Direct electrochemistry and electrocatalysis of horseradish peroxidase based on halloysite nanotubes/chitosan nanocomposite film

The novel halloysite nanotubes/chitosan (HNTs/Chi) composite films were firstly explored to utilize for the immobilization of horseradish peroxidase (HRP) and their bioelectrochemical properties were studied, in which the biopolymer chitosan was used as a binder to increase film adherence on glassy carbon (GC) electrode. UV-vis and FTIR spectroscopy demonstrated that HRP in the composite film could retain its native secondary structure. A pair of well-defined redox peaks of HRP was obtained at the HRP/HNTs/Chi composite film-modified electrode, exhibiting its fast direct electron transfer (DET). Furthermore, the immobilized HRP displayed its good electrocatalytic activity for the reduction of hydrogen peroxide (H₂O₂). The results demonstrate that the HNTs/Chi composite film may improve the enzyme loading with the retention of bioactivity and greatly promote the direct electron transfer, which can be attributed to its unique tubular structure, high specific surface area, and good biocompatibility.     

Horseradish peroxidase immobilized in TiO2 nanoparticle films on pyrolytic graphite electrodes: direct electrochemistry and bioelectrocatalysis

Horseradish peroxidase (HRP)-TiO₂ film electrodes were fabricated by casting the mixture of HRP solution and aqueous titania nanoparticle dispersion onto pyrolytic graphite (PG) electrodes and letting the solvent evaporate. The HRP incorporated in TiO₂ films exhibited a pair of well-defined and quasi-reversible cyclic voltammetric peaks at about −0.35 V versus saturated calomel electrode (SCE) in pH 7.0 buffers, characteristic of HRP-Fe(III)/Fe(II) redox couple. The electron exchange between the enzyme and PG electrodes was greatly enhanced in the TiO₂ nanoparticle film microenvironment. The electrochemical parameters such as apparent heterogeneous electron transfer rate constant (k_s) and formal potential (E°′) were estimated by fitting the data of square wave voltammetry with nonlinear regression analysis. The HRP-TiO₂ film electrodes were quite stable and amenable to long-time voltammetric experiments. The UV-Vis spectroscopy showed that the position and shape of Soret absorption band of HRP in TiO₂ films kept nearly unchanged and were different from those of hemin or hemin-TiO₂ films, suggesting that HRP retains its native-like tertiary structure in TiO₂ films. The electrocatalytic activity of HRP embedded in TiO₂ films toward O₂ and H₂O₂ was studied. Possible mechanism of catalytic reduction of H₂O₂ with HRP-TiO₂ films was discussed. The HRP-TiO₂ films may have a potential perspective in fabricating the third-generation biosensors based on direct electrochemistry of enzymes.     

Bioelectrocatalytic and biosensing properties of horseradish peroxidase covalently immobilized on (3-aminopropyl)trimethoxysilane-modified titanate nanotubes

Titanate nanotubes (TiNT) surface modified with (3-aminopropyl)trimethoxysilane were employed as a support for covalent immobilization of horseradish peroxidase (HRP) by using 1,4-benzoquinone as a coupling agent. Composite film-electrodes consisting of HRP-modified TiNT embedded into the porous carbon powder/Nafion matrix were fabricated and their applicability in direct bioelectrocatalytic reduction of H₂O₂ and H₂O₂ biosensing were investigated. An efficient direct electron transfer between the immobilized HRP molecules and the electrode was observed in the presence of H₂O₂ at potentials lower than 600 mV (vs. Hg/Hg₂Cl₂/3.5 M KCl). For the HRP–TiNT-modified electrodes polarized at 0 mV, a linear dependence of the bioelectrocatalytic current on the concentration of H₂O₂ was observed up to the concentration of H₂O₂ equal to 10 μM, with the sensitivity of (1.10 ± 0.01) AM⁻¹ cm⁻² and the detection limit of 35 nM.     

A hydrogen peroxide sensor based on a horseradish peroxidase/polyaniline/carboxy-functionalized multiwalled carbon nanotube modified gold electrode

