共查询到20条相似文献,搜索用时 15 毫秒
1.
Krzysztof Miecznikowski James A. Cox Adam Lewera Pawel J. Kulesza 《Journal of Solid State Electrochemistry》2000,4(4):199-204
We describe a sol-gel approach by which iron hexacyanoferrate is immobilized in silica in a manner suited to investigation
by electrochemistry in the absence of a contacting liquid phase. Such physicochemical parameters as concentration of redox
sites (C
o) and apparent (effective) diffusion coefficient (D
app) are estimated by performing cyclic voltammetric and potential step experiments in two time regimes, which are characterized
by linear and spherical diffusional patterns, respectively. Values of D
app and C
o thereby obtained are 2.0 × 10−6 cm2 s−1 and 1.4 × 10−2 mol dm−3. The D
app value is larger than expected for a typical solid redox-conducting material. Analogous measurements done in iron(III) hexacyanoferrate(III)
solutions of comparable concentrations, 1.0 × 10−2 and 5.0 × 10−3 mol dm−3, yield D
app on the level of 5–6 × 10−6 cm2 s−1. Thus, the dynamics of charge propagation in this sol-gel material is almost as high as in the liquid phase. The residual
water in the silica, along with the pore structure, are important to the overall mechanism of charge transport, which apparently
is limited by physical diffusion rather than electron self-exchange. Under conditions of a solid state voltammetric experiment
which utilizes an ultramicroelectrode, encapsulated iron hexacyanoferrate redox centers seem to be in the dispersed colloidal
state rather than in a form of the rigid polymeric film.
Received: 8 April 1999 / Accepted: 13 August 1999 相似文献
2.
The diffusion coefficient of water into thin polymer layers of glutar aldehyde cross-linked atelocollagen type I matrix (sample
1, the typical layer thickness was about 0.065 × 10−3 m) at 23 °C was 1.142 × 10−10 m2 s−1. At twice the concentration of the cross-linking agent (sample 2) the diffusion coefficient was 2.795 × 10−10 m2 s−1. This increase was attributed to the more ordered morphology and the creation of ordered microvoids in the film. A larger
surface area is then available for the transport of diffusing molecules, allowing a higher penetration rate of the solvent.
Received: 11 January 2000/Accepted: 6 May 2000 相似文献
3.
Hui Du Jianyu He Sicen Wang Langchong He 《Analytical and bioanalytical chemistry》2010,397(5):1947-1953
The dissociation equilibrium constant (K
D) is an important affinity parameter for studying drug–receptor interactions. A vascular smooth muscle (VSM) cell membrane
chromatography (CMC) method was developed for determination of the K
D values for calcium antagonist–L-type calcium channel (L-CC) interactions. VSM cells, by means of primary culture with rat
thoracic aortas, were used for preparation of the cell membrane stationary phase in the VSM/CMC model. All measurements were
performed with spectrophotometric detection (237 nm) at 37 °C. The K
D values obtained using frontal analysis were 3.36 × 10−6 M for nifedipine, 1.34 × 10−6 M for nimodipine, 6.83 × 10−7 M for nitrendipine, 1.23 × 10−7 M for nicardipine, 1.09 × 10−7 M for amlodipine, and 8.51 × 10−8 M for verapamil. This affinity rank order obtained from the VSM/CMC method had a strong positive correlation with that obtained
from radioligand binding assay. The location of the binding region was examined by displacement experiments using nitrendipine
as a mobile-phase additive. It was found that verapamil occupied a class of binding sites on L-CCs different from those occupied
by nitrendipine. In addition, nicardipine, amlodipine, and nitrendipine had direct competition at a single common binding
site. The studies showed that CMC can be applied to the investigation of drug–receptor interactions. 相似文献
4.
The electrochemical behaviors of metol on an ionic liquid N-butylpyridinium hexafluorophosphate modified carbon paste electrode (IL-CPE) were studied in this paper. The results indicated
that a pair of well-defined quasi-reversible redox peaks of metol appeared with the decrease of overpotential and the increase
of redox peak current, which was the characteristics of electrocatalytic oxidation. The electrocatalytic mechanism was discussed
and the electrochemical parameters were calculated with results of the charge-transfer coefficient (α) as 0.45, the electrode reaction rate constant (k
s) as 4.02 × 10−3 s−1, and the diffusion coefficient (D) as 6.35 × 10−5 cm2/s. Under the optimal conditions, the anodic peak current was linear with the metol concentration in the range of 5.0 × 10−6 ∼ 1.0 × 10−3 mol/L (n = 11, γ = 0.994) and the detection limit was estimated as 2.33 × 10−6 mol/L (3σ). The proposed method was successfully applied to determination of metol content in synthetic samples and photographic solutions. 相似文献
5.
Jun Yue Bai Liang Wang Hong Jing Wang Peng Fei Huang Yu Qing Zhao Sheng Di Fan 《Mikrochimica acta》2006,156(3-4):321-326
The electrochemical behavior of epinephrine (EP) at a mercaptoacetic acid (MAA) self-assembled monolayer modified gold electrode
was studied. The MAA/Au electrode is demonstrated to promote the electrochemical response of epinephrine by cyclic voltammetry.
