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131.
To increase the solubility and film forming ability of polybenzimidazole (PBI), poly(N‐methylbenzimidazole) (PNMBI) with different degrees of methylation was synthesized. Chemical structure, degree of substitution, and solubility of PNMBI was studied. PNMBI is easier to be doped with acid than PBI. The basicity of PNMBI was improved with the introduction of methyl groups on the imidazole moiety. Effects of methylation degree, H3PO4 content and temperature on proton conductivity of PNMBI doped H3PO4 was studied. Proton conductivity of H3PO4 doped PNMBI‐1.2 membranes increases with increasing doping level. Temperature dependence of proton conductivity of H3PO4 doped PNMBI‐1.2 membranes follows the Arrhenius law. With an increase in the degree of substitution, proton conductivity of H3PO4 doped PNMBI decreases dramatically. The proton transport mechanism was also discussed. The proton conductivity of PNMBI/H3PO4 is mainly contributed by proton hopping or Grotthuss mechanism. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
132.
Maria Bocheska Maria Hoffmann Urszula Lesiska Emilia Luks Wanda Radecka-Paryzek 《Tetrahedron》2005,61(52):12307-12313
New compounds: 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diisopropoxyphosphorylpropoxy)calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-methoxyethoxyphosphorylpropoxy)calix[4]arene (2) were synthesized and their ionophoric properties in ion-selective membrane electrodes were studied in comparison with already described by us 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diethoxyphophorylpropoxy)calix[4]arene (3). Complexes of 1 with calcium(II), lanthanum(III), europium(III) and gadolinium(III) nitrates were prepared in direct reaction of the ligand and appropriate metal salts. They were characterized by spectral data (IR, UV/Vis, luminescence, NMR, ESI-MS) and elemental analysis. The similarity in complexing behavior of the (dialkoxyphosphoryl)propoxy-calix[4]arenes toward calcium and some lanthanides was observed. 相似文献
133.
Poly(N‐vinyl‐2‐pyrrolidone‐crotonic acid) [P(VP/CrA)] hydrogels were prepared by irradiating the ternary mixture of VP/CrA and crosslinking agent ethylene glycol dimethacrylate (EGDMA) in water by γ rays at ambient temperature. Differential scanning calorimetry and thermogravimetric analysis were performed to evaluate the thermal properties of ionized networks and to establish if they showed thermal differences that could be related to the CrA content in the gel system. The volume swelling ratio of P(VP/CrA) hydrogels were investigated as a function of the pH in the immersing solution. The volume swelling ratio of these hydrogels increased with an increase in pH and a decrease CrA content in the hydrogel. The volume swelling ratio of the hydrogels was also evaluated using an equation, based on the Flory—Huggins thermodynamic theory, the phantom network theory of James–Guth and Donnan theory of swelling of weakly charged ionic gels for determination of the molecular weight between crosslinks and the polymer–solvent interaction parameter (χ). Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
134.
135.
A photocurable acrylate matrix nitrate-sensitive membrane containing 2-nitrophenyl n-octyl ether as mediator and tetraalkylammonium nitrate as an active compound is described. The photocuring was achieved by the use of photoinitiators containing diaryliodonium chloride. This acrylate membrane is patternable via a photolithographic process with a only slight loss of electrochemical characteristics. 相似文献
136.
Present proteomics and biomedicine require sensitive analytical methods for all proteins. Recent progress in electrochemical analysis of peptides and proteins based on their intrinsic electroactivity is reviewed. Tyrosine and/or tryptophan‐containing proteins are oxidizable at carbon electrodes. At mercury electrodes all peptides and proteins (about 13 peptides and >25 proteins were tested) produce chronopotentiometric peak H at nanomolar concentrations. This peak is sensitive to changes in protein structure. Microliter sample volumes are sufficient for the analysis. Electrochemical methods can be used in studies of nucleic acid‐protein interactions and can be applied in biomedicine. Examples of such applications in neurogenerative diseases and cancer are presented. 相似文献
137.
《Electroanalysis》2003,15(11):961-968
The electrochemically initiated reaction of p‐phenylenediamines with sulfide in aqueous media is well documented. We now report the adaptation of this chemistry into nonaqueous media. This is critically appraised as a means of detecting sulfide. The electrochemically initiated reaction of N,N‐diethyl‐p‐phenylenediamine with sulfide is shown at both macro‐ and platinum microdisk electrodes with quantitative detection of sulfide produced by means of the enhanced currents observed upon its addition. The linear detection range for sulfide is dependent on the concentration of N,N‐diethyl‐p‐phenylenediamine present with a linear range from 28–3290 μM and a limit of detection of 22 μM achievable. This represents a large increase compared to that found previously in aqueous media and offers the prospect of more ready applications in high temperature systems. 相似文献
138.
