Simple and rapid voltammetric determination of morphine at electrochemically pretreated glassy carbon electrodes

A simple and rapid method for morphine detection has been described based on electrochemical pretreatment of glassy carbon electrode (GCE) which was treated by anodic oxidation at 1.75 V, following potential cycling in the potential range from 0 V to 1.0 V vs. Ag vertical bar AgCl reference electrode. The sensitivity for morphine detection was improved greatly and the detection limit was 0.2 mu M. The reproducibility of the voltammetric measurements was usually less than 3% RSD for six replicate measurements. Moreover, this method could readily discriminate morphine from codeine. And an electrochemical detection of morphine in spiked urine sample was succeeded with satisfactory results.

Efficient preparation of silver nanoplates assisted by non-polar solvents

In the paper, we report an efficient method to prepare high yield (up to 97%) of silver nanoplates. Synthesis of silver nanoplates was carried Out in a binary solvent system of N,N-dimethylformamide (DMF) and toluene, in which DMF served as the reductant and polyvinylpyrrolidone (PVP) as the capping agent. By increasing the ratio of toluene to DMF to 7:6, silver nanoplates can be Successfully synthesized; otherwise other shaped nanoparticles would be the major products. The nanoplate sample was characterized by TEM, HRTEM, SAED, XRD, AFM and UV-visible spectroscopy, proving the high nanoplate purity of this sample. The influence of toluene content, other solvents, AgNO3 concentration, preparation temperature and chloride ions was also examined, which suggests that the function of nonpolar solvents in this system is to enhance the PVP coverage on silver surface and, furthermore, to facilitate the preferential adsorption of PVP on two (I I I) facets of silver nanoplates.

ZnO-based hollow microspheres: Biopolymer-assisted assemblies from ZnO nanorods

Many efforts have been made in fabricating three-dimensional (3D) ordered zinc oxide (ZnO) nanostructures due to their growing applications in separations, sensors, catalysis, bioscience, and photonics. Here, we developed a new synthetic route to 3D ZnO-based hollow microspheres by a facile solution-based method through a water-soluble biopolymer (sodium alginate) assisted assembly from ZnO nanorods. The products were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectroscopy. Raman and photoluminescence spectra of the ZnO-based hollow microspheres were obtained at room temperature to investigate their optical properties. The hollow microspheres exhibit exciting emission features with a wide band covering nearly all the visible region. The calculated CIE (Commission Internationale d'Eclairage) coordinates are 0.24 and 0.31, which fall at the edge of the white region (the 1931 CIE diagram). A possible growth mechanism of the 3D ZnO superstructures based on typical biopolymer-crystal interactions in aqueous solution is tentatively proposed, which might be really interesting because of the participation of the biopolymer.

Carboxyl-cored dendrimer and toluene-assisted fabrication of uniform platinum nanodendrites at a water/oil interface and their potential application as a catalyst

Uniform platinum nanodendrites have been prepared at a water/oil interface by a facile catalyst-free method at room temperature. This is carried out by introducing NaBH4 into the platinum precursor solution in the presence of the second generation of carboxyl-cored dendrimer ([G-2]-CO2H dendrimer) and toluene to act as a protective agent and a linker, respectively. The average fractal dimension of 1.61 of the obtained platinum nanodendrites is calculated by analysing the transmission electron micrographs using the programs Fractal Dimension Version 1.1 and Fractal Dimension Calculator. Control experiments show that the fabrication of platinum nanodendrites can be operated with a wide parameter window, which undoubtedly raises the degree of control of the synthesis process. The potential application of such a nanostructure as a catalyst is investigated, and the results reveal that they show highly efficient catalytic properties for the typical redox reaction between hexacyanoferrate (III) and thiosulfate ions at 301 K.

The preparation of high activity DMFC Pt/C electrocatalysts using a pre-precipitation method

It is suggested that a Pt/C cathodic catalyst for the direct methanol fuel cell (DMFC) can be prepared with a pre-precipitation method, in which, H2PtCl6 is precipitated onto the carbon black as (NH4)(2)PtCl6 before H2PtCl6 is reduced to Pt. The electrocatalytic activity of this Pt/C-A catalyst for oxygen reduction is excellent because the Pt/C catalyst prepared with this pre-precipitation method possesses a small average particle size, low relative crystalinity and a large electrochemically active surface area. In addition, the pre-precipitation method is simple and economical and it can be used to prepare a Pt/C catalyst on a large scale.

