Application of immobilized hydrogenase to h2 storage in concentrated solutions of methyl viologen

It has been found that immobilized cells ofC. pasteurianum possessing hydrogenase activity efficiently catalyze reversible reduction of concentrated (up to 0.5M) solutions of methyl viologen with H₂. A 0.5M aqueous solution of methyl viologen dissolves 240 times as much H₂ as pure water under the same pressure of hydrogen. The experimentally obtained levels of methyl viologen reduction and H₂ evolution are in satisfactory agreement with theoretical calculations. The potential of concentrated solutions of methyl viologen containing immobilized hydrogenase as a H₂ storage medium is discussed.     

Continuous hydrogen photoproduction by Chlamydomonas reinhardtii

This study demonstrates, for the first time, that it is possible to couple sulfate-limited Chlamydomonas reinhardtii growth to continuous H₂ photoproduction for more than 4000 h. A two-stage chemostat system physically separates photosynthetic growth from H₂ production, and it incorporates two automated photobioreactors (PhBRs). In the first PhBR, the algal cultures are grown aerobically in chemostat mode under limited sulfate to obtain photosynthetically competent cells. Active cells are then continuously delivered to the second PhBR, where H₂ production occurs under anaerobic conditions. The dependence of the H₂ production rate on sulfate concentration in the medium, dilution rates in the PhBRs, and incident light intensity is reported.     

Amperometric biosensor with HRP immobilized on a sandwiched nano-Au / polymerized m-phenylenediamine film and ferrocene mediator

An amperometric biosensor has been developed for the determination of H₂O₂ in plant samples. Horseradish peroxidase (HRP) is immobilized on a sandwiched nano-Au particle / m-phenylenediamine polymer film by glutaraldehyde cross-linking. The film is formulated on the carbon paste electrode (CPE) blended with ferrocene as an electron transfer mediator. On the low concentration range, the current response is related to the H₂O₂ concentration linearly from 0 to 8×10^-6 M with a detection limit of 1.3×10^-7 M. On a wider concentration range of 8×10^-6 to 1.4×10^-4 M, the reciprocal of current response is linearly related to the reciprocal of H₂O₂ concentration. The apparent Michaelis-Menten constant (K_m^app) was calculated to be 0.0334 mM. The sensor has been tested by determining H₂O₂ concentration in plant leaf samples.     

THE P4 MOLECULE AND P4H+ ION

Abstract

Experimental findings as well as quantum chemical calculations indicate that the P₄ molecule has a remarkably low nucleophilicity. The P₄H₊ ion is predicted to have a ‘proton at apex’ configuration whereas a proton in the centre seems to be metastable. The influence of d orbitals on the stability of P₄ against 2 P₂ and 1/2 P₈, the photoelectron spectrum, and the valence electron density is discussed.     

A novel H(2)O(2) amperometric biosensor based on gold nanoparticles/self-doped polyaniline nanofibers

A new kind of gold nanoparticles/self-doped polyaniline nanofibers (Au/SPAN) with grooves has been prepared for the immobilization of horseradish peroxidase (HRP) on the surface of glassy carbon electrode (GCE). The ratio of gold in the composite nanofibers was up to 64%, which could promote the conductivity and biocompatibility of SPAN and increase the immobilized amount of HRP molecules greatly. The electrode exhibits enhanced electrocatalytic activity in the reduction of H₂O₂ in the presence of the mediator hydroquinone (HQ). The effects of concentration of HQ, solution pH and the working potential on the current response of the modified electrode toward H₂O₂ were optimized to obtain the maximal sensitivity. The proposed biosensor exhibited a good linear response in the range from 10 to 2000 μM with a detection limit of 1.6 μM (S/N = 3) under the optimum conditions. The response showed Michaelis–Menten behavior at larger H₂O₂ concentrations, and the apparent Michaelis–Menten constant K_m was estimated to be 2.21 mM. The detection of H₂O₂ concentration in real sample showed acceptable accuracy with the traditional potassium permanganate titration.     

[RuIII(EDTA)(H2O)]− catalyzed oxidation of biologically important thiols by H2O2

[Ru^III(EDTA)(H₂O)]^? (EDTA^4? = ethylenediaminetetraacetate) catalyzes the oxidation of biological thiols, RSH (RSH = cysteine, glutathione, N-acetylcysteine, penicillamine) using H₂O₂ as precursor oxidant. The kinetics of the oxidation process were studied spectrophotometrically as a function of [Ru^III(EDTA)(H₂O)]^?, [H₂O₂], [RSH], and pH (4–8). Spectral analyses and kinetic data are suggestive of a catalytic pathway in which the RSH reacts with [Ru^III(EDTA)] catalyst complex to form [Ru^III((EDTA)(SR)]^2? intermediate species. In the subsequent reaction step the oxidant, H₂O₂, reacts directly with the coordinated S of the [Ru^III((EDTA)(SR)]^2? intermediate leading to formation of the disulfido (RSSR) oxidation product (identified by HPLC and ESI-MS studies) of thiols (RSH). Based on the experimental results, a working mechanism involving oxo-transfer from H₂O₂ to the coordinated thiols is proposed for the catalytic oxidation.     

