de cerâmica vermelha, durante a fase de uso, propostas nesta pesquisa, apresentaram baixo coeficiente de variação e resposta técnica em 28 dias, representaram o fenômeno da difusão e se diferenciaram em seus cenários. / The use of hazardous waste in products constructive, technique known as stabilization by solidification (E/S), requires a thorough knowledge of its composition, technical and economic viability, and environmental assessment along the use and post-use of the product. When it comes to assessment of E/S product's during the phase of use, Brazil does not have an appropriate procedure to consider the physical characteristics of the sample and the scenario that encapsulated residue is exposed. The objective of this research is to evaluate the leaching of total chromium (Cr) in red ceramic monoliths during the use phase, by immersion and irrigation. Samples were prepared with addition of 0.05% chromium III oxide (Cr2O3), besides samples reference (without addition Cr2O3). Based on the pluviometric regime in the metropolitan area of Porto Alegre/RS, it was developed two methods for leaching to assess the effectiveness of E/S: immersion test and irrigation test. The first was carried out in order to simulate a hostile environment in a situation of long contact between the ceramic and the leachant and the second to a condition of exposure to acid rain or cycles of wetting and drying, allowing the assessment of the environmental performance of the material. A E/S Cr in red ceramic was above 99.90%. In samples with addition of Cr2O3 was leached 0.1243 ppm total Cr from immersion test, 0,01183 ppm from the irrigation test and 0.023 ppm in the standard leaching test of the Brazilian environmental standard for solid waste. The two forms of assessment the leachingin of total chromium in red ceramic monoliths during the use phase, proposal in this study, showed low coefficient of variation e technical answer in 28 days, exhibited the phenomenon of diffusion and differentiated themselves in their scenarios.

L’efficacité des cellules solaires peut être améliorée en exploitant pleinement la partie UV-bleue du spectre solaire, par un mécanisme de conversion de fréquence de type down-conversion. Ce processus utilisant des transferts d’énergie entre ions de terre rare (TR) ou métal de transition 3d (paires TR3+/Yb3+ avec TR = Pr, Tm,… et Cr3+/Yb3+) requiert des matrices à basse énergie de phonon pour réduire les relaxations non radiatives.Jusqu’à présent, les matériaux étudiés sont principalement sous forme de poudre polycristalline, ce qui limite leur utilisation à cause de la diffusion, ou de monocristaux dont le coût de fabrication est élevé.Dans le cadre de cette thèse, les verres fluorés à base de fluorozirconate ZLAG (ZrF4-LaF3-AlF3-GaF3) et ZBLA (ZrF4-BaF2-LaF3-AlF3) ont été préparés par la technique de fusion-coulée. Ces derniers sont adaptés du fait de leurs propriétés intrinsèques de transparence et de leur faible énergie de phonon. Les matériaux obtenus ont ensuite été caractérisés par, analyse thermique, diffraction des rayons X, microscopie électronique à transmission et luminescence.Des études par dynamique moléculaire et fluorescence par affinement de raies ont été effectuées sur la matrice ZLAG afin de suivre les modifications structurales lors du passage du verre à la vitrocéramique.La luminescence de l’ion Yb3+ a été observée dans l’infra-rouge à 980 nm sous excitation bleue dans toutes les séries étudiées, signature d’un transfert d’énergie. ans le verre ZLAG, l’efficacité atteint 92% pour le transfert d’énergie Pr3+ → Yb3+ et 65% pour le transfert d’énergie Tm3+ → Yb3+. L’efficacité est plus faible dans le verre ZBLA et la vitrocéramisation du verre ZLAG n’améliore pas les performances. / The efficiency of solar cells can be improved by fully exploiting the UV-blue portion of the solar spectrum, through a frequency converting mechanism of type downconversion. This process using energy transfer between rare earth ions (RE) or 3d transition metal (pairs RE3+/Yb3+ with TR = Pr, Tm,… and Cr3+/Yb3+) requires a matrix with low phonon energy to reduce non radiative relaxation.So far, the studied materials are mainly in the form of polycristalline powder, which limits their use due to diffusion or single crystals which manufacturing cost is high.As part of this thesis, fluoride glasses based on fluorozirconate ZLAG (ZrF4-LaF3-AlF3-GaF3) and ZBLA (ZrF4-LaF2-LaF3-AlF3) have been prepared by the melting-casting technique. These are suitable because of their intrinsic properties of transparency and low phonon energy. The resulting materials were then characterized by thermal analysis, X-ray diffraction, transmission electron microscopy and luminescence.Molecular Dynamics simulation and Fluorescence line narrowing of ZLAG matrix have been performed in order to investigate the structural modification during the transformation of the glass into the glass-ceramic.Luminescence of Yb3+ ion was observed in the near IR at 980 nm under blue excitation in all studied series, which is the signature of energy transfer. In the ZLAG glass, the efficiency reaches 92% for Pr3+ → Yb3+ energy transfer and 65% for Tm3+ → Yb3+ energy transfer. The efficiency is lower in the ZBLA glass and the ZLAG ceramisation does not improve the performances.