Zeolite supported gold nanoparticles for selective photooxidation of aromatic alcohols under visible light irradiation

With new photocatalysts of gold nanoparticles supported on zeolite supports (Au/zeolite), oxidation of benzyl alcohol and its derivatives into the corresponding aldehydes can proceed well with a high selectivity (99%) under visible light irradiation at ambient temperature. Au/zeolite photocatalysts were characterized by UV/Vis, XPS, TEM, XRD, EDS, BET, IR, and Raman techniques. The Surface Plasmon Resonance (SPR) effect of gold nanoparticles, the adsorption capability of zeolite supports, and the molecular polarities of aromatic alcohols were demonstrated to have an essential correlation with the photocatalytic performances. In addition, the effects of light intensity, wavelength range, and the role of molecular oxygen were investigated in detail. The kinetic study indicated that the visible light irradiation required much less apparent activation energy for photooxidation compared with thermal reaction. Based on the characterization data and the photocatalytic performances, we proposed a possible photooxidation mechanism.

Ion-molecule reactions of O,S-Dimethyl methylphosphonothioate : Evidence for intramolecular sulfur oxidation during VX perhydrolysis

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

Selective electrochemical epinephrine sensor using self-assembled monomolecular film of 1,8,15,22-tetraaminophthalocyanatonickel(II) on gold electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self-assembled monomolecular film (SAMF) of 1,8,15,22-tetraamino-phthalocyanatonickel(II) (4α-NiIITAPc) on Au electrode. The 4α-NiIITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α-NiIITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α-NiIITAPc SAMF modified electrode was found to be 1.94×10−2 cm s−1 which was much higher than that at the bare Au electrode. Further, it was found that 4α-NiIITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α-NiIITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.

Vapor phase oxidation of ethanol over thorium molybdate catalyst

Ethanol oxidation in the vapor phase was studied in an isothermal flow reactor using thorium molybdate catalyst in the temperature range 220–280 °C. Under these conditions the catalyst was highly selective to acetaldehyde formation. The rate data were well represented by a steady state two-stage redox model given by the equation: View the MathML source The parameters of the above model were estimated by linear and nonlinear least squares methods. In the case of nonlinear estimation the sum of the squares of residuals decreased. The activation energies and preexponential factors for the reduction and oxidation steps of the model, estimated by nonlinear least squares technique are: 9.47 kcal/mole, 9.31 g mole/ (sec) (g cat) (atm) and 9.85 kcal/mole, 0.17 g mole/(sec) (g cat) (atm)0.5, respectively. Oxidations of ethanol and methanol over thorium molybdate catalyst were compared under similar conditions.

Utility of microbes in organic-synthesis - selective transformations of acyclic isoprenoids by aspergillus-niger

Bioconversion of acyclic isoprenoids using a strain of Aspergillus niger results in hydroxylated metabolites with regio- and stereoselectivity. The organism carries out oxidation of the terminal allylic methyl group and the remote double bond in all the compounds tested (I-VII). However, these two activities seem to have preferential structural requirements. When an acyclic isoprenoid with a ketone functionality such as geranylacetone is used as the substrate, the organism also carries out the asymmetric reduction of the keto group. All the metabolites formed have been purified and characterized by conventional spectroscopic methods and quantification has been made by gas chromatographic analyses.

Peroxo-bridged divanadate as selective bromide oxidant in bromoperoxidation

Diperoxovanadate is effective only in presence of free vanadate in vanadium-dependent bromoperoxidation at physiological pH. Peroxide in the form of bridged divanadate complex (VOOV-type), but not the bidentate form as in diperoxovanadate, is proposed to be the oxidant of bromide. In order to obtain direct evidence, peroxo-divanadate complexes with glycyl-glycine, glycyl-alanine and glycyl-asparagine as heteroligands were synthesized. By elemental analysis and spectral studies they were characterized to be triperoxo-divanadates, [V2O2(O-2)(3)(peptide)(3)]. H2O, with the two vanadium atoms bridged by a peroxide and a heteroligand. The dipeptide seems to stabilize the peroxo-bridge by inter-ligand interaction, possibly hydrogen bonding. This is indicated by rapid degradation of these compounds on dissolving in water with partial loss of peroxide accompanied by release of bubbles of oxygen. The V-51-NMR spectra of such solutions showed diperoxovanadate and decavanadate (oligomerized from vanadate) as the products. Additional oxygen was released on treating these solutions with catalase as expected of residual diperoxovanadate. The solid compounds when added to the reaction mixtures showed transient, rapid bromoperoxidation reaction, but not oxidation of NADH or inactivation of glucose oxidase, the other two activities shown by a mixture of diperoxovanadate and vanadyl. This demonstration of peroxide-bridged divanadate as powerful, selective oxidant of bromide, active at physiological pH, should make it a possible candidate of mimic in the action of vanadium in bromoperoxidase proteins.

