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Singlet oxygen quantum yields (Φd) in water using beetroot extract and an array of LEDs

BONACIN, Juliano A.; ENGELMANN, Fábio M.; SEVERINO, Divinomar; TOMA, Henrique E.; BAPTISTA, Mauricio S.
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
67.6058%
It is proposed a simple and inexpensive strategy to determine singlet oxygen (¹O2) quantum yields (ΦΔ) of photosensitizers (PS) in water using beetroot extract containing betacyanin (Bc) and a set of light emitting diodes (LEDs) for excitation. Bc, a cationic natural dye, was obtained by flash chromatography purification from the red beet extract (Beta vulgaris) and employed as a convenient probe for ¹O2 detection. Solutions of Bc and PS were illuminated with an array of LEDs adapted in the cuvette compartment of a commercial spectrophotometer, and the decrease in Bc absorbance was followed as a function of time. Bc photobleaching decreased in de-aerated solution and increased in D2O, indicating the involvement of ¹O2. The observed photobleaching rate constant (k obs) was proportional to the LED intensity, concentration and ΦΔ of the PS. By keeping the light source constant we could estimate the overlap integral (R) between the LED emission and PS absorbance for different PS concentrations. The slope of R versus k obs is the value of the photobleaching rate constant (k), which was shown to be proportional to ΦΔ. Values of ΦΔ obtained by this method were compared with those obtained by measuring NIR (near infrared) emission for a series phenothiazine dyes.; É proposta uma estratégia simples e barata para determinar rendimentos quânticos (ΦΔ) de oxigênio singlete (¹O2) de fotossensibilizadores (PS) em água utilizando extrato de beterraba contendo betacianina (Bc) e um conjunto de diodos emissores de luz (LEDs) para excitação. Bc...

Singlet oxygen reacts with 2 `,7 `-dichlorodihydrofluorescein and contributes to the formation of 2 `,7 `-dichlorofluorescein

DAGHASTANLI, Nasser A.; ITRI, Rosangela; BAPTISTA, Mauricio S.
Fonte: WILEY-BLACKWELL Publicador: WILEY-BLACKWELL
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
57.41581%
There are controversial reports in the literature concerning the reactivity of singlet oxygen ((1)O(2)) with the redox probe 2`,7`-dichlorodihydrofluorescein (DCFH). By carefully preparing solutions in which (1)O(2) is quantitatively generated in the presence of DCFH, we were able to show that the formation rate of the fluorescent molecule derived from DCFH oxidation, which is 2`,7`-dichlorofluorescein (DCF), increases in D(2)O and decreases in sodium azide, proving the direct role of (1)O(2) in this process. We have also prepared solutions in which either (1)O(2) or dication (MB(center dot 2+)) and semi-reduced (MB(center dot)) radicals of the sensitizer and subsequently super-oxide radical (O(2)(center dot-)) are generated. The absence of any effect of SOD and catalase ruled out the DCFH oxidation by O(2)(center dot-), indicating that both (1)O(2) and MB(center dot 2+) react with DCFH. Although the formation of DCF was 1 order of magnitude larger in the presence of MB(center dot 2+) than in the presence of (1)O(2), considering the rate of spontaneous decays of these species in aqueous solution, we were able to conclude that the reactivity of (1)O(2) with DCFH is actually larger than that of MB(center dot 2+). We conclude that DCFH can continue to be used as a probe to monitor general redox misbalance induced in biologic systems by oxidizing radicals and (1)O(2).; FAPESP Fundacao de Amparo a Pesquisa do Estado de Sao Paulo; Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); CNPq Conselho Nacional de Desenvolvimento Cientifico e Tecnologico; Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Singlet oxygen generation in the reaction centers of Rhodobacter sphaeroides

