Assessing the impact of simulated ocean acidification on the photodegradation of selected microplastics.

This study investigated the impact of ocean acidification on the photodegradation of three microplastics (MPs): polypropylene (PP), expanded polystyrene (EPS), and ethylene-vinyl acetate (EVA), under accelerated UV radiation at three pH levels (i.e., 8.1, 7.8, and 7.5), simulating marine conditions. The acidification system simulated current and projected future environmental conditions. As expected, an increase in partial pressure of CO2, total inorganic carbon, bicarbonate ion, and CO2 resulted in more acidic pH levels, with the reverse being true for the carbonate ion. Structural changes of MPs were evaluated, revealing that all weathered samples underwent higher degradation rate compared to the virgin samples. The oxidation state and crystallinity of PP and EVA MPs were higher in samples exposed to the lowest pH, whereas no significant increase in the degradation rate of EPS samples was observed. Saltwater acidification in this study contributed to enhance the photo-oxidation of MPs depending on their polymeric composition.

Evaluation of Steady-State and Time-Resolved Fluorescence Spectroscopy as a Method for Assessing the Impact of Photo-Oxidation on Refined Soybean Oils.

The type of material used in packaging, lighting, and storage time can impact food quality during storage. This study aimed to investigate the progress of photosensitized oxidation in refined soybean oil using steady-state and time-resolved fluorescence spectroscopy. The experiment was conducted through accelerated photo-oxidation with Light-Emitting Diode (LED) in samples stored for ten days at room temperature (26.0 ± 2.0 °C) in clear polyethylene terephthalate (PET) packaging of different colors and different transmission spectra in the UV and visible range. Emission spectra were obtained with excitation at 373, 405, and 500 nm, resulting in two main emission peaks: the first with maximum emission between 430 and 555 nm and the second at around 660 nm. Fluorescence decay curves were obtained with excitation at 340 and 405 nm. The results indicated that transparent PET bottles are not effective in protecting soybean oil from photosensitized oxidation under the studied conditions. Strong correlations were observed between fluorescence parameters and peroxide and conjugated diene values, indicators of lipid oxidation progress. Fluorescence spectroscopy has several advantages over traditional methods as it is a simple, fast, low-cost, and low-waste technique.

Antioxidant pectins from eggplant (Solanum melongena) fruit exocarp, calyx and flesh isolated through high-power ultrasound and sodium carbonate.

Dried and milled eggplant fruit peel and calyces (PC) and mesocarp, placenta and core (Mes) were utilized as natural sources of valuable chemicals. Pectins were extracted with 0.1 M Na2CO3 (1 h; 23 °C). A high-power ultrasound (US) pretreatment (10 min net time; 12.76 W/cm2 power intensity) in 10:200 (g/mL) powder:water ratio led to the lowest solvent and energy consumptions after the subsequent 0.1 M Na2CO3 stirring, permitting the highest recoveries of uronic acid (UA) from PC and Mes (80.25 and 93.8 %, respectively). Homogalacturonans (>65 % w/w UA) of low degree of methylesterification, of acetylation, and 90,214-138,184 Da molecular weights with low polydispersity (≈1.32-1.40) were obtained. They included released ferulate (≈3.5 mg/100 g) esterified pectins. Antioxidants (caffeoylquinic acid, putrescine and spermidine derivatives, ß-carotene, lutein) gave additional technological value to their thickening effect as pectins protected tryptophan, tyrosine, alkyl side chains and sulfhydryl of skim milk proteins from UV-C photo-oxidation.

Preliminary research on metalized phthalocyanines synthesis. Evaluation as potential photosensitizer in photodynamic therapy

SUMMARY Introduction: Phthalocyanines are porphyrin-based dyes. They have plenty applications in different fields, including biomedical and chemical research. From a chemical point of view, Phthalocyanines are macrocyclictetraaza compounds, which mainly are made up of isoindol groups that confer aromaticity and planarity on Phthalocyanine structure. Unlike other kinds of porphyrin compounds, Phthalocyanine structure is able to chelate a lot of metals, which more often contribute to their huge variety of functions, including ROS generation, fluorescence, absorption spectra, and others. Aim: To evaluate phthalocyanines compounds owing their excellent photochemical and pharmaceutical properties that explain their wide use at the clinical and medical level. Methodology: We have carried out a meticulous search for scientific works related to the subject between April 2020 and April 2021, the most of them were written in English. As a result, we can say that, for studying Phthalocyanines' properties, the work can be separated into two issues: synthesis of the metalized phthalocyanines and photochemical and photobiological properties. Results: Phthalocyanines have plenty properties that are desirable to biomedical and pharmaceutical research. Because of their photochemical and photobiological properties, as well as ROS generation, Phthalocyanines are one of the photosenstitizers most widely used in photodynamic therapy. They also have antibacterial, antiviral and anticancer activities. In this sense, Phthalocyanine synthesis and in vitro studies are a very important scientific issue.