Performance evaluation of nonthermal plasma reactors for NO oxidation in diesel engine exhaust gas treatment

The discharge plasma-chemical hybrid process for NOinfinity removal from the flue gas emissions is an extremely effective and economical approach in comparison with the conventional selective catalytic reduction system. In this paper we bring out a relative comparison of several discharge plasma reactors from the point of NO removal efficiency. The reactors were either energized by ac or by repetitive pulses. Ferroelectric pellets were used to study the effect of pellet assisted discharges on gas cleaning. Diesel engine exhaust, at different loads; is used to approximately simulate the flue gas composition. Investigations were carried out at room temperature with respect to the variation of reaction products against the discharge power. Main emphasis is laid on the oxidation of NO to NO2, without reducing NOx concentration (i.e., minimum reaction byproducts), with least power consumption. The produced NO2 will be totally converted to N-2 and Na-2 SO4 using Na-2 SO3. The ac packed-bed reactor and pelletless pulsed corona reactor showed better performance, with minimum reaction products for a given power, when the NO concentration was low (similar to 100 ppm). When the engine load exceeds 50% (NO > 300 ppm) there was not much decrease in NO reduction and more or less all the reactors performed equally. The total operating cost of the plasma-chemical hybrid system becomes $4010/ton of NO, which is 1/3-1/5 of the conventional selective catalytic process.

Performance evaluation of nonthermal plasma reactors for NO oxidation in diesel engine exhaust gas treatment

The discharge plasma-chemical hybrid process for NO/sub x/ removal from the due gas emissions is an extremely effective and economical approach in comparison with the conventional selective catalytic reduction system. In this paper we bring out a relative comparison of several discharge plasma reactors from the point of NO removal efficiency. The reactors were either energized by AC or by repetitive pulses. Ferroelectric pellets were used to study the effect of pellet assisted discharges on gas cleaning. Diesel engine exhaust, at different loads, is used to approximately simulate the due gas composition. Investigations were carried out at room temperature with respect to the variation of reaction products against the discharge power. Main emphasis is laid on the oxidation of NO to NO/sub 2/, without reducing NOx concentration (i.e., minimum reaction byproducts), with least power consumption. The produced NO/sub 2/ will be totally converted to N/sub 2/ and Na/sub 2/SO/sub 4/ using Na/sub 2/SO/sub 3/. The AC packed bed reactor and pelletless pulsed corona reactor showed better performance, with minimum reaction products for a given power, when the NO concentration was low (/spl sim/100 ppm). At high engine loads (NO>300 ppm) there was not much decrease in NO/sub x/ reduction and more or less all the reactors performed equally. The paper discusses these observations in detail.

Synthesis of nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) solid solution exhibiting high CO oxidation and water gas shift activity

Nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) has been synthesized using a low temperature sonication method and characterized using XRD, TEM, XPS and H-2-TPR. The potential application of both the solid solutions has been explored as exhaust catalysts by performing CO oxidation. The addition of Si- and Fe-in Ce0.95Ru0.05O2-delta greatly enhanced the reducibility of Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe), as indicated by the H-2-TPR study. The oxygen storage capacity has been used to correlate surface oxygen reactivity to the CO oxidation activity. Both the compounds reversibly release lattice oxygen and exhibit excellent CO oxidation activity with 99% conversion below 200 degrees C. A bifunctional reaction mechanism involving CO oxidation by the extraction of lattice oxygen and rejuvenation of oxide vacancy with gas feed O-2 has been used to correlate experimental data. The performance of both the solid solutions has also been investigated for energy application by performing the water gas shift reaction. The present catalysts are highly active and selective towards the hydrogen production and a lack of methanation activity is an important finding of present study.

