A sensitive electrochemical approach for monitoring the effects of nano-Al2O3 on LDH activity by differential pulse voltammetry.

In this paper, a sensitive electrochemical approach for monitoring the effect of nano-Al(2)O(3) on lactate dehydrogenase (LDH) activity is established. It is based on the determination of reduction current of NAD(+) involved in enzyme promoting catalytic reaction of "pyruvate + NADH + H+ [see text]L D H lactate + NAD+" by differential pulse voltammetry (DPV). Various influencing factors including nano-type, nano-size, and adsorbed pollutant organics have been investigated. The experimental results show that the proposed electrochemical method is useful in monitoring and evaluating the toxic effects of nanoparticles, which might be suitable to the environmental pollutant's toxicity analysis.

Direct voltammetry of catalase immobilized on silica sol-gel and cysteine modified gold electrode and its application.

The direct voltammetry of catalase (CAT) immobilized in silica sol-gel film in the presence of cysteine on gold electrode was investigated. The CAT electrode showed a pair of well-defined and quasi-reversible cyclic voltammetry peaks. It can be used as an electrochemical biosensor for the determination of hydrogen peroxide. The calibration range of H(2)O(2) was from 1 to 30 micromolL(-1) and the detection limit was 0.4 micromolL(-1) at a signal-to-noise ratio of 3. The interaction of CAT and aluminum ion was also investigated based on the CAT-modified electrode. The electrochemical activity of the CAT-modified electrode was increased with the addition of Al(3+). The experimental results of voltammetry and fluorescence spectroscopy indicated that the conformation of CAT molecule was altered by the formation of Al-CAT complex with Al(3+), which may influence the activity of CAT.

Study on the interaction of copper-zinc superoxide dismutase with aluminum ions by electrochemical and fluorescent method.

The interaction of superoxide dismutase (SOD) with aluminum (Al) ions was investigated by cyclic voltammetry, fluorescence spectroscopy and synchronous fluorescence spectroscopy. The electrochemical activity of the SOD enzyme electrode was inhibited irreversibly by the addition of Al. Meanwhile, the static fluorescence quenching mechanism further revealed the existing of molecular complex of SOD with Al(3+). The association constant was obtained from Lineweaver-Burk plot. The experimental results of voltammetry and fluorescence spectroscopy indicated that the conformation of SOD molecule was altered by the formation of Al-SOD complex. It may influence the activity of SOD enzyme since the optimum action of SOD depends upon a particular configuration of electrostatic charges in the enzyme molecule.

Investigation of surface synergetic oxygen vacancy in CuO-CoO binary metal oxides supported on γ-Al2O3 for NO removal by CO.

The influence of CO pretreatment on the properties of CuO-CoO/γ-Al(2)O(3) catalysts was investigated by SEM, TEM, XRD, LRS, XPS, TPR, and in situ FT-IR techniques. And the activities were measured by NO removal by CO. It was shown that the CuO-CoO/γ-Al(2)O(3) catalysts following CO pretreatment exhibited extremely high activity and selectivity. The interaction between copper oxide and cobalt oxide upon the γ-Al(2)O(3) support before and after CO pretreatment was tentatively discussed in the view of incorporation model. According to this model, the dispersed Cu-O-Co species could be reduced to Cu-□-Co species by CO pretreatment, which was considered to be the primary active component for this reaction. FT-IR results suggested that CO was apt to adsorb on Cu(+) sites rather than Co(2+) while the NO adsorbates could convert to much more stable species with the temperature increasing. Undoubtedly, it was the surface synergetic oxygen vacancy coupled with the adjacent Cu and Co ions that guaranteed the reaction well processing over the CO pretreated samples. As a result, a possible mechanism was tentatively proposed.

Investigation of the physicochemical properties of CuO-CoO binary metal oxides supported on γ-Al2O3 and their activity for NO removal by CO.

The dispersion and physicochemical behaviors of CuO-CoO binary metal oxides supported on γ-Al(2)O(3) were characterized by XRD, LRS, XPS, H(2)-TPR, and in situ FT-IR techniques. Their activities were evaluated by NO-CO model reaction. The results indicated that (a) for lower loadings, CuO and CoO were able to be highly dispersed on the surface of γ-Al(2)O(3) support; (b) the interaction between dispersed CuO and CoO upon γ-Al(2)O(3) was discussed in the view of incorporation model. According to this model and obtained results, the surface dispersed Cu-O-Co species were considered to exist on the surface of γ-Al(2)O(3); (c) CO or/and NO adsorption FT-IR results evidenced that the surface dispersed copper species could be reduced to lower valence by CO and the NO adsorption species converted with the increase in the temperature; (d) the surface dispersed Cu-O-Co species could be reduced to active Cu-□-Co species by CO among the mixture atmosphere. The formation of the surface synergetic oxygen vacancy (SSOV) was a crucial factor in the process of the NO-CO reaction. And a possible reaction pathway was tentatively proposed to discuss the NO-CO reaction based on all of these results.

The promotion effect of titania nanoparticles on the direct electrochemistry of lactate dehydrogenase sol-gel modified gold electrode.