Introducción: las ftalocianinas son tintes porfirínicos. Tienen muchas aplicaciones en diferentes campos, incluida la investigación biomédica y química. Desde el punto de vista químico, las ftalocianinas son compuestos macrocíclicos de tetraaza. Se componen principalmente de grupos isoindol que confieren aromaticidad y planaridad a la estructura de la ftalocianina. Esta última es capaz de quelar muchos metales, que con mayor frecuencia contribuyen a su gran variedad de funciones, incluida la generación de EROS, la fluorescencia, los espectros de absorción y otros. Objetivo: evaluar algunos derivados de ftalocianinas gracias a las excelentes propiedades fotoquímicas y farmacéuticas que explican su amplio uso a nivel clínico y médico. Metodología: hemos realizado una búsqueda minuciosa de trabajos científicos relacionados con el tema entre abril de 2020 y abril de 2021, la mayoría de ellos escritos en inglés. Como resultado, podemos decir que, para estudiar las propiedades de las ftalocianinas, el trabajo se puede dividir en dos temas: síntesis de las ftalocianinas metalizadas y propiedades fotoquímicas y ffotobiológicas. Resultados: las ftalocianinas tienen muchas propiedades que son deseables para la investigación biomédica y farmacéutica. Por sus propiedades fotoquímicas y fotobiológicas, así como por la generación de EROS, las ftalocianinas son uno de los fotosensibilizadores más utilizados en terapia fotodinámica. También tienen actividades antibacterianas, antivirales y anticancerígenas. En este sentido, la síntesis de ftalocianina y los estudios in vitro son un tema científico muy importante.

Introdução: as ftalocianinas são corantes à base de porfirinas. Eles têm muitas aplicações em diferentes campos, incluindo pesquisas biomédicas e químicas. Do ponto de vista químico, as ftalocianinas são compostos macrocíclicos tetraaza, que são constituídos principalmente por grupos isoindol que conferem aromaticidade e planaridade à estrutura das ftalocianinas. Ao contrário de outros tipos de compostos de porfirina, a estrutura da ftalocianina é capaz de quelar uma grande quantidade de metais, que mais frequentemente contribuem para sua enorme variedade de funções, incluindo geração de ROS, fluorescência, espectro de absorção e outros. Objetivo: avaliar alguns derivados de ftalocianinas graças às excelentes propriedades fotoquímicas e farmacêuticas que explicam a sua ampla utilização a nível clínico e médico. Metodologia: efetuamos uma busca minuciosa de trabalhos científicos relacionados ao assunto entre abril de 2020 e abril de 2021, a maioria deles redigidos na língua inglesa. Como resultado, podemos dizer que, para estudar as propriedades das ftalocianinas, o trabalho pode ser dividido em duas questões: síntese das ftalocianinas metalizadas e propriedades fotoquímicas e fotobiológicas. Resultados: as ftalocianinas têm muitas propriedades desejáveis para a pesquisa biomédica e farmacêutica. Pelas suas propriedades fotoquímicas e fotobiológicas, além da geração de ROS, as ftalocianinas são um dos ffotossensibilizantes mais amplamente utilizados na terapia fotodinàmica e processos fototóxicos. Eles também têm atividades antibacteriana, antiviral e anticàncer. Nesse sentido, a síntese de ftalocianina e os estudos in vitro são uma questão científica muito importante.

Photochemical Csp2-H bond thiocyanation and selenocyanation of activated arenes, batch and continuous-flow approaches.

