The catalytic oxidation of phenol with H2O2 by metalloporphyrins as peroxidase mimics

Summary Three metalloporphyrin complexes are used as peroxidase mimics in the oxidation of phenol by hydrogen peroxide.A kinetic model for the titled reaction is constructed.     

Carbon nanodots as peroxidase mimetics and their applications to glucose detection

Carbon nanodots (C-Dots) were found to possess intrinsic peroxidase-like activity, and could catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) by H(2)O(2) to produce a colour reaction. This offers a simple, sensitive and selective colorimetric method for glucose determination in serum.     

Double electropolymer modified platinum electrode to follow the kinetic process H2O2 + ascorbic acid. Influence of the reaction on amperometric biosensor applications

A Pt electrode modified by a polypyrrole/poly(orthophenylenediamine) bilayer membrane able to entrap large molecules such as glucose oxidase was used to investigate (at 27°C and pH 7) the kinetics of ascorbic acid (AA) oxidation by hydrogen peroxide (H₂O₂ + AA → 2H₂O + DAA) by following the H₂O₂ concentration as a function of time. The largely unmatched rejection characteristics of this device towards AA permitted it to operate even in the presence of high AA/H₂O₂ ratios, e.g. 1000: 1. Under these conditions, pseudo-first-order kinetic constant values ranging from 3.26 × 10⁻³ to 4.10 × 10⁻³ s⁻¹ were obtained at [AA] = 2 mM and initial [H₂O₂] = 2 μM. The potential influence of the above reaction on sensitivity and reliability of H₂O₂-detecting biosensors in the presence of AA is discussed critically, taking into account also the recent, and sometimes conflicting, literature views on the problem.     

MOF derived Co3O4/N-doped carbon nanotubes hybrids as efficient catalysts for sensitive detection of H2O2 and glucose

Developing enzyme-free sensors with high sensitivity and selectivity for H2O2 and glucose is highly desirable for biological science.Especially,it is attractive to exploit noble-metal-free nanomaterials with large surface area and good conductivity as highly active and selective catalysts for molecular detection in enzyme-free sensors.Herein,we successfully fabricate hollow frameworks of Co3O4/N-doped carbon nanotubes(Co3O4/NCNTs)hybrids by the pyrolysis of metal-organic frameworks followed by calcination in the air.The as-prepared novel hollow Co3O4/NCNTs hybrids exhibit excellent electrochemical performance for H2O2 reduction in neutral solutions and glucose oxidation in alkaline solutions.As sensor electrode,the Co3O4/NCNTs show excellent non-enzymatic sensing ability towards H2O2 response with a sensitivity of 87.40μA(mmol/L)^-1 cm^-2,a linear range of 5.00μmol/L-11.00 mmol/L,and a detection limitation of 1μmol/L in H2O2 detection,and a good glucose detection performance with 5μmol/L.These excellent electrochemical performances endow the hollow Co3O4/NCNTs as promising alternative to enzymes in the biological applications.     

Amperometric biosensor based on reductive H2O2 detection using pentacyanoferrate-bound polymer for creatinine determination

Pentacyanoferrate-bound poly(1-vinylimidazole) (PVI[Fe(CN)₅]) was selected as a mediator for amperometric creatinine determination based on the reductive H₂O₂ detection. Creatinine amidohydrolase (CNH), creatine amidohydrolase (CRH), sarcosine oxidase (SOD), peroxidase (POD), and PVI[Fe(CN)₅] were crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE) on a glassy carbon (GC) electrode for a creatinine biosensor fabrication. Reduction current was monitored at −0.1 V in the presence of creatinine and O₂. It is revealed that PVI[Fe(CN)₅] is suitable as a mediator for a bioelectrocatalytic reaction of POD, since PVI[Fe(CN)₅] neither reacts with reactants nor works as an electron acceptor of SOD. The amounts of PVI[Fe(CN)₅], PEGDGE, and enzymes were optimized toward creatinine detection. Nafion as a protecting film successfully prevented the enzyme layer from interferences. The detection limit and linear range in creatinine determination were 12 μM and 12–500 μM (R² = 0.993), respectively, and the sensitivity was 11 mA cm⁻² M⁻¹, which is applicable for urine creatinine tests. The results of the creatinine determination for four urine samples measured with this proposed method were compared with Jaffe method, and a good correlation was obtained between the results.     

