Affinity‐tuned peroxidase‐like activity of hydrogel‐supported Fe3O4 nanozyme through alteration of crosslinking concentration

In this work, we evaluated the effect of crosslinking concentration on the affinity of poly (2‐acrylamido‐2‐methyl‐1‐propansulfonic acid) (PAMPS) hydrogel‐supported Fe₃O₄ nanozyme towards substrates (tetramethylbenzidine (TMB) and H₂O₂). The peroxidase‐like catalytic activity of PAMPS/Fe₃O₄ nanozyme was discussed with respect to crosslinking concentration of PAMPS hydrogel for the oxidation of TMB in the presence of H₂O₂ at room temperature. High catalytic activity was achieved due to good dispersion of Fe₃O₄ nanozyme in the hydrogel network and strong affinity of PAMPS hydrogel‐supported Fe₃O₄ nanozyme towards substrates. The affinity between the hydrogel‐supported Fe₃O₄ nanozyme and substrates can be improved by regulating the crosslinking concentration of PAMPS hydrogel without other trenchant experimental conditions. In addition, the result indicated that H₂O₂ can be detected even at a concentration as low as 1.5 × 10^?6 mol L^?1 with a linear detection range of 1.5–9.8 × 10^?6 mol L^?1. Such investigations not only showed a new approach to improve the affinity and peroxidase‐like activity of Fe₃O₄ nanozyme, but also verified its potential application in bio‐detection and environmental chemistry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43065.     

Effect of Rare Earth Doping on the Catalytic Activity of Copper‐Containing Hydrotalcites in Phenol Hydroxylation

The copper‐containing hydrotalcites (Cu‐HTLcs) are synthesized under microwave irradiation, the effect of rare earth elements (RE) on the synthesis of Cu‐HTLcs, wherein RE stands for rare earth elements, e.g., La, Y, Sm and Ce, is also investigated in the present work. The hydrotalcite structure of the synthesized samples is verified by XRD and FT‐IR. The results of their catalytic performances in phenol hydroxylation show that the doped rare earth elements can promote the catalytic activity of Cu‐HTLcs, exhibiting a good trend as follows: La>Y>Sm>Ce. XPS results show that the Cu⁺ species are produced after the interaction of La‐Cu‐HTLcs with H₂O₂. Combining with the catalytic test results, we propose a new mechanism about the generation of HO ^. radicals in phenol hydroxylation, it is assumed that HO‐Cu⁺‐OH species are first formed by the reduction of HO‐Cu²⁺‐OH located in hydrotalcites in the presence of H₂O₂, and then react with H₂O₂ to give rise to HO^. radicals.     

Effect of Nano‐Copper Oxide and Copper Chromite on the Thermal Decomposition of Ammonium Perchlorate

The catalytic effect on the thermal decomposition behavior of ammonium perchlorate (AP) of p‐type nano‐CuO and CuCr₂O₄ synthesized by an electrochemical method has been investigated using differential scanning calorimetry as a function of catalyst concentration. The nano‐copper chromite (CuCr₂O₄) showed best catalytic effects as compared to nano‐cupric oxide (CuO) in lowering the high temperature decomposition by 118 °C at 2 wt.‐%. High heat releases of 5.430 and 3.921 kJ g⁻¹ were observed in the presence of nano‐CuO and CuCr₂O₄, respectively. The kinetic parameters were evaluated using the Kissinger method. The decrease in the activation energy and the increase in the rate constant for both the oxides confirmed the enhancement in catalytic activity of AP. A mechanism based on an electron transfer process has also been proposed for AP in the presence of nano‐metal oxides.     

