Polymethine cyanine dyes in beta-cyclodextrin solution: multiple equilibria and chemical oxidation

Absorption and fluorescence spectroscopy, electrochemical techniques, and semiempirical calculations were employed to characterize the multiple complexation equilibria between two polymethine cyanine dyes (IR-786 and Indocyanine green-ICG, 5) and beta-cyclodextrin (beta-CD, L), as well as the chemical reactivity of the complexed and uncomplexed species against the oxidizing agents hypochlorite (HC) and hydrogen peroxide (HP). IR-786 dimerization is favored with the increase in beta-CD concentration in the form of (SL)(2) complexes. In the case of ICG, free dimers (D) and SL complexes are favored. Both IR-786 and ICG react and discolor in the presence of HC and HP. For IR-786, the reaction with HP and HC proceeds with observed rate constants of 10(-3) and 0.28 s(-1) and second-order rate constants (k(2)) of similar to 10(-3) and 10(4) M(-1) s(-1), respectively. The intermediate species observed in the bleaching reactions of IR-786 and ICG were shown, by cyclic voltammetry and VIS absorption, to result from one electron oxidation. IR-786 complexed with beta-CD is protected against bleaching in the presence of HP and HC by factors of 20 and 4, respectively. This protection was not observed in ICG complexes. Superdelocalizability profile of both dyes and frontier orbital analysis indicates that beta-CD does not protect ICG from oxidation by HP or HC, whereas the 2:2 IR-786/beta-Cd complex is able to avoid the oxidation of IR-786. We concluded that the decrease in the chemical reactivity of the dyes against oxidant agents in the presence of beta-CD is due to the formation of (SL)(2) complexes. Copyright (C) 2010 John Wiley & Sons, Ltd.

Single-wall carbon nanotubes modified with organic dyes: Synthesis, characterization and potential cytotoxic effects

This work deals with the covalent functionalization of single-wall carbon nanotubes (SWNTs) with phenosafranine (PS) and Nile Blue (NB) dyes. These dyes can act as photosensitizers in energy and electron transfer reactions, with a potential to be applied in photodynamic therapy. Several changes in the characteristic Raman vibrational features of the dyes suggest that a covalent modification of the nanotubes with the organic dyes occurs. Specifically, the vibrational modes assigned to the NH(2) moieties of the dyes are seen to disappear in the SWNT-dye nanocomposites, corroborating the bond formation between amine groups in the dyes and carboxyl groups in the oxidized nanotubes. The X-ray absorption (XANES) data also show, that the intense band at 398.6 eV attributed to 1s -> 2p pi* transition of the nitrogen of the aromatic PS ring, is shifted due to the bonding with the carbonic structure of the SWNTs. The cytotoxicity data of dyes-modified SWNT composites in the presence and absence of light shows that the SWNT-NB (4 mu g/mL) composite presents a good photodynamic effect, namely a low toxicity in the dark, higher toxicity in the presence of light and also a reduced dye photobleaching by auto-oxidation. (C) 2010 Elsevier B.V. All rights reserved.

Triphenylmethane dyes, an alternative for mediated electronic transfer systems in glucose oxidase biofuel cells

The bioelectrochemical behavior of three triphenylmethane (TPM) dyes commonly used as pH indicators, and their application in mediated electron transfer systems for glucose oxidase bioanodes in biofuel cells was investigated. Bromophenol Blue, Bromothymol Blue, Bromocresol Green were compared bio-electrochemically against two widely used mediators, benzoquinone and ferrocene carboxy aldehyde. Biochemical studies were performed in terms of enzymatic oxidation, enzyme affinity, catalytic efficiency and co-factor regeneration. The different features of the TPM dyes as mediators are determined by the characteristics in the oxidation/reduction processes studied electrochemically. The reversibility of the oxidation/reduction processes was also established through the dependence of the voltammetric peaks with the sweep rates. All three dyes showed good performances compared to the FA and BQ when evaluated in a half enzymatic fuel cell. Potentiodynamic and power response experiments showed maxima power densities of 32.8 mu W cm(-2) for ferrocene carboxy aldehyde followed by similar values obtained for TPM dyes around 30 mu W cm(-2) using glucose and mediator concentrations of 10 mmol L(-1) and 1.0 mmol L(-1), respectively. Since no mediator consumption was observed during the bioelectrochemical process, and also good redox re-cycled processes were achieved, the use of triphenylmethane dyes is considered to be promising compared to other mediated systems used with glucose oxiclase bioanodes and/or biofuel cells. (C) 2011 Elsevier Inc. All rights reserved.