H2O2-sensitive quantum dots for the label-free detection of glucose

A novel label-free detection system based on CdTe/CdS quantum dots (QDs) was designed for the direct measurement of glucose. Herein we demonstrated that the photoluminescence (PL) of CdTe/CdS QDs was sensitive to hydrogen peroxide (H₂O₂). With d-glucose as a substrate, H₂O₂ that intensively quenched the QDs PL can be produced via the catalysis of glucose oxidase (GOx). Experimental results showed that the decrease of the QDs PL was proportional to the concentration of glucose within the range of 1.8 μM to 1 mM with the detection limit of 1.8 μM under the optimized experimental conditions. In addition, the QD-based label-free glucose sensing platform was adapted to 96-well plates for fluorescent assay, enhancing the capabilities and conveniences of this detection platform. An excellent response to the concentrations of glucose was found within the range of 2-30 mM. Glucose in blood and urine samples was effectively detected via this strategy. The comparison with commercialized glucose meter indicated that this proposed glucose assay system is not only simple, sensitive, but also reliable and suitable for practical application. The high sensitivity, versatility, portability, high-throughput and low cost of this glucose sensor implied its potential in point-of-care clinical diagnose of diabetes and other fields.     

Intrinsic peroxidase-like catalytic activity of nitrogen-doped graphene quantum dots and their application in the colorimetric detection of H2O2 and glucose

In this paper, the highly intrinsic peroxidase-like catalytic activity of nitrogen-doped graphene quantum dots (N-GQDs) is revealed. This activity was greatly dependent on pH, temperature and H₂O₂ concentration. The experimental results showed that the stable N-GQDs could be used for the detection of H₂O₂ and glucose over a wide range of pH and temperature, offering a simple, highly selective and sensitive approach for their colorimetric sensing. The linearity between the analyte concentration and absorption ranged from 20 to 1170 μM for H₂O₂ and 25 to 375 μM for glucose with a detection limit of 5.3 μM for H₂O₂ and 16 μM for glucose. This assay was also successfully applied to the detection of glucose concentrations in diluted serum and fruit juice samples.     

Electrocatalytic H2O2 amperometric detection using gold nanotube electrode ensembles

Arrays of nanoscopic gold tubes were prepared by electroless plating of the metal within the pores of nanoporous polycarbonate track-etched membranes. A procedure for fabricating an ensemble of enzyme-modified nanoelectrodes has been developed based on the efficient immobilization of horseradish peroxidase (HRP) to the gold nanotubes array using self-assembled monolayers (mercaptoethylamine or mercaptopropionic acid) as anchoring layers. Hydrogen peroxide (H₂O₂) was determined electrochemically by using gold nanoelectrode ensembles (NEE) functionalized or not in phosphate buffer solution (PB) with or without a mediator (hydroquinone, H₂Q). Bare NEE displays a remarkable sensitivity (14 μA mM⁻¹ in H₂Q at −0.1 V versus Ag/AgCl) compared to a classical gold macroelectrode (0.41 μA mM⁻¹). The gold nanoparticles that form the tubular structure act as excellent catalytic surfaces towards the oxidation and the reduction of H₂O₂. The HRP modified NEE presents a slightly lower sensitivity (9.5 μA mM⁻¹) than bare NEE. However, this system presents an enhanced limit of detection (up to 4 × 10⁻⁶ M) and a higher selectivity towards the detection of H₂O₂ over a wide range of potentials. The lifetime, fabrication reproducibility and measurement repeatability of the HRP enzyme electrode were evaluated with satisfactory results.     

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.     