UCHOA, Adjaci F.; KNOX, Peter P.; TURCHIELLE, Rozane; SEIFULLINA, Nurania Kh.; BAPTISTA, Mauricio S.
Fonte: SPRINGER Publicador: SPRINGER
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
57.689326%
Singlet oxygen ((1)O(2)) generation in the reaction centers (RCs) of Rhodobacter sphaeroides wild type was characterized by luminescent emission in the near infrared region (time resolved transients and emission spectra) and quantified to have quantum yield of 0.03 +/- 0.005. (1)O(2) emission was measured as a function of temperature, ascorbate, urea and potassium ferricyanide concentrations and as a function of incubation time in H(2)O: D(2)O mixtures. (1)O(2) was shown to be affected by the RC dynamics and to originate from the reaction of molecular oxygen with two sources of triplets: photoactive dimer formed by singlet-triplet mixing and bacteriopheophytin formed by direct photoexcitation and intersystem crossing.

Generation and suppression of singlet oxygen in hair by photosensitization of melanin

CHIARELLI-NETO, Orlando; PAVANI, Christiane; FERREIRA, Alan S.; UCHOA, Adjaci F.; SEVERINO, Divinomar; BAPTISTA, Mauricio S.
Fonte: ELSEVIER SCIENCE INC Publicador: ELSEVIER SCIENCE INC
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
67.689326%
We have studied the spectroscopic properties of hair (white, blond, red, brown, and black) under illumination with visible light, giving special emphasis to the photoinduced generation of singlet oxygen ((1)O(2)). Irradiation of hair shafts (lambda(ex)>400 nm) changed their properties by degrading the melanin. Formation of C3 hydroperoxides in the melanin indol groups was proven by (1)H NMR. After 532-nm excitation, all hair shafts presented the characteristic (1)O(2) emission (lambda(em) = 1270 nm), whose intensity varied inversely with the melanin content. (1)O(2) lifetime was also shown to vary with hair type, being five times shorter in black hair than in blond hair, indicating the role of melanin as a (1)O(2) suppressor. Lifetime ranged from tenths of a nanosecond to a few microseconds, which is much shorter than the lifetime expected for (1)O(2) in the solvents in which the hair shafts were suspended, indicating that (1)O(2) is generated and suppressed inside the hair structure. Both eumelanin and pheomelanin were shown to produce and to suppress (1)O(2), with similar efficiencies. The higher amount of (1)O(2) generated in blond hair and its longer lifetime is compatible with the stronger damage that light exposure causes in blond hair. We propose a model to explain the formation and suppression of (1)O(2) in hair by photosensitization of melanin with visible light and the deleterious effects that an excess of visible light may cause in hair and skin. 2011 Published by Elsevier Inc.; FAPESP; Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); Farma Service Bioextract; Farma Service Bioextract

Cytometric quantification of singlet oxygen in the human malaria parasite Plasmodium falciparum

Butzloff, Sabine; Groves, Matthew R.; Wrenger, Carsten; Mueller, Ingrid B.
Fonte: WILEY-BLACKWELL; HOBOKEN Publicador: WILEY-BLACKWELL; HOBOKEN
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
67.903696%
The malaria parasite Plasmodium falciparum proliferates within human erythrocytes and is thereby exposed to a variety of reactive oxygen species (ROS) such as hydrogen peroxide, hydroxyl radical, superoxide anion, and highly reactive singlet oxygen (1O2). While most ROS are already well studied in the malaria parasite, singlet oxygen has been neglected to date. In this study we visualized the generation of 1O2 by live cell fluorescence microscopy using 3-(p-aminophenyl) fluorescein as an indicator dye. While 1O2 is found restrictively in the parasite, its amount varies during erythrocytic schizogony. Since the photosensitizer cercosporin generates defined amounts of 1O2 we have established a new cytometric method that allows the stage specific quantification of 1O2. Therefore, the parasites were first classified into three main stages according to their respective pixel-area of 200600 pixels for rings, 7001,200 pixels for trophozoites and 1,4002,500 pixels for schizonts. Interestingly the highest mean concentration of endogenous 1O2 of 0.34 nM is found in the trophozoites stage, followed by 0.20 nM (ring stage) and 0.10 nM (schizont stage) suggesting that 1O2 derives predominantly from the digestion of hemoglobin. (c) 2012 International Society for Advancement of Cytometry