Herein, we report an eco-friendly photochemical oxidative Csp2-H thiocyanation and selenocyanation of activated arenes. The reaction proceeds under Violet LED irradiation in the presence of K2S2O8, which quickly oxidizes KSCN and KSeCN, finally producing arylthio/selenocyanates. Using this benign, atom-economic protocol, the desired chalcogenide products were obtained regioselectively, with isolated yields that range from very good to excellent. Although, mechanistic study indicates that it is difficult to distinguish between a radical to a SEAr reaction mechanism between the photo-induced formed •SCN, for the former, or NCSSCN, for the latter, to the aromatic heterocycles. The inhibition experiment together with the observed reactivity and regioselectivity, would be in agreement with the latter. The synthetic methodology designed could be successfully adapted to continuous-flow systems in a segmented-flow regime, employing the organic phase as the product reservoir. Using this setup, the advantage of the latter can be demonstrated by reducing the reaction time and improving the product yields. Similarly, the scaling up of the reaction to gram scale resulted in favorable outcomes by the flow setup, which installs the photo-flow chemistry as a powerful tool to be included into routine reaction procedures, which have great relevance for the pharmaceutical industry.

Effects of natural light and depth on rates of photo-oxidation of dissolved organic carbon in a major black-water river, the Rio Negro, Brazil.

Systems rich in terrigenous dissolved organic carbon (DOC), like the Rio Negro, can contribute significant amounts of carbon dioxide back to the atmosphere and support important microbial communities. We investigated photo-oxidation in the Rio Negro: (1) the depth to which light causes complete photo-oxidation to CO2 and changes in DOC structure, (2) the daily rate of change of absorbance indices, (3) the relationship between sub-surface rates of photo-oxidation to CO2 and light exposure, (4) the areal rates of photo-oxidation, and (5) the stability of fluorophore signals. Experiments were run in an outdoor pool of Rio Negro water, under natural sunlight during the dry seasons of 2015 and 2018. In 2018, rates of complete photo-oxidation and changes in absorbance indices decayed exponentially, approaching their asymptotes between 9 and 15 cm depth. In 2015, direct absorbance indices ceased changing at 14 cm depth. Fluorescence of humic acid-like moieties continued to decrease, sometimes to 35-43 cm depth. This indicates that partial photo-oxidation of DOC, and thus interaction with the microbial community, occurs to greater depths than previously expected. Areal rates of CO2 production were 28.8 and 39.3 mg C m-2 d-1 (two experiments, October 2018). Sub-surface (1.1 cm) rates were strongly related to light levels, reaching a maximum of 0.68 mg C l-1 d-1 in September. Complete photo-oxidation ceased below 29.6 mW cm-2 d-1 UV radiation, providing a daily baseline for observable production of CO2. Absorbance indices changed by 9 to 14% d-1 at high light levels, except for R254/365 (4.4% d-1). Fluorophore emission ranges were stable between 2014 and 2018, indicating that emissions can be compared across time and space. This study contributes to better estimates and understanding of photo-oxidation in tropical, black-water rivers, which will be useful for carbon modelling.

Photo-oxidation of lysozyme triggered by riboflavin is O2-dependent, occurs via mixed type 1 and type 2 pathways, and results in inactivation, site-specific damage and intra- and inter-molecular crosslinks.

Photosensitized protein oxidation is a promising tool for medical procedures such as photochemical tissue bonding (PTB). We have recently reported that the binding of rose Bengal, a sensitizer employed in PTB, to lysozyme modulates the photooxidation and crosslinking of this protein. In this work we examined the photooxidation and crosslinking of lysozyme mediated by riboflavin (RF) an endogenous sensitizer also employed in PTB. We hypothesized that since RF does not bind strongly to proteins, the mechanism(s) and extent of enzymatic inactivation, amino acid modification and protein crosslinking would be dependent on the presence of O2, and differ to that induced by rose Bengal. This hypothesis was tested using UV-visible spectrophotometry, isothermal titration calorimetry (ITC), SDS-PAGE gels, quantification of amino acid consumption, and LC-MS analysis of sites of modification and crosslinks. Under N2, limited damage was detected arising from type 1 (radical) chemistry with formation of specific intra- (Tyr20-Tyr23) and inter- (Tyr23-Trp108) molecular crosslinks. In contrast, the presence of O2 triggered extensive protein damage through mixed type 1 and type 2 (1O2) mechanisms leading to Trp, Met, Tyr and His oxidation, loss of enzymatic activity and protein dimerization. LC-MS analysis provided evidence for crosslinking via radical-radical recombination reactions (Trp28-Tyr53), and secondary reactions involving nucleophilic attack of the side-chain amine of Lys116 on carbonyl groups. Overall, this behavior is in marked contrast to that detected with rose Bengal indicating that the mechanisms and sites of photo-oxidative damage, and consequences for protein function, can be modulated by the choice of sensitizing dye.

