Thesis (M.S.)--Rochester Institute of Technology, 1995. / Typescript. Includes bibliographical references (leaves 130-131).

Thesis (M.S.)--University of Missouri-Columbia, 2004. / Typescript. Vita. Includes bibliographical references (leaf 58). Also available on the Internet.

Thesis (Ph.D.)--University of Florida, 2004. / Title from title page of source document. Document formatted into pages; contains 96 pages. Includes Vita. Includes bibliographical references.

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2007. / Dickson, Robert, Committee Chair ; Barry, Bridgette, Committee Member ; Fahrni, Christoph, Committee Member ; Fernandez, Facundo, Committee Member ; Srinivasarao, Mohan, Committee Member.

Made available in DSpace on 2016-05-17T16:51:52Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-11-27. Added 1 bitstream(s) on 2016-05-17T16:55:49Z : No. of bitstreams: 1 000863712_20170110.pdf: 884354 bytes, checksum: 9a614c3a6fbd6b8ab01037743ea320f5 (MD5) Bitstreams deleted on 2017-01-11T12:50:20Z: 000863712_20170110.pdf,. Added 1 bitstream(s) on 2017-01-11T12:50:59Z : No. of bitstreams: 1 000863712.pdf: 5082887 bytes, checksum: 2828da2340b50810c6223ed7cd8103d5 (MD5) / Efluentes industriais contendo corantes são diariamente liberados no meio ambiente. O lançamento de efluentes têxteis provoca uma degradação ambiental considerável, modificando a coloração natural e prejudicando o sistema biológico aquático. Dentre esses corantes, a classe de corantes trifenilmetano é largamente empregada na indústria têxtil e apresenta problemas à saúde pública e ao meio ambiente quando despejados nos efluentes, devido à alta toxicidade e difícil degradação. Uma alternativa para a detecção e quantificação destes compostos é o desenvolvimento de sensores biomiméticos com transdução óptica, empregando como sistema de reconhecimento polímeros molecularmente impressos (MIP). A vantagem desta metodologia é a boa seletividade, sensibilidade, estabilidade dos MIP e baixo custo dos materiais empregados. O presente trabalho explora diferentes sínteses de polímeros impressos para os corantes têxteis: Vermelho Básico 9 (BR9), Verde Ácido 16 (AG16) e Verde de Metila (MG). Para isso foram avaliadas sínteses com diferentes monômeros funcionais e proporções molares entre os reagentes empregados para a polimerização. Todos os MIP apresentaram melhor desempenho na proporção 1:3:200 de molécula molde, monômero funcional e monômero estrutural, respectivamente. O corante BR9 mostrou boa interação com o monômero funcional ácido 2-acrilamino-2-metilpropano sulfônico por meio de ligação de hidrogênio, enquanto que os corantes AG16 e MG apresentaram afinidade com o monômero 1-vinilimidazol, por meio de interação íon-dipolo e π-cátion, respectivamente. Os MIP para os corantes BR9 e AG16 apresentaram boa porcentagem de religação (70 e 86%, respectivamente), fatores de impressão bastante satisfatórios (1,82 e 6,91, respectivamente) alta seletividade frente a outros corantes têxteis e grande eficiência na extração dos respectivos corantes em amostra... / Industrial effluents containing dyes are daily released to the environment. The launch of textile effluents causes a considerable environmental degradation, changing the natural color and harming the aquatic biological system. Among these dyes, the class of triphenylmethane dyes is widely used in the textile industry and it presents problems to public health and the environment when discharged in the effluent due to the high toxicity and difficult degradation. An alternative for the detection and quantification of these compounds is the development of biomimetic sensors with optical transduction, employing Molecularly Imprinted Polymers (MIP) as recognition system. The advantage of this methodology is the good selectivity, sensitivity and stability of the MIP and low cost of materials. This work explores different synthesis of MIP for the textile dyes: Basic Red 9 (BR9), Acid Green 16 (AG16) and Methyl Green (MG). For this, the syntheses were evaluated with different functional monomers and molar ratios among the reagents employed for the polymerization. All MIP showed better performance in the ratio 1:3:200 of template, functional monomer and structural monomer, respectively. The dye BR9 showed good interaction with the functional monomer 2-acrylamido-2-methyl-1-propanesulfonic acid by hydrogen bonding, while the dyes MG and AG16 have affinity with the monomer 1-vinylimidazole, by electrostatic and π-cation interaction, respectively. MIP for dyes BR9 and AG16 have good percentage of rebinding (70 and 86%, respectively), satisfactory imprinting factor (1.82 e 6.91, respectively), high selectivity in comparison with other textile dyes and high efficiency in extraction of the respective dyes in sample of textile industrial effluent, presenting recoveries around of 100%. However, the MIP for the dye MG has not presented satisfactory results, with rebinding values below 20%. Probably the MIP performance...