Novel properties of melanins include promotion of DNA strand breaks, impairment of repair, and reduced ability to damage DNA after quenching of singlet oxygen

Suzukawa, Andreia Akemi; Vieira, Alessandra; Winnischofer, Sheila Maria Brochado; Scalfo, Alexsandra Cristina; Di Mascio, Paolo; Ferreira, Ana Maria da Costa; Ravanat, Jean-Luc; Martins, Daniela de Luna; Rocha, Maria Eliane Merlin; Martinez, Glaucia Regin
Fonte: ELSEVIER SCIENCE INC; NEW YORK Publicador: ELSEVIER SCIENCE INC; NEW YORK
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
57.689326%
Melanins have been associated with the development of melanoma and its resistance to photodynamic therapy (PDT). Singlet molecular oxygen (102), which is produced by ultraviolet A solar radiation and the PDT system, is also involved. Here, we investigated the effects that these factors have on DNA damage and repair. Our results show that both types of melanin (eumelanin and pheomelanin) lead to DNA breakage in the absence of light irradiation and that eumelanin is more harmful than pheomelanin. Interestingly, melanins were found to bind to the minor grooves of DNA, guaranteeing close proximity to DNA and potentially causing the observed high levels of strand breaks. We also show that the interaction of melanins with DNA can impair the access of repair enzymes to lesions, contributing to the perpetuation of DNA damage. Moreover, we found that after melanins interact with 102, they exhibit a lower ability to induce DNA breakage; we propose that these effects are due to modifications of their structure. Together, our data highlight the different modes of action of the two types of melanin. Our results may have profound implications for cellular redox homeostasis, under conditions of induced melanin synthesis and irradiation with solar light. These results may also be applied to the development of protocols to sensitize melanoma cells to PDT. (c) 2012 Elsevier Inc. All rights reserved.; Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (Brasilia...

Hidroperóxidos de lipídios como fonte biológica de oxigênio singlete: estudos com marcação isotópica, espectrometria de massas e luminescência; Lipid hydroperoxides as a biological source of singlet oxygen: studies using isotopic labelling, mass spectrometry and luminescence

Miyamoto, Sayuri
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 08/04/2005 PT
Relevância na Pesquisa
57.81768%
Evidências apontam para o envolvimento da peroxidação lipídica em diversas patologias. Os hidroperóxidos de lipídios (LOOH) são os produtos primários da peroxidação lipídica e sua decomposição resulta em produtos de maior reatividade e toxicidade, como os radicais peroxila. Esses radicais desempenham papel importante na propagação da peroxidação lipídica e também podem gerar oxigênio molecular singlete (1O2) por meio da combinação de dois radicais peroxila. Neste trabalho investigamos a possibilidade dos LOOH, em particular dos hidroperóxidos de ácido linoléico (LAOOH), de servirem como fonte 1O2 na presença de oxidantes de relevância biológica como metais, peroxinitrito ou ácido hipocloroso. A formação de 1O2 foi claramente demonstrada na reação de LAOOH com esses oxidantes pelas detecções (i) da emissão bimolecular na região espectral do vermelho (λ>570 nm), (ii) da emissão monomolecular no infravermelho-próximo (λ=1270 nm), (iii) do espectro de emissão no infravermelho, e (iv) da intensificação e supressão da luminescência na presença de D2O e azida, respectivamente. Além disso, os mecanismos de reação foram estudados utilizando LAOOH marcados com oxigênio-18 (LA18O18OH) e captadores químicos específicos para 1O2 aliada à tecnica de detecção por HPLC acoplada à espectrometria de massa. Os resultados mostraram a formação de 1O2 marcado [18(1O2) ] na reação de LA18O18OH com os três oxidantes...

