Enhanced sunlight photocatalytic activity of Ag3PO4 decorated novel combustion synthesis derived TiO2 nanobelts for dye and bacterial degradation

This study demonstrates the synthesis of TiO2 nanobelts using solution combustion derived TiO2 with enhanced photocatalytic activity for dye degradation and bacterial inactivation. Hydrothermal treatment of combustion synthesized TiO2 resulted in unique partially etched TiO2 nanobelts and Ag3PO4 was decorated using the co-precipitation method. The catalyst particles were characterized using X-ray diffraction analysis, BET surface area analysis, diffuse reflectance and electron microscopy. The photocatalytic properties of the composites of Ag3PO4 with pristine combustion synthesized TiO2 and commercial TiO2 under sunlight were compared. Therefore the studies conducted proved that the novel Ag3PO4/unique combustion synthesis derived TiO2 nanobelt composites exhibited extended light absorption, better charge transfer mechanism and higher generation of hydroxyl and hole radicals. These properties resulted in enhanced photodegradation of dyes and bacteria when compared to the commercial TiO2 nanocomposite. These findings have important implications in designing new photocatalysts for water purification.

White luminescence in Dy3+ doped BiOCl phosphors and their Judd-Ofelt analysis

White-light emitting Dy3+ doped layered BiOCl phosphors were synthesized by the solid state route and their structure was confirmed by the Rietveld refinement method. On substitution of Dy3+ ion to Bi3+-site in BiOCl, the photoluminescence spectra exhibit blue (F-4(9/2) -> H-6(15/2)), yellow (F-4(9/2) -> H-6(13/2)) and red (F-4(9/2) -> H-6(11/2)) emissions which function together to generate white light. It was found that the emission intensity increases up to 9 mol% of Dy3+ and then quenched due to dipole-dipole interaction. Judd-Ofelt theory and radiative properties suggest that the present phosphors have a long lifetime, high quantum efficiency, excellent color purity and better stimulated emission cross-section compared to reported Dy3+ doped compounds. The obtained color chromaticity results are close to the National Television System Committee standard and clearly establish the bright prospects of these phosphors in white luminescence. (C) 2015 Elsevier Ltd. All rights reserved.

White luminescence in Dy3+ doped BiOCl phosphors and their Judd-Ofelt analysis

White-light emitting Dy3+ doped layered BiOCl phosphors were synthesized by the solid state route and their structure was confirmed by the Rietveld refinement method. On substitution of Dy3+ ion to Bi3+-site in BiOCl, the photoluminescence spectra exhibit blue (F-4(9/2) -> H-6(15/2)), yellow (F-4(9/2) -> H-6(13/2)) and red (F-4(9/2) -> H-6(11/2)) emissions which function together to generate white light. It was found that the emission intensity increases up to 9 mol% of Dy3+ and then quenched due to dipole-dipole interaction. Judd-Ofelt theory and radiative properties suggest that the present phosphors have a long lifetime, high quantum efficiency, excellent color purity and better stimulated emission cross-section compared to reported Dy3+ doped compounds. The obtained color chromaticity results are close to the National Television System Committee standard and clearly establish the bright prospects of these phosphors in white luminescence. (C) 2015 Elsevier Ltd. All rights reserved.

Stimuli and shape responsive `boron-containing' luminescent organic materials

Recent advancements of material science and its applications have been immensely influenced by the modern development of organic luminescent materials. Among all organic luminogens, boron containing compounds have already established their stature as one of the indispensable classes of luminescent dyes. Boron, in its various forms e. g. triarylboranes, borate dyes and boron clusters, has attracted considerable attention owing to its several unique and excellent photophysical features. In very recent times, beyond the realms of solution-state studies, luminescent boron-containing compounds have emerged as a large and versatile class of stimuli responsive materials. Based on several fundamental concepts of chemistry, researchers have come up with an admirable variety of boron-containing materials with AIE (aggregation-induced emission), mechano-responsive luminescence, thermoresponsive-luminescence as well as a number of purely organic phosphorescent materials and other standalone examples. The unique chemical as well as physical properties of boron-containing compounds are largely responsible for the development of such materials. In this review these new findings are brought together.

Avaliação de Metodologia para Controle e Medição de Cor em Efluentes Têxteis.

