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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
21

Nonadiabatic quantum molecular dynamics with hopping. III. Photoinduced excitation and relaxation of organic molecules

Fischer, Michael, Handt, Jan, Schmidt, Rüdiger 09 September 2014 (has links) (PDF)
Photoinduced excitation and relaxation of organic molecules (C2H4 and CH2NH+2) are investigated by means of nonadiabatic quantum molecular dynamics with hopping (NA-QMD-H), developed recently [Fischer, Handt, and Schmidt, paper I of this series, Phys. Rev. A 90, 012525 (2014)]. This method is first applied to molecules assumed to be initially ad hoc excited to an electronic surface. Special attention is drawn to elaborate the role of electron-nuclear correlations, i.e., of quantum effects in the nuclear dynamics. It is found that they are essential for a realistic description of the long-time behavior of the electronic relaxation process, but only of minor importance to portray the short-time scenario of the nuclear dynamics. Migration of a hydrogen atom, however, is identified as a quantum effect in the nuclear motion. Results obtained with explicit inclusion of an fs-laser field are presented as well. It is shown that the laser-induced excitation process generally leads to qualitatively different gross features of the relaxation dynamics, as compared to the field-free case. Nevertheless, the nuclear wave packet contains all subtleties of the cis-trans isomerization mechanism as observed without a laser field.
22

Nonadiabatic quantum molecular dynamics with hopping. III. Photoinduced excitation and relaxation of organic molecules

Fischer, Michael, Handt, Jan, Schmidt, Rüdiger January 2014 (has links)
Photoinduced excitation and relaxation of organic molecules (C2H4 and CH2NH+2) are investigated by means of nonadiabatic quantum molecular dynamics with hopping (NA-QMD-H), developed recently [Fischer, Handt, and Schmidt, paper I of this series, Phys. Rev. A 90, 012525 (2014)]. This method is first applied to molecules assumed to be initially ad hoc excited to an electronic surface. Special attention is drawn to elaborate the role of electron-nuclear correlations, i.e., of quantum effects in the nuclear dynamics. It is found that they are essential for a realistic description of the long-time behavior of the electronic relaxation process, but only of minor importance to portray the short-time scenario of the nuclear dynamics. Migration of a hydrogen atom, however, is identified as a quantum effect in the nuclear motion. Results obtained with explicit inclusion of an fs-laser field are presented as well. It is shown that the laser-induced excitation process generally leads to qualitatively different gross features of the relaxation dynamics, as compared to the field-free case. Nevertheless, the nuclear wave packet contains all subtleties of the cis-trans isomerization mechanism as observed without a laser field.
23

Extratos vegetais na proteção de membranas contra o dano fotoinduzido / Plant extracts in membrane protection against photoinduced damage

Silva, Daniela Rodrigues 23 September 2016 (has links)
O mercado de produtos cosméticos, especialmente aqueles que têm na sua composição constituintes naturais, está em franca expansão. Uma das razões desta expansão é que os extratos vegetais têm eficácia na proteção contra os efeitos da exposição solar, sendo que o mecanismo de ação envolve principalmente o efeito antioxidante, diminuindo ou inibindo os danos gerados pelos radicais livres e/ou por outros compostos oxidantes. Este efeito protetor dos extratos vegetais tem motivado o interesse das indústrias do ramo, especialmente no entendimento dos mecanismos de dano e proteção. Além do efeito antioxidante, demonstrou-se recentemente que compostos vegetais podem também exercer efeito protetor através da proteção de membranas. No entanto, a relação entre a capacidade antioxidante desses compostos e a eficiência de proteção de membranas ainda não foi estabelecida. Neste trabalho, pretende-se quantificar a eficácia relativa dos extratos vegetais em termos de proteção de membranas. / The market of cosmetics, especially those who have in their composition natural constituents, is booming. One reason for this increase is that the plant extracts are effective in protecting against the effects of solar exposure, and the mechanism of action involves mainly the antioxidant effect, decreasing or inhibiting the damage caused by free radicals and / or other oxidizing compounds. This protective effect of plant extracts has motivated the interest of the sector industries, especially in the understanding of the mechanisms of injury and protection. In addition to the antioxidant effect, it was demonstrated recently that plant compounds may also exert a protective effect by the protective membrane. However, the relationship between the antioxidant capacity of these compounds and membranes protecting efficiency has not been established. In this work, it is intended to quantify the relative efficacy of the plant extracts in terms of membrane protection.
24