Estudo da imobilização de porfirinas em sílica nanoparticulada e da sua interação com oxigênio e ferro: possíveis aplicações biomédicas e analíticas; Study of the immobilization of porphyrins in silica nanoparticles and their interaction with oxygen and iron: possible biomedical and analytical applications

Silva, Paulo Rogerio da
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 17/12/2008 PT
Relevância na Pesquisa
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O presente estudo teve por objetivo desenvolver metodologias para imobilização de sondas moleculares fluorescentes em matrizes de sílica de tamanho controlado, bem como estudar a interação das sondas livres e imobilizadas com oxigênio e ferro. A classe de fluoróforos escolhida foi a das porfirinas, que apresentam baixa solubilidade em água e têm seu uso limitado, apesar de apresentarem pelo menos duas propriedades interessantes: (i) interagem com oxigênio formando oxigênio singlete, sendo candidatas a drogas para terapia fotodinâmica, e (ii) têm sua fluorescência suprimida ao complexarem metais, podendo atuar como sondas fluorescentes. A imobilização de porfirinas em esferas de sílica de tamanho inferior a 100 nm foi realizada através de um processo sol-gel ou pelo uso de microemulsões. O método sol-gel exigiu a modificação prévia da molécula da porfirina com reagente organosilano e resultou em esferas na faixa de 70 nm. O método da microemulsão dispensou a modificação da porfirina e resultou em esferas na faixa de 30 nm, muito estáveis em água. Os fluoróforos imobilizados preservaram suas propriedades óticas e a sua capacidade de gerar oxigênio singlete. Os estudos envolvendo a detecção de oxigênio singlete foram realizados pelo método físico direto...

Atividade de mieloperoxidase e produção de oxigênio singlete em neutrófilos e células monocíticas; Activity of Myeloperoxidase and singlet oxygen production in neutrophils and monocytic cells

Cruz, Wilton Antonio da Silva
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 09/09/2010 PT
Relevância na Pesquisa
67.745913%
A enzima mieloperoxidase (MPO), presente em leucócitos da linhagem granulocítica e monocítica, tem papel fundamental na produção de espécies reativas de oxigênio (ERO). Existem fortes evidências que alguns produtos gerados a partir de reações catalisadas por mieloperoxidase (MPO) tenham papel na sinalização celular. Dentre estes produtos, chama atenção o oxigênio singlete (1O2). Em fagócitos, esta ERO poderia participar tanto do processo de morte de patógenos, quanto da sinalização de eventos da inflamação. O nosso grupo de pesquisa trabalha com a hipótese de que a localização da MPO, e consequentemente, os sítios de produção de 1O2 definem a função da enzima e do 1O2. O interesse particular no 1O2 deve-se também ao fato de que sua detecção não é trivial e relativamente pouco é conhecido sobre sua produção por sistemas biológicos se comparado a outras EROs. Neste estudo trabalhamos com a questão da localização de MPO em neutrófilos e monócitos humanos e com a detecção de 1O2 através da utilização de sondas específicas. Nos experimentos realizados avaliamos a produção de 1O2 pela utilização da sonda 9,10 difenilantraceno (DPA) e também empregando o éster 9,10-antracenil-3-bispropionato de etila (ABPE) como captador de 1O2. Apesar da proposta de uso do DPA revestindo partículas a serem fagocitadas ter sido feita anteriormente (Garcia F....

