In situ infrared spectroelectrochemical studies on adsorption and oxidation of nucleic acids at glassy carbon electrode

The adsorption and oxidation of yeast RNA and herring sperm DNA (HS DNA) at glass carbon (GC) electrode are studied by differential pulse voltammetry (DPV) and in situ FTIR spectroelectrochemistry. Two oxidation peaks of yeast RNA are obtained by DPV, whose peak potentials shift negatively with increasing pH. The peak currents decrease gradually in successive scans and no corresponding reduction peaks occur, thus indicating that the oxidation process of yeast RNA is completely irreversible. The IR bands in the 1200-1800 cm-l range, attributed to the stretching and ring vibrations of nucleic acid bases, show the main spectral changes when the potential is shifted positively, which gives evidence that the oxidation process takes place in the base residues. The oxidation process of HS DNA is similar to that of yeast RNA. The results both from DPV and in situ FTIR spectroelectrochemistry confirm that the guanine and adenine residues can be oxidized at the electrode surface, which is consistent with the oxidation mechanism of nucleic acids proposed previously. (C) 2001 Elsevier Science B.V. All rights reserved.

In-situ microscopic Fourier transform infrared spectroelectrochemistry of redox mechanism for electroactive species in polyelectrolyte

Studies for the development of the in-situ microscopic FTIR spectroelectrochemistry (MFTIRS) have been carried out in polyethylene glycol(PEG) polyelectrolyte, Redox reaction mechanisms of various electroactive substances involving inorganic salt, organic compound and inorganic polymeric particles have been studied.

In-situ Fourier transform infrared spectroelectrochemistry as a probe of the glassy carbon electrode chemically modified by nickel (II)-cyanometallates

A new nickel (II)-cyanometallates modified on glassy carbon electrode was prepared by a new method and studied by cyclic voltammetry and in situ Fourier transform infrared (FTIR) spectroelectrochemistry. It was found that the NiHCF film existed in two forms: Ni2Fe(II)-(CN)(6) and M2NiFe(II)(CN)(6), Fe(CN)(3)(6-) codeposited in the NiHCF film existing in free cation or bridged-bond state depended on the property of the cations in electrolyte: in NaCl and LiCl solution, it is in bridges-bonded, but in HCl and KCl, it is free.

Influence of cation concentration on 7,7,8,8-tetracyanoquinodimethane in polyelectrolyte by using in-situ microscopic Fourier transform infrared spectroelectrochemistry

The ion pair between the dianion of 7,7,8, 8-tetracyanoquinodimethane(TCNQ) and Li+ were investigated by in - situ microscopic Fourier transform infrared( FTIR) spectroelectrochemical technique. The effect of ion pair increases with increasing the concentration of cation. We observed a new band at 2130 cm(-1).

Cyclic voltammetric and in situ Fourier transform infrared spectroelectrochemical studies on the reaction of Cd2+ on the plussian blue/platinum modified electrode

Plussian blue(PB)/Pt modified electrode Tvas studied in the CdCl2 electrolyte solution by cyclic voltammetry and in situ FTIR spectroelectrochemistry. It was found that Cadmium ion was capable of substituting the high-spin iron of PB in an electrochemically induced substitution reaction and hexacyanoferrate cadmium (CdHCF) can be formed in the PB film. But PB and CdHCF in mixture film showed their own electrochemistry properties without serious effect on each other. The mechanism of substitution reaction has been given in detail.

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.

Rapid automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water by reverse-flow injection with chemiluminescence detection during the process of water treatment

Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL), The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10(-6) mu g ml(-1) for Fe(II) and the linear range extents up to 1.0 x 10(-4) and 5 x 10(-6) mu g ml(-1) for Mn(II) cover a linear range to 1.0 x 10(-4) mu g ml(-1). This method was used for automated in-situ monitoring of total dissolved iron and total dissolved in underground water during water treatment. (C) 1997 Elsevier Science B.V.

