Large Field Enhancement of Nanocoral Structures on Porous Si Synthesized from Rice Husks.

Silicon (Si) is a highly abundant, environmentally benign, and durable material and is the most popular semiconductor material; and it is used for the field enhancement of dielectric materials. Porous Si (PSi) exhibits high functionality due to its specific structure. However, the field enhancement of PSi has not been clarified sufficiently. Herein, we present the field enhancement of PSi by the fluorescence intensity enhancement of a dye molecule. The raw material used for producing PSi was rice husk, a biomass material. A nanocoral structure, consisting of spheroidal structures on the surface of PSi, was observed when PSi was subjected to chemical processes and pulsed laser melting, and it demonstrated large field enhancement with an enhancement factor (EF) of up to 545. Confocal microscopy was used for EF mapping of samples before and after laser melting, and the maps were superimposed on nanoscale scanning electron microscope images to highlight the EF effect as a function of microstructure. Nanocoral Si with high EF values were also evaluated by analyzing the porosity from gas adsorption measurements. Nanocoral Si was responsible for the high EF, according to thermodynamic calculations and agreement between experimental and calculation results as determined by Mie scattering theory.

Solar assisted photocatalytic degradation of organic pollutants in the presence of biogenic fluorescent ZnS nanocolloids.

The main aim of this study was to ascertain the photocatalytic degradation of organic pollutants present in aqueous phase using fluorescent biogenic ZnS nanocolloids produced from an endophytic fungus Aspergillus flavus. The degradation studies were carried out using different organic pollutants such as methyl violet (MV), 2,4-dichlorophenoxyacetic acid (2,4-D) and paracetamol (PARA) for 120 min, 270 min and 240 min, respectively, at pH varying from 3.0 to 11.0. The results from this study indicate that the degradation efficiency of ZnS nanocolloids for MV, 2,4-D and PARA were 87%, 33% and 51%, respectively, at the optimum concentration of 100 mg/L of the tested organic pollutants. At different time intervals, the samples were analyzed for their chemical oxygen demand (COD) and total organic carbon (TOC) contents. The reduction of COD and TOC were 78% and 74% for MV at 120 min; 55.5% and 57.2% for 2,4-D at 270 min and 47.6% and 44.5% for PARA at 240 min, respectively. The degradation pathway was determined based on the mass spectrum and the intermediates formed; in addition, the interaction between organic pollutants and nanocolloids was also elucidated based on atomic force microscopy (AFM) and fluorescence spectrum.

A bivalent cationic dye enabling selective photo-inactivation against Gram-negative bacteria.

A piperazine-modified Crystal Violet was found to be able to selectively inactivate Gram-negative bacteria upon visible light irradiation but left Gram-positive bacteria less damaged, which can serve as a blueprint for the development of novel narrow-spectrum agents to replenish the current arsenal of photodynamic antimicrobial chemotherapy (PACT).

Decolorization of Crystal Violet by ultrasound/heterogeneous Fenton process.

Activated-carbon-supported iron oxides were prepared and used as a catalyst in an integrated ultrasound/heterogeneous Fenton process for the decolorization of Crystal Violet. A synergistic effect was observed when ultrasound was combined with the heterogeneous Fenton process. The decolorization efficiency increased with the increasing power density and catalyst dosage, but decreased with the increase of initial pH value. There exists an optimal hydrogen peroxide concentration for decolorization. Catalyst stability was evaluated by measuring iron leaching in solution. The decolorization efficiency was 88% under the optimal conditions. Toxicity test with Daphnia magna showed that the acute toxicity of dye solution decreased significantly after the treatment by the heterogeneous sono-Fenton process.

Investigation of preparation conditions and photocatalytic efficiency of nano ZnO using different polysaccharides.

The development of a complete set of extensive studies combining both the preparation factors of catalysts and photocatalytic experimental factors for the photodegradation of methylene blue, crystal violet, and Congo red using effective nano zinc oxide (ZnO) obtained from polysaccharides (chitosans, corn starch, and sodium alginate) as chelating agents was the main objective of this study. The influence of nature of polysaccharides, ratio of reactants, calcination temperatures during preparation process, and effects of photocatalytic experimental conditions on photodegradation was investigated. Corn starch and sodium alginate were found to be effective chelating agents and optimum preparation parameters were set as 3:3 % ratio of reactants and 450 °C calcination temperature to prepare nano ZnO with good photocatalytic activity. The order of organic dyes based on their photodegradation rates was arranged as crystal violet > methylene blue > Congo red. Our findings shed light on the optimization of both preparation conditions of photocatalysts and photocatalytic experimental conditions.

Mechanistic pathways differences between P25-TiO(2) and Pt-TiO(2) mediated CV photodegradation.