Electrocatalytic oxidation of dopamine at a cobalt hexacyanoferrate modified glassy carbon electrode prepared by a new method

A stable electroactive thin film of cobalt hexacyanoferrate (CoHCF) was electrochemically deposited on the surface of a glassy carbon (GC) electrode with a new and simple method. The cyclic voltammograms of the CoHCF Film modified GC (CoHCF/GC) electrode prepared by this method exhibit two pairs of well-defined redox peaks, at scan rates up to 200 mV s(-1). The advantage of this method is that it is easy to manipulate and to control the surface coverage of CoHCF on the electrode surface. The modified electrode shows good electrocatalytic activity towards the electrochemical reaction of dopamine (DA) in a 0.1 mol dm (3) KNO3 + phosphate buffer solution (pH 7.0). The rate constant of the electrocatalytic oxidation of DA at the CoHCF/GC electrode is determined by employing rotating disk electrode measurements.

Incorporation of surface-derivatized gold nanoparticles into electrochemically generated polymer films

Stable colloidal solutions of gold nanoparticles surface-derivatized with a thiol monolayer have been prepared using two-phase (water-nitrobenzene) reduction of AuCl4- by sodium borohydride in the presence of 2-mercapto-3-n-octylthiophene (MOT). This kind of surface-functionalized gold nanoparticles can be easily incorporated into the poly(3-octylthiophene) (POT) films on electrode in the process of electrochemical polymerization leading to POT-gold nanoparticle (POT-Au) composite films. Scanning probe microscopy (SPM) and X-ray photoelectric spectroscopy (XPS) have been employed to characterize the surface-derivatized particles and the resulting films. The method of incorporation of nanoparticles into polymer by surface-derivatization and in situ polymerization can also be employed to prepare many other polymer-nanoparticle compostie materials.

Rapid molecular weight determination of recombinant hirudin by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The molecular weight of recombinant hirudin ( rHV-2) was determined rapidly by matrix-assisted laser desorption/ionization time of fight mass spectrometry (MALDI-TOF-MS). The effects of the three types of matrixes were compared and discussed, alpha-cynao-4-hydroxycinnamic acid was proved to be the best matrix. It showed that MALDI-TOF-MS was superior to the traditional method of molecular weight determination of the biological macromolecules. The mass spectrum data proved that the primary structure of rHV-2 was correct and there was no amino acid deletion, mutation and modification in its expression, refolding and purification.

The electrochemically induced conformational transition of disulfides in bovine serum albumin studied by thin layer circular dichroism spectroelectrochemistry

The conformational transition of disulfides in bovine serum albumin (BSA) induced by electrochemical redox reaction of disulfides were monitored by in-situ circular dichroism (CD) spectroelectrochemistry, with a long optical path thin layer cell and analyzed by a singular value decomposition least square (SVDLS) method. Electrochemical reduction of disulfides drives the left-handed conformation of disulfides changed into the right-handed. At open circuit, eight of the 17 disulfides were of left-handed conformation. Four of the 17 disulfides took part in the electrochemical reduction with an EC mechanism. Only one-fourth of the reduced disulfides returned to left-handed conformation in the re-oxidation process. Some parameters of the electrochemical reduction process, i.e. the number of electrons transferred and electron transfer coefficient, n=8, alphan=0.15, apparent formal potential, E-1(0') = -0.65(+/-0.01) V, standard heterogeneous electron transfer rate constant, k(1)(0) = (2.84 +/- 0.14)x 10(-5) cm s(-1) and chemical reaction equilibrium constant, K-c=(5.13 +/- 0.12) x 10(-2), were also obtained by double logarithmic analysis based on the near-UV absorption spectra with applied potentials. (C) 2001 Elsevier Science B.V. All rights reserved.

