Polymerization of micelles under irradiation with UV light

Micelle formation behavior of sodium salts of fatty acids containing double bond at the chain end, sodium 10-undecenoate (Na-10-U) and sodium 8-nonenoate (Na-8-N), was examined with measurement of electric conductivity of their aqueous solutions, and the plot of the electric conductivity against the concentration for each fatty acid was found to show two break points; at 0,044 and 0,12mol/1 for Na-10-U and at 0,16 and 0,44 mol/1 for Na-8-N. The similar behaviors of the aqueous solutions were also found with the measurements of the maximum amount of solubilized benzene into the aqueous solution and of the solution viscosity, and the concentrations corresponding to the break points were assumed to be first and second critical micelle concentrations (CMC's), respectively. Polymerization of the sodium salts under irradiation with UV light was investigated. For each fatty acid, the amount of the obtained polymer was very small at very low concentrations of the fatty acid, but it increased rapidly with increasing concentration of the monomer at concentrations higher than the first CMC and then mildly at the concentrations higher than the second CMC. Number-average degrees of polymerization of the polymers obtained were measured with a gel permeation chromatography technique and found to be up to 13 for Na-10-U and 8,5 for Na-8-N.     

Photoassisted oxygenation of alkane catalyzed by ruthenium complexes using 2,6-dichloropyridine N-oxide under visible light irradiation

The chloro(Me(2)SO)ruthenium(II) complexes with tris(2-pyridylmethyl)amine or its derivative catalyses the selective, stereospecific, and photoregulative alkane oxidation in the presence of 2,6-dichloropyridine N-oxide under visible light irradiation.     

Photocatalytic activity of silicon nanowires under UV and visible light irradiation

The communication reports on the high performance of hydrogen-terminated silicon nanowires and silicon nanowires coated with metal (Ag, Cu) nanostructures for the photodegradation of rhodamine B under UV and visible light irradiation.     

Photoassisted degradation of dye pollutants in aqueous TiO2 dispersions under irradiation by visible light

The photoassisted degradation of two dye compounds, erythrosine and rhodamine B, has been investigated in an aqueous TiO₂ dispersion under irradiation by visible light. The compounds can be easily decomposed photochemically by visible light, which provides possibly a new approach for the treatment of dye pollutants in wastewater.     

Chemical analysis of bleach and hydroxide-based solutions after decontamination of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX)

Detailed chemical analysis of solutions used to decontaminate chemical warfare agents can be used to support verification and forensic attribution. Decontamination solutions are amongst the most difficult matrices for chemical analysis because of their corrosive and potentially emulsion-based nature. Consequently, there are relatively few publications that report their detailed chemical analysis. This paper describes the application of modern analytical techniques to the analysis of decontamination solutions following decontamination of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). We confirm the formation of N,N-diisopropylformamide and N,N-diisopropylamine following decontamination of VX with hypochlorite-based solution, whereas they were not detected in extracts of hydroxide-based decontamination solutions by nuclear magnetic resonance (NMR) spectroscopy or gas chromatography-mass spectrometry. We report the electron ionisation and chemical ionisation mass spectroscopic details, retention indices, and NMR spectra of N,N-diisopropylformamide and N,N-diisopropylamine, as well as analytical methods suitable for their analysis and identification in solvent extracts and decontamination residues.     

Fate of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX) on soil following accelerant-based fire and liquid decontamination