Catalytic decomposition of H2O2 on Co3O4 doped with MgO and V2O5

The effects of doping of Co₃O₄with MgO (0.4–6 mol%) and V₂O₅ (0.20–0.75 mol%) on its surface and catalytic properties were investigated using nitrogen adsorption at −196°C and decomposition of H₂O₂ at 30–50°C. Pure and doped samples were prepared by thermal decomposition in air at 500–900°C, of pure basic cobalt carbonate and basic carbonate treated with different proportions of magnesium nitrate and ammonium vanadate. The results revealed that, V₂O₅ doping followed by precalcination at 500–900°C did not much modify the specific surface area of the treated Co₃O₄ solid. Treatment of Co₃O₄ with MgO at 500–900°C resulted in a significant increase in the specific surface area of cobaltic oxide. The catalytic activity in H₂O₂ decomposition, of Co₃O₄ was found to suffer a considerable increase by treatment with MgO. The maximum increase in the catalytic reaction rate constant (k) measured at 40°C on Co₃O₄ due to doping with 3 mol% MgO attained 218, 590 and 275% for the catalysts precalcined at 500, 700 and 900°C, respectively. V₂O₅-doping of Co₃O₄ brought about a significant progressive decrease in its catalytic activity. The maximum decrease in the reaction rate constant measured at 40°C over the 0.75 mol% V₂O₅-doped Co₃O₄ solid attained 68 and 93% for the catalyst samples precalcined at 500 and 900°C, respectively. The doping process did not modify the activation energy of the catalyzed reaction but much modified the concentration of catalytically active constituents without changing their energetic nature. MgO-doping increased the concentration of CO³⁺–CO²⁺ ion pairs and created Mg²⁺–CO³⁺ ion pairs increasing thus the number of active constituents involved in the catalytic decomposition of H₂O₂. V₂O₅-doping exerted an opposite effect via decreasing the number of CO³⁺–CO²⁺ ion pairs besides the possible formation of cobalt vanadate.     

Near-infrared H2O2 production via dual pathways of O2 reduction and H2O oxidation

<正>Hydrogen peroxide(H₂O₂) is a chemical that is widely of interest in both environmental and energy fields. On the one hand, as a clean oxidant, H₂O₂ has been commonly used in the field of bleaching, disinfection, and advanced oxidation processes. On the other hand, H₂O₂ has also been explored as a liquid fuel alternative to H₂ or fossil fuels in fuel cells due to its high energy density. However, the current ind...     

Determination of Calcium and Copper in Feedstuffs by Atomic Absorption Spectrometry Following a Digestion Procedure with H2SO4 + H2O2

Feedstuffs can be effectively dissolved by treatment with concentrated sulfuric acid and 30% hydrogen peroxide in approximately 30 min for the rapid determination of elements at both the 1% level and the trace level by flame and electrothermal atomic absorption spectrometry, respectively. This paper reports a new determinative method for calcium (10 g · kg⁻¹) and copper (10 mg · kg⁻¹) based on this procedure. The relative standard deviation of the results was typically ca. 5%.     

Cross-linked lipoic acid nanocapsules serve as H2O2 amplifier to strengthen the H2O2-sensitive prodrug activation

The H₂O₂ -triggered prodrug activation represents a hot topic while the low H₂O₂ level of cancer cells hindered the complete activation of parent drugs and resulted in the poor therapeutic effect. Here, we developed an H₂O₂ amplifier fabricated by crosslinked lipoic acid nanocapsules(cLANCs), which would selectively elevate the intracellular H₂O₂ level of cancer cells 3.4-fold higher than that of untreated ca...     

Graphene oxide–MnO_2 nanocomposite-modified glassy carbon electrode as an efficient sensor for H_2O_2

In this study, a new facile preparation method of nanocomposites consisting of graphene oxide and manganese dioxide nanowires(GO/MnO_2 NW_s) was developed. The morphology, structure and composition of the resulted products were characterized by transmission electron microscopy, X-ray diffraction and N_2 adsorption and desorption. The GO/MnO_2 nanocomposite was used as an electrode material for non-enzymatic determination of hydrogen peroxide. The proposed sensor exhibits excellent electrocatalytic performance for the determination of hydrogen peroxide in phosphate buffer solution(PBS, pH7) at an applied potential of 0.75 V. The non-enzymatic biosensor for determination of hydrogen peroxide displayed a wide linear range of 4.90 mmol L~(-1)–4.50 mmol L~(-1)with a correlation coefficient of 0.9992, a low detection limit of 0.48 mmol L~(-1) and a high sensitivity of 191.22μA(mmol L~(-1))~(-1)cm~(-2)(signal/noise, S/N = 3). Moreover, the non-enzymatic biosensor shows an excellent selectivity.     