Photocatalytic Decolorization of Commercial Acid Dyes using Solar Irradiation

This work investigates the solar heterogeneous photocatalytic degradation of three commercial acid dyes: Blue 9 (C.I. 42090), Red 51 (C.I. 45430), and Yellow 23 (C.I. 19140). TiO(2) P25 from Degussa was used as the photocatalyst. The dyes were completely degraded within 120 min of treatment in the following increasing order of removal rate: Blue 9 < Yellow 23 < Red 51. The photocatalytic color removal process was well described by a two-first-order in-series reaction, followed by another first-order reaction. Photolytic experiments showed that this process is quite inefficient and highly selective towards Red 51 only. The dyes` solution was completely decolorized and organic matter removals up to 99% were achieved with photocatalysis. The lack of selectivity and the possibility of using solar light to excite the photocatalyst are promising results regarding the feasibility of this technology.

Analytical Assessment of a Home Made Capillary Electrophoresis Equipment with Linear Charge Coupled Device for Visible Light Absorption Detection in the Determination of Food Dyes

The performance of modular home made capillary electrophoresis equipment with spectrophotometric detection, at a visible region by means of a miniaturized linear charge coupled device, was evaluated for the determination of four food dyes. This system presents a simple but efficient home made cell detection scheme. A computer program that converts the spectral data after each run into the electropherograms was developed to evaluate the analytical parameters. The dyes selected for analytical evaluation of the system were Brilliant Blue FCF, Fast Green FCF, Sunset Yellow FCF, and Amaranth. Separation was carried out in a 29cm length and 75 mu m I.D fused silica capillary, using 10mmolL-1 borate buffer at pH 9, with separation voltage of 7.5kV. The detection limits for the dyes were between 0.3 and 1.5mgL-1 and the method presented adequate linearity over the ranges studied, with correlation coefficients greater than 0.99. The method was applied for determination and quantification of these dyes in fruit juices and candies.

Electrochemical degradation of the dye reactive orange 16 using electrochemical flow-cell

Electrochemical removals of color and organic load from solutions containing the dye reactive orange 16 (RO16) were performed in an electrochemical flow-cell, using a platinum working electrode. The influence of the process variables flow-rate, such as NaCl concentration, applied potential and solution pH, were studied. The best color removal achieved was 93% (λ = 493 nm) after 60 min at 2.2 V vs. RHE electrolysis, using 1.00 g L-1 NaCl as supporting electrolyte. The rises in the concentration of NaCl and applied potential increased the color removal rate. The best total organic carbon removal (57%) was obtained at 1.8 V, without the separating membrane, indicating that the ideal conditions for the color removal are not necessarily the same as those to remove the total organic carbon. The degradation efficiency decreased with the solution pH decrease.

The effect of using mixed initiator systems on the efficiency of photopolymerization of dental resins

A study was performed in order to determine the efficiency of the simultaneous use of the photoinitiators phenylpropanedione (PPD) and camphorquinone (CQ) in the polymerization of acrylic polymers and evaluate possible mechanisms leading to synergism or antagonism. It was found that efficiencies of both initiators taken individually are higher than that of their mixture, indicating that when both dyes are used simultaneously there will be an energy transfer from the more efficient initiator (CQ) to the less efficient one (PPD). Also, there was no proof of any reaction between the amine present in the CQ formulation and the PPD excited state.

Degradação de corantes ácidos por processos oxidativos avançados usando um reator com disco rotatório de baixa velocidade

Three technologies were tested (TiO2/UV, H2O2/UV, and TiO2/H2O2/UV) for the degradation and color removal of a 25 mg L-1 mixture of three acid dyes: Blue 9, Red 18, and Yellow 23. A low speed rotating disc reactor (20 rpm) and a H2O2 concentration of 2.5 mmol L-1 were used. The dyes did not significantly undergo photolysis, although they were all degraded by the studied advanced oxidation processes. With the TiO2/H2O2/UV process, a strong synergism was observed (color removal reached 100%). Pseudo first order kinetic constants were estimated for all processes, as well as the respective apparent photonic efficiencies.

Stability of fruit bases and chocolate fillings

Syrups with high sugar content and dehydrated fruits in its composition can be added to chocolate fillings to reduce the need of artificial flavor and dyes attributing a natural appeal to the product. Fruit bases were produced with lyophilized strawberry, passion fruit, and sliced orange peel. Rheological dynamic oscillatory tests were applied to determine the products stability and tendency of shelf life. Values of G´< G´´ were observed for strawberry and passion fruit flavor, whereas values of G´ > G´´ were found for orange flavor during the 90 days of storage. It was observed that shear stress values did not vary significantly suggesting product stability during the studied period. For all fillings, it was found a behavior similar to the fruit base indicating that it has great influence on the filling behavior and its stability. The use of a sugar matrix in fillings provided good shelf life for the fruit base, which could be kept under room temperature conditions for a period as long as one year. The good stability and storage conditions allow the use of fruit base for handmade products as well as for industrialized products.