Effect of metal oxidation state on FRET: a Cu(I) silent but selectively Cu(II) responsive fluorescent reporter and its bioimaging applications

Copper(II) and copper(I) complexes of a newly designed and crystallographically characterized Schiff base (HL) derived from rhodamine hydrazide and cinnamaldehyde were isolated in pure form formulated as Cu(L)(NO3)] (L-Cu) (1) and Cu(HL)(CH3CN)(H2O)]ClO4 (HL-Cu) (2), and characterized by physicochemical and spectroscopic tools. Interestingly, complex 1 but not 2 offers red fluorescence in solution state, and eventually HL behaves as a Cu(II) ions selective FRET based fluorosensor in HEPES buffer (1 mM, acetonitrile-water: 1/5, v/v) at 25 degrees C at biological pH with almost no interference of other competitive ions. The dependency of the FRET process on the +2 oxidation state of copper has been nicely supported by exhaustive experimental studies comprising electronic, fluorimetric, NMR titration, and theoretical calculations. The sensing ability of HL has been evaluated by the LOD value towards Cu(II) ions (83.7 nM) and short responsive time (5-10 s). Even the discrimination of copper(I) and copper(II) has also been done using only UV-Vis spectroscopic study. The efficacy of this bio-friendly probe has been determined by employing HL to detect the intercellular distribution of Cu(II) ions in HeLa cells by developing image under fluorescence microscope.

Selective growth of single phase VO2(A, B, and M) polymorph thin films

We demonstrate the growth of high quality single phase films of VO2(A, B, and M) on SrTiO3 substrate by controlling the vanadium arrival rate (laser frequency) and oxidation of the V atoms. A phase diagram has been developed (oxygen pressure versus laser frequency) for various phases of VO2 and their electronic properties are investigated. VO2(A) phase is insulating VO2(B) phase is semi-metallic, and VO2(M) phase exhibits a metal-insulator transition, corroborated by photoelectron spectroscopic studies. The ability to control the growth of various polymorphs opens up the possibility for novel (hetero) structures promising new device functionalities. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

MPTP activates ASK1-p38 MAPK signaling pathway through TNF-dependent Trx1 oxidation in parkinsonism mouse model

Activation of apoptosis signal regulating kinase 1 (ASK1)-p38 MAPK death signaling cascade is irn plicated in the death of dopaminergic neurons in substantia nigra in Parkinson's disease (PD). We investigated upstream activators of ASK1 using an MPTP mouse model of parkinsonism and assessed the temporal cascade of death signaling in ventral midbrain (VMB) and striatum (ST). MPTP selectively activated ASK1 and downstream 1)38 MAPK in a time dependent manner in VMB alone. This occurred through selective protein thiol oxidation of the redox-sensitive thiol disulfide oxidoreductase, thiorcdoxin (Trxl), resulting in release of its inhibitory association with ASK1, while glutathione-S-transferase ji 1 (GSTM1) remained in reduced form in association with ASK1. Levels of tumor necrosis factor (TNF), a known activator of ASK1, increased early after MPTP in VMB. Protein ovariation netvvork analysis (PCNA) using protein states as nodes revealed TNF to be an important node regulating the ASK1 signaling cascade. In confirmation, blocking MPTP-mecliated TNF signaling through intrathecal administration of TNFneutralizing antibody prevented Trxl oxidation and downstream ASK1-p38 MAPK activation. Averting an early increase in TNF, which leads to protein thiol oxidation resulting in activation of ASK1-p38 signaling, may be critical for neuroprotection in PD. Importantly, network analysis can help in understanding the cause/effect relationship within protein networks in complex disease states. (C) 2015 Published by Elsevier Inc.

Stimuli-responsive colorimetric and NIR fluorescence combination probe for selective reporting of cellular hydrogen peroxide

Hydrogen peroxide (H2O2) is a key reactive oxygen species and a messenger in cellular signal transduction apart from playing a vital role in many biological processes in living organisms. In this article, we present phenyl boronic acid-functionalized quinone-cyanine (QCy-BA) in combination with AT-rich DNA (exogenous or endogenous cellular DNA), i.e., QCy-BA subset of DNA as a stimuli-responsive NIR fluorescence probe for measuring in vitro levels of H2O2. In response to cellular H2O2 stimulus, QCy-BA converts into QCy-DT, a one-donor-two-acceptor (D2A) system that exhibits switch-on NIR fluorescence upon binding to the DNA minor groove. Fluorescence studies on the combination probe QCy-BA subset of DNA showed strong NIR fluorescence selectively in the presence of H2O2. Furthermore, glucose oxidase (GOx) assay confirmed the high efficiency of the combination probe QCy-BA subset of DNA for probing H2O2 generated in situ through GOx-mediated glucose oxidation. Quantitative analysis through fluorescence plate reader, flow cytometry and live imaging approaches showed that QCy-BA is a promising probe to detect the normal as well as elevated levels of H2O2 produced by EGF/Nox pathways and post-genotoxic stress in both primary and senescent cells. Overall, QCy-BA, in combination with exogenous or cellular DNA, is a versatile probe to quantify and image H2O2 in normal and disease-associated cells.