NiCo2O4对H2O2在碱性溶液中电化学还原反应的催化行为

利用溶胶-凝胶法合成纳米NiCo2O4,并利用X射线衍射和透射电镜分析其结构和表面形貌. 结果表明NiCo2O4具有尖晶石结构, 平均粒径约为15 nm. 利用电势线性扫描和恒电势法测定了其对H2O2在碱性溶液中电化学还原反应的催化性能. 发现NiCo2O4对H2O2电化学还原具有高的催化活性和稳定性, 在H2O2浓度低于0.6 mol·L-1时, 其电化学还原反应主要通过直接还原途径进行. 以NiCo2O4为阴极催化剂的Al-H2O2半燃料电池在室温下的开路电压达1.6 V; 在1.0 mol·L-1 H2O2溶液中, 峰值功率密度达209 mW·cm-2, 此时电流密度为220 mA·cm-2.     

Na4H3[SiW9Al3(H2O)3O37]·12H2O/H2O: a new system for selective oxidation of alcohols with H2O2 as oxidant

This work describes a catalytic system consisting of both Na₄H₃[SiW₉Al₃(H₂O)₃O₃₇]·12H₂O(SiW₉Al₃) and water as solvents (a small quantity of organic solvents were used as co-solvent for a few substrates) that can be good for selective oxidation of alcohols to ketones (aldehydes) using 30% H₂O₂ without any phase-transfer catalyst under mild reaction conditions. The catalyst system allows easy product/catalyst separation. Under the given conditions, the secondary hydroxyl group was highly chemoselectively oxidized to the corresponding ketones in good yields in the presence of primary hydroxyl group within the same molecule, and hydroxides are selectively oxidized even in the presence of alkene. Benzylic alcohols were selectively oxidized to the corresponding benzaldehydes in good yields without over oxidation products in solvent-free conditions. Nitrogen, oxygen, sulfur-based moieties, at least for the cases where these atoms are not susceptible to oxidation, do not interfere with the catalytic alcohol oxidation.     

Cu3B2O6/CuB2O4单晶的制备及其可见光催化降解亚甲基蓝

以醋酸铜/硝酸铜和硼酸为原料,柠檬酸作发泡剂,采用溶胶-凝胶法制得了高纯度的单晶结构硼酸铜（Cu₃B₂O₆/CuB₂O₄）. 利用X射线衍射（XRD）、扫描电镜（SEM）、高分辨率透射电镜（HRTEM）、热重-差热分析（TGDTA）等对样品进行了表征,并考察了Cu₃B₂O₆/CuB₂O₄在可见光（400 nm<λ<1100 nm）下对亚甲基蓝（MB）溶液的催化降解性能. 结果表明,两种结构的硼酸铜都具有良好的光催化性能. 当亚甲基蓝的初始浓度为50 mg·L^-1,催化剂用量为1 g·L^-1,光照6 h后,CuB₂O₄对亚甲基蓝的光催化降解率为63.36%,Cu₃B₂O₆对亚甲基蓝的光催化降解率为99.52%. 紫外-可见漫反射光谱（UV-Vis DRS）结果表明,Cu₃B₂O₆的中间能态宽度为1.78 eV,小于CuB₂O₄的中间能态宽度（1.95 eV）,且Cu₃B₂O₆的禁带宽度较窄（E_g=2.34 eV）,不仅可以发生价带顶与中间能态的电子跃迁,同时可以发生禁带间的电子跃迁,所以Cu₃B₂O₆比CuB₂O₄具有更高的可见光催化性能.     

A novel three-dimensional malonate-bridged complex {[Cu4(4,4′- bpy)8(mal)2(H2O)4](ClO4)2(H2O)4(CH3OH)2}n

A novel malonate-bridged copper (II) compound of formula {[Cu₄(4,4′-bpy)₈(mal)₂(H₂O)₄](ClO₄)₂(H₂O)₄(CH₃OH)₂}_n (4,4′-bpy = 4,4′-bipyridine; mal = malonate dianion) has been prepared and structurally characterized by X-ray crystallography. This compound exhibits a novel three-dimensional network being composed of Cu-4,4′-bipyridine layers which are pillared by malonate bridge ligands. The copper(II) ions has two different coordination environment.     

n-Hexane cracking over heteropoly acids, 2. Catalytic activity and thermal stability of H4SiW12O40, H6P2W18O62 and H6P2W21O71(H2O)3

The catalytic activity of three heteropoly acids has been studied in n-hexane cracking. Only H₄SiW₁₂O₄₀ does not decompose into oxides at the reaction temperature. Its acidic form is active in cracking but its dehydration leads to an inactive compound.

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-. H₄SiW₁₂O₄₀ . , .