Evaluation of luminol-H2O2-KIO4 chemiluminescence system and its application to hydrogen peroxide, glucose and ascorbic acid assays

(A) novel chemiluminescence (CL) system was evaluated for the determination of hydrogen peroxide, glucose and ascorbic acid based on hydrogen peroxide, which has a catalytic-cooxidative effect on the oxidation of luminol by KIO4. Hydrogen peroxide can be directly determined by luminol-KIO4 -H2O2 CL system. The detection limit was 3.0 x 10(-8) mol l(-1) and the calibration graph was linear over the range of 2.0 x 10(-7)-6.0 x 10(-4) mol l(-1). The relative standard deviation of H2O2 was 1.1% for 2.0 x 10(-6) mol l(-1) (N = 11). Glucose was indirectly determined through measuring the H2O2 generated by the oxidation of glucose in the presence of glucose oxidase at pH 7.6. The present method provides a source for H2O2, which, in turn, coupled with the luminol-KIO4-H2O2 CL reaction system. The CL was linearly correlated with glucose concentration of 0.6-110 mu g ml(-1). The relative standard deviation was 2.1% for 10 mu g ml(-1) (N = 11). Detection limit of glucose was 0.08 mu g ml(-1). Ascorbic acid was also indirectly determined by the suppression of luminol-KIO4-H2O2 CL system. The calibration curve was linear over the range of 1.0 x 10(-7)-1.0 x 10(-5) mol l(-1) of ascorbic acid. The relative standard deviation was 1.0% for 8.0 x 10(-7) mol l(-1) (N = 11). Detection limit of ascorbic acid was 6.0 x 10(=8) mol l(-1). These proposed methods have been applied to determine glucose, ascorbic acid in tablets and injection. (C) 1999 Elsevier Science B.V. All rights reserved.

Dimerization of hydroxylated species of m-aminophenol by cytochrome c with hydrogen peroxide

The cytochrome c and hydrogen peroxide-dependent oxidation of m-aminophenol was investigated by electrochemistry and spectrophotometry. The results indicated that the hydroxylated species of m-aminophenol have at least two conjugated substituted groups on the ring system (most possibly, its oxidized form 2-hydroxy-4-iminoquinone), and that the degradation of cytochrome c by hydrogen peroxide can also be prevented in the presence of m-aminophenol. The hydroxyl radical scavengers, mannitol and sodium benzoate, almost completely eliminate the hydroxylation of m-aminophenol. But oxo-heme species scavenger, uric acid, does not inhibit the hydroxylation. Combining the results of mass spectrum, nuclear magnetic resonance and element analysis with that of spectrophotometry, electrochemistry and chemical scavengers, it is suggested that cytochrome c may act as a peroxidase, which facilitates the hydroxylation and subsequent dimerization of m-aminophenol. (C) 1998 Elsevier Science B.V. All rights reserved.

Investigation of oxygen- and hydrogen peroxide-reduction on platinum particles dispersed on poly(o-phenylenediamine) film modified glassy carbon electrodes

Composite membrane modified electrodes were prepared by electrochemical deposition of platinum particles in a poly(o-phenylenediamine) (PPD) him coated on glassy carbon (GC) electrodes. The modified electrodes showed high catalytic activity towards the reduction of oxygen and hydrogen peroxide. A four-electron transfer process predominated the reduction process. The pH dependence and the stability of the electrodes were also studied.

Electrochemical probe of hydroxylation of 4-nitrophenol by cytochrome c with hydrogen peroxide

The reaction of hydrogen peroxide with cytochrome c makes them coupled to lead to the hydroxylation of 4-nitrophenol. In situ electrochemical probe was used to detect the hydroxylation of 4-nitrophenol, which can avoid the tedious extraction procedure, the loss of the active species and the interference of some colored substances in the detection of 4-nitrocatechol by spectroscopic method. The hydroxyl radical scavengers mannitol and sodium benzoate did not eliminate hydroxylation, but the inhibitory effect of uric acid on the hydroxylation lead to the formation of the ferryl species of the protein during the reaction. These studies suggest that the electrochemical probe might efficiently detect the trace 4-nitrocatechol from the onset of the hydroxylation reaction and thus provides a more sensitive tool.