In the event of alleged use of organophosphorus nerve agents, all kinds of environmental samples can be received for analysis. These might include decontaminated and charred matter collected from the site of a suspected chemical attack. In other scenarios, such matter might be sampled to confirm the site of a chemical weapon test or clandestine laboratory decontaminated and burned to prevent discovery. To provide an analytical capability for these contingencies, we present a preliminary investigation of the effect of accelerant-based fire and liquid decontamination on soil contaminated with the nerve agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). The objectives were (a) to determine if VX or its degradation products were detectable in soil after an accelerant-based fire promoted by aviation fuel, including following decontamination with Decontamination Solution 2 (DS2) or aqueous sodium hypochlorite, (b) to develop analytical methods to support forensic analysis of accelerant-soaked, decontaminated and charred soil and (c) to inform the design of future experiments of this type to improve analytical fidelity. Our results show for the first time that modern analytical techniques can be used to identify residual VX and its degradation products in contaminated soil after an accelerant-based fire and after chemical decontamination and then fire. Comparison of the gas chromatography–mass spectrometry (GC-MS) profiles of VX and its impurities/degradation products from contaminated burnt soil, and burnt soil spiked with VX, indicated that the fire resulted in the production of diethyl methylphosphonate and O,S-diethyl methylphosphonothiolate (by an unknown mechanism). Other products identified were indicative of chemical decontamination, and some of these provided evidence of the decontaminant used, for example, ethyl 2-methoxyethyl methylphosphonate and bis(2-methoxyethyl) methylphosphonate following decontamination with DS2. Sample preparation procedures and analytical methods suitable for investigating accelerant and decontaminant-soaked soil samples are presented. VX and its degradation products and/or impurities were detected under all the conditions studied, demonstrating that accelerant-based fire and liquid-based decontamination and then fire are unlikely to prevent the retrieval of evidence of chemical warfare agent (CWA) testing. This is the first published study of the effects of an accelerant-based fire on a CWA in environmental samples. The results will inform defence and security-based organisations worldwide and support the verification activities of the Organisation for the Prohibition of Chemical Weapons (OPCW), winner of the 2013 Nobel Peace Prize for its extensive efforts to eliminate chemical weapons.     

Supercritical fluid extraction of chemical warfare agent simulants from soil

Chemical warfare agent simulants are efficiently recovered from 2-ppm spikes in 1 g of Rocky Mountain Arsenal Standard Soil using methanol-carbon dioxide (5:95) at 300 atm for 2 min at 60°C. Recoveries (n = 3) were 79 ± 23% for dimethylmethylphosphonate, 93 ± 14% for 2-chloroethylethyl sulfide, 92 ± 13% for diisopropylfluorophosphate and 95 ± 17% for diisopropylmethylphosphonate. Recoveries are higher than, but less precise than those achieved from a 5-min ultrasonic micro-scale extraction using methanol. Much less laboratory waste is generated than the current standard organic solvent extraction method (33 g of soil shaken with 100 ml of chloroform).     

Corner capping of silsesquioxane cages by chemical warfare agent simulants

The room-temperature uptake and reactivity of gas-phase methyl dichlorophosphate (MDCP) and trichlorophosphate (TCP) within trisilanolphenyl-polyhedral oligomeric silsesquioxane (POSS) Langmuir-Blodgett films are investigated. The halogenated phosphate molecules are found to readily diffuse into and react with the hybrid inorganic-organic silicon-oxide films under ambient conditions. Reflection absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), and fast atom bombardment-mass spectrometry (FAB-MS) measurements suggest that the chlorophosphates undergo hydrolysis with the silanol groups of the POSS LB-film. Substitution and elimination reactions appear to cap the corner of the POSS molecules, leaving a surface-bound phosphoryl group and a resulting structure that is highly stable at elevated temperatures.     

Photodegradation of dye pollutants on TiO_2 pillared bentonites under UV light irradiation

TiO2 pillared bentonite samples dried under different conditions are used to degrade 2,4-dichlorophenol and orange II under UV light irradiation. The supercritical dried sample exhibits a high activity for the photodegradation of 2,4-dichlorophenol and orange II due to its structural features. TOC and COD are measured during the degradation of 2,4-dichlorophenol under UV light irradiation using P25 and TiO2 pillared bentonite samples dried under different conditions. The clay-based catalysts can be readily separated by filtration or sedimentation.     