Filmes Langmuir-Blodgett de poliuretanos funcionalizados com azobenzenos e suas propriedades de armazenamento óptico / Langmuir-Blodgett films of functionalized polyurethanes and their optical storage properties

Santos Junior, David Sotero dos 09 November 2000 (has links)
Neste trabalho foram feitas as sínteses de dois poliuretanos utilizando-se o corante DR19 (4-(bis-N-2-hidroxietil)amino-4\'-nitroazobenzeno), o DR19MDI-PU derivado do 4,4\' difenilmetano-diisocianato e o DR19IPDI-PU derivado diisocianato de isofurona. O corante foi sintetizado e caracterizado por espectroscopia na região do infravermelho (FTIR), espectroscopia na região do ultravioleta visível (UV-Vis) e ressonância magnética nuclear de próton (HRMN). Os polímeros foram caracterizados por FTIR, UV-Vis, termogravimetria e calorimetria diferencial de varredura. As massas molares, Mn e Mw, e a polidispersividade foram determinadas por cromatografia de exclusão por tamanho. Um estudo sistemático foi realizado sobre as propriedades dos filmes de Langmuir destes polímeros. Monocamadas do DR19IPDI-PU puro apresentaram uma área maior por monômero, ao contrário do esperado porque sua unidade repetitiva é menor do que a do DR19MDI-PU. Entretanto, nos filmes mistos com estearato de cádmio (CdSt), na razão de 50:50% em massa, a área foi essencialmente a mesma para os dois polímeros, o que foi atribuído à influência do CdSt na agregação das macromoléculas. Isto foi confirmado pela forte interação entre CdSt e DR19MDI-PU que fez com que o potencial de superfície do filme misto fosse maior do que o dos filmes dos componentes puros. Apesar de os filmes de Langmuir dos polímeros puros serem estáveis, eles não eram passíveis de transferência para substratos sólidos, e por isso filmes Langmuir-Blodgett (LB) foram produzidos a partir dos filmes mistos com CdSt. Os filmes fabricados eram do tipo Y, com taxa de transferência próxima de 1. Medidas de espectroscopia óptica comprovaram a existência do CdSt e dos polímeros nos filmes LB e que a quantidade de material transferida em cada deposição foi a mesma. A agregação também afetou as propriedades dos filmes LB mistos, com os filmes de DR19MDI-PUICdSt apresentando um espectro UV-vis. característico de agregação do tipo H, ao contrário do caso de filmes LB de outros azopolímeros, incluindo o DR19IPDI-PU. Nos filmes LB, os domínios de CdSt e do polímero estão separados, como indicado por medidas de difração de Raios X, que mostraram picos de Bragg intensos característicos de estruturas com um espaçamento de bicamadas muito próximo do valor encontrado para filmes de CdSt puro. A fotoisomerização dos filmes LB foi investigada realizando-se ciclos de escrita-apagamento do processo de armazenamento óptico. A birrefringência induzida opticamente é estável, podendo ser eliminada com luz kircularmente polarizada. Ela aumenta com a potência do laser de escrita, antes de atingir a saturação. A potência de saturação é maior para o DR19MDIPU, provavelmente devido à agregação nestes filmes. Efeitos de agregação foram comprovados a partir de comparações dos resultados dos filmes LB com filmes obtidos por centrifugação dos polímeros investigados. A birrefringência máxima nos filmes LB diminui com o número de camadas depositadas porque o