Made available in DSpace on 2015-03-03T11:52:58Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-08-04Bitstream added on 2015-03-03T12:06:46Z : No. of bitstreams: 1 000810601.pdf: 3682345 bytes, checksum: 5a5ce68c56bcdb820403436504978b3f (MD5) / Due to the use of dyes hair and the your high dilution in wastewater and water treatment plants after incomplete treatment, the demand for increasingly sensitive and robust analytical methods for its quantification is highly relevant. Thus, the present work describes the construction of two sensors for quantification of hair dyes. The first was the development of a glassy carbon electrode modified with composite MWCNTs-CHT for simultaneous determination of PPD and RSN in samples of commercial hair dye and in samples of tap water. The Ipa of RSN and PPD presented 60% and 100% increase, respectively, in modified electrode compared to the electrode without modification. The reaction between both was monitored by spectrophotometry in the region UV-Vis, mass spectrometry and electrochemical oxidation where it was possible to diagnose the formation of the Bandrowski base and other related products the hair coloring. An analytical curve for PPD and RSN was constructed and finding a linear range in the interval of 0.55 to 21.2 mg L-1 with detection limit of 0.79 and 0.58 mg L-1, respectively. The method was applied to samples of tap water with recovery around 100% and in sample of commercial hair dye (EMBELLEZE MAXTON? (2.0 preto natural)), finding 24.10 and 10.34 mg g-1 of dye for PPD and RSN, respectively. The method was valeted by spectrophotometry. Other electroanalytical method was developed using screen printed electrode modified with grapheme for determining of the temporary dye BA-41 in 0,1 mol L-1 of B-R buffer pH 6,90. The peak current is 1,300% greater when compared with screen printed and glassy carbon electrodes, both unmodified. Through the technique of square wave voltammetry, the method was optimized of multivariate form using factorial design 24 and Doehlert matrix. Under optimized conditions of f (67 Hz), pH (6,90), ?E (128 mV) and Esw (6 mV), we constructed a calibration curve with a...

abstract: Intimate coupling of Ti2 photocatalysis and biodegradation (ICPB) offers potential for degrading biorecalcitrant and toxic organic compounds much better than possible with conventional wastewater treatments. This study reports on using a novel sponge-type, Ti2-coated biofilm carrier that shows significant adherence of Ti2 to its exterior and the ability to accumulate biomass in its interior (protected from UV light and free radicals). First, this carrier was tested for ICPB in a continuous-flow photocatalytic circulating-bed biofilm reactor (PCBBR) to mineralize biorecalcitrant organic: 2,4,5-trichlorophenol (TCP). Four mechanisms possibly acting of ICPB were tested separately: TCP adsorption, UV photolysis/photocatalysis, and biodegradation. The carrier exhibited strong TCP adsorption, while photolysis was negligible. Photocatalysis produced TCP-degradation products that could be mineralized and the strong adsorption of TCP to the carrier enhanced biodegradation by relieving toxicity. Validating the ICPB concept, biofilm was protected inside the carriers from UV light and free radicals. ICPB significantly lowered the diversity of the bacterial community, but five genera known to biodegrade chlorinated phenols were markedly enriched. Secondly, decolorization and mineralization of reactive dyes by ICPB were investigated on a refined Ti2-coated biofilm carrier in a PCBBR. Two typical reactive dyes: Reactive Black 5 (RB5) and Reactive Yellow 86 (RY86), showed similar first-order kinetics when being photocatalytically decolorized at low pH (~4-5), which was inhibited at neutral pH in the presence of phosphate or carbonate buffer, presumably due to electrostatic repulsion from negatively charged surface sites on Ti2, radical scavenging by phosphate or carbonate, or both. In the PCBBR, photocatalysis alone with Ti2-coated carriers could remove RB5 and COD by 97% and 47%, respectively. Addition of biofilm inside macroporous carriers maintained a similar RB5 removal efficiency, but COD removal increased to 65%, which is evidence of ICPB despite the low pH. A proposed ICPB pathway for RB5 suggests that a major intermediate, a naphthol derivative, was responsible for most of the residual COD. Finally, three low-temperature sintering methods, called O, D and DN, were compared based on photocatalytic efficiency and Ti2 adherence. The DN method had the best Ti2-coating properties and was a successful carrier for ICPB of RB5 in a PCBBR. / Dissertation/Thesis / M.S. Biological Design 2011