Ozone synthesis under UV irradiation

The main parameters governing the ozone concentration and the yield of an ozone generator were studied: the power and frequency of the voltage applied to UV lamp, temperature, and humidity of air. The relationship between these parameters and the ozone concentration was established.     

Optimization of various photocatalytic reaction parameters of Degussa P25 under UV irradiation

Solar photocatalysis is an Advanced Oxidation Process (AOP), used as a sustainable green technology for waste water treatment. Material engineering is one of the most widely reported strategies to develop efficient photocatalysts. However, material engineering is a time consuming and costly process. Recently it has been reported that optimization of photocatalytic reaction parameters can also enhance the photocatalytic performance substantially. In this study, an attempt was made to optimize the adsorption/desorption equilibrium and dispersion of the photocatalyst for improving the photocatalytic performance of the commercial photocatalyst Degussa P25 using Methylene Blue as the probe pollutant. The adsorption/desorption equilibrium studies were carried out under various conditions such as with and without stirring and sonication. Effect of dispersion of photocatalyst on photocatalytic performance was studied under various conditions such as stirring, sonication and with the help of homogenization. The result shows that the adsorption/desorption equilibrium was obtained under low stirring condition, within an optimal time of 20–30 min. In the study of the dispersion of photocatalysts to improve the photocatalytic performance, it is seen that dispersion under sonication showed highest photocatalytic performance under UV light irradiation. Interestingly, the use of homogenizer with higher range of rpm was not able to improve the photocatalytic performance of DP25 than stirring at lower range due to the shadow effect. Based on the above result this study gives an overview of the role of dispersion in improving the overall photocatalytic performance of the photocatalysts.     

Microbead chemical switches: an approach to detection of reactive organophosphate chemical warfare agent vapors

In this article, we describe the preparation and application of microbeads that exhibit a "turn on" fluorescence response within seconds of exposure to diethyl chlorophosphate (DCP) vapor. This sensing approach is modeled after the mechanism for acetylcholinesterase enzyme activity inhibition and uses a specific and irreversible reaction between phosphoryl halides and a fluorescent indicator. The microbeads are fabricated by adsorbing fluoresceinamine (FLA) onto carboxylate-functionalized polymer microbeads coated with poly(2-vinylpyridine) (PVP). When the microbeads are subjected to DCP vapor, the conversion of FLA into a phosphoramide causes a rapid and intense fluorescence increase. The PVP layer provides a high density of proton-accepting pyridine nitrogen sites that neutralize the HCl released during the reaction, thereby maintaining high product fluorescence, even after vapor exposure. No significant response is observed when the microbeads are subjected to other nerve agent simulants, a mustard gas simulant, and volatile organics. The size, sensitivity, and subsecond response of these microbeads make them suitable for nerve agent vapor detection and inclusion into microbead sensor arrays.     

Hydrogen bond-mediated recognition of the chemical warfare agent soman (GD)

NMR titration studies in acetonitrile-d(3)/DMSO-d(6) mixtures demonstrate that diindolylurea-based receptors can form complexes with the organophosphorus nerve agent soman in organic solution.     

The Cu- and Zn-complex-catalyzed methanolysis of the chemical warfare nerve agents soman,sarin, and VX

The catalytic methanolysis of the chemical warfare nerve agents soman, sarin, and VX was investigated by using Cu or Zn complexes. Although VX withstood decontamination, the decomposition yield being around 96%, the soman and sarin deposited on different surfaces were almost fully destroyed under ambient conditions. The catalytic tests performed on a wide range of contaminated surfaces confirm the activity of the investigated catalytic systems, these complexes being suitable, from an economical point of view, for use in the formulation of a possible decomposition kit with military or civilian applicability.     