grau de ordenamento diminui quando um grande número de camadas é depositado, analogamente ao observado em filmes LB e de outros azopolímeros / Two polyurethanes have been synthesized with the functionalization with azobenzene dye, namely DR19 (4-(bis-N-2-hydroxyethyl)amino-4\'-nitroazobenzene). The dye was also synthesized as part of the work, and its structure was confirmed by infrared spectroscopy (FTIR), Ultraviolet visible spectroscopy (UV-Vis) and proton nuclear magnetic resonance (H-RMN). The resultant polymers, DR19IPDI-PU and DR19MDIPU, were characterized by FTIR, Uv-Vis providing results as expected from the anticipated molecular structures. Their molecular weights, Mn and Mw, and their polydispersity were determined by size-exclusion chromatography. Thermogravimetry and differential scanning calorimetry were also employed. A systematic investigation was carried out on the monolayer properties of these polymers. While monolayers of pure DR19MDI-PU displayed a larger area per repeat unit, contrary to expected as its unit is smaller than DR19IPDI-PU, their mixed monolayers with cadmium stearate (CdSt) (50:50% in weight) had the same area as the mixed monolayers of DR19IPDIPU. This was attributed to the influence of CdSt on the aggregation of DR19MDI-PUmacromolecules, which was confirmed by the strong interaction between CdSt and DR19MDI-PU that led to a monolayer surface potential for the mixed monolayer which was higher than for the value of both separate components. Eventhoughthe Langmuir monolayers of the pure polymers were stable at the airlwater interface, their b transferability was poor and therefore Langmuir-Blodgett (LB) films were produced from the mixed monolayers with CdSt, leading to Y-type films with near unity transfer ratios. Optical spectroscopy measurements confirmed the presence of CdSt as well as the polymer in the LB films, and also that the amount of material deposited in each transfer step was the same. Aggregation also played an important role in the properties of the transferred mixed LB films, as films from DR19MDI-PUICdSt displayed a UV-vis. spectrum characteristic of H-aggregates, unlike the case of LB films from other azobenzene-containing polymers, including DR19IPDI-PU. In the LB films, the domains of CdSt and polymer appear separately, as indicated by X-ray diffraction which showed intensive Bragg peaks which were characteristic of structures with a bilayer thickness very close to that of pure CdSt films. Photoisomerization of the LB films was investigated by performing writing-erasing cycles of optical storage processes. The photoinduced birefringence was stable, and could be eliminated by impinging circularly polarized light on the film. It increased with the power of the writing laser before reaching saturation. The power for saturation was higher for DR19MDI-PU, probably due to the aggregation of these films. Effects from aggregation were confirmed uponcomparing data for LB films with those from spin-coated films of the polymers investigated. The maximumbirefringence in the LB films decreased with the number of layers because the degree of order decreases as a large number of layers are deposited, similarly to the observed with LB films of other azobenzene-containing polymers
25