《Electroanalysis》2005,17(20):1865-1869
A novel anion‐selective PVC membrane electrode based on bis‐[(3‐ferrocenyl)‐(2‐crotonic acid)] copper(II) complex [Cu(II)‐BFCA] as neutral carrier is described, which demonstrates excellent potentiometric response characteristics toward thiocyanate ion and anti‐Hofmeister selectivity sequence in following order: SCN?>I?>ClO >Sal?>Br?>NO >Cl?≈NO >SO >SO . The electrode shows a near‐Nernstian response for thiocyanate ion in a wide range of 9.0×10?7–1.0×10?1 M with a detection limit 6.8×10?7 M and a slope of ?59.1 mV/decade in pH 5.0 of phosphate buffer solution at 20 °C. The influences of lipophilic cationic and anionic additives on the response properties of the electrode were investigated. High sensitivity and wide linear dynamic range were observed for the electrode in the presence of hexadecyltrimethylammoniumborate (HTAB) as a lipophilic cationic additive. The electrode was successfully applied to the determination of thiocyanate ion in waste water and human saliva. 相似文献
139.
A solid state copper(II) ion sensor is reported based on the application of electropolymerized undoped (neutral) polycarbazole
(PCz) and polyindole (PIn) modified electrodes. The new sensor shows high selectivity to Cu2+ ions with a detection limit of 10–5 M. PCz and PIn are formed respectively by the anodic oxidation of 50 mM carbazole and 5 mM indole monomers in dichloromethane
containing 0.1 M tetrabutylammonium perchlorate on a platinum electrode using a single compartment cell. Potentiostatic polymerization
of both the monomers are carried out at 1.3 V and 1.0 V vs. Ag/AgCl, respectively. Perchlorate ions were electrochemically
removed from the polymer films by applying – 0.2 V vs. Ag/AgCl. Polymer-coated electrodes are incubated in 1 M KCl solution
for 8 h followed by incubation in distilled water for 2 h before using as a metal ion sensor. The undoped PCz and PIn electrodes
were found to be highly selective and sensitive for Cu2+ ions with little selectivity for Pb2+ and negligible response towards Ag+, Hg2+, Cu+, Ni2+, Co2+, Fe2+, Fe3+ or Zn2+. Potentiometric responses for Cu2+ ions are recorded for both the sensor electrodes together with a double-junction Ag/AgCl reference electrode. Calibration
curves for Cu2+ are reported for both ion sensors. The polymer-modified electrodes were found to be stable for several weeks.
Electronic Publication 相似文献
140.
Elena E. Ferapontova John Castillo Dmitri Hushpulian Vladimir Tishkov Tatiana Chubar Irina Gazaryan Lo Gorton 《Electrochemistry communications》2005,7(12):1291-1297
Direct electron transfer (DET) reactions of recombinant tobacco peroxidase (rTOP), namely direct electroreduction of Compound I/Compound II and heme Fe3+/2+ conversion, were studied on gold electrodes. rTOP of wild type, non-glycosylated, was produced using an Escherichia coli expression system. At pH 5.0, the redox potential for direct electrochemical transformation of the Fe3+/2+ of the peroxidase heme was −143 mV vs. AgAgCl, and 0.26 ± 0.07 pmol of the adsorbed rTOP were in DET contact with the gold electrode. The total amount of the adsorbed rTOP estimated from QCM data was 53 ± 5 pmol/cm2 or 1.67 pmol when referred to the surface area of the electrodes used for electrochemical measurements. Of 1.67 pmol of adsorbed rTOP, only 0.76 pmol were catalytically active. DET between Au and the enzyme was also studied in the reaction of the bioelectrocatalytic reduction of H2O2 by cyclic voltammetry and amperometric detection of H2O2 at +50 mV with rTOP-modified Au electrodes placed in a wall-jet flow-through electrochemical cell. Maximal bioelectrocatalytic current response of the rTOP-modified gold electrodes to H2O2 was observed at pH 5.0 and stemmed from its bioelectrocatalytic reduction based on DET between Au and the active site of rTOP. Kinetic analysis of the DET reactions gave 52% of the adsorbed rTOP molecules active in DET reactions (0.4 pmol of adsorbed catalytically active rTOP, correspondingly), which correlated well with the non-catalytic-voltammetry data. DET was characterised by a heterogeneous ET rate constant of 13.2 s−1, if one takes into account the QCM data, and 19.6 s−1, if the amount of rTOP estimated from the data on DET transformation of Fe3+/2+ couple of rTOP is considered. The sensitivity for H2O2 obtained for the rTOP-modified Au electrodes was 0.7 ± 0.1 A M−1 cm−2. These are the first ever-reported data on DET reactions of anionic plant peroxidases on bare gold electrodes. 相似文献