A copper-hydrogen peroxide redox system induces dityrosine cross-links and chemokine oligomerisation

The activity of the chemoattractant cytokines, the chemokines, in vivo is enhanced by oligomerisation and aggregation on glycosaminoglycan (GAG), particularly heparan sulphate, side chains of proteoglycans. The chemokine RANTES (CCL5) is a T-lymphocyte and monocyte chemoattractant, which has a minimum tetrameric structure for in vivo activity and a propensity to form higher order oligomers. RANTES is unusual among the chemokines in having five tyrosine residues, an amino acid susceptible to oxidative cross-linking. Using fluorescence emission spectroscopy, Western blot analysis and LCMS-MS, we show that a copper/H2O2 redox system induces the formation of covalent dityrosine cross-links and RANTES oligomerisation with the formation of tetramers, as well as higher order oligomers. Amongst the transition metals tested, namely copper, nickel, mercury, iron and zinc, copper appeared unique in this respect. At high (400 µM) concentrations of H2O2, RANTES monomers, dimers and oligomers are destroyed, but heparan sulphate protects the chemokine from oxidative damage, promoting dityrosine cross-links and multimer formation under oxidative conditions. Low levels of dityrosine cross-links were detected in copper/H2O2-treated IL-8 (CXCL8), which has one tyrosine residue, and none were detected in ENA-78 (CXCL5), which has none. Redox-treated RANTES was fully functional in Boyden chamber assays of T-cell migration and receptor usage on activated T-cells following RANTES oligomerisation was not altered. Our results point to a protective, anti-oxidant, role for heparan sulphate and a previously unrecognised role for copper in chemokine oligomerisation that may offer an explanation for the known anti-inflammatory effect of copper-chelators such as penicillamine and tobramycin.

Structural characterization of hydrogen peroxide‐oxidized anthracites by X-ray diffraction, Fourier transform infrared spectroscopy, and Raman spectra

The structural characteristics of raw coal and hydrogen peroxide (H2O2)-oxidized coals were investigated using scanning electron microscopy, X-ray diffraction (XRD), Raman spectra, and Fourier transform infrared (FT-IR) spectroscopy. The results indicate that the derivative coals oxidized by H2O2 are improved noticeably in aromaticity and show an increase first and then a decrease up to the highest aromaticity at 24 h. The stacking layer number of crystalline carbon decreases and the aspect ratio (width versus stacking height) increases with an increase in oxidation time. The content of crystalline carbon shows the same change tendency as the aromaticity measured by XRD. The hydroxyl bands of oxidized coals become much stronger due to an increase in soluble fatty acids and alcohols as a result of the oxidation of the aromatic and aliphatic C‐H bonds. In addition, the derivative coals display a decrease first and then an increase in the intensity of aliphatic C‐H bond and present a diametrically opposite tendency in the aromatic C‐H bonds with an increase in oxidation time. There is good agreement with the changes of aromaticity and crystalline carbon content as measured by XRD and Raman spectra. The particle size of oxidized coals (<200 nm in width) shows a significant decrease compared with that of raw coal (1 μm). This study reveals that the optimal oxidation time is ∼24 h for improving the aromaticity and crystalline carbon content of H2O2-oxidized coals. This process can help us obtain superfine crystalline carbon materials similar to graphite in structure.

Crystal structures of the potassium and rubidium salts of (3,5-dichlorophenoxy)acetic acid: Two isotypic coordination polymers

The two-dimensional coordination polymeric structures of the hydrated potassium and rubidium salts of (3,5-dichlorophenoxy)acetic acid, (3,5-D) namely, poly[mu-aqua-bis[mu3-2-(3,5-dichlorophenoxy)acetato]potassium, [K2(C8H5Cl2O3)2 (H2O)]n (I) and poly[mu-aqua-bis[mu3-2-(3,5-dichlorophenoxy)acetato]dirubidium] [Rb2(C8H5Cl2O3)2 (H2O)]n (II), respectively have been determined and are described. The two compounds are isotypic and the polymer is based on centrosymmetric dinuclear bridged complex units. The irregular six-coordination about the metal centres comprises a bridging water molecule lying on a twofold rotation axis, the phenoxy O-atom donor and and a triple bridging carboxylate O-atom of the oxoacetate side chain of the 3,5-D ligand in a bidentate chelate mode, the second carboxy O-donor, also bridging. The K-O and Rb-O bond-length ranges are 2.7238(15)--2.9459(14) and 2.832(2)--3.050(2) \%A respectively and the K...K and Rb...Rb separations in the dinuclear unit are 4.0214(7) and 4.1289(6) \%A, respectively. Within the two-dimensional layers which lie parallel to (100), the coordinated water molecule forms an O---H...O hydrogen bond to the single bridging carboxylate O atom.