Absorção fotoinduzida de onda contínua (CW-PIA) em polímeros semicondutores / Continuous wave photoinduced absorption (CW-PIA) in semiconducting polymers

Aprile, Nathália Pio 07 December 2015 (has links)
Existem algumas técnicas destinadas ao estudo das características fotofísicas de materiais orgânicos ou dispositivos eletrônicos e optoeletrônicos a base de semicondutores orgânicos. A exemplo disso, a técnica de espectroscopia de absorção fotoinduzida de onda contínua (Continuous Wave Photoinduced Absorption/cw-PIA) apresenta grande sensibilidade como método destinado ao estudo dos processos eletrônicos envolvendo espécies excitadas de vida longa. Esta técnica emprega dois feixes ópticos distintos, um para excitação da amostra e outro (feixe de prova) para investigar os estados excitados remanescentes em amostra após bombeio óptico. O presente trabalho tem como objetivo a construção, desenvolvimento e caracterização de um aparato experimental para espectroscopia cw-PIA. A montagem bem sucedida da técnica foi testada em filme do polímero semicondutor P3HT, em filme de blenda (1:1) de P3HT/PCBM (comumente utilizada como camada ativa em células solares orgânicas) e em filmes automontados camada-a-camada (LbL) do tipo doador-aceitador de carga (P3KHT/P6N), sendo que a molécula P6N foi sintetizada pelo Grupo de Polímeros Bernhard Gross do IFSC-USP. Os filmes LbL de P3KHT/P6N, em comparação aos filmes blenda de P3HT/PCBM, demonstraram uma eficiência maior quanto a geração de portadores de carga com tempo de vida longo. / There are some techniques for the study of photophysical characteristics of organic materials or electronic and optoelectronic devices based on organic semiconductors. For example, the technique of continuous wave photoinduced absorption spectroscopy (cw-PIA) is a highly sensitive method for the study of the electronic processes involving long-lived excited species. This technique uses two distinct optical beams, one for sample excitation and another for probing the excited states remaining in the sample after optical pumping. The present work aims at the construction, development and characterization of an experimental apparatus for cw-PIA spectroscopy. The successful implementation of the technique was tested in a film of the semiconducting polymer P3HT and of the blend (1:1) P3HT/ PCBM (usually employed as active layer in organic solar cells), and also in a Layer-by-Layer (LbL) film of donor-acceptor molecules P3KHT/P6N, where the P6N molecule has been synthesized by Polymer Group Bernhard Gross at IFSC- USP. The comparison between P3KHT / P6N LbL film and the blend P3HT/PCBM has demonstrated higher charge carrier generation efficiency (with long lifetime) for the LbL film.
26

Estudo de birrefrigência fotoinduzida em filmes automontados de azopolímeros e azocorantes / Study of photoinduced birefrigence, in layer-by-layer films containing azopolymer and azodye