Estudo do papel de lesões oxidativas ao DNA mitocondrial na morte celular induzida por geradores de oxigênio singlete; Study of the role of oxidative damage to the mtDNA on the cell death induced by singlet oxygen generators

Romagna, Carolina Domeniche
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 05/07/2012 PT
Relevância na Pesquisa
67.862827%
Mitocôndrias desempenham um papel central na homeostase celular. Estas organelas se diferem das demais não só por suas múltiplas funções, mas por terem seu próprio genoma, distinto do genoma nuclear. Estas organelas também participam de mecanismos de morte celular de forma central nos três mecanismos mais conhecidos: apoptose, necrose e autofagia. O mtDNA está localizado na face interna da membrana mitocondrial, onde são geradas grandes quantidades de Espécies Reativas de Oxigênio (EROs). Em consequência, o mtDNA acumula modificações oxidativas, mesmo em condições normais de metabolismo. Entretanto as respostas celulares ao acúmulo de lesões no mtDNA ainda não são claras. Para investigarmos se lesões oxidativas no mtDNA causam morte celular, propomos um modelo no qual oxigênio singlete é gerado especificamente na mitocôndria, pela ação de fotossensibilizadores com diferentes localizações celulares (azul de metileno, AM, e cristal violeta, CV, citosólicos; Ro 19-8022, Ro, citosólico e nuclear). Mostramos, por microscopia confocal, que os corantes tem a localização esperada em células HeLa. Além disso, observamos que o AM gera oxigênio singlete proporcionalmente a concentração do corante e dose de fotoativação. Mostramos que células tratadas com os corantes diminuem a velocidade de duplicação 24 h após o tratamento...

Singlet oxygen quantum yields (Φd) in water using beetroot extract and an array of LEDs

Bonacin,Juliano A.; Engelmann,Fábio M.; Severino,Divinomar; Toma,Henrique E.; Baptista,Mauricio S.
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/01/2009 EN
Relevância na Pesquisa
67.6058%
It is proposed a simple and inexpensive strategy to determine singlet oxygen (¹O2) quantum yields (ΦΔ) of photosensitizers (PS) in water using beetroot extract containing betacyanin (Bc) and a set of light emitting diodes (LEDs) for excitation. Bc, a cationic natural dye, was obtained by flash chromatography purification from the red beet extract (Beta vulgaris) and employed as a convenient probe for ¹O2 detection. Solutions of Bc and PS were illuminated with an array of LEDs adapted in the cuvette compartment of a commercial spectrophotometer, and the decrease in Bc absorbance was followed as a function of time. Bc photobleaching decreased in de-aerated solution and increased in D2O, indicating the involvement of ¹O2. The observed photobleaching rate constant (k obs) was proportional to the LED intensity, concentration and ΦΔ of the PS. By keeping the light source constant we could estimate the overlap integral (R) between the LED emission and PS absorbance for different PS concentrations. The slope of R versus k obs is the value of the photobleaching rate constant (k), which was shown to be proportional to ΦΔ. Values of ΦΔ obtained by this method were compared with those obtained by measuring NIR (near infrared) emission for a series phenothiazine dyes.

The role of singlet oxygen and oxygen concentration in photodynamic inactivation of bacteria

Maisch, Tim; Baier, Jürgen; Franz, Barbara; Maier, Max; Landthaler, Michael; Szeimies, Rolf-Markus; Bäumler, Wolfgang
Fonte: National Academy of Sciences Publicador: National Academy of Sciences
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
48.269307%
New antibacterial strategies are required in view of the increasing resistance of bacteria to antibiotics. One promising technique involves the photodynamic inactivation of bacteria. Upon exposure to light, a photosensitizer in bacteria can generate singlet oxygen, which oxidizes proteins or lipids, leading to bacteria death. To elucidate the oxidative processes that occur during killing of bacteria, Staphylococcus aureus was incubated with a standard photosensitizer, and the generation and decay of singlet oxygen was detected directly by its luminescence at 1,270 nm. At low bacterial concentrations, the time-resolved luminescence of singlet oxygen showed a decay time of 6 ± 2 μs, which is an intermediate time for singlet oxygen decay in phospholipids of membranes (14 ± 2 μs) and in the surrounding water (3.5 ± 0.5 μs). Obviously, at low bacterial concentrations, singlet oxygen had sufficient access to water outside of S. aureus by diffusion. Thus, singlet oxygen seems to be generated in the outer cell wall areas or in adjacent cytoplasmic membranes of S. aureus. In addition, the detection of singlet oxygen luminescence can be used as a sensor of intracellular oxygen concentration. When singlet oxygen luminescence was measured at higher bacterial concentrations...