Binding of rose bengal to lysozyme modulates photooxidation and cross-linking reactions involving tyrosine and tryptophan.

This work examined the hypothesis that interactions of Rose Bengal (RB2-) with lysozyme (Lyso) might mediate type 1 photoreactions resulting in protein cross-linking even under conditions favoring 1O2 formation. UV-visible spectrophotometry, isothermal titration calorimetry (ITC), and docking analysis were employed to characterize RB2--Lyso interactions, while oxidation of Lyso was studied by SDS-PAGE gels, extent of amino acid consumption, and liquid chromatography (LC) with mass detection (employing tryptic peptides digested in H218O and H2O). Docking studies showed five interaction sites including the active site. Hydrophobic interactions induced a red shift of the visible spectrum of RB2- giving a Kd of 4.8 µM, while data from ITC studies, yielded a Kd of 0.68 µM as an average of the interactions with stoichiometry of 3.3 RB2- per Lyso. LC analysis showed a high consumption of readily-oxidized amino acids (His, Trp, Met and Tyr) located at different and diverse locations within the protein. This appears to reflect extensive damage on the protein probably mediated by a type 2 (1O2) mechanism. In contrast, docking and mass spectrometry analysis provided evidence for the generation of specific intra- (Tyr23-Tyr20) and inter-molecular (Tyr23-Trp62) Lyso cross-links, and Lyso dimer formation via radical-radical, type 1 mechanisms.

Photochemical generation of reactive intermediates from urban-waste bio-organic substances under UV and solar irradiation.

Singlet oxygen (1O2), hydroxyl radicals (•OH), and excited triplet states of organic matter (3OM*) play a key role in the degradation of pollutants in aquatic environments. The formation rates and quantum yields (Φ) of these reactive intermediates (RI) through photosensitized reactions of dissolved organic matter (DOM) have been reported in the literature for decades. Urban biowaste-derived substances (UW-BOS), a form of organic matter derived from vegetative and urban waste, have recently been shown to be efficient sensitizers in the photo-degradation of different contaminants. Nevertheless, no quantitative measurements of photo-oxidant generation by UW-BOS have been reported. In this study, the formation quantum yields of 1O2 and •OH, as well as quantum yield coefficients of TMP degradation (indicative of 3OM* formation), were quantified for two UW-BOS samples, under 254-nm UV radiation or simulated sunlight and compared to a DOM standard from the Suwanee River (SRNOM). Values of Φ for UW-BOS samples ranged from Φ(+1O2) = 8.0 to 8.8 × 10-3, Φ(+•OH) = 4.1 to 4.3 × 10-6, and f TMP = 1.22 to 1.23 × 102 L Einstein-1 under simulated sunlight and from Φ(+1O2) = 1.4 to 2.3 × 10-2, Φ(+•OH) = 1.3 to 3.5 × 10-3, and f TMP = 3.3 to 3.9 × 102 L Einstein-1 under UV. Although UW-BOS are not necessarily better than natural DOM regarding photosensitizing properties, they do sensitize the production of RI and could potentially be used in engineered treatment systems.

Weathering of field-collected floating and stranded Macondo oils during and shortly after the Deepwater Horizon oil spill.

Chemical analysis of large populations of floating (n=62) and stranded (n=1174) Macondo oils collected from the northern Gulf of Mexico sea surface and shorelines during or within seven weeks of the end of the Deepwater Horizon oil spill demonstrates the range, rates, and processes affecting surface oil weathering. Oil collected immediately upon reaching the sea surface had already lost most mass below n-C8 from dissolution of soluble aliphatics, monoaromatics, and naphthalenes during the oil's ascent with further reductions extending up to n-C13 due to the onset of evaporation. With additional time, weathering of the floating and stranded oils advanced with total PAH (TPAH50) depletions averaging 69±23% for floating oils and 94±3% for stranded oils caused by the combined effects of evaporation, dissolution, and photo-oxidation, the latter of which also reduced triaromatic steroid biomarkers. Biodegradation was not evident among the coalesced floating oils studied, but had commenced in some stranded oils.