Perinotto, Angelo Cesar 29 April 2005 (has links)
Neste trabalho foi estudada a influência da arquitetura molecular e das condições de fabricação de filmes sobre a birrefringência fotoinduzida em filmes automontados de um azopolímero comercial PS-119 ou do corante Brilliant Yellow (BY) como espécies fotorreativas. Os filmes automontados foram fabricados a partir de seis policátions, a saber, poli(alilamina hidroclorada) (PAH), poli(c1oreto de dodecildimetilamônio) (PDAC) (com 3 massas molares diferentes), poli(etileno imina) (PEI) e dendrímero poli(amidoamina) geração 4 (PAMAM-G4). No processo de fabricação o substrato era imerso alternadamente em solução aquosa de policátions e poliânions nos pHs 4, 6 e 8. O crescimento dos filmes foi monitorado por espectroscopia UV-VIS. após cada etapa de adsorção. Um aumento linear do pico em 480 nm, atribuído a transição , indicou que a mesma quantidade de material era adsorvida em cada passo de deposição. A birrefringência foi opticamente induzida usando-se um laser de 532 nm Nd-YAG. Dentre as propriedades dos filmes automontados, a que mais variou de um sistema para outro foi o tempo de escrita característico, definido como o tempo necessário para atingir 50% da birrefringência máxima. Este tempo dependia do polieletrólito e do pH da solução de partida. Os filmes PEI/PS-119 em pH 8 e PDAC(HMW)/PS-119, em pH 4, PAWBY em pH 8, e PDAC(HMW)/BY em pH 4, forneceram os seguintes tempos característicos: 34 min, 0,5 min, 10 min e 3 s, respectivamente. Estas grandes variações nos tempos de escrita estão relacionadas as diferenças nas estruturas dos policátions, que determinam a intensidade das interações entre os polieletrólitos. Os baixos tempos para PDAC, por exemplo, são atribuídos as menores interações com o poliânion, já que a carga do PDAC, um sal quaternário, sofre efeito de blindagem por grupos CH3. Mencione-se que o tempo de escrita para os filmes automontados de PDACIBY é o menor já relatado para filmes automontados, sendo da mesma ordem de grandeza dos filmes obtidos por spin-coating ou técnica de Langmuir-Blodgett (LB). A birrefringência residual, após o desligamento do laser de escrita, foi superior a 78% em todos os sistemas estudados, demonstrando a utilidade de filmes automontados para dispositivos de memória óptica permanente. / This work was aimed at investigating the influence of the molecular architecture and film fabrication on the photoinduced birefi-ingence of layer-by-layer (LbL) films containing the azopolymer PS 119® or the azodye Brylliant Yellow (BY) as photoreactive materials. The LbL films were produced with six polications, viz.: poly(allylamine hydrochloride) (PAH), poly(diallyldimethylammonium chloride) (PDAC) (with three different molecular weights), poly(ethy1eneimine) (PEI) and generation 4 dendrimer poly(amidoamine) (PAMAM-G4). They were prepared via the alternate immersion of a substrate into the polycationic and polyanionic aqueous solutions, at concentrations of 0.5 mg/mL at three pHs: 4, 6 and 8. The assembly of multilayers was monitored aRer each adsorption step by UV-VIS spectroscopy. A linear increase was observed in the peak at 480 nm, assigned to the transition of the azobenzene moiety, indicating that the same amount of material was deposited at each deposition step. Birefringence was optically induced in films using a 532 nm NdYAG laser. Among the LbL properties, the characteristic writing time - corresponding to the time to achieve 50% of maximum birefiingence - was the quantity that most varied with the materials and experimental conditions employed. The writing time was estimated as 34 min. for PEI/PS-119 with solution at pH 8 films, 0.5 min. for PDAC(HMW)/PS-119, pH 4 films, ca. 10 min. for PAWBY, pH 8 films and 3 s for PDAC(HMW)íBY, pH 4 films. These differences in writing times are probably related to the structural differences of the polycations, which determine the degree of interactions between polycation and polyanion. Indeed, interactions between polyanion and PDAC are expected to occur to a lesser extent (in comparison to the other films) due to the hindering promoted by the dimethyl group in the quaternary ammonium salt, minimizing the interaction with sulfonated groups from PS-119 or BY. With less interaction the azobenzene groups are more mobile, thus causing the writing time to be shorter for PDACIpolyanion films. It should be stressed that the writing time for PDAC/BY is the shortest ever reported for LbL films, being of the same order of magnitude of writing times in cast and Langmuir-Blodgett (LB) films. The residual birefringence, aRer the writing laser was switched off, was at least 78% for all systems, indicating that these LbL films are suitable for long-term optical memories.
27

Aspectos químicos e fotoquímicos de liberação controlada de óxido nítrico a partir de complexos nitrosilos de rutênio: ensaios farmacológicos e de citotoxicidade. / Chemical and photochemical aspects of control nitric oxide release from nitrosyl ruthenium complexes: pharmacological and cytotoxic assays.