Effects of Ga doping on Pt/CeO2‐Al2O3 catalysts for propane dehydrogenation

This paper describes catalytic consequencesThis paper describes catalytic consequences of Pt/CeO₂‐Al₂O₃ catalysts promoted with Ga species for propane dehydrogenation. A series of PtGa/CeO₂‐Al₂O₃ catalysts were prepared by a sequential impregnation method. The as‐prepared catalysts were characterized employing N₂ adsorption‐desorption, X‐ray diffrtaction, temperature programmed reduction, O₂ volumetric chemisorption, H₂‐O₂ titration, and transmission electron microscopy. We have shown that Ga³⁺ cations are incorporated into the cubic fluorite structure of CeO₂, enhancing both lattice oxygen storage capacity and surface oxygen mobility. The enhanced reducibility of CeO₂ is indicative of higher capability to eliminate the coke deposition and thus is beneficial to the improvement of catalytic stability. Density functional theory calculations confirm that the addition of Ga is prone to improve propylene desorption and greatly suppress deep dehydrogenation and the following coke formation. The catalytic performance shows a strong dependence on the content of Ga addition. The optimal loading content of Ga is 3 wt %, which results in the maximal propylene selectivity together with the best catalytic stability against coke accumulation. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4365–4376, 2016     

Probing Superoxide Dismutases through Radiation Chemistry

Superoxide dismutases (SODs) are metalloenzymes that likely evolved to remove superoxide (O₂^.−) from cells. These enzymes span a range of three uniquely different protein structures and four different metals to enable a similar overall chemistry, the catalytic and accelerated conversion of superoxide to oxygen and hydrogen peroxide. Superoxide dismutases have the attractive feature that the substrate (O₂^.−) for the catalytic reaction is easily generated using radiation chemistry, allowing the ability to follow catalysis on a fast time scale under a wide variety of conditions. This review will show how the utility of radiation chemistry was realized and enabled mechanistic understanding immediately upon discovery of these enzymes. It will then highlight some applications of pulse radiolysis, carried out in this laboratory, that illustrate mechanistic details of the enzyme function for a variety of wild-type and mutant superoxide dismutases.     

A Single Mutation Increases the Activity and Stability of Pectobacterium carotovorum Nitrile Reductase

Nitrile reductases are considered to be promising and environmentally benign nitrile‐reducing biocatalysts to replace traditional metal catalysts. Unfortunately, the catalytic efficiencies of the nitrile reductases reported so far are very low. To date, all attempts to increase the catalytic activity of nitrile reductases by protein engineering have failed. In this work, we successfully increased the specific activity of a nitrile reductase from Pectobacterium carotovorum from 354 to 526 U g_prot^?1 by engineering the substrate binding pocket; moreover, the thermostability was also improved (≈2‐fold), showing half‐lives of 140 and 32 h at 30 and 40 °C, respectively. In the bioreduction of 2‐amino‐5‐cyanopyrrolo[2,3‐d]pyrimidin‐4‐one (preQ₀) to 2‐amino‐5‐aminomethylpyrrolo[2,3‐d]pyrimidin‐4‐one (preQ₁), the variant was advantageous over the wild‐type enzyme with a higher reaction rate and complete conversion of the substrate within a shorter period. Homology modeling and docking analysis revealed some possible origins of the increased activity and stability. These results establish a solid basis for future engineering of nitrile reductases to increase the catalytic efficiency further, which is a prerequisite for applying these novel biocatalysts in synthetic chemistry.     

Platinum Nanoparticles Anchored on TiO2/C Nanowires as a High Performance Catalyst for Hydrogen Peroxide Eletroreduction

In this paper, we employed the as‐prepared TiO₂/C core/shell nanoarrays (TiO₂/C) obtained by a facile thermal evaporation method as a three‐dimensional (3D) architecture to support Pt nanoparticles through an optimized electrodeposition process. The morphology and structure of the as‐prepared electrode are characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Its catalytic performance towards H₂O₂ electroreduction in basic medium is evaluated by linear sweep voltammetry (LSV) and chronoamperometry (CV). Results revealed that the electrode exhibits significantly high catalytic activity. The current density reached –0.172 A cm⁻² in 1 mol dm⁻³ NaOH and 0.5 mol dm⁻³ H₂O₂ at –1.1 V (vs. Ag/AgCl). This high performance might be due to the 3D electrode architecture inheriting the high electronic conductivity from carbon shell and providing a short pathway for the ion diffusion, and the using of Pt owning an excellent catalytic activity.     