Avaliação da estabilidade foto-oxidativa dos óleos de canola e de milho em presença de antioxidantes sintéticos / Evaluation of stability photo-oxidative of canola oil and corn oilin the presence of synthetic antioxidants

A estabilidade dos óleos vegetais à oxidação depende do equilíbrio entre a composição e a presença de pró-oxidantes e antioxidantes. O objetivo deste estudo consistiu em avaliar o efeito da presença de antioxidantes sintéticos durante o processo de foto-oxidação dos óleos de canola e milho. As amostras dos óleos de canola e milho em presença e em ausência dos antioxidantes butil-hidroxitolueno (BHA), propil galato (PG) e terc butil-hidroquinona (TBHQ), foram submetidas ao estresse foto-oxidativo. A reação de foto-oxidação seguiu uma cinética de primeira ordem. A constante de velocidade no período de 20 dias de foto-oxidação evidenciou que o antioxidante PG apresentou maior efeito protetor para o óleo de canola e o TBHQ para o óleo de milho. A partir dos dados de UV e RMN de ¹H, no período de 60 dias, constatou-se que os três antioxidantes apresentaram um efeito protetor a foto-oxidação. Os dados de UV evidenciaram aumento de absorção da banda em 232 nm devido à foto-oxidação e formação de dienos conjugados. A redução da intensidade de absorção desta banda na foto-oxidação com o tempo de exposição revelou que a proteção, tanto para o óleo de canola como para o de milho, foi mais efetiva com o antioxidante PG. Os índices de oxidação Roa e fração residual de hidrogênios (H) dialílicos, alílicos e vinílicos também evidenciaram que o antioxidante PG apresentou o melhor desempenho na proteção dos dois tipos de óleo.(AU)

The stability of vegetable oils in relation to oxidation depends on the balance between the composition and the presence of antioxidants and pro-oxidants. The objective of this study was to evaluate the effect of the presence of antioxidants in vegetable oils in the protection of photo-oxidation. Samples of canola oil and corn oil in the presence and absence of the antioxidants, butylated hydroxytoluene (BHA), propyl gallate (PG) and tert-butylhydroquinone (TBHQ), were subjected to photo-oxidative stress at room temperature for 60 days. The photo-oxidation reaction followed a first order kinetics. The rate constant for the period of 20 days of photo-oxidation showed that the PG antioxidant showed greater protective effect for canola oil and TBHQ showed a greater protective effect for corn oil. The UV and ¹H NMR data at 60 days showed that the three antioxidants had a protective effect on photo-oxidation. The UV data showed increased absorption at the 232nm band due to photo-oxidation and the formation of conjugated dienes. The reduction in intensity of this absorption band in photo-oxidation with time of exposure revealed that the protection, both for the canola oil and for the corn oil, was more effective with the PG antioxidant. The rates of Roa oxidation and residual fraction of diallyl, allyl and vinyl hydrogens also showed that the PG antioxidant showed the best performance in protecting both oils.(AU)

Avaliação da estabilidade foto-oxidativa dos óleos de canola e de milho em presença de antioxidantes sintéticos / Evaluation of stability photo-oxidative of canola oil and corn oilin the presence of synthetic antioxidants

A estabilidade dos óleos vegetais à oxidação depende do equilíbrio entre a composição e a presença de pró-oxidantes e antioxidantes. O objetivo deste estudo consistiu em avaliar o efeito da presença de antioxidantes sintéticos durante o processo de foto-oxidação dos óleos de canola e milho. As amostras dos óleos de canola e milho em presença e em ausência dos antioxidantes butil-hidroxitolueno (BHA), propil galato (PG) e terc butil-hidroquinona (TBHQ), foram submetidas ao estresse foto-oxidativo. A reação de foto-oxidação seguiu uma cinética de primeira ordem. A constante de velocidade no período de 20 dias de foto-oxidação evidenciou que o antioxidante PG apresentou maior efeito protetor para o óleo de canola e o TBHQ para o óleo de milho. A partir dos dados de UV e RMN de ¹H, no período de 60 dias, constatou-se que os três antioxidantes apresentaram um efeito protetor a foto-oxidação. Os dados de UV evidenciaram aumento de absorção da banda em 232 nm devido à foto-oxidação e formação de dienos conjugados. A redução da intensidade de absorção desta banda na foto-oxidação com o tempo de exposição revelou que a proteção, tanto para o óleo de canola como para o de milho, foi mais efetiva com o antioxidante PG. Os índices de oxidação Roa e fração residual de hidrogênios (H) dialílicos, alílicos e vinílicos também evidenciaram que o antioxidante PG apresentou o melhor desempenho na proteção dos dois tipos de óleo.