Marchesi, Mario Sergio Pereira 18 August 2008 (has links)
O óxido nítrico (NO) é um versátil agente biológico, atuando em diversas partes do organismo, tais como cérebro, artérias, sistema imunológico, fígado e pulmões. Alterações nos níveis basais de NO são relacionadas a causas de diversas doenças como hipertenção, câncer, doença de Raymond´s e agregação plaquetária. Visando suprir tal deficiência, mostrou-se de grande valia a obtenção de fármacos capazes de liberar quantidades significativas de NO e de maneira controlada. Uma das possibilidades é o uso de compostos de coordenação, com centro metálico rutênio coordenado ao ligante nitrosil, os quais possuem como característica liberação de NO por estímulo externo. Neste trabalho foram estudados as propriedades químicas, fotoquímicas, farmacológicas e tumoricidas do complexo trans-[RuC(MAC)NO]2+, onde MAC é 1,4,8,11-tetraazaciclotetradecano (cyclam) ou 1,4,8,12-tetraazaciclopentadecano ([15]aneN4), na presença do fotossensibilizador [Ru(NH3)5pz]2+. Os estudos fotoquímicos mostraram que o fotossensibilizador utilizado, [Ru(NH3)5pz]2+, possui tempo de vida no estado excitado de 113 ps, e apresenta processos de transferências eletrônicas e de energia fotoinduzida com o oxigênio molecular, gerando espécies reativas de oxigênio (EROS) como oxigênio singlete e ânion superóxido. Na presença do complexo macrocíclico trans-[RuC(MAC)NO]2+ a irradiação luminosa de [Ru(NH3)5pz]2+ na região do visível proporciona trasferência eletrônica fotoinduzida entre o fotosenssibilizador e o complexo nitrosilo com concomitante formação de NO. O rendimento quântico de NO (NO) é dependente do meio e é de cerca de 10-4 Einstein.mol.cm-1 em meio aquoso sob argônio e 10-2 Einstein.mol.cm-1 em meio oxigenado. Os estudos farmacológicos mostraram que a mistura proposta, em tampão fosfato pH 7,4, promoveu 75% de dilatação em musculatura de aorta pré-contraída com KC enquanto que, quando incorporados em sistemas carreadores de fármacos como emulsão óleo-em-água, HEG gel e membrana sol-gel, promoveram 40%, 35% e 35% de dilatação, respectivamente. A via vasodilatadora foi detectada como sendo pela ativação da GMPc (guanosina monofosfato cíclica), através da quantificação da concentração de cálcio citosólico. Os estudos das atividades anti-tumorais com os complexos doadores de NO foram realizados com linhagens celulares do tipo B16F10, Melan A, HL-60 WMs e Jurkat. Estes experimentos mostraram redução da viabilidade celular dos melanomas entre 50% e 75%, não apresentou ação em células normais (MelanA), mostrando-se seletivos ás células neoplasicas; e 95% de redução da viabilidade celular das células leucêmica (HL-60). Os resultados obtidos e descritos neste trabalho permitem vislumbrar que o uso de espécies doadoras de NO e oxigênio singlete possam ser utilizados no futuro em terapia clínica. / Nitric oxide (NO) is a multipurpose biological agent that shows important role in brain, arteries, immunological system, liver and lungs. The NO basal level alterations have correlation with several diseases as hypertension, cancer, Raymonds disease and platelet aggregation. Aiming supply this deficient NO level, it was necessary propose new compounds that can release NO at controlled manner. One of the possibilities is utilize nitrosyl ruthenium complexes that have ability to release NO under external stimulus. In this work we have studied, the chemical, photochemical, pharmacological and anti-tumoral properties of the trans-[RuC(MAC)NO]2+ complex, were MAC is 1,4,8,11-tetraazacyclotetradecane (cyclam) or 1,4,8,12-tetraazacyclopentadecane ([15]aneN4), in the presence of the sensitizer [Ru(NH3)5pz]2+. The photochemical studies of [Ru(NH3)5pz]2+ complex showed excited state lifetime of 113 ps and presented photoinduced electron and energy transfer with oxygen resulting in reactive oxygen species (ROS) generation as singlet oxygen and superoxide anion. In the presence of trans-[RuC(MAC)NO]2+ complex, the visible light irradiation of [Ru(NH3)5pz]2+ causes photoinduced electron transfer between the photosensitizer and the nitrosyl ruthenium complex resulting NO generation. The quantum yield (NO) is milieu dependent and showed 10-4 Einstein.mol.cm-1 in inert atmosphere and 10-2 Einstein.mol.cm-1 in aerated aqueous solution. The pharmacological studies showed that the proposed mixture in phosphate buffer, under visible irradiation, induce 75% of relaxation in aorta pre-contracted with KC while this system incorporated into drug delivery system as water-in-oil emulsion, HEG gel and sol-gel membrane, the nitric oxide generated induced 40%, 35% and 35% of relaxation, respectively. The quantification of cytosolic calcium concentration, using confocal image, showed that vasodilatation pathway observed was via cGMP (cyclic guanosine monophosphate) activation. The anti-tumoral studies using NO donors were carried out for B16F10, Melan A, HL-60, WMs and Jurkat cells. Those experiments showed decrease from 50% to 75% of cell viability of tumor cells and no toxicity in melanoma cells and 95% of reduction of leukemic cells (HL-60). The obtained results described in this work permit to glimpse that the use of NO donor species and singlet oxygen maybe is a useful tool in the future in clinical therapy.
28