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 × 10⁻⁵ to 7.40 × 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.     

Removal of SO2 from Gas Streams by Oxidation using Plasma-Generated Hydroxyl Radicals

The key problem for the removal of SO₂ by electrical discharge methods is how to obtain the hydroxyl radicals at high concentration and large production rates. With the micro-gap discharge method, O₂ and H₂O in simulated gas streams (N₂/O₂/H₂O/SO₂) are ionized into a large number of OH^. radicals to oxidize SO₂ into SO₃ which reacts with H₂O forming H₂SO₄ droplets at 120 °C in the absence of any catalyst or absorbent. The droplets are captured with an electrostatic precipitator. As a result, conversion of SO₂ to primarily H₂SO₄ is limited by the generation of OH^. radicals. By increasing the reduced field and concentrations of O₂ and H₂O, the amount of OH^. radicals increase resulting in more removal of SO₂ from gas streams. The removal efficiency of SO₂ reaches 100% when the residence time is only 0.74 s. Therefore, a new gas-phase oxidation method for removal of SO₂ without NH₃ additive is found.     

A novel nonenzymatic hydrogen peroxide sensor based on MnO2/graphene oxide nanocomposite

A new electrocatalyst, MnO₂/graphene oxide hybrid nanostructure was successfully synthesized for the nonenzymatic detection of H₂O₂. The morphological characterization was examined by scanning electron microscopy and transmission electron microscopy. The MnO₂/graphene oxide based electrodes showed high electrochemical activity for the detection of H₂O₂ in alkaline medium. The nonenzymatic biosensors displayed good performance along with low working potential, high sensitivity, low detection limit, and long-term stability, which could be attributed to the high surface area of graphene oxide providing for the deposition of MnO₂ nanoparticles. These results demonstrate that this new nanocomposite with the high surface area and electrocatalytic activity offers great promise for new class of nanostructured electrode for nonenzymatic biosensor and energy conversion applications.     

Sonocatalytic degradation of C.I. Reactive Red 198 in H2O2-based Systems

This study elucidated the effects of pH on the decolorization of C.I. Reactive Red 198 (RR198) in US, UV/H₂O₂, US/H₂O₂ and UV/US/H₂O₂ systems. The synergistic effects in US/H₂O₂ and UV/US/H₂O₂ systems were also evaluated. At pH 4, 7 and 10, the decolorization rates of RR198 followed the order UV/US/H₂O₂ > UV/H₂O₂ > US > US/H₂O₂.     

Prussian Blue electrodeposited on MWNTs-PANI hybrid composites for H2O2 detection

A Prussian Blue (PB)/polyaniline (PANI)/multi-walled carbon nanotubes (MWNTs) composite film was fabricated by step-by-step electrodeposition on glassy carbon electrode (GCE). The electrode prepared exhibits enhanced electrocatalytic behavior and good stability for detection of H₂O₂ at an applied potential of 0.0 V. The effects of MWNTs thickness, electrodeposition time of PANI and rotating rate on the current response of the composite modified electrode toward H₂O₂ were optimized to obtain the maximal sensitivity. A linear range from 8 × 10⁻⁹ to 5 × 10⁻⁶ M for H₂O₂ detection has been observed at the PB/PANI/MWNTs modified GCE with a correlation coefficient of 0.997. The detection limit is 5 × 10⁻⁹ M on signal-to-noise ratio of 3. To the best of our knowledge, this is the lowest detection limit for H₂O₂ detection. The electrode also shows high sensitivity (526.43 μA μM⁻¹ cm⁻²) for H₂O₂ detection which is more than three orders of magnitude higher than the reported.     

Etude de la deshydratation de Ca(H2PO4)2·H2O et de sa reaction avec CaSO4 par ATD-ATG couplees

The dehydration of Ca(H₂PO₄)₂·H₂O was examined with simultaneous DTA and TG. This dehydration permitted clearly the apparation of the following phases: Ca(H₂PO₄)₂·0.5H₂O, Ca(H₂PO₄)₂, Ca₃(HP₂O₇)₂, Ca₂HP₃O₁₀ et Ca(PO₃)₂. The reaction of Ca(H₂PO₄)₂·H₂O and CaSO₄ was also examined with the same technics. It was found that the decomposition of CaSO₄ takes place for relatively low temperature (between 600°C and 800°C).     