Structures and vibrational spectra of C-2 and LaC2+ clusters

C-2 and LaC2+ were studied using Hartree-Fock(HF), B3LYP (Becke 3-paremeter-Lee-Yang-Parr) density functional method, second-order Moller-Plesset perturbation (MP2) and coupled cluster singles and doubles with non-iterative triples(CCSD(T)) methods. The basis set employed was LANL1DZ. Geometries, vibrational frequencies and other quantities were reported. The results showed that for C-2, all the methods performed well for low spin state (singlet), while only HF and B3LYP remained so for high spin state (triplet). For LaC2+, four isomers were presented and fully optimized. The results suggested that linear isomers with C-infinity v and D-infinity h symmetries were predicted to be saddle points on the energy surface for all the methods, while for isomers with C-2 upsilon and C-s symmetries, they were local minima except C-2 upsilon at B3LYP level, and were isoenergetic at HF, MP2 and CCSD(T) levels, near isoenergetic at B3LYP level. From the differences between HOMO and LUMO, it is also known that the isomers with C-2 upsilon and C-s symmetries offer the largest values and therefore correspond to the most stable structure. For La-C bond lengths, B3LYP gives the shortest, the order is B3LYP

Synthesis and crystal structure of chiral bis(cyclopentadienyl) samarium Schiff base complexes bearing intramolecular C-C bond formation and hydrogen transfer

SmCl3, reacted with CpNa (Cp = Cyclopentadienyl) in the ratio of 1:3 in THF, which then was reacted with (S)-(+)-N-1-(phenylethyl) salicylideneamine/toluene to yield the title complex, [GRAPHICS] The X-ray crystal structure determination of the title complex reveals that 1 is a dimer with intramolecular C-C bond formation and hydrogen transfer, which leads to the configuration turnover of the carbon atom at the benzyl position of the ligand, while those of the newly formed asymmetric centers may have either Ii or S type configurations. (C) 1998 Elsevier Science Ltd. All rights reserved.

Theoretical investigation of LaC2 and LaC2+ clusters

LaC2 (with doublet and quartet states) and LaC2+ (with singlet and triplet states) cluster have been studied by using the B3LYP (Becke three-parameter/Lee-Yang-Parr) density functional method and the HF (Hartree-Fock) method with LANLIDZ basis set. For each cluster, four possible isomers in C-2v, C-s, C-proportional to v and D-proportional to h symmetries have been investigated. The results indicate that structures in C-s symmetry are local minima in all cases and, in most cases (particularly for high spin states), our initial guess in C-s symmetry converges to structures in C-2v symmetry. For the isomers in C-2v, C-proportional to v and D-proportional to h symmetries, local minima were found to be dependent on the method and spin state. The two clusters may also exist as linear chains. The ordering of the binding energies for the isomers in all spin states is C-s similar to C-2v < C-proportional to v < D-proportional to h. The ionization potential of LaC2 is reported as well. (C) 1998 Elsevier Science B.V.

Theoretical investigation of LaC3n+ (n = 0, 1, 2) clusters by density functional theory

LaC3n+ (n = 0, 1, 2) clusters have been studied using B3LYP (Becke 3-parameter-Lee-Yang-Parr) density functional method. The basis set is Dunning/ Huzinaga valence double zeta for carbon and [2s2p2d] for lanthanum, denoted LANL1DZ. Four isomers are presented for each cluster; two of them are edge binding isomers with C-2 upsilon symmetry, the other two are Linear chains with C-infinity upsilon symmetry. Meanwhile, two spin states for each isomer, that is, singlet and triplet for LaC3+, doublet and quartet for LaC3 and LaC32+, respectively, are also considered. Geometries, vibrational frequencies, infrared intensities, and other quantities are reported and discussed. The results indicate that at some spin states; the C-2 upsilon symmetry isomers are the dominant structures, while for the other spin states, linear isomers are energetically favored. (C) 1998 John Wiley & Sons, Inc.

Structure, Stability and Vibrational Spectra of LaC_5~n(n=-1,0,+1) Clusters

用密度泛含方法研究了ＬａＣ５ｎ（ｎ＝－１，０，＋１）分子簇的结构和稳定性及振动光谱，对这个六原子体系提出了三种可能构型，点群结构为Ｃ２ｖ对称性．第一个构型为Ｌａ接在弯曲的Ｃ５链上，第二个是Ｌａ通过二个键与Ｃ５环相连第三个是Ｌａ通过一个键与Ｃ５环相连；结果表明，第一个构型即当Ｌａ接在弯曲的Ｃ５链上时能量最低．振动光谱分析指出，当ｎ＝－１时，第二个构型为局域极小值；当ｎ＝＋１时，第一个和第二个构型为局域极小值；对ｎ＝０，局域极小值没有找到.