Selective preconcentration of chemical warfare agent degradation products using a zirconia preconcentration column

Zirconia (ZrO(2)) has strong Lewis acid sites which have an affinity for the strongly electronegative phosphonate group of organo-phosphates. To investigate whether this affinity can be used for selective preconcentration, the retention of methyl, ethyl, and propylphosphonic acid (MPA, EPA and PPA) and inorganic anion matrix components on ZrO(2) was investigated. Only organo-phosphates and sulfate exhibited retention on zirconia. After preconcentration, the retained species were eluted from ZrO(2) by 0.75 mM Na(2)CO(3), and separated by a Dionex Ionpac AS11 anion-exchange column (250 mm x 2 mm I.D.) and a Hypercarb RPLC column (50 mm x 4.6 mm I.D., 3 microm) in series followed by suppressed conductivity detection. Calibration curve showed a linear response for MPA, EPA and PPA in the range of 0.01 microM to 1 microM (R(2)>0.9989). Detection limits after preconcentration of a 10 mL sample were 0.16, 0.19 and 0.16 microg/L for MPA, EPA, and PPA, respectively.     

New selenium‐based iniferter agent for living free radical polymerization of styrene under UV irradiation

P,P‐Diphenyl phosphinodiselenoic acid benzyl ester was synthesized and used as a mediator for the polymerization of styrene under UV–vis irradiation. Moderately controlled evidence was found: linear polymerization kinetics, linear evolution of molecular weight with monomer conversion, and relatively narrow molecular weight distribution (1.5–2.0). The structure of the obtained polymers was characterized using NMR and oxidative eliminaton. Based on polymerization results, an iniferter mechanism was proposed for the current polymerization system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A quantum chemical study of reactions of DNA bases with sulphur mustard: a chemical warfare agent

Reactions of the sulphonium ion of sulphur mustard (SM⁺¹) at the N7, N3 and O6 sites of guanine, N7, N3 and N1 sites of adenine, O2 and N3 sites of cytosine and O2 and O4 sites of thymine were studied theoretically in gas phase and aqueous media employing density functional theory (DFT) and second order Møller–Plesset perturbation (MP2) theory. The B3LYP, B3PW91 and B1B95 functionals of DFT and the 6-31+G* and AUG-cc-pVDZ basis sets were used in the calculations. Basis set superposition error was treated using the counterpoise method by single point energy calculations at the B3LYP/6-31+G* level in gas phase. The present study explains the mechanism of alkylation of the DNA bases and shows that SM⁺¹ would form stable adducts at the endocyclic nitrogen sites of the DNA bases, and at the O6 site of guanine and the O2 site of cytosine. Formation of adducts at the N7 site of guanine and N3 site of adenine are found to be most favored and next most favored respectively, which agrees with experimental observations.     

紫外和可见光照射下Fe-TiO2复合材料催化低浓度芳香族有机污染物降解（英文）

Fe‐TiO2 photocatalysts with different ratios of Fe to Ti were prepared by a sol‐gel process using tetra‐n‐butyl titanium and iron(III) nitrate as Ti and Fe sources, respectively. The photocatalytic function of the prepared composites was examined for the decomposition of low‐concentration(0.1 ppm) airborne benzene, toluene, ethyl benzene, and o‐xylene(BTEX). The Fe‐TiO2 composites were characterized by energy dispersive X‐ray spectroscopy, X‐ray diffraction, UV‐visible spectroscopy, and Fourier transform infrared spectroscopy. The time‐series ratios of outlet to inlet concentrations of toluene, ethyl benzene, and o‐xylene target chemicals, as determined by the Fe‐TiO2 composites under visible light exposure, were lower than or similar to those of the reference TiO2 photocatalyst. Moreover, the time‐series ratios of outlet to inlet concentrations of the three compounds, as determined for the Fe‐TiO2 composites, increased as the ratio of Fe to Ti increased from 0.001 to 0.010. In contrast, under UV exposure, the time‐series ratios of outlet to inlet concentrations of BTEX, determined for the Fe‐TiO2 composites, were similar to or higher than those obtained from the reference TiO2 photocatalyst. Fe‐TiO2 composites with an optimal Fe to Ti ratio could effectively be applied for the purification of low‐concentration aromatic organic pollutants.