The promotion effect of titania nanoparticles (nano-TiO(2)) on the direct electron transfer between lactate dehydrogenase (LDH) and the silica sol-gel modified gold electrode was investigated by adding nano-TiO(2) (50 nm) in the modification process. This nano-TiO(2)-LDH electrode showed a pair of quasi-reversible cyclic voltammetry peaks with the formal potential of 70 mV (vs. SCE). Compared to the previous result of LDH modified electrode with only an irreversible cathodic peak, an anodic peak appeared and the cathodic peak potential shifted to the positive direction on this nano-TiO(2)-LDH electrode, which demonstrated that the direct electrochemistry of LDH was enhanced by nano-TiO(2). We supposed that the direct electrochemistry of LDH may be due to the redox reaction of some electroactive amino acids in the LDH molecule. The surface morphologies of electrodes characterized by SEM indicated that LDH was successfully immobilized on the sol-gel matrix and also had some interactions with nano-TiO(2). This electrode can be used as a biosensor for the determination of lactic acid. The calibration range of lactic acid was from 1.0 to 20 micromolL(-1) and the detection limit was 0.4 micromolL(-1). Meanwhile, the small K(m)(app) value (2.2 micromolL(-1)) suggested that LDH possessed high enzymatic activity and good affinity to lactic acid owing to the promotion effect of nano-TiO(2).

Studies on the effects of Al(III) on the lactate dehydrogenase activity by differential pulse voltammetry.

In this paper, differential-pulse voltammetry (DPV) was applied to study the effects of aluminum (Al(III)) on the lactate dehydrogenase (LDH) activity, K(m)(NADH) and nu(max) in the enzyme promoting catalytic reaction of "Pyruvate+NADH+H(+)right arrow over left arrowLDHLactate+NAD(+)" by monitoring DPV reduction current of NAD(+). The changes of Al's influence on the LDH activities caused by the concentration of LDH, pH, temperature as well as Al speciation including Al hydroxide (Al-OH), Al fluoride (Al-F) and organically complexing Al (Al-Org) compounds have been investigated. The results showed that the effects of Al on the LDH activity exhibited two kinds of behaviors under different conditions, i.e. inhibitory effects or slightly increased LDH activity at low concentrations and inhibited at high concentrations. To analyze the values of K(m)(NADH) and nu(max) of LDH reaction system in the absence and presence of 0.04mmol/L Al(III), it was found that the types of the inhibition of Al(III) varied with experimental conditions. The comparisons of effects of Al(III) with Pb(II), Cd(II) and Cr(III) on the LDH activities were also inspected.

Photolytic and thermal properties of a new series of intramolecular bridged alkyl cobaloxime complexes.

The photolytic kinetic properties of a new series of intramolecular bridged alkyl cobaloxime complexes Br(O-C(3)H(6)-(dmgH))(dmgH))Co(III)(2), [H(2)O(O-C(3)H(6)-(dmg))(dmgH(2))]Co(III)[ClO(4)(3), ]Py(O-C(3)H(6)-(dmg))(dmgH(2))[Co(III)]ClO(4)(4), [Bzm(O-C(3)H(6)-(dmg))(dmgH(2))]Co(III)[ClO(4)(5) and ]Im(O-C(3)H(6)-(dmg))(dmgH(2))[Co(III)]ClO(4)(6) and their precursor aqua-(3-bromopropyl)cobaloximes (1) were investigated by UV-Vis spectroscopy. The products of photolytic solutions were characterized by both ESI-MS and (1)H-NMR techniques. Our results revealed a carbon-center radical that is produced from Co-C bond cleavage under photolysis might be linked to the equatorial ligand and thus retained in the proximity of Co(II)-complex. The thermo-gravimetric analysis of complex 2 gives the same conclusion.

Synthesis and crystal structures of a new series of intramolecular bridged alkylcobaloxime complexes.

A new series of intramolecular bridged alkylcobaloxime complexes were prepared by heating a solution of aqua-(3-bromopropyl)cobaloxime (1) through an intramolecular nucleophilic substitution. They are characterized by EA, ESI-MS, and (1)H NMR. Crystal structures of Br(O-C(3)H(6)-(dmgH))(dmgH)Co(III) (2), [H(2)O(O-C(3)H(6)-(dmg))(dmgH(2))Co(III)]ClO(4) (3), [Py(O-C(3)H(6)-(dmg))(dmgH(2))Co(III)]ClO(4) (4), [Bzm(O-C(3)H(6)-(dmg))(dmgH(2))Co(III)]ClO(4) (5), and Im(O-C(3)H(6)-(dmg))(dmgH)Co(III) (6') were determined by X-ray diffraction. It is revealed that an intramolecular tri-methylene bridge exists between cobalt and one of the equatorial oxime oxygens forming a six-membered ring in the complexes. Additionally, the axial bases have some influences in their structure parameters, for example, Co-L bond lengths; folding angles in equatorial ligands; hydrogen atom positions in O-H-O bridge; and the orientations of those L planes with respect to the equatorial planes.