Theoretical Investigation of LaC~n and La_2C~n(n=-1,0,+1)Clusters

用密度泛函方法研究了ＬａＣｎ及Ｌａ２Ｃｎ（ｎ＝－１，０，＋１）分子簇的结构和稳定性．对Ｌａ２Ｃｎ体系，提出了两种可能构型，其中一种具有Ｃ２ｖ对称性，另一种具有Ｄ∞ｈ对称性．计算结果表明，对Ｌａ２Ｃｎ，当ｎ＝＋１，－１时，线状结构最稳定，并且在ｎ＝＋１时，Ｃ２ｖ结构极不稳定有收敛向线状结构的趋势．而当ｎ＝０时，Ｃ２ｖ结构最稳定．最后还计算了ＬａＣ和Ｌａ２Ｃ分子簇的电子亲和势和离化能.

Generation of chiral bis(cyclopentadienyl)neodymium Schiff base complex bearing internal C-C bond formation and hydrogen transfer

NdCl3 reacts with excess CpNa (Cp=Cyclopentadienyl) in THF, followed by sequent treatment with (S)-(+)-N-(1-phenylethyl)salicylideneamine led to the formation of title compound, [GRAPHICS] The X-ray structure determination shows that it is a dimer with internal C-C bond formation and hydrogen transfer between one of Cp ring and the C=N bond of Schiff base ligand. (C) 1997 Elsevier Science S.A.

Theoretical investigation of LaCn+ (n=2-8) clusters

LaCn+ (n = 2-8) have been studied using Hartree-Fock (HF) and B3LYP density functional method. The results indicated that at both levels, isomers with C-2v, C-s symmetry for n = 2, and edge insertion isomer for n = 4, 6, 8, as well as edge binding isomer for n = 3, 5, 7 were found as ground states. This is in good agreement with experimental results. The exceptional case is for n = 6 at B3LYP level, in which edge insertion and edge binding isomers were computed to be near isoenergetic. (C) 1997 Elsevier Science B.V.

Theoretical investigation of small lathanum carbide clusters

LaC2+, LaC22+, LaC3 and LaC3- clusters have been studied using B3LYP density functional method. Four isomers with C-2v, C-s, C-infinity v and D-infinity h symmetry were presented for LaC2+ and LaC22+. Meanwhile, two spin states, namely, singlet and triplet for LaC2+, doublet and quartet for LaC22+ were considered The results indicated that ring isomers with C-2v and C-s symmetry are the most stable for La-C2(+) at both spin states and for LaC22+ at quartet state. Whereas for LaC22+ at doublet state, linear isomer with C-infinity v symmetry is energetically favored, For LaC3 and LaC3- clusters,, three isomers have been presented for each cluster, that is, two ring isomers with C-2v symmetry ( in one of them, La forms two single bonds with two carbons, and in another, La forms a double bond with carbon), and one linear isomer with C-infinity v symmetry. The results revealed that the ring isomer in which La forms two single bonds with carbons is the lowest in energy.

Catalysis of copper-containing transition metal hydrotalcite-like compounds in the phenol hydroxylation with hydrogen peroxide

Hydrotalcite-like compounds containing carbonate ion as the interlayer anion were prepared by coprecipitation under low supersaturation condition by mixing an aqueous solution of metal nitrates with an aqueous solutions of NaOH and Na2CO3, at room temperature, maintaining pH = 8-10 with vigorous stirring, Following the mixing, the resulting heavy slurry was aged at 353 K for 18 h with vigorous stirring, The precipitate was then filtered, washed several times with hot distilled water and dried in air at 353 K overnight, In this way, CuMI AlCO3-HTLcs and M-I AlCO3-HTLcs were synthesized and characterized by means of XRD and IR, The catalysis of the above mentioned HTLcs were investigated in the phenol hydroxylation with H2O2. The results indicated that all of the copper-containing HTLcs had a higher catalytic activity in the reaction, However, those catalysts that did not contain copper had no catalytic activity in this reaction, This means that copper was the active center in the phenol hydroxylation. Meanwhile, the mechanism was also proposed, which could be used to explain the main reason for higher activity for CuCuAlCO3-HTLcs in the phenol hydroxylation and the effect of Mg2+, Zn2+, Co2+, Ni2+ on activity of CuMI AlCO3-HTLcs.

Chemical polymerization of aniline with hydrogen peroxide as oxidant

Oxidative polymerization of aniline in the presence of H2O2/Fe2+/HCl was carried out, and polyaniline obtained showed similar molecular structure compared to that prepared in (NH4)(2)S2O8 system.