Diffusion‐Controlled Oxygen Reduction on Multi‐Copper Oxidase‐Adsorbed Carbon Aerogel Electrodes without Mediator

Bioelectrocatalytic reduction of O₂ into water was archived at diffusion‐controlled rate by using enzymes (laccase from Trametes sp. and bilirubin oxidase from Myrothecium verrucaria, which belong to the family of multi‐copper oxidase) adsorbed on mesoporous carbon aerogel particle without a mediator. The current density was predominantly controlled by the diffusion of dissolved O₂ in rotating‐disk electrode experiments, and reached a value as large as 10 mA cm^–2 at 1 atm O₂, 25 °C, and 8,000 rpm on the laccase‐adsorbed electrode. The overpotential of the bioelectrocatalytic reduction of O₂ was 0.4–0.55 V smaller than that observed on a Pt disk electrode. Without any optimization, the laccase‐adsorbed biocathode showed stable current intensity of the O₂ reduction in an air‐saturated buffer at least for 10 days under continuous flow system.     

Preparation of NiCo2O4 Nanosheet Arrays and its High Catalytic Performance for H2O2 Electroreduction

Ni foam supporting‐NiCo₂O₄ nanosheet arrays (NiCo₂O₄/Ni foam) are successfully prepared by electrodeposition of the hydroxide precursor, followed by a thermal treatment in air without any template and surfactant. The morphology of NiCo₂O₄ nanosheet arrays is characterized by scanning electron microscope and transmission electron microscopy. The structure is analyzed using X‐ray diffractometer, X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The catalytic performance of NiCo₂O₄/Ni foam electrode for H₂O₂ electroreduction in KOH solution is evaluated by means of cycle voltammetry and chronoamperometry, which exhibits an excellent catalytic performance and superior stability for H₂O₂ electroreduction. The reduction current density of H₂O₂ on NiCo₂O₄/Ni foam electrode is 0.378 A cm⁻² at –0.4 V in the solution containing 3.0 mol L⁻¹ KOH + 0.4 mol L⁻¹ H₂O₂, which is much larger than that on other metal oxides reported previously.     

Multi‐phase electro‐chemical catalytic oxidation of wastewater

The removal of organic pollutants from synthetic wash wastewater by a combined multi‐phase electro‐catalytic oxidation method was evaluated using porous graphite as anode and cathode, and CuO–Co₂O₃–PO₄^3? modified kaolin as catalyst. The synergic effect on COD removal was studied when integrating the electro‐chemical reactor with the effective modified kaolin in a single undivided cell; the results showed that higher COD removal efficiency was obtained than those obtained using the individual processes. Under optimal conditions of pH 3, 30 mA cm^?2 current density, very effective reduction of organic pollutants was achieved with this combined electro‐chemical method. High removal efficiency (90%) of the chemical oxygen demand (COD) was obtained in 60 min in the treatment of simulated wash wastewater (anionic surfactant, sodium dodecyl benzene sulfonate [DBS]). This method was also applied to treat wastewater form paper‐making and resulted in a COD reduction of 84%. Based on the investigation, a possible mechanism of this combined electro‐chemical process was proposed. The pollutants in wastewater could be decreased by the high reactive OH? that were produced via the decomposition of electro‐generated H₂O₂ activated by the synergic effect of electro‐field and catalyst. The results indicate that the multi‐phase catalytic electro‐chemical oxidation process is a promising technique for wastewater treatment. Copyright © 2006 Society of Chemical Industry     

Oxidative coupling of 2,6‐dimethylphenol catalyzed by copper(II) complexes in aqueous solution

The oxidative coupling reaction of 2,6‐dimethylphenol (DMP) with H₂O₂ catalyzed by four copper(II) complexes was investigated in Tris‐HNO₃ buffer solution at 25°C. The kinetics of formation of diphenoquinone (DPQ, 4‐(3,5‐dimethyl‐4‐oxo‐2,5‐cyclohexadienylidene)‐2,6‐dimethyl‐2,5‐cyclohexadienone) from DMP was studied in detail. The kinetic parameters k₂ and K_m were obtained in the pH range of 6.0–9.0. The copper(II) complexes exhibited the optimal catalytic activity at around pH 7.0. The pH effect was reasonably explicated by the catalytic kinetic model suggested in this work. The catalytic mechanism was discussed. The deprotonized associated radical LCu^I(OH^?)‐^?OOH was suggested as the possible predominant species to oxidize DMP. The C? C and C? O coupling products were analyzed and the ratio of poly (2,6‐dimethyl‐1,4‐phenylene ether) (PPE) to DPQ was also evaluated. Both in weak acidic (pH < 6.5) and in alkaline aqueous solution (pH > 8) were suitable to the C? O coupling reaction in our catalytic systems. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Heteromeric assembled polypeptidic artificial hydrolases with a six-helical bundle scaffold