A vanadate-stimulated NADH oxidase in erythrocyte membrane generates hydrogen peroxide

Oxidation of NADH by rat erythrocyte plasma membrane was stimulated by about 50-fold on addition of decavanadate, but not other forms of vanadate like orthovanadate, metavanadate aad vanadyl sulphate. The vanadate-stimulated activity was observed only in phosphate buffer while other buffers like Tris, acetate, borate and Hepes were ineffective. Oxygen was consumed during the oxidation of NADH and the products were found to be NAD+ and hydrogen peroxide. The reaction had a stoichiometry of one mole of oxygen consumption and one mole of H2O2 production for every mole of NADH that was oxidized. Superoxide dismutase and manganous inhibited the activity indicating the involvement of superoxide anions. Electron spin resonance in the presence of a spin trap, 5, 5prime-dimethyl pyrroline N-oxide, indicated the presence of superoxide radicals. Electron spin resonance studies also showed the appearance of VIV species by reduction of VV of decavanadate indicating thereby participation of vanadate in the redox reaction. Under the conditions of the assay, vanadate did not stimulate lipid peroxidation in erythrocyte membranes. Extracts from lipid-free preparations of the erythrocyte membrane showed full activity. This ruled out the possibility of oxygen uptake through lipid peroxidation. The vanadate-stimulated NADH oxidation activity could be partially solubilized by treating erythrocyte membranes either with Triton X-100 or sodium cholate. Partially purified enzyme obtained by extraction with cholate and fractionation by ammonium sulphate and DEAE-Sephadex was found to be unstable.

Synthesis and electrocatalytic properties of manganese dioxide for non-enzymatic hydrogen peroxide sensing

Manganese dioxide nanoparticles were synthesized by chemical reduction route at different growth temperatures of 40 degrees C, 80 degrees C, 100 degrees C and were characterized using X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Cyclic Voltammetry (CV) and chronoamperometry (CA) analysis. FESEM results show that on increasing growth temperature the morphology changes from clusters into mixture of rods and flakes. XPS analysis reveals the formation of MnO2. Then these particles were immobilized on Pt electrode. A platinum (Pt) electrode modified with low dimensional MnO2 was investigated as a chronoamperometric (CA) sensor for hydrogen peroxide sensing (H2O2). The sample prepared at 100 degrees C shows good electrocatalytic ability for H2O2 sensing when compared with the samples prepared at 40 degrees C and 80 degrees C. At an operating potential of 0.3 V vs. Ag/AgCl catalytic oxidation of the analyte is measured for chronoamperometric (CA) monitoring. The CA signals are linearly proportional to the concentration of H2O2. It is also found that the morphology of the nanostructure plays a vital role in the detection of H2O2. (C) 2014 Elsevier Ltd. All rights reserved.

MoNi/gamma-Al2O3 Catalyst: Preparation and Catalytic Activity for Acetic Acid Hydrotreating

MoNi/gamma-Al2O3 catalysts were prepared by the impregnation method. The catalyst samples were characterized by XRD and TPR. The effects of Mo promoter content and the catalyst reducing temperature Oil hydrotreatment activity of the catalyst were studied under 200 degrees C and 3 MPa hydrogen pressure using acetic acid as the model compound. The XRD results indicate that the addition of Mo promoter is beneficial to the uniformity of nickel species on the catalyst and decreases the Interaction between nickel species and the support Which results in the decrease the of NiAl2O4 spinel formation. The addition of Mo promoter also decreases the reducing temperature of the catalyst. After the catalyst of 0.06 MoNi/gamma-Al2O3 being reduced Under the atmosphere of H-2/N-2(5/95, V/V), nickel oxide was reduced to Ni-0. The reaction was promoted obviously upon the addition of the MoNi/gamma-Al2O3 catalyst reduced at 600 degrees C. The Mo-modified Ni/gamma-Al2O3 catalyst reduced at 600 degrees C displayed the highest activity during the reaction, the conversion of acetic acid reached the highest point of 33.2%. The products included ethyl acetate and water.

Fluorescence Hydrogen Peroxide Probe Based on a Microstructured Polymer Optical Fiber Modified with a Titanium Dioxide Film

A highly sensitive microstructured polymer optical fiber (MPOF) probe for hydrogen peroxide was made by forming a rhodamine 6G-doped titanium dioxide film on the side walls of array holes in an MPOF. It was found that hydrogen peroxide only has a response to the MPOF probe in a certain concentration of potassium iodide in sulfuric acid solution. The calibration graph of fluorescence intensity versus hydrogen peroxide concentration is linear in the range of 1.6 x 10(-7) mol/L to 9.6 x 10(-5) mol/L. The method, with high sensitivity and a wide linear range, has been applied to the determination of trace amounts of hydrogen peroxide in a few real samples, such as rain water and contact lens disinfectant, with satisfactory results.