Os processos de beneficiamento têxtil, como o alvejamento, a purga, o tingimento e as lavagens são reconhecidamente impactantes ao meio ambiente, tanto do ponto de vista de consumo de água, quanto da geração de efluentes. Os efluentes têxteis oriundos dos processos de beneficiamento se caracterizam por apresentarem elevadas concentrações de substâncias emulsificantes, íons cloreto, sólidos e matéria orgânica, além de alta toxicidade. Mas sem dúvida, o maior problema desses efluentes deve-se a presença de corantes e pigmentos. Alguns parâmetros físico-químicos importantes no controle da poluição hídrica são de difícil medição e consequente monitoramento, principalmente pela ausência de legislação que expresse de maneira clara e objetiva os limites destes parâmetros. Este fato permite avaliações dúbias e contestações aos órgãos ambientais. Especificamente no caso do parâmetro cor, esta subjetividade obriga muitas indústrias a empregarem valores de controle de cor oriundos de outros estados, ou até mesmo de outros países. No Rio de Janeiro, de acordo com a NT-202-R-10 do INEA, o critério para cor é estar virtualmente ausente no efluente. Neste contexto, este estudo avaliou algumas metodologias empregadas na determinação da cor em um efluente têxtil. Para a medição de cor, foram empregadas três metodologias descritas na literatura. A primeira metodologia desenvolvida para análise de água, também utilizada para efluentes líquidos, se baseia em medições espectrofotométricas em um único comprimento de onda padrão (450nm ou 465nm), tendo como referência soluções de Pt-Co. Essa metodologia não abrange todas as tonalidades do espectro de cores possíveis para os efluentes têxteis. O segundo método se baseia na medição em três comprimentos de onda (436, 525 e 620nm), denominado índice DFZ. O último método investiga os valores máximos de absorbância, na faixa entre 350 e 700nm, na amostra. Os resultados obtidos mostraram que as correções dos valores de medição de cor utilizando os valores máximos de absorbância expressaram melhor a realidade dos dados experimentais, visto que eliminam um possível erro causado pela restrita faixa de detecção do método tradicional, numa região do espectro típica para tonalidades encontradas na água.

The synthesis and characterization of novel liquid crystalline, meso-tetra[4-(3,4,5-trialkoxybenzoate)phenyl]porphyrins

Five, novel, meso-tetra[4-(3,4,5-trialkoxybenzoate)phenyl]porphyrins and their metal complexes were synthesized and their molecular structures were confirmed by H-1 NMR, FTIR spectroscopy and elemental analysis. Mesomorphic studies using DSC, polarizing optical microscope and X-ray diffraction revealed that all compounds exhibited thermotropic columnar mesophases over a wide mesophase temperature range and low liquid crystalline-crystal line transition temperature. (c) 2007 Elsevier Ltd. All rights reserved

The synthesis and properties of meso-tetra(4-alkylamidophenyl)porphyrin liquid crystals and their Zn complexes

A series of novel, long-chain-substituted, porphyrin derivatives, meso-tetra (4-alkylamidophenyl) porphyrin ligands and their Zn complexes (alkyl = 8,10,12,14,16,18) were prepared by acylation of the amino groups of 5,10,15,20-tetra(4-aminophenyl)porphyrin by alkyl chloride. Mesomorphism was investigated by DSC, polarized optical microscopy (POM) and X-ray diffraction (XRD). Only ligands containing chains > 12 carbon atoms displayed liquid crystalline behaviour, which exhibited a high phase transition temperature and a broad mesophase temperature span, Zn complexes showed no liquid crystalline behaviour. Cyclic voltammetry, luminescence spectra and surface photovoltage spectroscopy revealed that covalent linking of an alkylamido group to the tetraphenylporphyrin molecule influences, significantly, the properties of the porphyrin macrocycle.

Biomimetic emulators of high potential peroxygenases: Implications in bioremediation and metabolic studies

Nowadays, classical (bio)remediation processes are affected by some economical and environmental drawbacks. These approaches often seem to be inadequate, particularly in the perspective of sustainable green processes. Since immobilized metalloporphines can emulate the active site of peroxidases and peroxygenases, their use in several bioremediation processes has been analyzed in this work. The described catalytic reactions use bioinspired, homogenized or heterogenized, commercial porphines and showed a remarkable ability to catalyze substrates oxidation at the expenses of different oxidants such as Oxone and hydrogen peroxide. The biomimetic catalysts have been also investigated about their peroxidase- and peroxygenase-like catalysis and ability to emulate lignolytic peroxidases action and substrate specificity. The adducts showed a remarkable ability to catalyze veratryl alcohol (widely recognized as a simple model compound of lignin) oxidation at the expenses of H2O2. In the perspective of broadening industrial applications of the described catalysts, the oxidation of several pollutants such as durable textile dyes and inorganic sulfides, has been attempted with quite promising results, and some findings open the way toward industrial scaling-up. Accordingly, the inexpensiveness of the synthesis and the mild operational conditions allow these adducts to be proposed as applicable catalysts also for industrial large-scale processes. Besides, these synthetic models are helpful also to understand the behavior of pharmaceuticals, antifungal drugs in this case, in the environment, and to predict the drug metabolism by cytochromes P450. The biomimetic catalysts, for the studied cases, also proved to be much more efficient than the corresponding enzymes.

Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems

Coloured effluents from textile industries are a problem in many rivers and waterways. Prediction of adsorption capacities of dyes by adsorbents is important in design considerations. The sorption of three basic dyes, namely Basic Blue 3, Basic Yellow 21 and Basic Red 22, onto peat is reported. Equilibrium sorption isotherms have been measured for the three single component systems. Equilibrium was achieved after twenty-one days. The experimental isotherm data were analysed using Langmuir, Freundlich, Redlich-Peterson, Temkin and Toth isotherm equations. A detailed error analysis has been undertaken to investigate the effect of using different error criteria for the determination of the single component isotherm parameters and hence obtain the best isotherm and isotherm parameters which describe the adsorption process. The linear transform model provided the highest R2 regression coefficient with the Redlich-Peterson model. The Redlich-Peterson model also yielded the best fit to experimental data for all three dyes using the non-linear error functions. An extended Langmuir model has been used to predict the isotherm data for the binary systems using the single component data. The correlation between theoretical and experimental data had only limited success due to competitive and interactive effects between the dyes and the dye-surface interactions.

Stratification and Monitoring of Juvenile Idiopathic Arthritis Patients by Synovial Proteome Analysis

Juvenile idiopathic arthritis (JIA) comprises a poorly understood group of chronic, childhood onset, autoimmune diseases with variable clinical outcomes. We investigated whether profiling of the synovial fluid (SF) proteome by a fluorescent dye based, two-dimensional gel (DIGE) approach could distinguish patients in whom inflammation extends to affect a large number of joints, early in the disease process. SF samples from 22 JIA patients were analyzed: 10 with oligoarticular arthritis, 5 extended oligoarticular and 7 polyarticular disease. SF samples were labeled with Cy dyes and separated by two-dimensional electrophoresis. Multivariate analyses were used to isolate a panel of proteins which distinguish patient subgroups. Proteins were identified using MALDI-TOF mass spectrometry with expression further verified by Western immunoblotting and immunohistochemistry. Hierarchical clustering based on the expression levels of a set of 40 proteins segregated the extended oligoarticular from the oligoarticular patients (p <0.05). Expression patterns of the isolated protein panel have also been observed over time, as disease spreads to multiple joints. The data indicates that synovial fluid proteome profiles could be used to stratify patients based on risk of disease extension. These protein profiles may also assist in monitoring therapeutic responses over time and help predict joint damage. © 2009 American Chemical Society.

NMR analysis of Nile Blue (C I Basic Blue 12) and Thionine (C I 52000) in solution

The dyes Nile Blue (C I Basic Blue 12) and Thionine (C I 52000) were examined in both ionic and neutral forms in different solvents using NMR and UV-visible spectroscopy to firmly establish the structures of the molecules and to assess the nature and extent of their aggregation H-1 and C-13 NMR assignments and chemical shift data were used together with nuclear Overhauser effect information to propose a self-assembly structure These data were supplemented with variable temperature dilution and diffusion-based experimental results using H-1 NMR spectroscopy thereby enabling extended aggregate structures to be assessed in terms of the relative strength of self-association and the extent to which extended aggregates could form (C) 2010 Elsevier Ltd All rights reserved

TUNING COLOURIMETRIC AND FLUOROMETRIC GAS SENSORS FOR CARBON-DIOXIDE

The basic theory behind conventional colourimetric and fluorimetric optical sensors for CO2 is examined and special attention is given to the effect on sensor response of the key parameters of initial base concentration and dye acid dissociation constant, K(D). Experimental results obtained in aqueous solution using a variety of different dyes and initial base concentrations are consistent with the predictions made by the theoretical model. A series of model-generated pK(D) versus %CO2 curves for different initial base concentrations allow those interested in constructing an optical CO2 sensor to readily identify the optimum dye/initial base combination for their sensor; the response of the sensor can be subsequently fine-tuned through a minor variation in the initial base concentration. The model and all its predictions appear also to apply to the new generation of plastic film CO2 sensors which have just been developed.

Tunable thermomorphism and applications of ionic liquid analogues of Girard's reagents

A series of ionic liquids based on Girard's reagents was synthesised. Their tunable thermomorphic behaviour with water was demonstrated, and slight modifications in the cationic structure led to drastic changes in their water miscibility. Their phase behaviour, involving monophasic–biphasic transitions, drove a number of practical applications, including scavenging water-soluble dyes and the extraction of metals from water.

A novel fluorescent bisazomethine dye derived from 3-hydroxyquinoxaline-2- carboxaldehyde and 2,3-diaminomaleonitrile

A novel bisazomethine Schiff base was synthesised by the condensation of 3-hydroxyquinoxaline-2- carboxaldehyde and 2,3-diaminomaleonitrile. 1H NMR, 13C NMR, HPLC and FT-IR studies revealed that the compound exists in two major tautomeric forms. The Schiff base exhibits positive absorption and fluorescent solvatochromism and displays dual fluorescence with large stoke shifts. Cyclic voltammetric analysis of the compound in 1:1 methanol–THF was influenced by scan rate. Thermal analysis of the compound was undertaken using TG–DTA and DSC