The stability of vegetable oils in relation to oxidation depends on the balance between the composition and the presence of antioxidants and pro-oxidants. The objective of this study was to evaluate the effect of the presence of antioxidants in vegetable oils in the protection of photo-oxidation. Samples of canola oil and corn oil in the presence and absence of the antioxidants, butylated hydroxytoluene (BHA), propyl gallate (PG) and tert-butylhydroquinone (TBHQ), were subjected to photo-oxidative stress at room temperature for 60 days. The photo-oxidation reaction followed a first order kinetics. The rate constant for the period of 20 days of photo-oxidation showed that the PG antioxidant showed greater protective effect for canola oil and TBHQ showed a greater protective effect for corn oil. The UV and ¹H NMR data at 60 days showed that the three antioxidants had a protective effect on photo-oxidation. The UV data showed increased absorption at the 232nm band due to photo-oxidation and the formation of conjugated dienes. The reduction in intensity of this absorption band in photo-oxidation with time of exposure revealed that the protection, both for the canola oil and for the corn oil, was more effective with the PG antioxidant. The rates of Roa oxidation and residual fraction of diallyl, allyl and vinyl hydrogens also showed that the PG antioxidant showed the best performance in protecting both oils.

Interações moleculares na adesão celular em suportes sólidos e o efeito de fotossensibilizadores porfirínicos / Molecular interactions in cell adhesion on solid substrates and the effect of porphyrinic photosensitizers

A adesão celular está ligada à formação e disseminação de metástases, a principal causa de óbito de pacientes diagnosticados com câncer. O objetivo deste trabalho foi investigar in vitro o efeito de fotossensibilizadores na adesão celular. Foram utilizadas porfirinas comerciais (PpIX, CPpI, TSPP, TMPyP e Zn(II)TMPyP) e um fotossensibilizador sintetizado através da ligação de poli-L-lisina à protoporfirina IX (PLLPpIX). A adesão celular foi estudada por RICM, técnica que permite quantificar a área de contato entre uma célula e um substrato por binarização das imagens digitais utilizando limiares apropriados. A técnica foi padronizada e revelou dois regimes de adesão celular: um limitado e outro não limitado pela quantidade de proteína de adesão adsorvida na superfície. Neste último foi observada lise celular. Todos os fotossensibilizadores estudados foram capazes de aumentar a adesão celular na ausência de irradiação comparados ao controle sem fotossensibilizador, o que não havia sido observado nos ensaios de resistência à tripsinização normalmente utilizados para estudar o efeito de fotossensibilizadores na adesão celular. Quanto maior a anfifilicidade do fotossensibilizador, maior foi o efeito na adesão, o que é explicado pela capacidade das moléculas em se intercalarem na membrana, mudando a sua rigidez. Este aumento da adesão no escuro correlaciona com a diminuição da migração segundo ensaios de ferida. A análise do padrão de expressão de integrinas na superfície celular revela que o aumento da adesão correlaciona com o aumento na expressão de αV. Quando os fotossensibilizadores estão concentrados na região perimembranar (1 minuto de incubação) e as células são irradiadas, há um aumento da adesão em relação ao controle sem fotossensibilizador, mas uma diminuição em relação ao controle tratado com o fotossensibilizador e não irradiado, o que implica que a PDT leva a uma diminuição da adesão celular e não a um aumento como reportado na literatura. Com 3h de incubação, PLLPpIX impede a adesão celular, enquanto PpIX praticamente não muda a adesão comparado ao controle não irradiado. Esta ausência do efeito da irradiação sugere que a PpIX afeta a adesão celular principalmente devido a sua intercalação na membrana e não devido à formação de espécies reativas. Com 3h de incubação os fotossensibilizadores não se encontram na membrana e, portanto, o efeito na adesão celular é indireto e também não está relacionado à diferenças na eficiência de internalização. O comportamento observado deve ter relação com diferenças de citolocalização. Outro processo que pode alterar a adesão celular é a oxidação das proteínas do soro fetal bovino. Como observado nos estudos de fotossensibilização de células, PLLPpIX foi capaz de impedir a adesão celular, diferentemente da PpIX. A maior eficiência da PLLPpIX foi associada a presença do polímero, o qual força por questões estéricas que a interação da PLLPpIX com a albumina, o componente majoritário do soro, fique restrita à superfície da proteína, deixando o fotossensibilizador disponível para interagir com o oxigênio molecular e gerar oxigênio singlete. Assim, a funcionalização com um polímero tornou a PpIX capaz de modular a adesão celular tanto agindo dentro da célula quanto na matriz extracelular