Single Cell Responses to Spatially-Controlled Photosensitized Production of Extracellular Singlet Oxygen

Pedersen, Brian Wett; Sinks, Louise E.; Breitenbach, Thomas; Schack, Nickolass B.; Vinogradov, Sergei A.; Ogilby, Peter R.
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
48.257246%
The response of individual HeLa cells to extracellularly produced singlet oxygen was examined. The spatial domain of singlet oxygen production was controlled using the combination of a membrane-impermeable Pd porphyrin-dendrimer, which served as a photosensitizer, and a focused laser, which served to localize the sensitized production of singlet oxygen. Cells in close proximity to the domain of singlet oxygen production showed morphological changes commonly associated with necrotic cell death. The elapsed post-irradiation “waiting period” before necrosis became apparent depended on (a) the distance between the cell membrane and the domain irradiated, (b) the incident laser fluence and, as such, the initial concentration of singlet oxygen produced, and (c) the lifetime of singlet oxygen. The data imply that singlet oxygen plays a key role in this process of light-induced cell death. The approach of using extracellularly-generated singlet oxygen to induce cell death can provide a solution to a problem that often limits mechanistic studies of intracellularly photosensitized cell death: it can be difficult to quantify the effective light dose, and hence singlet oxygen concentration, when using an intracellular photosensitizer.

Reevaluation of analytical methods for photogenerated singlet oxygen

Nakamura, Keisuke; Ishiyama, Kirika; Ikai, Hiroyo; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi; Kohno, Masahiro
Fonte: the Society for Free Radical Research Japan Publicador: the Society for Free Radical Research Japan
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
48.257246%
The aim of the present study is to compare different analytical methods for singlet oxygen and to discuss an appropriate way to evaluate the yield of singlet oxygen photogenerated from photosensitizers. Singlet oxygen photogenerated from rose bengal was evaluated by electron spin resonance analysis using sterically hindered amines, spectrophotometric analysis of 1,3-diphenylisobenzofuran oxidation, and analysis of fluorescent probe (Singlet Oxygen Sensor Green®). All of the analytical methods could evaluate the relative yield of singlet oxygen. The sensitivity of the analytical methods was 1,3-diphenylisobenzofuran < electron spin resonance < Singlet Oxygen Sensor Green®. However, Singlet Oxygen Sensor Green® could be used only when the concentration of rose bengal was very low (<1 µM). In addition, since the absorption spectra of 1,3-diphenylisobenzofuran is considerably changed by irradiation of 405 nm laser, photosensitizers which are excited by light with a wavelength of around 400 nm such as hematoporphyrin cannot be used in the 1,3-diphenylisobenzofuran oxidation method. On the other hand, electron spin resonance analysis using a sterically hindered amine, especially 2,2,6,6-tetramethyl-4-piperidinol and 2,2,5,5-tetramethyl-3-pyrroline-3-carboxamide...

Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling☆

Riethmüller, Michaela; Burger, Nils; Bauer, Georg
Fonte: Elsevier Publicador: Elsevier
Tipo: Artigo de Revista Científica
Publicado em 17/07/2015 EN
Relevância na Pesquisa
48.257246%
Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2.) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8...