We have developed a polyaniline/carboxy-functionalized multiwalled carbon nanotube (PAn/MWCNTCOOH) nanocomposite by blending the emeraldine base form of polyaniline (PAn) and carboxy-functionalized multiwalled carbon nanotubes (MWCNT) in dried dimethyl sulfoxide (DMSO) at room temperature. The conductivity of the resulting PAn/MWCNTCOOH was 3.6 × 10⁻³ S cm⁻¹, mainly as a result of the protonation of the PAn with the carboxyl group and the radical cations of the MWCNT fragments. Horseradish peroxidase (HRP) was immobilized within the PAn/MWCNTCOOH nanocomposite modified Au (PAn/MWCNTCOOH/Au) electrode to form HRP/PAn/MWCNTCOOH/Au for use as a hydrogen peroxide (H₂O₂) sensor. The adsorption between the negatively charged PAn/MWCNTCOOH nanocomposite and the positively charged HRP resulted in a very good sensitivity to H₂O₂ and an increased electrochemically catalytical current during cyclic voltammetry. The HRP/PAn/MWCNTCOOH/Au electrode exhibited a broad linear response range for H₂O₂ concentrations (86 μM–10 mM). This sensor exhibited good sensitivity (194.9 μA mM⁻¹ cm⁻²), a fast response time (2.9 s), and good reproducibility and stability at an applied potential of −0.35 V. The construction of the enzymatic sensor demonstrated the potential application of PAn/MWCNTCOOH nanocomposites for the detection of H₂O₂ with high performance and excellent stability.     

Study on initiating approach of (3-(tert-butylperoxy)propyl) trimethoxysilane on the polymerization of acrylonitrile as an initiator*

(3-(tert-butylperoxy)propyl) trimethoxysilane (TBPT), is a tailor-made new style silane coupling agent with peroxide group, which have ability of initiating polymerization. This study used TBPT to generate free radical, and initiated the polymerization of acrylonitrile (AN), thereby forming polyacrylonitrile (PAN) in two approaches, thermal initiation system and redox initiation system. Meanwhile this study bonded TBPT onto nano-TiO₂ to get modified nano-TiO₂ by means of the coupling function of TBPT, and then made the peroxide group of the modified nano-TiO₂ decompose and initiate the polymerization of AN in thermal initiation system and redox initiation system respectively. The products were investigated and analyzed by FTIR, XPS and TG. The result showed that on one hand, in the products of the thermal initiation there was PAN, which both attached and unattached to the modified nano-TiO₂; on the other hand, in the products of the redox initiation system the PAN unattached to the modified nano-TiO₂ was produced, while the PAN attached to the modified nano-TiO₂ was not.     

Sonochemical synthesis of magnetic core–shell Fe3O4@ZrO2 nanoparticles and their application to the highly effective immobilization of myoglobin for direct electrochemistry

In this study, bifunctional Fe₃O₄@ZrO₂ magnetic core–shell nanoparticles (NPs), synthesized by a simple and effective sonochemical approach, were attached to the surface of a magnetic glassy carbon electrode (MGCE) and successfully applied to the immobilization/adsorption of myoglobin (Mb) for constructing a novel biosensor platform. With the advantages of the magnetism and the excellent biocompatibility of the Fe₃O₄@ZrO₂ NPs, Mb could be easily immobilized on the surface of the electrode in the present of external magnetic field and well retained its bioactivity, hence dramatically facilitated direct electron transfer of Mb was demonstrated. The proposed Mb/Fe₃O₄@ZrO₂ biofilm electrode exhibited excellent electrocatalytic behaviors towards the reduction of H₂O₂ with a linear range from 0.64 μM to 148 μM. This presented system avoids the complex synthesis for protecting Fe₃O₄ NPs, supplies a simple, effective and inexpensive way to immobilize protein, and is promising for construction of third-generation biosensors and other bio-magnetic induction devices.     

A novel platform of hemoglobin on core–shell structurally Fe3O4@Au nanoparticles and its direct electrochemistry

A novel platform, which hemoglobin (Hb) was immobilized on core–shell structurally Fe₃O₄/Au nanoparticles (simplified as Fe₃O₄@Au NPs) modified glassy carbon electrode (GCE), has been developed for fabricating the third biosensors. Fe₃O₄@Au NPs, characterized using transmission electron microscope (TEM), scanning electron microscope (SEM) and energy dispersive spectra (EDS), were coated onto GCE mediated by chitosan so as to provide larger surface area for anchoring Hb. The thermodynamics, dynamics and catalysis properties of Hb immobilized on Fe₃O₄@Au NPs were discussed by UV–visible spectrum (UV–vis), electrochemical impedance spectroscopy (EIS), electrochemical quartz crystal microbalance technique (EQCM) and cyclic voltammetry (CV). The electrochemical parameters of Hb on Fe₃O₄@Au NPs modified GCE were further carefully calculated with the results of the effective working area as 3.61 cm², the surface coverage concentration (Γ) as 1.07 × 10⁻¹² mol cm⁻², the electron-transfer rate constant (K_s) as 1.03 s⁻¹, the number of electron transferred (n) as 1.20 and the standard entropy of the immobilized Hb (ΔS⁰′) as calculated to be −104.1 J mol⁻¹ K⁻¹. The electrocatalytic behaviors of the immobilized Hb on Fe₃O₄@Au NPs were applied for the determination of hydrogen peroxide (H₂O₂), oxygen (O₂) and trichloroacetic acid (TCA). The possible functions of Fe₃O₄ core and Au shell as a novel platform for achieving Hb direct electrochemistry were discussed, respectively.     