Investigation of a series of synthetic cationic porphyrins using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to study a series of synthetic cationic porphyrins as the perchlorate and bromide salts. This work presents the analytical results for the porphyrins obtained using 2,5-dihydroxybenzoic acid (DHB) and 1,8,9-anthratriol as matrices. The selective use of matrix affects ion formation from these porphyrins. By using DHB as the matrix, we not only observed [M - nCIO(4)](+) (n = 1-4) ions, but also obtained [2M - nCIO(4)](+) (n = 2-7) ions from the synthetic cationic porphyrins. The space volume of the side chains (R groups) and the nature of the anions (Br- or CIO4-) affected the relative importance of monomeric and dimeric ions of the porphyrin. The possible mechanisms of desorption and ionization of these cationic porphyrins were also considered in this study. MALDI-TOFMS proved to be a very useful method for obtaining structural information on these synthetic cationic porphyrins. Copyright (C) 1999 John Whey & Sons, Ltd.

Determination of purity and molecular weight of calmodulin by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The purity and molecular weight of calmodulin have been determined by means of matrix-assisted laser desorption/ionization time of flight mass spectrometry, and the results have been discussed. The experimental results demonstrate that this method is high sensitive and rapid as compared with other traditional methods.

Application of matrix-assisted laser desorption/ionization-time of flight-mass spectrometry and sodium dodecyl sulfate-polyacrylamide gel electrophoresis in determining arginine esterase from snake venom

Using matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS). The homogeneities and molecular weights of three arginine esterases from snake venom, which possessing therapeutic use in myocardial infarction, were determined and compared, MALDI-TOF-MS is possessed of high accuracy, high sensitivity and rapidity. MALDI-TOF-MS and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) can provide complementary and confirmatory results information. MALDI-TOF-MS can be directly used as an important method for the purification of snake venom complexes successfully.

A simple method for the selective enrichment of endohedral metallofullerenes

The concentration of a polar solvent DMF extract was found to be very effective for the selective enrichment of endohedral metallofullerenes against empty fullerenes. As the solvent evaporated, endohedral metallofullerenes were effectively enriched in the solution, while most of empty fullerenes (especially C-60 and C-70) were precipitated because of their scant solubility in DMF. Matrix-assisted laser-desorption-ionization time-of-fligh mass spectrometry analysis indicated that the purity of endohedral metallofullerenes increased dramatically after concentration of the DMF extract solution. Upon transferring the extract into toluene, a solution containing significantly enriched endohedral metallofullerenes was obtained. The different solubilities of endohedral metallofullerenes versus empty fullerenes are considered to account for this selective enrichment of endohedral metallofullerenes.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of phospholipase A(2) and fibrinolytic enzyme, two enzymes obtained from Chinese Agkistrodon blomhoffii Ussurensis venom

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to analyze two enzymes, phospholipase AZ and fibrinolytic enzyme isolated from Chinese Agkistrodon blomhoffii Ussurensis venom. Using sinapinic acid as the matrix, positive ion mass spectra of the enzymes were obtained, In addition to the dominant protein [M+H](+) ions, multimeric and multiply charged ions were also observed in the mass spectra, The higher the concentration of the enzymes, the more multiply charged polymer and multimeric ions were detected, Our results indicate that MALDI-TOFMS can provide a rapid and accurate method for molecular weight determination of snake venom enzymes, Mass accuracies of 0.1 and 0.3 % were achieved by analysis of highly dialyzed phospholipase A2 and fibrinolytic enzyme, and these results are much better than those obtained using sodium dodecyl sulfate-palyacrylamide gel electrophoresis. MALDI-TOFMS thus provides a reliable method to determine the purity and molecular weight of these enzymes, which are of potential use as therapeutants, Copyright (C) 1999 John Wiley & Sons, Ltd.

A study of Aconitum alkaloids from aconite roots in Aconitum carmichaeli Debx using matrix-assisted laser desorption ionization mass spectrometry

In the present paper a study of C-19-diterpene type of aconitum alkaloids, extracted from aconite roots in Aconitum carmichaeli Debx has been made using matrix-assisted laser desorption/ionization time of Eight mass spectrometry (MALDI-TOFMS), The results demonstrated that the aconitum alkaloids from aconite roots can be determined simultaneously by this method, which was found to be superior to other analytical methods with regard to speed and sensitivity. Fourteen known aconitum alkaloids, including aconitines, benzoylaconitines and lipoaconitines, were assigned in the methanol extract and three compounds not reported before have been targeted separation. The evaluation of the efficiency of different extractions has been studied. These results suggested that the differences of the polarity and basicity of aconitine, and benzoylaconitines and lipoaconitines result from the C-8 constituent groups that are easily lost under MALDI, (C) 1998 John Wiley & Sons, Ltd.