Singlet oxygen quantum yields from halogenated chlorins: potential new photodynamic therapy agents

Pineiro, Marta; Pereira, Mariette M.; Rocha Gonsalves, A. M. d'A.; Arnaut, Luis G.; Formosinho, Sebastião J.
Fonte: Universidade de Coimbra Publicador: Universidade de Coimbra
Tipo: Artigo de Revista Científica Formato: aplication/PDF
ENG
Relevância na Pesquisa
67.982896%
Flash photolysis and photoacoustic calorimetry were used to measure the energy-transfer rates and singlet oxygen quantum yields originated by the triplet states of halogenated tetrakisphenylporphyrins and related chlorins in aerated toluene. The chlorins ([lambda]max[approximate]660 nm, [var epsilon][approximate]3×104 M-1 cm-1) have long-lived triplet states (>12 [mu]s) in the absence of molecular oxygen, and in its presence the singlet oxygen production quantum yields of the 2-chloro and 2,6-dichlorophenyl derivatives are 0.89±0.05 and 0.98±0.02, respectively. The high absorptivity in the red, the photostability and the efficiency of these chlorins in producing singlet oxygen suggests a ground for the development of better sensitisers for photodynamic therapy.; http://www.sciencedirect.com/science/article/B6TGY-41YG70D-7/1/de6fc7896eaf9c58239551fa798e3e7b

Synthesis of 2-(n-(N,N,N-trimethyl)-n-alkyl)-5-alkylfuryl halides - Useful probes for studying singlet oxygen dynamics and equilibria in microcompartmentalized systems

Lemp Miranda, Else Mónica; Meléndrez Cancino, Mónica Ximena; Zanocco Loyola, Antonio Luis; Günther Sapunar, Germán; Castañeda, F.
Fonte: ELSEVIER SCIENCE SA Publicador: ELSEVIER SCIENCE SA
Tipo: Artículo de revista
EN
Relevância na Pesquisa
68.11425%
Three lipid-soluble furan derivatives, 2,5-disubstituted with different n-alkyl chains, and a terminal trimethylammonium group were obtained by reaction of a metalated monoalkylfuran with alkyl dihalides under conditions of thermodynamic control and subsequent reaction with gaseous trimethylamine. These compounds are useful probes for studying singlet oxygen dynamics and equilibria in microcompartmentalized systems because they react very rapidly with singlet oxygen, physical quenching can be neglected, and medium effects on reactivity are small. Location of the probe, completely incorporated in the lipidic bilayer, is predictable and controllable from structural modifications and the small reactive moiety does not modify significantly the vesicle chain packing. Steady-state and time-resolved kinetics employing 2-(4-(NN, V-trimethyl)-butyl)-5-dodecylfuryI bromide to monitoring singlet oxygen give a value of 0.27 for the singlet oxygen partitioning constant between the lipidic and aqueous pseudophases of 10 mM large unilamellar dioctadecyldimethylarnmonium chloride (DODAC) vesicles. The steady-state singlet oxygen concentration, sensed by this furan derivative in the microphase, was 2.7 x 10(-11) M. (C)

Formação de oxigênio singlete O2 (1Δg) por fagócitos; Singlet oxygen formation O2 (1Δg) by phagocytes

Garcia, Flavia
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 20/10/2005 PT
Relevância na Pesquisa
57.862827%
Neste trabalho avaliamos a formação de oxigênio singlete in vitro em fagócitos, (células mononucleares e neutrófilos) isolados de sangue periférico humano, e eosinófilos, de lavado bronco alveolar de camundongos balb/c, ativados por estímulo partículado: zimosan opsonizado contendo o 9,10difenilantraceno (DPA) adsorvido como sonda captadora de 1O2. Por este método, a formação do 1O2 pode ser verificada pela formação do 9,10-difenilantraceno endoperóxido (DPAO2), que é detectado por HPLC. Observamos, que os fagócitos formam 1O2 e que esta formação parece ocorrer de forma diferenciada para os dois tipos celulares (neutrófilos e células mononucleares). Visando ampliar os estudos anteriores sobre o papel da melatonina (MLT) no processo inflamatório, foi testado seu efeito em fagócitos e a relação na produção de 1O2 destas células. Observamos que MLT inibe a formação de 1O2 totalmente no caso de neutrófilos e parcialmente no caso de células mononucleares e eosinófilos. Paralelamente, foi desenvolvida a síntese de um novo captador químico de 1O2, o éster 9,10-antracenil-3-bispropionato de etila (ABPE), cuja finalidade principal é o acúmulo no interior da célula, depois de sofrer hidrólise enzimática. Esta sonda...