Poly(o-toluidine dihydrochloride): Spectral Characterization and Synthesis of Eskolite Nanoparticles

Poly(o-toluidine?·?2HCl) and its doped polymers with Mn and Cr ions have been synthesized and characterized by FT-IR, UV–Vis. and thermogravimetrical analyses. Potassium dichromate has been used as an initiator and a dopant of chromium in CrPOT preparation. The effect of doping on thermal and optical properties of Poly(o-toluidine dihydrochloride) has been discussed.

CrPOT has been used as a precursor of Cr₂O₃ nanoparticles through thermal decomposition rout. The obtained nanoparticles have been characterized by X-ray diffraction and high resolution transmission electron microscope. The results indicated that Cr₂O₃ exists in hexagonal structure as mesoporous Eskolit with average particle size of 48?nm. Optical band gap measurements indicated that Eskolite nanoparticles have wider band gap than the bulk.     

Acid-Base Properties of Alumina-Supported M2O3 (M=B, Ga, In) Catalysts

The acid-base properties of -Al₂O₃ and alumina-supported B₂O₃, Ga₂O₃ and In₂O₃ have been determined by microcalorimetry of ammonia and sulfur dioxide adsorption. From the adsorption of NH₃, it was found that the addition of B₂O₃ on alumina leads to an increase of the number of acid sites, while Ga₂O₃ and In₂O₃ additives caused a decrease in the acidity of alumina. Using SO₂ as a probe molecule to study the basicity, the number of surface basic sites on alumina was found to be strongly decreased by the addition of boron oxide, while it was only slightly affected by the addition of gallium oxide and decreased by the addition of indium oxide. The differential heats of adsorption are discussed as a function of the coverage by the probe molecules. The electronic properties of the oxides are examined in order to explain the acid-base properties of the supported oxides.     

Characterization and conversion determination of stable PEDOT latex nanoparticles synthesized by emulsion polymerization

In this research, poly(3,4-ethylenedioxythiophene) (PEDOT) latex nanoparticles with good colloidal stability were prepared by emulsion polymerization and the conversions of EDOT were determined. Two kinds of oxidants, Iron(III) p-toluenesulfonate Fe(OTs)₃ and hydrogen peroxide H₂O₂, were introduced to decrease the use of iron salt and therefore reduce the particle coagulation. The ferrous ions (Fe²⁺) produced during the polymerization would be re-oxidized back to the reactive ferric ions (Fe³⁺) with the help of H₂O₂. This cyclic oxidation-reduction process resulted in the sustained regeneration of Fe³⁺ ions and led to a higher conversion. A dark blue PEDOT latex with long-term dispersion stability was obtained when Fe(OTs)₃ and H₂O₂ were added in sequence. The results obtained from dynamic light scattering and TEM measurements showed that the sizes of nanoparticles were around 100 nm. To determine the conversion of EDOT, two methods (gravimetric analysis and UV-visible method) were used and compared. For the first time, the UV-visible method was established to quantitatively determine the conversion of EDOT monomer. From the measurement, the conversion of EDOT in this system was determined as 74-75%. The PEDOT film prepared by drying the latex solution had conductivity up to 6.3 S/cm.     

Synthesis of di(methylphenyl)methane over heteropolyacids (H3PW12O40) catalysts

Catalytic synthesis of di(methylphenyl)methane (CH₃C₆H₄CH₂C₆H₄CH₃, DMPMs) from toluene and formaldehyde were investigated over various solids acids. At 140 °C and toluene/HCHO = 5/1, the conversion of HCHO over zeolite (Hβ, H-mordenite, HX, HY and HZSM-5) is limited, while heteropolyacids (H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀ and H₃PMo₁₂O₄₀) exhibited higher activity and DMPMs selectivity. The best yield of DMPMs reached 81.5% (conversion of HCHO nearly 100%). H₃PW₁₂O₄₀ could be recovered by simply drying and the recycle-used catalyst remained its activity and structure in five runs.     