Comparação da percepção de fadiga e de capacidade para o trabalho entre trabalhadores têxteis de empresas que se encontram em diferentes estágios de responsabilidade social empresarial no estado de São Paulo, Brasil

OBJETIVOS: Comparar as características demográficas e as percepções da capacidade para o trabalho, fadiga e condições de trabalho entre trabalhadores de indústrias têxteis que estejam em diferentes estágios de responsabilidade social empresarial (RSE). MÉTODOS: Em estudo transversal, 126 trabalhadores de três empresas e cinco fábricas responderam a questionário de caracterização demográfica, condições e estilos de vida, a autoavaliações sobre fadiga, condições de trabalho e capacidade para o trabalho. As empresas foram classificadas em dois grupos de pontuação de indicadores de RSE (o grupo um de menor pontuação e o grupo dois de maior pontuação), com base nas respostas dadas em questionário específico. RESULTADOS: Não foram encontradas diferenças (p > 0,05) nos resultados de capacidade para o trabalho, fadiga e na maior parte dos dados demográficos obtidos entre os trabalhadores dos dois grupos. As melhores condições de trabalho, no grupo de maior pontuação (p = 0,008), deveram-se principalmente ao fornecimento de refeições nas fábricas. CONCLUSÕES: O desenvolvimento e a implementação de projetos de RSE não implicam, necessariamente, em melhores condições de trabalho ou em percepções dos trabalhadores de menor fadiga ou maior capacidade para o trabalho, em relação a empresas que não dispõem desses projetos. Por tratar-se de estudo transversal com população reduzida e como a capacidade para o trabalho pode diminuir com o envelhecimento do trabalhador novos estudos, preferencialmente longitudinais, deverão ser realizados, com populações maiores.

Quantificação de tecido conjuntivo do músculo cardíaco em equinos de tração através de técnicas histoquímicas e morfométricas

Os cardiomiócitos são sustentados e inseridos em um esqueleto de tecido conjuntivo, este possui distribuição desigual de acordo com as propriedades das distintas regiões em que se encontra. O propósito deste estudo foi quantificar a proporção de tecido conjuntivo em relação à disposição de cardiomiócitos dos ventrículos direito e esquerdo e no septo interventricular do miocárdio de seis equinos subnutridos, adultos, sendo quatro machos e duas fêmeas, sem raça definida e utilizados para tração. Com auxílio de paquímetro eletrônico digital, avaliou-se a altura do ventrículo esquerdo, a largura do coração, assim como sua circunferência, as espessuras das paredes livres dos ventrículos e do septo interventricular. Os fragmentos relativos ao terço médio do septo interventricular e das paredes livres dos ventrículos foram submetidos à técnica histológica convencional. Os blocos foram cortados com espessura de 5µm e corados com Picrosirius Red, Tricromo de Gomori e Tricromo de Azan para evidenciação do tecido conjuntivo. As lâminas foram analisadas com uso do microscópio óptico digital acoplado ao programa de análise de imagens Image-Pro Plus®. A proporção média de tecido conjuntivo no ventrículo esquerdo foi de 6,1±3,7%, no septo interventricular foi obtida a média de 6,8±3,6% e no ventrículo direito a média foi de 6,1±3,1%. Ao aplicarmos teste H de Kruskal-Wallis, verificamos que ocorreu diferença estatística entre os diferentes corantes utilizados em relação às regiões avaliadas. No teste de correlação de Pearson, não foi encontrado padrão de correlação entre a espessura das regiões analisadas e a proporção de tecido conjuntivo.

Thermo-solvatochromism in binary mixtures of water and ionic liquids: on the relative importance of solvophobic interactions

The thermo-solvatochromism of 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), has been studied in mixtures of water, W, with ionic liquids, ILs, in the temperature range of 10 to 60 degrees C, where feasible. The objectives of the study were to test the applicability of a recently introduced solvation model, and to assess the relative importance of solute-solvent solvophobic interactions. The ILs were 1-allyl-3-alkylimidazolium chlorides, where the alkyl groups are methyl, 1-butyl, and 1-hexyl, respectively. The equilibrium constants for the interaction of W and the ILs were calculated from density data; they were found to be linearly dependent on N(C), the number of carbon atoms of the alkyl group; van't Hoff equation (log K versus 1/T) applied satisfactorily. Plots of the empirical solvent polarities, E(T) (MePMBr(2)) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w), showed non-linear, i.e., non-ideal behavior. The dependence of E(T) (MePMBr(2)) on chi(w), has been conveniently quantified in terms of solvation by W, IL, and the ""complex"" solvent IL-W. The non-ideal behavior is due to preferential solvation by the IL and, more efficiently, by IL-W. The deviation from linearity increases as a function of increasing N(C) of the IL, and is stronger than that observed for solvation of MePMBr(2) by aqueous 1-propanol, a solvent whose lipophilicity is 12.8 to 52.1 times larger than those of the ILs investigated. The dependence on N(C) is attributed to solute-solvent solvophobic interactions, whose relative contribution to solvation are presumably greater than that in mixtures of water and 1-propanol.