98 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-10-03T14:59:45Z No. of bitstreams: 1 Dissertação_Jefferson_Silva_2012_Quimica.pdf: 1947075 bytes, checksum: 25582d9f2d2ee577efefaac8a9ab46e1 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-10-03T15:01:11Z (GMT) No. of bitstreams: 1 Dissertação_Jefferson_Silva_2012_Quimica.pdf: 1947075 bytes, checksum: 25582d9f2d2ee577efefaac8a9ab46e1 (MD5) / Made available in DSpace on 2013-10-03T15:01:12Z (GMT). No. of bitstreams: 1 Dissertação_Jefferson_Silva_2012_Quimica.pdf: 1947075 bytes, checksum: 25582d9f2d2ee577efefaac8a9ab46e1 (MD5) Previous issue date: 2012 / A fotocatálise heterogênea tem sido apontada como uma alternativa efetiva para o tratamento de efluentes industriais de difícil degradação, a fim de minimizar o impacto ambiental associado ao seu descarte ineficiente. Neste trabalho foi avaliada a atividade de catalisadores TiO2, sintetizados pelo método Pechini variando-se a razão molar (ácido cítrico)/(cátion metálico) de 2:1 (P21), 3:1 (P31), 4:1 (P41) e 5:1 (P51) em três sistemas fotocatalíticos: fotodegradação do azo-corante alaranjado de metila (CI Acid Orange 52) em solução aquosa, fotorredução do íon mercúrio (II) em solução aquosa, separadamente, e no sistema binário fotodegradação do alaranjado de metila/ fotorredução do mercúrio (II). Dentre as reações fotocatalíticas envolvendo o sistema contendo solução aquosa de alaranjado de metila, foi observada a alta eficiência do catalisador P21 na descoloração total da solução em 90 minutos, provavelmente devido à formação da fase anatásio pura. Além disso, os resultados mostraram que o corante pode ser degradado por fotocatálise sem a dissolução de O2 e que o catalisador P21 possuiu bom desempenho no estudo da desativação ao manter o mesmo comportamento em três ciclos reacionais de 240 minutos. Foi observado também, uma representativa degradação da molécula do azo-corante atingindo Demanda Química de Oxigênio (DQO) < 40 mgO2.L-1 em 90 minutos de reação. No estudo da atividade fotocatalítica dos catalisadores na fotorredução do mercúrio (II) foi observada a maior atividade cinética do catalisador P21 demonstrada pela significativa diminuição da concentração do mercúrio em 10 minutos de reação. A maior capacidade de adsorção deste corante pode ter influenciado neste resultado. Foi avaliada a variação de alguns parâmetros reacionais nas reações tais como: pH (4 ou 7), concentração inicial do cátion Hg+2 (10, 20 ou 40 mg.L-1) e concentração do catalisador (1 ou 2 g.L-1) utilizando os catalisadores P21 e P51. Os resultados mostraram que o conjunto de parâmetros que proporcionou a maior taxa de redução foi: pH 7, concentração inicial 10 mg.L-1 e 1 g.L-1 de catalisador. Neste teste, foi possível a redução da concentração de mercúrio (II) para valores menores do que os aceitos pela maioria das instituições de regulamentação ambiental. Foi realizado, também, o estudo do efeito da adição de três compostos orgânicos (etanol, ácido oxálico e ácido cítrico) e NaCl nos sistemas reacionais com os catalisadores P21 e P51 e com a variação do pH (4 ou 7). Foi observado que as taxas de adsorção foram maiores nas soluções com pH 7 o que, de forma geral, influenciou diretamente na maior taxa de fotorredução destes sistemas. Por fim, nos sistemas fotocatalíticos binários (alaranjado de metila/Hg+2) foi possível observar que a presença de íons metálicos diminui a taxa de descoloração do corante, provavelmente, devido à desativação do catalisador provocada pela deposição de mercúrio metálico na superfície do catalisador. / Salvador

Understanding the properties of electronically interacting molecular chromophores, which involve internally coupled electronic-vibrational motions, is important to the spectroscopy of many biological systems. Here we apply linear absorption, circular dichroism, and two-dimensional fluorescence spectroscopy to study the local structure and excited state dynamics of excitonically coupled cyanine dimers that are rigidly positioned within the sugar-phosphate backbones of the DNA. Dimer probes were positioned within the double-stranded DNA duplex and at the single-strand/double-stranded DNA junction to examine the positional dependence of the structural variation and fluctuations. We interpret spectroscopic measurements in terms of the Holstein vibronic dimer model, from which we obtain information about the local conformation of the dimer probe locally within their respective DNA environments. We show that the exciton-coupling strength of the dimer-DNA construct can be systematically varied with temperature below the double-stranded – single-strand DNA denaturation transition. Using time-resolve 2DFS measurements we observed long lived vibronic coherences in the system. The properties of the cyanine DNA construct we determine suggest that it may be employed as a useful model system to test fundamental concepts of protein DNA interactions and the role of electronic-vibrational coherence in electronic energy migration within exciton-coupled biomolecular arrays. This dissertation contains previously published and unpublished co-authored material.

The purpose of this review is to compile preclinical and clinical results on phthalocyanines (Pcs) as photosensitizers (PS) for Photodynamic Therapy (PDT) and contrast agents for fluorescence imaging. Indeed, Pcs are excellent candidates in these fields due to their strong absorbance in the NIR region and high chemical and photo-stability. In particular, this is mostly relevant for their in vivo activation in deeper tissular regions. However, most Pcs present two major limitations, i.e., a strong tendency to aggregate and a low water-solubility. In order to overcome these issues, both chemical tuning and pharmaceutical formulation combined with tumor targeting strategies were applied. These aspects will be developed in this review for the most extensively studied Pcs during the last 25 years, i.e., aluminium-, zinc- and silicon-based Pcs.