Chemiluminescence studies of radiation induced oxidation of various polyethylenes

The chemiluminescence (CL) emission from three kinds of polyethylene, HDPE, LLDPE and LDPE, which had been exposed to 80 kGy dose from Co-60 in both air and nitrogen, has been examined. CL measurement was done under both nitrogen and oxygen atmosphere. The results show that the CL emission from irradiated samples does not result from irradiation itself, but from the oxidation reactions occurring during and after irradiation. Addition of 1 phr of an antioxidant, Irganox 1010, can effectively inhibit the radiation induced oxidation in LLDPE and LDPE. In the case of HDPE, however, it was found that pure HDPE has the best resistance to radiation-induced oxidation of the polymers examined in this work. However, incorporation of Irganox 1010 was found to have not only a stabilizing effect against radiation induced oxidation, but also to promote the oxidation in some cases.

CRYSTAL-STRUCTURE AND INFRARED-SPECTRA OF A LANTHANUM COORDINATION COMPOUND WITH GLYCINE, ([LA(GLY)S-CENTER-DOT-2H2O]CENTER-DOT(CLO4)3)N

A lanthanum coordination compound with glycine {[La(Gly)3.2H2O].(ClO4)3}n (Gly = NH+ 3-CH2-COO-) was synthesized and obtained in the form of single crystals. Its X-ray crystal structure has been determined and the IR spectrum has been studied. Crystallo

INFRARED-SPECTRA OF DIMETHYLPHOSPHATE LANTHANIDE COMPLEXES

The infrared spectra of the crystalline solid samples of rare earth(III) dimethylphosphates Ln(DMP)3 (Ln = La, Ce, Nd) in the range 4000-100 cm-1 are discussed. It is shown that the spectra may be treated by dividing Ln(DMP)3 into two parts, an OP(OCH3)2O bridge and a LnO6 distortion octahedron. The absorption bands above 500 cm-1 may be clearly assigned. However, vibrational assignments in the far-infrared region are tentative.

AN INFRARED SPECTROSCOPIC STUDY ON THE STRUCTURAL PHASE-TRANSITIONS OF LAURYLAMMONIUM CHLORIDE

Infrared spectroscopy was used to study the structural phase, transitions of laurylammonium chloride in the temperature range from 290 to 365K. It was shown that there is a solid-solid phase transition at 339 K with a pre-transition at 327 K. The infrared spectra indicated that virgin crystals at room temperature form a well-ordered phase with all-trans hydrocarbon chains, and the lengths of N-H...Cl hydrogen bonds are different. The spectra suggested that the gauche conformers begin to appear at temperature above 327 K. The spectra at high temperature over 339 K demonstrated that the interaction between the chains decreases, the partial ''melting'' of the chains is obvious, and the hydrogen bonds (N-H...Cl) have the same lengths. The main transition and pre-transition are mainly assigned to the intramolecular and intermolecular order-disorder changes, respectively.

AN INFRARED SPECTROSCOPIC CHARACTERIZATION OF THE SOLID SOLID BEHAVIOR OF DODECYLAMMONIUM CHLORIDE

The infrared spectra of the bilayer system dodecylammonium chloride has been studied as a function of temperature. Unusual splitting of some vibrational modes helps us to characterize the structure of different solid states. This study provided the evidence for the occurrence of an order-disorder phase transition whose onset occurs at 327 K and its completion ends at 339 K. In the low temperature phase below 327 K, the virgin crystals form a well-ordered phase with all-transhydrocarbon chains. In the intermediate state between 327 and 339 K, the data demonstrate the introduction of intramolecular as well as intermolecular disorder. The coexistence of solid and liquid-crystal-like states is shown by the persistence of factor group splittings together with the existence of defect bands in the wide intermediate temperature range. In the high temperature phase over 339 K the crystals convert to a liquid-crystal-like system with extensive motional and conformational disorder, but still show characteristics in their infrared spectra which indicate the presence of ordered segments in the hexagonal solid phase.

AN INFRARED SPECTROSCOPIC STUDY OF THE STRUCTURAL PHASE-TRANSITION IN THE PEROVSKITE-TYPE LAYER COMPOUND [N-C16H33NH3]2COCL4

The solid-solid phase transitions in the perovskite-type layer compound [n- C16H33NH3]2CoCl4 have been studied by infrared spectroscopy. A new phase transition at 340 K was found by comparison with differential scanning calorimetry results. A temperature dependence study of the infrared spectra provides evidence of the occurrence of structural phase transitions related to the dynamics of the alkylammonium ions and hydrogen bonds. The main transition at 374 K corresponds to the conformational order-disorder change in the chain, which probably couples with reorientational motions of the NH3 polar heads. GTG or GTG' defects appear in the high temperature disordered phase.