Understanding solvation

The effects of solvents on different chemical phenomena, including reactivity, spectroscopic data, and swelling of biopolymers can be rationalized by use of solvatochromic probes, substances whose UV-vis spectra, absorption, or emission are sensitive to the properties of the medium. Thermo-solvatochromism refers to the effect of temperature on solvatochromism. The study of both phenomena sheds light on the relative importance of the factors that contribute to solvation, namely, properties of the probe, those of the solvent (acidity, basicity, dipolarity/polarizability, and lipophilicity), and the temperature. Solvation in binary solvent mixtures is complex because of ""preferential solvation"" of the probe by some component of the mixture. A recently introduced solvent exchange model is based on the presence in the binary solvent mixture of the organic component (molecular solvent or ionic liquid), S, water, W, and a 1:1 hydrogen-bonded species (S-W). Solvation by the latter is more efficient than by its precursor solvents, due to probe-solvent hydrogen-bonding and hydrophobic interactions; dimethyl sulfoxide (DMSO)-W is an exception. Solvatochromic data are employed in order to explain apparently disconnected phenomena, namely, medium effect on the pH-independent hydrolysis of esters, (1)H NMR data of water-ionic liquid (IL) mixtures, and the swelling of cellulose.

A hybrid material assembled by anthocyanins from acai fruit intercalated between niobium lamellar oxide

Organic-inorganic hybrid materials can be prepared dispersing organic species into well-defined inorganic nanoblocks. This paper describes the immobilization of natural dyes from the extract of the Brazilian acai-fruit into two types of layered hexaniobate precursors derived from H(2)K(2)Nb(6)O(17): (i) colloidal dispersion of niobate exfoliated nanoparticles and (ii) niobate pre-intercalated with tetraethylammonium cations (TEA(+)). The restacking of exfoliated particles in the presence of acai anthocyanins promotes their intercalation and produces stacked layers showing large basal spacing (ca. 50 angstrom). The TEA(+) pre-intercalated niobate provides particles with lower content of dye species than the exfoliated precursor but with higher degree of organization and regularity according to X-ray diffraction data and images obtained by electron microscopies. Vibrational (FTIR and Raman) and (13)C NMR spectroscopies indicate the presence of flavylium cations in the hybrid materials and spectral profiles characteristic of glycosylated anthocyanidins. According to thermal analysis results, the purplish hybrids materials are more stable than the free acai-dyes. One hybrid sample was heated under air up to 170 degrees C and maintained at this temperature for 240 min. No weight loss events were observed and the sample retained its original color, indicating that the intercalation of anthocyanin into hexaniobate increases its thermal stability. Considering the structural, chemical, optical and thermal properties of the synthesized hybrid materials, they might be good candidates to be investigated for future specialized applications.

PKC beta II inhibition attenuates myocardial infarction induced heart failure and is associated with a reduction of fibrosis and pro-inflammatory responses

Protein kinase C beta II (PKC beta II) levels increase in the myocardium of patients with end-stage heart failure (HF). Also targeted overexpression of PKC beta II in the myocardium of mice leads to dilated cardiomyopathy associated with inflammation, fibrosis and myocardial dysfunction. These reports suggest a deleterious role of PKC beta II in HF development. Using a post-myocardial infarction (MI) model of HF in rats, we determined the benefit of chronic inhibition of PKC beta II on the progression of HF over a period of 6 weeks after the onset of symptoms and the cellular basis for these effects. Four weeks after MI, rats with HF signs that were treated for 6 weeks with the PKC beta II selective inhibitor (beta IIV5-3 conjugated to TAT(47-57) carrier peptide) (3 mg/kg/day) showed improved fractional shortening (from 21% to 35%) compared to control (TAT(47-57) carrier peptide alone). Formalin-fixed mid-ventricle tissue sections stained with picrosirius red, haematoxylin and eosin and toluidine blue dyes exhibited a 150% decrease in collagen deposition, a two-fold decrease in inflammation and a 30% reduction in mast cell degranulation, respectively, in rat hearts treated with the selective PKC beta II inhibitor. Further, a 90% decrease in active TGF beta 1 and a significant reduction in SMAD2/3 phosphorylation indicated that the selective inhibition of PKC beta II attenuates cardiac remodelling mediated by the TGF-SMAD signalling pathway. Therefore, sustained selective inhibition of PKC beta II in a post-MI HF rat model improves cardiac function and is associated with inhibition of pathological myocardial remodelling.