Enzyme efficiency results from the cooperation of functional groups in the catalytic site. In order to mimic a natural enzyme, a definite 3D scaffold must be carefully designed so that the functional groups can work cooperatively. During the HIV‐1 fusion process, the gp41 N‐ and C‐terminal heptad repeat regions form a coiled‐coil six‐helical bundle (6HB) that brings the viral and target cell membranes into close proximity for fusion. We used 6HB as the molecular model for a novel scaffold for the design of an artificial enzyme, in which the modified C34 and N36 peptides formed a unique 6HB structure through specific molecular recognition, and the position and orientation of the side‐chain groups on this scaffold were predictable. The histidine modified 6HB C34_H13/20/N36_H15/22 showed enzyme‐like hydrolytic activity towards p‐nitrophenyl acetate (PNPA; k_cat/K_M=3.66 M ^?1 s^?1) through the cooperation of several inter‐ or intrahelical imidazole groups. Since the catalytic activity of 6HB depends on the C‐ and N‐peptide assembly, either HIV fusion inhibitors that can compete with the formation of catalytic 6HB or denaturants that can destroy the ordered structure were able to modulate its activity. Further engineering of the solvent‐exposing face with Glu^?‐Lys⁺ salt bridges enhanced the helicity and the stability of 6HB. As a result, the population and stability of cooperative catalytic units increased. In addition, the Glu^?‐Lys⁺‐stabilized 6HB SC35_H13/20/N36_H15/22 had increased catalytic efficiency (k_cat/K_M=6.30 M ^?1 s^?1). A unique 6HB system was specifically assembled and provided a scaffold sufficiently stable to mimic the function of enzymes or other biomolecules.     

Decomposition of Carboxylic Acids in Water by O3, O3/H2O2, and O3/Catalyst

This paper studies the decomposition of formic, oxalic and maleic acids by O₃, O₃/catalyst, and O₃/H₂O₂. The catalytic effect of Co²⁺, Ni²⁺, Cu²⁺, Mn²⁺, Zn²⁺, Cr³⁺, and Fe²⁺ ions is investigated. The results showed that—Co²⁺ and Mn²⁺ have the highest catalytic activity for the decomposition of oxalic acid while the catalytic effect of the studied ions is insignificant on the rate of decomposition of formic acid. Maleic acid decomposes by ozone into formic acid and glyoxylic acid, which subsequently oxidizes to oxalic acid. Though the studied ions have no effect on the decomposition of maleic acid, they have a significant effect on the produced oxalic and glyoxylic acids. In the presence of Cu²⁺ ions glyoxylic acid is mainly transformed into formic acid and traces of oxalic acid. In such case, a complete decomposition of maleic acid and its degradation products is achieved within 45 min. The results also show that combining H₂O₂ with O₃ results in an increase in the rate of decomposition of oxalic acid. However, O₃/H₂O₂ system is less active than O₃/Co²⁺ or O₃/Mn²⁺.     

Catalytic Methanation of Carbon Dioxide by Active Oxygen Material CexZr1−xO2 Supported Ni?Co Bimetallic Nanocatalysts