Au Modified F-TiO2 for Efficient Photocatalytic Synthesis of Hydrogen Peroxide

In this work, Au-modified F-TiO₂ is developed as a simple and efficient photocatalyst for H₂O₂ production under ultraviolet light. The Au/F-TiO₂ photocatalyst avoids the necessity of adding fluoride into the reaction medium for enhancing H₂O₂ synthesis, as in a pure TiO₂ reaction system. The F⁻ modification inhibits the H₂O₂ decomposition through the formation of the ≡Ti–F complex. Au is an active cocatalyst for photocatalytic H₂O₂ production. We compared the activity of TiO₂ with F⁻ modification and without F⁻ modification in the presence of Au, and found that the H₂O₂ production rate over Au/F-TiO₂ reaches four times that of Au/TiO₂. In situ electron spin resonance studies have shown that H₂O₂ is produced by stepwise single-electron oxygen reduction on the Au/F-TiO₂ photocatalyst.     

A facile one-pot interfacial synthesis of Pt nanoparticles/polypyrrole composites and their application for non-enzymatic sensing hydrogen peroxide

Pt nanoparticles (PtNPs)/polypyrole (PPy) composites were successfully prepared through a facile one-pot interfacial polymerization of pyrrole by using H₂PtCl₆ as the oxidant for the first time. The as-prepared PPy was granular particles with particle size within a few hundred nanometers, on which PtNPs (1.7–3.5) nm were homogeneously dispersed. The PtNPs/PPy composites displayed excellent electrocatalytic activity toward redox of H₂O₂. The non-enzyme sensor constructed with PtNPs/PPy composites displayed good sensing ability toward H₂O₂ at ?0.1 V with a significantly high sensitivity of 6056 μAmM^?1cm^?2 and a low detection limit of 1.8 μM (S/N = 3).     

AgGaS2-type photocatalysts for hydrogen production under visible light: Effects of post-synthetic H2S treatment

Bulky AgGaS₂ was synthesized as a p-type semiconductor photocatalyst by a conventional solid state reaction under N₂ flow for hydrogen production under visible light. To remove impurity phases involved in the synthesized material and improve crystallinity, the material was treated at various temperatures of 873-1123 K under H₂S flow. Impurity phases were identified as β-Ga₂O₃ and Ag₉GaS₆ with the cell refinements of XRD and the local coordination structure around gallium atom in AgGaS₂ was investigated by EXAFS. As the H₂S-treatment temperature increased, the contribution from impurity phases was diminished. When the temperature reached 1123 K, the impurity phases were completely removed and the material showed the highest photocatalytic activity. Thus, the post-synthetic H₂S treatment could be applied for the synthesis of sulfide-type photocatalysts with high activity.     

Colorimetric detection of hydrogen peroxide and lactate based on the etching of the carbon based Au-Ag bimetallic nanocomposite synthesized by carbon dots as the reductant and stabilizer

In this report, carbon-based gold core silver shell Au-Ag bimetallic nanocomposite (Au-Ag/C NC) was synthesized using carbon dots (C-dots) as the reductant and stabilizer by a facile green sequential reduction approach. The structure and morphology of the nanocomposite are characterized by ultraviolet–visible spectroscopy (UV–Vis), Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM). The as synthesized Au-Ag/C NC exhibits good optic response toward hydrogen peroxide (H₂O₂) without adding any other chromogenic agents. The characteristic surface plasmon resonance (SPR) absorbance peak of Au-Ag/C NC declined and red-shifted with the solution color changing from reddish orange to light pink when adding H₂O₂ owing to the etching effect of H₂O₂ towards Ag. Thus, a simple colorimetric and UV strategy for sensitive detection of H₂O₂ is proposed. It provides the wide linear range for detection of H₂O₂ from 0.8–90 μM and 90–500 μM, and the detection limit was as low as 0.3 μM (S/N = 3). In addition, this colorimetric strategy can also be applied to directly distinguish and detect of lactate by naked eye and UV–Vis. The linear range of colorimetric sensing towards lactate was 0.1–22 μM and 22–220 μM, which was successfully applied in the analysis of lactate in human serum.     

Transformation of 2,4-dichlorophenol by H2O2/UV-C, Fenton and photo-Fenton processes: Oxidation products and toxicity evolution

In the present study, H₂O₂/UV-C, Fenton and photo-Fenton treatment of 2,4-dichlorophenol was compared in terms of oxidation products and acute toxicity. The oxidation products were identified by gas chromatography-mass spectroscopy, high performance liquid chromatography and ion chromatography, whereas changes in acute toxicity were evaluated by the Vibrio fischeri luminescence inhibition assay. H₂O₂/UV-C and photo-Fenton processes ensured complete 2,4-dichlorophenolremoval, detoxification and significant mineralization. Hydroquinone and formic acid were identified as the common oxidation products of the studied advanced oxidation processes investigated. 3,5-dichloro-2-hydroxybenzaldehyde, phenol, 4-chlorophenol and 2,5-dichlorohydroquinone were identified as the additional H₂O₂/UV-C oxidation products of 2,4-dichlorophenol. Acute toxicity decreased with decreasing 2,4-dichlorophenol and increasing chloride release.