Effects of O3, O3/H2O2 and Coagulation on Natural Organic Matter and Arsenic Removal from Typical Northern Serbia Source Water

The objectives of this study were to investigate the effects of ozone and the O₃/H₂O₂ process on FeCl₃ coagulation efficiency for the removal of the high content of natural organic matter (NOM) and arsenic (As) from groundwater (DOC = 9.27 ± 0.92 mg/L; 51.7 ± 16.4 µg As/L). Arsenic and NOM removal mechanisms during coagulation/flocculation are well investigated. However, data concerning arsenic removal in the presence of NOM, which is the subject of this article, are still insufficient. Laboratory and pilot plant test results have shown that the competition of NOM and As for adsorption sites on the coagulant surface have great influence on coagulation/flocculation efficiency for their removal. With both oxidation pre-treatments, arsenic content after the coagulation process was less than 2.0 µg/L in treated water. Application of ozone has a lower influence on coagulation efficacy in terms of DOC reduction, compared to the O₃/H₂O₂ process with the same ozone dose.     

Electro-Magnetic Polyfuran/Fe3O4 Nanocomposite: Synthesis,Characterization, Antioxidant Activity,and Its Application as a Biosensor

Herein, the authors report the synthesis of electro-magnetic polyfuran/Fe₃O₄ nanocomposites using Fe₃O₄ magnetic nanoparticles of different content as nucleation sites via in situ chemical oxidation polymerization method. Surface, structural, morphological, thermal, electrical and magnetic properties of the nanocomposites were studied by FT-IR, UV-visible spectroscopies, XRD, FESEM, TGA, four probe, and VSM, respectively. The effect of Fe₃O₄ nanoparticles content on the electrical conductivity and magnetization of nanocomposites was studied. The obtained polyfuran and polyfuran/Fe₃O₄ nanocomposites were analyzed for their antioxidant activity using 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. In addition, polyfuran/Fe₃O₄ nanocomposites have been investigated for application as electrochemical biosensor.     

Valine-Coated Magnetic Nanoparticles: Synthesis,Characterization, and Application in Removal of Cd(II) Ions from Aqueous Solution

A novel Valine coated magnetic nano-particles (MNPs-Val) has been synthesized for the removal of Cd(II) ions from aqueous solution. The MNPs-Val were developed by electrostatic attraction of valine (C₅H₁₁NO₂) on the bare surface of Fe₃O₄ nanoparticles and characterized by using FT-IR, XRD, SEM, and TEM analysis. The morphology and average particles size 15-27 nm of MNPs-Val were analyzed by SEM and TEM. The coated MNPs were applied for adsorptive removal of Cd(II) ions from aqueous solutions. Factors affecting the adsorption of Cd(II) ions on the MNPs-Val surface such as the pH, temperature, adsorbent dosage, and contact time were investigated which have significant effect on the metal ion removal. The Cd(II) ions adsorption equilibrium on the MNPs-Val could be achieved in 35 min at the optimized pH 5 and follow the pseudo-second order kinetics model. The experimental data for the adsorption of Cd(II) was followed by the Langmuir isotherm and the maximum adsorption capacity was obtained at 0.2 g L^?1 adsorbent dose at 308 K.     

Melamine-(H2SO4)3/melamine-(HNO3)3 instead of H2SO4/HNO3: a safe system for the fast oxidation of thiols and sulfides under solvent-free conditions

Melamine reacted with neat sulfuric acid and fuming nitric acid readily to form two new organic solid acids, namely melamine-(H₂SO₄)₃ and melamine-(HNO₃)₃. Mixture of them acts as a unique powerful system instead of a hazardous H₂SO₄/HNO₃ system for the direct oxidation of thiols. Also, this system can oxidize the sulfides in the presence of a catalytic amount of KBr and few drops of water. This procedure offers advantages such as very low reaction time, simple work-up, excellent yield and matching with some green chemistry protocols.     

Direct electron-transfer and electrochemical catalysis of hemoglobin immobilized on mesoporous Al2O3