A series of active oxygen material Ce_xZr_1?xO₂‐supported Ni? Co bimetallic nanosized catalysts were prepared by coprecipitation method, which is simple and fit for industrial use with lower cost than other methods. The effect of CeO₂/ZrO₂ mole ratio, Co metal addition, and PEG‐6000 addition were investigated. The catalysts were characterized through X‐ray diffraction, H₂ thermal‐programmed reduction, N₂ adsorption, Raman spectroscopy, CO pulse chemisorption, X‐ray photoelectron spectroscopy, oxygen storage capacity, and transmission electron microscopy‐energy dispersive X‐ray analysis. Modifications of the structural and redox properties of these materials were evaluated in relation to their catalytic performances. Particularly, the relationship between the active oxygen sites of the catalysts and their catalytic performances was investigated. The interaction between active metals (Ni and Co) and Ce_xZr_1?xO₂ support was found to be very important for catalytic performance. The active oxygen site of Ce_xZr_1?xO₂ can considerably improve catalytic performance. Appropriate Co metal addition also remarkably enhanced the catalytic stability and activity. Moreover, PEG‐6000 addition can improve the Brunauer–Emmett–Teller surface area and active metal dispersion of catalysts to improve their performances. The nanosized catalyst 15 wt % Ni‐5 wt % Co/Ce_0.25Zr_0.75O₂ prepared by adding 5 wt % PEG‐6000 achieved almost 85% CO₂ conversion and 98% selectivity to methane at 280°C when the gas hourly space velocity was 10,000 h^?1. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2567–2576, 2013     

Highly stable Fe/γ‐Al2O3 catalyst for catalytic wet peroxide oxidation

BACKGROUND: A highly stable Fe/γ‐Al₂O₃ catalyst for catalytic wet peroxide oxidation has been studied using phenol as target pollutant. The catalyst was prepared by incipient wetness impregnation of γ‐Al₂O₃ with an aqueous solution of Fe(NO₃)₃· 9H₂O. The influence of pH, temperature, catalyst and H₂O₂ doses, as well as the initial phenol concentration has been analyzed. RESULTS: The reaction temperature and initial pH significantly affect both phenol conversion and total organic carbon removal. Working at 50 °C, an initial pH of 3, 100 mg L^?1 of phenol, a dose of H₂O₂ corresponding to the stoichiometric amount and 1250 mg L^?1 of catalyst, complete phenol conversion and a total organic carbon removal efficiency close to 80% were achieved. When the initial phenol concentration was increased to 1500 mg L^?1, a decreased efficiency in total organic carbon removal was observed with increased leaching of iron that can be related to a higher concentration of oxalic acid, as by‐product from catalytic wet peroxide oxidation of phenol. CONCLUSION: A laboratory synthesized γ‐Al₂O₃ supported Fe has shown potential application in catalytic wet peroxide oxidation of phenolic wastewaters. The catalyst showed remarkable stability in long‐term continuous experiments with limited Fe leaching, < 3% of the initial loading. Copyright © 2010 Society of Chemical Industry     

Synthesis of 1‐Naphthol by a Natural Peroxygenase Engineered by Directed Evolution

There is an increasing interest in enzymes that catalyze the hydroxylation of naphthalene under mild conditions and with minimal requirements. To address this challenge, an extracellular fungal aromatic peroxygenase with mono(per)oxygenase activity was engineered to convert naphthalene selectively into 1‐naphthol. Mutant libraries constructed by random mutagenesis and DNA recombination were screened for peroxygenase activity on naphthalene together with quenching of the undesired peroxidative activity on 1‐naphthol (one‐electron oxidation). The resulting double mutant (G241D‐R257K) obtained from this process was characterized biochemically and computationally. The conformational changes produced by directed evolution improved the substrate's catalytic position. Powered exclusively by catalytic concentrations of H₂O₂, this soluble and stable biocatalyst has a total turnover number of 50 000, with high regioselectivity (97 %) and reduced peroxidative activity.     

Melt polycondensation of L‐lactic acid to poly(L‐lactic acid) with Sn(II) catalysts combined with various metal alkoxides