Utilizing a CdTe quantum dots-enzyme hybrid system for the determination of both phenolic compounds and hydrogen peroxide

In this paper, we attempt to construct a simple and sensitive detection method for both phenolic compounds and hydrogen peroxide, with the successful combination of the unique property of quantum dots and the specificity of enzymatic reactions. In the presence Of H2O2 and horseradish peroxidase, phenolic compounds can quench quantum dots' photoluminescence efficiently, and the extent of quenching is severalfold to more than 100-fold increase. Quinone intermediates produced from the enzymatic catalyzed oxidation of phenolic compounds were believed to play the main role in the photoluminescence quenching.

Esterification of acetic acid with N-butanol over the catalysts of surface hydrophobicity and lipophobicity

A series of silica-supported silicotungstic acid catalysts (H4SiW12O40, abbreviated as HSiW), modified with various loadings of Teflon (HSiW/SiO2-Teflon), were prepared by impregnation method. The surface properties of the catalysts were studied by means of XRD, BET, NH3-TPD and the Drop Shape Analyzer (DSA) measurements. Both the surface hydrophobicity and the surface lipophobicity of HSiW/SiO2-Teflon catalysts are enhanced by means of the addition of Teflon.

C-60 trianion-mediated electrocatalysis and amperometric sensing of hydrogen peroxide

Heterogeneous electrocatalytic reduction of hydrogen peroxide (H2O2) by C-60 is reported for the first time. C-60 is embedded in tetra octyl ammonium bromide (TOAB) film and is characterized by scanning electron microscopy and cyclic voltammetry. Electrocatalytic studies show that the trianion of C-60 mediates the electrocatalytic reduction of H2O2 in aqueous solution containing 0.1 M KCl. Application of such film modified electrode as an amperometric sensor for H2O2 determination is also examined.

Hydrogen peroxide biosensor based on direct electrochemistry of soybean Peroxidase immobilized on single-walled carbon nanohorn modified electrode

Single-walled carbon nanohorns (SWCNHs) were used as a novel and biocompatible matrix for fabricating biosensing devices. The direct immobilization of acid-stable and thermostable soybean peroxidase (SBP) on SWCNH modified electrode surface can realize the direct electrochemistry of enzyme. Cyclic voltammogram of the adsorbed SBP displays a pair of redox peaks with a formal potential of -0.24V in pH 5 phosphate buffer solution.

Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor

A new amperometric biosensor for hydrogen peroxide was developed based on cross-linking horseradish peroxidase (HRP) by glutaraldehyde with multiwall carbon nanotubes/chitosan (MWNTs/chitosan) composite film coated on a glassy carbon electrode. MWNTs were firstly dissolved in a chitosan solution. Then the morphology of MWNTs/chitosan composite film was characterized by field-emission scanning electron microscopy. The results showed that MWNTs were well soluble in chitosan and robust films could be formed on the surface. HRP was cross-linked by glutaraldehyde with MWNTs/chitosan film to prepare a hydrogen peroxide biosensor. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for H2O2 in the absence of a mediator. The linear range of detection towards H2O2 (applied potential: -0.2 V) was from 1.67 x 10(-5) to 7.40 x 10(-4) M with correction coefficient of 0.998. The biosensor had good repeatability and stability for the determination of H2O2. There were no interferences from ascorbic acid, glucose, citrate acid and lactic acid.

Effects of acetic acid on product selectivity in gas phase oxidative dehydrogenation of cyclohexane

The effect of adding acetic acid on the product distribution in gas phase oxidative dehydrogenation of cyclohexane over alpha(1)-VOPO4 catalyst was investigated. The role of acetic acid in the reaction process was put forward. The proposed mechanism is that acetic acid take precedence of cyclohexane adsorbing on the active sites of alpha(1)-VOPO4 catalyst to form isolated active site. Thus, cyclohexene species can desorb quickly from the active sites, avoiding its deep oxidation dehydrogenation. Almost 100% selectivity to cyclohexene could be obtained when the molar ratio of acetic acid to cyclohexane was 12.9:1 at 450 degrees C, the conversion of cyclohexane was 6.9%.

Mass-transfer kinetics of ytterbium extraction with sec-nonylphenoxy acetic acid

The extraction kinetics of ytterbium with sec-nonylphenoxy acetic acid (CA-100) in heptane have been investigated using a constant interfacial area cell with laminar flow. The influence of stirring speed and temperature on the rate indicated that the extraction rate was controlled by the experiment conditions. The plot of interfacial area on the rate showed a linear relationship. This fact together with the low solubility in water and strong surface activity of CA-100 at heptane-water interfaces made the interface the most probable locale for the chemical reactions. The influences of extractant concentration and hydrogen ion concentration on the extraction rate were investigated, and the forward and reverse rate equations for the ytterbium extraction with CA-100 were also obtained. Based on the experimental data, the apparent forward extraction rate constant was calculated. Interfacial reaction models were proposed that agree well with the rate equations obtained from experimental data.