The direct electrochemistry of hemoglobin (Hb) has been achieved by immobilizing Hb on mesoporous Al₂O₃ (meso-Al₂O₃) film modified glassy carbon (GC) electrode. Meso-Al₂O₃ shows significant promotion to the direct electron-transfer of Hb, thus it exhibits a pair of well defined and quasi-reversible peaks with a formal potential of −0.345 V (vs. SCE). The electron-transfer rate constant (k_s) is estimated to be 3.17 s⁻¹. The immobilized Hb retains its biological activity well and shows high catalytic activity to the reduction of hydrogen peroxide (H₂O₂) and nitrite (NO₂⁻). Under the optimized experimental conditions, the catalytic currents are linear to the concentrations of H₂O₂ and NO₂⁻ in the ranges of 0.195-20.5 μM and 0.2-10 mM, respectively. The corresponding detection limits are 1.95 × 10⁻⁸ M and 3 × 10⁻⁵ M (S/N = 3). The resulting protein electrode has high thermal stability and good reproducibility due to the protection effect of meso-Al₂O₃. Ultraviolet visible (UV-vis) absorption spectra and reflection-absorption infrared (RAIR) spectra display that Hb keeps almost natural structure in the meso-Al₂O₃ film. The N₂ adsorption-desorption experiments show that the pore size of meso-Al₂O₃ is about 14.4 nm, suiting for the encapsulation of Hb (average size: 5.5 nm) well. Therefore, meso-Al₂O₃ is an alternative matrix for protein immobilization and biosensor preparation.     

Metal-organic framework Cu3 (BTC)2(H2O)3 catalyzed Aldol synthesis of pyrimidine-chalcone hybrids

A typical metal organic framework, [Cu₃ (BTC)₂(H₂O)₃, BTC = 1,3,5-benzene tricarboxylate] has been used for the synthesis of pyrimidine-chalcones. We have explored a green synthesis of pyrimidine chalcones under Cu₃(BTC)₂ catalysis by Aldol condensation. Easy isolation of product, excellent yield, and recyclable catalyst makes this reaction eco-friendly. The technology was demonstrated to be applicable to the synthesis of a host of chemical hybrids.     

Use of a Reflectance Spectroscopy Accessory for Optical Characterization of ZnO-Bi(2)O(3)-TiO(2) Ceramics

The optical band-gap energy (E(g)) is an important feature of semiconductors which determines their applications in optoelectronics. Therefore, it is necessary to investigate the electronic states of ceramic ZnO and the effect of doped impurities under different processing conditions. E(g) of the ceramic ZnO + xBi(2)O(3) + xTiO(2), where x = 0.5 mol%, was determined using a UV-Vis spectrophotometer attached to a Reflectance Spectroscopy Accessory for powdered samples. The samples was prepared using the solid-state route and sintered at temperatures from 1140 to 1260 °C for 45 and 90 minutes. E(g) was observed to decrease with an increase of sintering temperature. XRD analysis indicated hexagonal ZnO and few small peaks of intergranular layers of secondary phases. The relative density of the sintered ceramics decreased and the average grain size increased with the increase of sintering temperature.     

Redox polymer-based reagentless horseradish peroxidase biosensors: Influence of the molecular structure of the polymer

Reagentless amperometric biosensors were prepared using a variety of nitrogen donor groups containing co-polymers. The polymers were coordinated with Os-bis-N,N-(2,2′-bipyridil)-dichloride via a ligand exchange reaction thus assuring an efficient electron-transfer pathway between the polymer-entrapped horseradish peroxidase and the electrode surface by means of a sequence of electron-hopping steps. The impact of structural features of the polymer such as spacer length between the Os-complex and the polymer backbone or the ratio of 4-vinylpyridine and butylmethacrylate in a co-polymer on the activity of the horseradish peroxidase biosensors was investigated.     

Alumina-supported Mn(II), Co(II), Ni(II) and Cu(II) N,N-bis(salicylidene)-2,2-dimethylpropane-1,3-diamine complexes: Synthesis, characterization and catalytic oxidation of cyclohexene with tert-butylhydroperoxide and hydrogen peroxide

New square-planar manganese(II), copper(II), nickel(II) and cobalt(II) complexes of a tetradentate Schiff-base ligand “N,N-bis(salicylidene)-2,2-dimethylpropane-1,3-diamine, H₂[salpnMe₂]” have been prepared and characterized by elemental analyses, IR, UV–Vis, conductometric and magnetic measurements. The results suggest that the symmetrical Schiff-base is a bivalent anion with tetradentate N₂O₂ donors derived from the phenolic oxygen and azomethine nitrogen. The formulae was found to be [M(salpnMe₂)] for the 1:1 non-electrolytic complexes. Alumina-supported metal complexes (ASMC; [M(salpnMe₂)/Al₂O₃]) catalyze the oxidation of cyclohexene with tert-buthylhydroperoxide (TBHP) and hydrogen peroxide. Oxidation of cyclohexene with TBHP gave 2-cyclohexene-1-one, 2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene whereas, oxidation with H₂O₂ resulted in the formation of cyclohexene oxide and cyclohexene-1,2-diol. Manganese(II) complex supported on alumina “[Mn(salpnMe₂]–Al₂O₃” shows significantly higher catalytic activity than other catalysts.