Melt polycondensation of L ‐lactic acid (LA) was examined in the presence of binary catalyst systems consisting of SnCl₂·2H₂O and metal alkoxides as co‐catalysts. Among the co‐catalysts examined, viz (Al(O ⁱPr)₃,Ti(O ⁱPr)₄,Y(O ⁱPr)₃,Si(OEt)₄ and Ge(OEt)₄), Ge(OEt)₄ was found to be the most effective in enhancing the catalytic activity of Sn(II). With an optimized composition of SnCl₂·2H₂O–Ge(OEt)₄, the molecular weight (M_n) of PLLA reached 40 000 Da in a short reaction time (<15 h) at the optimum reaction conditions of 180 °C and 10 Torr. This catalyst system was also superior to the conventional single metal ion catalysts such as Sn(II) in terms of racemization and discolouration of the resultant polymer. The metal alkoxides, added as co‐catalysts, should work as oxo acids that can effectively control the catalytic activity of Sn(II) ion in the direct polycondensation of LA, in a manner similar to that of proton acids. © 2003 Society of Chemical Industry     

Preparation and modification of polythiophene–organic montmorillonite composite

Polythiophene‐organic montmorillonite (PTP‐OMMT) composites were prepared via Fe³⁺‐H₂O₂ catalytic oxidation system at room temperature in water (medium) within the presence of sodium dodecyl benzene sulfonate. The PTP‐OMMT composite made from 2 g/ml solution of OMMT/TP with reacting for 12 h shown the highest conductivity (3.44 × 10⁻⁵ S/cm). The prepared PTP‐OMMT was modified with aniline (ANI) and pyrrole (PY) under Fe³⁺‐H₂O₂ and ammonium persulfate (APS) oxidation systems. The conductivity of PANI‐(PTP‐OMMT) and PPY‐(PTP‐OMMT) reached the range from 10⁻² S/cm to 10⁻¹ S/cm, showing a growth of 10³ to 10⁴ times. Fourier transform infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) revealed that thiophene enter into OMMT to form intercalation compounding, which undamaged after ANI and PY modification. Thermogravimetric analysis (TGA) comfirmed the improved thermostability of PTP‐OMMT and the decreased thermostability of modified materials. Scanning electron microscopy (SEM) indicated that modified materials under Fe³⁺‐H₂O₂ oxidation system presented regular spherical structures. POLYM. COMPOS., 37:2503–2510, 2016. © 2015 Society of Plastics Engineers     

On the nature of Ti(IV)‐pillared layered metal hydroxides prepared from green,water‐soluble Ti‐peroxide

Ti‐peroxide pillared layered double hydroxides (LDHs) have been prepared for the first time using water‐soluble Ti‐peroxide as an intercalating precursor. It is novel and alluring that the whole preparation procedure does not involve any usage of organic or chlorine‐containing hazards. Intercalated into the LDH interlayer region, Ti‐peroxide is prevented partially from condensation in the solvent evaporation. The interlayer Ti? O₂ unit exists in triangular (η²) structure with C_2ν symmetry in most cases, giving an interlayer gallery of 0.50–0.60 nm. But in the case of pH 4.0, monodentate (η¹) structure is also observed, giving an interlayer gallery of 0.70 nm. All the Ti‐peroxide pillared LDHs prepared in this work show catalytic activity in the selective oxidation of thioether. The Ti‐peroxide introduced into the interlayer regions of Mg/Al LDH with a particle size of around 50–120 nm exhibits better recyclability than Ti‐peroxide gel, either in bulk or adsorbed on the exterior surface of LDH particles. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Preparation of γ‐Fe2O3 Catalysts and their deNOx Performance: Effects of Precipitation Conditions

Magnetic γ‐Fe₂O₃ catalysts were prepared by microwave‐assisted coprecipitation utilizing the direct‐titrate and back‐titrate precipitation technique with different precipitants, namely, (NH₄)₂CO₃, NaOH, Na₂CO₃, and NH₄OH, which were evaluated in the selective catalytic reduction of NO_x with NH₃. The optimum γ‐Fe₂O₃ catalyst preparation method was direct titration with NH₄OH as the precipitant, which exhibits high deNO_x efficiency. This direct titration was effective to maintain the proper crystallization degree of γ‐Fe₂O₃, improve the pore structure, and suppress the formation of α‐Fe₂O₃ phase, being advantageous to get tiny and uniform discrete γ‐Fe₂O₃ particles with high activity in selective catalytic reduction. NH₄⁺‐based precipitants in direct titration leads to an increase of the surface O/Fe atom ratio, and more lattice oxygen sites are exposed to the crystal surface.