Cell adhesion is associated to the formation and spread of metastasis, the leading cause of death in cancer patients. The aim of this study was to investigate, in vitro, the effect of photosensitizers in cell adhesion. Five commercial porphyrins (PpIX, CPpI, TSPP, TMPyP e Zn(II)TMPyP) and Protoporphyrin IX covalently tethered to poli-L-lysine (PLLPpIX) were used. Cell adhesion was mainly studied by RICM, a technique that allows quantifying the contact area between a cell and a substrate for binarization of digital images using appropriate thresholds. The technique was standardized and disclosed two systems for cell adhesion: a system limited by the amount of adhesion proteina adsorbed on the surface and another one no limited, in which cell lysis was observed. All photosensitizers were able to enhance cell adhesion in the absence of irradiation compared to control without photosensitizer, which had not been observed in the trypsinization resistance tests usually used to study the effect of photosensitizers in cell adhesion. The greater the amphiphilicity of the photosensitizer, the greater was the effect on cell adhesion. This is explained by the ability of molecules to fit in the membrane, changing its tension. This increased adhesion correlates with the decrease in migration according to wound healing assays. Analysis of the integrin expression pattern on cell surface reveals that increased adhesion correlates with increased expression of alpha V. When photosensitizers are concentrated in the perimembranar region (1 minute of incubation) and cells are irradiated, there is an increase in adhesion when compared to control without photosensitizer, but a decrease relative to controls treated with the photosensitizer without irradiation, implying that PDT leads to a reduction of cell adhesion and not to an increase as reported in the literature. With 3h of incubation PLLPpIX prevents cell adhesion, while PpIX practically does not change the adhesion compared to dark control. This lack of effect of irradiation suggests that PpIX affects cell adhesion primarily because of its intercalation into the membrane and not due to the formation of reactive species. With 3h of incubation the photosensitizers are not on the membrane and therefore the effect on cell adhesion is indirect and it is not also related to differences in uptake efficiency. The observed behavior must be related to differences in subcellular localization arising from differences in molecular structure. Another process that can alter the cell adhesion is serum protein oxidation. As noted in the studies with cells, photosensitization of serum with PLLPpIX (but not with PpIX) was capable of preventing cell adhesion. The greater efficiency of PLLPpIX was associated with the presence of the polymer, which, by the steric hindrance, forces that interaction of PLLPpIX with albumin, the major serum component, is restricted to the protein surface, leaving the photosensitizer available to interact with molecular oxygen and generate singlet oxygen. Thus, the functionalization of a polymer has turned PpIX capable of modulating cell adhesion by acting both within and outside (in extracellular matrix) the cell

Synthesis, photochemical and photoinduced antibacterial activity studies of meso-Tetra(pyren-1-yl)porphyrin and its Ni, Cu and Zn complexes.

The synthesis of the meso-tetra(pyren-1-yl)porphyrin (1) was successfully accomplished by means of the pyrrole condensation with pyrene-1-carb-aldehyde in acidic media. Its metallization was carried out in an almost quantitative yield to obtain the corresponding complexes of Ni(II) (2), Cu(II) (3) and Zn (4). Their photophysical properties such as fluorescence quantum yield and energy transfer to oxygen for an efficient generation of singlet oxygen were determined. Their photophysical and photochemical properties were compared with those of other similar porphyrin derivatives such as tetraphenylporphyrin and tetranaphthylporphyrin. Photochemical studies on their effectiveness as photosensitizer were carried out by means of the photoinduced oxidation of aromatic alcohols like Î-naphthol to naphthoquinone. The antibacterial photoactivity assay for compounds 1â4 was testeted against Escherichia coli (ATCC 8739) and its proliferation and viability were measured by chemiluminescence. An efficient inactivation of E. coli was observed. This was more efficient for compounds 2 and 3, following the direct relationship to high generation of singlet oxygen by these compounds.