The Crystal Violet (CV) dye represented one of the major triphenylmethane dyes used in textile-processing and some other industrial processes. Various metals doped titanium dioxide (TiO(2)) photocatalysts have been studied intensively for the photodegradation of dye in wastewater treatment. In order to understand the mechanistic detail of the metal dosage on the activities enhancement of the TiO(2) based photocatalyst, this study investigated the CV photodegradation reactions under UV light irradiation using a Pt modified TiO(2) photocatalyst. The results showed that Pt-TiO(2) with 5.8% (W/W) Pt dosage yielded optimum photocatalytic activity. Also the effect of pH value on the CV degradation was well assessed for their product distributions. The degradation products and intermediates were separated and characterized by HPLC-ESI-MS and GC-MS techniques. The results indicated that both the N-de-methylation reaction and the oxidative cleavage reaction of conjugated chromophore structure occurred, but with significantly different intermediates distribution implying that Pt doped TiO(2) facilitate different degradation pathways compared to the P25-TiO(2) system.

Microwave induced catalytic degradation of crystal violet in nano-nickel dioxide suspensions.

Nickel oxide catalyst was obtained by precipitation-oxidation method with the assistance of microwave irradiation. The samples were characterized by X-ray diffraction, Raman spectrophotometer, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, surface area and porosity analyzer. On the basis of the results, the as-prepared product was nano-NiO(2) with OH group and active oxygen. The catalytic activity of the as-prepared product might be attributed to its microwave absorbing property and the role of active oxygen, OH group under microwave irradiation. The microwave induced catalytic degradation process (MICD) with as-prepared product was further applied to degrade triphenylmethane dye crystal violet (CV). 97% of a 100 mg L(-1) sample of CV was rapidly degraded in 5 min with the corresponding 81% TOC removal. The main intermediates were separated and identified by LC-ESI-MS and GC-MS techniques. The LC-ESI-MS analytical results demonstrated that a series of N-de-methylation products were obtained in a stepwise manner, namely mono-, di-, tri-, tetra-, penta-, and hexa-de-methylated CV species. Nine organic acids with benzene ring and four low molecular acids were yielded with the assistance of GC-MS. The proposed degradation pathways were discussed in this study. The degradation processes might include N-de-methylation, destruction of conjugated structure and opening-benzene ring. MICD, as a potential technique with wide application perspective, can be used to purify triphenylmethane dye wastewater with nanosized nickel dioxide.

Radiochromic leuco dye micelle hydrogels: II. Low diffusion rate leuco crystal violet gel.

Radiation-sensitive hydrogels offer the capability of verifying intricate dose distributions in three-dimensional (3D) space conveniently in a single measurement with sub-millimetre spatial resolution. In this study, a new radiochromic hydrogel called leuco crystal violet (LCV) micelle gel is introduced. Upon irradiation, LCV converts to crystal violet (CV(+)). Triton X-100 micelles are used to provide the required hybrid-interfacing environment to dissolve LCV. The diffusion coefficient of the LCV gel has been measured to be 0.036 +/- 0.001 mm(2) h(-1), which is a factor of 25 times less than the standard radiochromic ferrous xylenol-orange (FX) gel; LCV gels without Triton X-100 micelles have a diffusion coefficient of 0.33 +/- 0.02 mm(2) h(-1). The LCV gel formulation contains: 1 mM LCV, 25 mM trichloroacetic acid, 4 mM Triton X-100 and 4% w/w gelatin. The primary innovative feature of this 3D hydrogel is that the radiation-induced CV(+) dye is more soluble in the Triton X-100 micelles than in the surrounding water which consequently leads to more stable post-irradiation dose distributions. A dosimetric characterization revealed that the dose response is reproducible to within 1% over three separate batches, independent of energy, dose rate and dose fractionation but is affected by the temperature ( approximately 4% per degree C) during irradiation. LCV micelle gels scanned optically with a yellow light source are a promising system for 3D dose verification. They may prove to be, especially, useful for scanning large volume dosimeters (i.e. 20 cm) since they are easily manufactured, transparent and near colourless prior to irradiation.

Photocatalytic degradation of dyes in aqueous solution operating in a fluidised bed reactor.

This work reports a preliminary design of a new photochemical reactor and its application to photochemical degradation of two dyes, Crystal Violet and Azure B, operating in both batch and continuous processes. A novel kind of photocatalyst, consisting of ZnO immobilised in alginate gel beads, which is able to photodegrade organic dyes effectively, has been employed in the present study. When this photocatalyst, at a concentration of 1 g of ZnO per litre of alginate gel at 3%, was employed in batch process, almost total decolourisation of Crystal Violet in reaction times lower than 120 min was observed. Operating in continuous process at different residence times, it was possible to achieve a total decolourisation of both Crystal Violet and Azure B. Moreover, the total organic carbon content (TOC) was reduced to 90% in the former and to 52% in the latter. These results indicated that the photoreactor developed in the present work was able to degrade effectively dyes of different structures, revealing the non-specificity of the system.

Effect of self-association and protein binding on the photochemical reactivity of triarylmethanes. Implications of noncovalent interactions on the competition between photosensitization mechanisms type I and type II.