Photoinduced electron transfer in [N]phenylenes

Dosche, Carsten, Mickler, Wulfhard, Löhmannsröben, Hans-Gerd, Agent, Nicolas, Vollhardt, K. Peter C. January 2007 (has links)
First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants kq and the free energy change of the electron transfer (ΔG0CS ) could be described by the Rehm-Weller equation. From the experimental results, a reorganization energy λ of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic ΔG0CS can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state.
29

Investigating the effect of membrane anchoring on photoinduced electron transfer pyrazoline based fluorescent probes

Hofmekler, Jonathan 18 November 2011 (has links)
Fluorescence microscopy is a powerful analytical tool for visualizing biological processes at the subcellular level. In this regard, 1,3,5-triarylpyrazoline based fluorescent probes which act as "turn-on" probes, have been extensively researched. These probes achieve their fluorescence "turn-on" response by inhibition of fluorescence quenching by acceptor-excited photoinduced electron transfer upon binding of an analyte. It has been recently shown that some fluorescent probes used in biological research form colloids composed of nanoparticles, due to their hydrophobic character. This hydrophobic character can also lead to partitioning of the probe into cellular membranes. Colloid formation and membrane partitioning may affect the probes' photophysical properties such as absorption and emission wavelength and quantum yields. Recently, a series of 1,3,5-triarylpyrazolines synthesized in our group by M. T. Morgan, showed no formation of aggregates in aqueous buffer. Surprisingly, these probes increased their fluorescence intensity in the presence of liposomes. The photoinduced electron transfer process is greatly affected by the polarity of the medium in which the probe is used. In this study, the effect of membrane proximity on the photoinduced electron transfer process for pyrazoline based "turn-on" probes has been investigated. A series of water soluble 1,3,5-triarylpyrazolines have been synthesized in which a N,N-dialkylaniline moiety acts as an electron donor and a proton acceptor and an alkylated sulfonamide moiety acts as a molecular anchor for interaction with neutral and anionic liposomes.
30

Fluorescence Determination Of Monosaccharides And Catecholamines By Using Dansylaminophenyl Boronic Acid

Seckin, Ebru Zeliha 01 January 2005 (has links) (PDF)
In sugar industry, determination of invert sugars (fructose and glucose) provides information about the quality, process control and characteristics of the produced fructose and glucose syrups. Determination of invert sugar is also important for wine industries. In wine process, fructose and glucose are converted to ethanol by fermentation and the type of wine is designated by the amount of invert sugar remained. Fast and reliable invert sugar detection techniques are required to check the quality of wine throughout the fermentation process. Cathecholamines (eg. dopamine and epinephrine) are diol containing compounds which play important roles in higher animals&rsquo / physicomotor activities, learning, sleeping, memory and immune system. They also affect brain functions. Inbalances in dopamine level in brain result in a number of psychiatric disorders, particularly schizophrenia and Parkinson disease. Catecholamines are present in relatively high amounts in drugs. Many efforts have been made to develop analytical procedures for their rapid, simple and accurate determination. For these reasons, catecholamine quantification is important in the field of pharmacy and medicine. Boronic acids interact with 1,2 or 1,3-diol containing compounds, such as fructose, glucose and dopamine, rapidly and reversibly. Hence, boronic acids are used as the recognition moeity in the construction of photoinduced electron transfer (PET) fluorophores specific for saccharides and catecholamines. In this study, a flow injection analysis system has been developed for the rapid and selective recognition of fructose and glucose in wine and in commercial sugar syrups / dopamine and epinephrine in pharmaceutical injections by using dansylaminophenyl boronic acid (DAPB) which is a fluorescent PET molecule.

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