Formation and geminate quenching of singlet oxygen in purple bacterial reaction center

Arellano, Juan B.; Yousef, Yaser A.; Melo, Thor Bernt; Mohamad, Samsun B. B.; Cogdell, Richard J.; Naqvi, K. Razi
Fonte: Elsevier Publicador: Elsevier
Tipo: Artículo Formato: 275854 bytes; image/tiff
ENG
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The phosphorescence of singlet oxygen (X-1*) photosensitized by the carotenoidless reaction center (RC) of Rhodobacter sphaeroides 826.1 has been investigated, using H2O and D2O as the suspending media. To enhance (under neutral conditions) the triplet quantum yield of the special pair P-870 (P) by the radical pair mechanism, the quinone acceptor Q(A) was removed by means of a chemical treatment. The phosphorescence signal fits the functional form P-0[exp (-t/tau) - exp(-t/zeta)], regardless of whether X-1* is sensitized by P-dagger or M-dagger (where the dagger denotes triplet excitation and M is a water-soluble molecule). The time constant was identified with the decay time of X-1*; when P-dagger is the sensitizer, one finds zeta((1))(P) = 3.3 +/- 0.3 ps, and ((2) = 34 3 Vs, where the superscripts 1 and 2 refer to H2O and D2O, respectively; the corresponding values for sensitization by Mt (in the absence of RC) are M l = 3.7 +/- 0.4 Vs, and M l = 75 5 Vs. The addition of RC's to the solution of M in D2O reveals that the RC is a quencher of X-1*; however, for equal concentrations of the RC, zeta((2))(P) < zeta((2))(M), showing that X-1* is deactivated, after its entry into the suspending medium, mainly by the solvent or the same RC which acts as the sensitizer. The values of tau(P) are similar in both solvents...

Bacteriochlorophyll e monomers, but not aggregates, sensitize singlet oxygen: implications for a self-photoprotection mechanism in chlorosomes.

Arellano, Juan B.; Melo, Thor Bernt; Borrego, Carles M.; Naqvi, K. Razi
Fonte: American Society for Photobiology Publicador: American Society for Photobiology
Tipo: Artículo Formato: 412592 bytes; application/pdf
ENG
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Sensitization of singlet delta oxygen (O2(1Δg)) by bacteriochlorophyll e (BChle) has been investigated to gain a better understanding of the photoprotection mechanism(s) operating in chlorosomes of green photosynthetic bacteria. The sensitization process has been studied in media where BChle forms monomers (acetone and aqueous solutions containing 0.5% Triton X-100 [TX]) and in systems where BChle aggregates, namely, aqueous solutions containing 0.003% monogalactosyl diglyceride (MGDG) and chlorosomes (control as well as hexanol perturbed) from Chlorobium phaeobacteroides strain CL1401. In Ar-purged acetone, BChle triplets (BChle†) have a lifetime of a few tens of microseconds; however, in air-saturated acetone, quenching of BChle† by ground-state oxygen (O2(3Σ−g)) and formation of O2(1Δg) take place. The O2(1Δg) so formed is susceptible to quenching by BChle0, a ground-state BChle molecule. A Stern–Volmer analysis reveals a linear fit between the decay rate of O2(1Δg) and the BChle concentration. The rate constants for the quenching of O2(1Δg) by BChle0 and for the deactivation of O2(1Δg) by the solvent come out to be kq= (1.4 ± 0.1) × 10^9 M−1 s−1 and k0= (18.5 ± 0.7) × 10^3 s−1, respectively. The absolute quantum yield of O2(1Δg) sensitization by BChle monomers is 0.65 ± 0.15 in air-saturated acetone. In aqueous phase...