We have explored the photochemical behavior of cationic triarylmethane dye monomers and dimers free in solution and noncovalently bound to bovine serum albumin (BSA) and examined how self-association and the formation of host-guest complexes involving biopolymers and photosensitizers affect the competition between the photosensitization type I and type II mechanisms. Our results have clearly indicated that tri-para-substituted triarylmethane dyes bind efficiently to albumin as monomers and dimers and, interestingly, that the formation of dye aggregates in aqueous solutions is actually assisted by the protein. Protein-assisted dye aggregation takes place under conditions of high biopolymer loading (high [dye]/[protein] ratios), as attested by the appearance of a hypsochromically shifted absorption band (H-band) that overlaps with the spectral shoulder of the respective dye monomer. As predicted by the molecular exciton theory, the intersystem crossing efficiency in H-type dimers is expected to be higher than in the respective dye monomers, and photoinduced electron transfer events are intrinsically favored in dye aggregates as a result of the physical contact between donor and acceptor. We have found that when triarylmethanes are noncovalently bound to BSA their photoreactivity undergoes a remarkable enhancement, and that the photooxidation mechanism type I is particularly favored in the macromolecular environment. A comparative examination of the behavior of triarylmethane dyes with that of methylene blue have shown that in the case of methylene blue the binding phenomenon also favor the type I mechanism.

Prevention of Chagas' disease resulting from blood transfusion by treatment of blood: toxicity and mode of action of gentian violet.

Blood transfusion is the second most important mechanism of transmission of Chagas' disease. Gentian violet, a cationic dye, is currently used in blood banks in endemic areas in attempts to eliminate such transmission. A photodynamic action of gentian violet has been demonstrated in Trypanosoma cruzi. Visible light causes photoreduction of gentian violet to a carbon-centered radical. Under aerobic conditions this free radical autooxidizes generating superoxide anion whose dismutation yields hydrogen peroxide. This photodynamic action of gentian violet is thus probably mediated by the oxygen reduction products. Since irradiation with visible light in the presence of sodium ascorbate reduces the effective dose and time of contact of the dye with T. cruzi-infected blood, a possible application of these findings can be envisaged. In addition to this photodynamic action, an uncoupling effect of gentian violet on mitochondrial oxidative phosphorylation has been described in rat liver and T. cruzi mitochondria. Gentian violet released respiratory control, hindered ATP synthesis, enhanced ATPase activity, released the inhibition of State 3 respiration by oligomycin, and produced swelling of isolated rat liver mitochondria or T. cruzi mitochondria in situ. Taken together, these results indicate that the T. cruzi mitochondrion is the main target of gentian violet toxicity in the dark.

Enhancement of the cytotoxicity of crystal violet against Trypanosoma cruzi in the blood by ascorbate.

Blood transfusion is the second most important mechanism of transmission of Chagas' disease, and crystal violet is currently used in blood banks in endemic areas in attempts to eliminate such transmission. A photodynamic action of crystal violet against Trypanosoma cruzi trypomastigotes in blood has been detected. This action was enhanced by addition of sodium ascorbate. Photoirradiation of whole blood containing crystal violet increased the concentration of ascorbyl radical and the generation of superoxide anion. Similar results were observed in incubations containing ascorbate and crystal violet in the absence of blood. Hydrogen peroxide generation was also detected in these incubations, thus confirming redox cycling of crystal violet under aerobic conditions. Since photoirradiation and addition of sodium ascorbate reduces significantly the effective dose and time of contact of crystal violet with T. cruzi-infected blood, a possible practical application of these findings is envisaged.

Photosensitization by the trypanocidal agent crystal violet. Type I versus type II reactions.

The photoreduction of crystal violet to a carbon-centered radical was detected directly by electron spin resonance (ESR) spectroscopy under anaerobic conditions. The linewidth (0.9 G) of this radical was less broad than the linewidth (11.0 G) of the free radical obtained in Trypanosoma cruzi incubations. No crystal violet radical could be detected under aerobic conditions. However, crystal violet was found to convert oxygen to superoxide anion and hydrogen peroxide in the presence of light. This superoxide anion and hydrogen peroxide formation was greatly enhanced by reducing agents such as NAD(P)H. In addition, irradiation of crystal violet did not generate detectable amounts of singlet oxygen.

Light-enhanced free radical formation and trypanocidal action of gentian violet (crystal violet).

Transmission of Chagas' disease by transfusion of blood containing Trypanosoma cruzi has often been reported, and gentian violet, a triarylmethane dye, is widely used by blood banks in attempts to eliminate such transmission. In a study of intact trypanosomes, gentian violet was found to undergo a one-electron reduction to produce a carbon-centered free radical as demonstrated by electron spin resonance spectroscopy. Either reduced nicotinamide adenine dinucleotide or the reduced dinucleotide phosphate could serve as a source of reducing equivalents for the production of this free radical by homogenates of Trypanosoma cruzi. The formation of this free radical, and the trypanocidal action of gentian violet, were enhanced by light. The enhanced free radical formation may be the basic cause of the selective toxicity of gentian violet to Trypanosoma cruzi.