The possible reaction mechanism is also discussed. The diffusion coefficient D of EP is 6.85 × 10−6 cm2 s−1. In 0.1 mol L−1 phosphate buffer (pH 7.20), a sensitive oxidation peak was observed at 0.177 V, and the peak current is proportional to the
concentration of EP in the range of 1.0 × 10−5–2.0 × 10−4 mol L−1 and 1.0 × 10−7–1.0 × 10−6 mol L−1. The detection limit is 5 × 10−8 mol L−1. The modified electrode is highly stable and can be applied to the determination of EP in practical injection samples. The
method is simple, quick, sensitive and accurate. 相似文献
6.
Biljana Šmit Biljana Petrović Sofija Sovilj Dragan Čanović Živadin D. Bugarčić 《Monatshefte für Chemie / Chemical Monthly》2008,139(10):1197-1202
The reactions of cisplatin with nizatidine and ranitidine were studied in D2O at pD 7.4 and 298 K by means of 1H NMR spectroscopy. The second order rate constants, k
2, for the reaction of cisplatin with nizatidine is (2.71 ± 0.11) × 10−4 M
−1 s−1, and for the reaction with ranitidine (6.72 ± 0.17) × 10−4 M
−1 s−1. The reactions of nizatidine and ranitidine were also studied with other Pd(II) and Pt(II) complexes. The set of the complexes
was selected because of their difference in reactivity, steric hindrance, and binding properties.
Correspondence: Prof. Dr. Živadin D. Bugarčić, Faculty of Science, University of Kragujevac, Radoja Domanovića 12, 34000 Kragujevac,
Serbia. 相似文献
7.
Functionalized polypyrrole films were prepared by incorporation of Fe(CN)6
3− as doping anion during the electropolymerization of pyrrole at a glassy carbon electrode from aqueous solution. The electrochemical
behavior of the Fe(CN)6
3−/Fe(CN)6
4− redox couple in polypyrrole was studied by cyclic voltammetry. An obvious surface redox reaction was observed and dependence
of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole film with ferrocyanide incorporated
was demonstrated by oxidation of ascorbic acid at the optimized pH of 4 in a glycine buffer. The catalytic effect for mediated
oxidation of ascorbic acid was 300 mV and the bimolecular rate constant determined for surface coverage of 4.5 × 10−8 M cm−2 using rotating disk electrode voltammetry was 86 M−1 s−1. Furthermore, the catalytic oxidation current was linearly dependent on ascorbic acid concentration in the range 5 × 10−4–1.6 × 10−2 M with a correlation coefficient of 0.996. The plot of i
p versus v
1/2 confirms the diffusion nature of the peak current i
p.
Received: 12 April 1999 / Accepted: 25 May 1999 相似文献
8.
Maria das Graças Nunes Matos Vivian Gouveia Diniz Cesar Augusto Moraes de Abreu Augusto Knoechelmann Valdinete Lins da Silva 《Adsorption》2009,15(1):75-80
Heavy metals can be removed from effluents and recovered using physico-chemical mechanisms as biosorption processes. In this
work “Arribada” seaweed biomass was employed to assess its biosorptive capacity for the chromium (Cr3+) and lead (Pb2+) cations that usually are present in waste waters of plating industries. Equilibrium and kinetic experiments were conducted
in a mixed reactor on a batch basis. Biosorption equilibrium and fluid-solid mass transfer constants data were analyzed through
the concept of ion exchange sorption isotherm. The respective equilibrium exchange constants (K
eqCr=173.42, K
eqPb=58.86) and volumetric mass transfer coefficients ((k
mCr
a)′=1.13×10−3 s−1, (k
mPb
a)′=0.89×10−3 s−1) were employed for the dynamic analysis of Cr and Pb sorption in a fixed-bed flow-through sorption column. The breakthrough
curves obtained for both metals were compared with the predicted values by the heterogeneous model (K
eqCr=171.29, K
eqPb=60.14; k
mCr
a=7.81×10−2 s−1, k
mPb
a=2.43×10−2 s−1), taking into account the mass transfer process. The results suggest that these algae may be employed in a metal removal/recovery
process at low cost.
An erratum to this article can be found at 相似文献
9.
Sayed Medhi Ghoreishi Mohsen Behpour Mohammad Hassan Motaghedi Fard 《Journal of Solid State Electrochemistry》2012,16(1):179-189
In this work, we investigate the electrochemical activity of dopamine (DA) and uric acid (UA) using both a bare and a modified
carbon paste electrode as the working electrode, with a platinum wire as the counter electrode and a silver/silver chloride
(Ag/AgCl) as the reference electrode. The modified carbon paste electrode consists of multi-walled carbon nanotubes (>95%)
treated with α-cyclodextrine, resulting in an electrode that exhibits a significant catalytic effect toward the electro-chemical
oxidation of DA in a 0.2-M Britton–Robinson buffer solution (pH 5.0). The peak current increases linearly with the DA concentration
within the molar concentration ranges of 2.0 × 10−6 to 5.0 × 10−5 M and 5.0 × 10−5 to 1.9 × 10−4 M. The detection limit (signal to noise >3) for DA was found to be 1.34 × 10−7 M, respectively. In this work, voltammetric methods such as cyclic voltammetry, chronoamperometry, chronocuolometry, differential
pulse and square wave voltammetry, and linear sweep and hydrodynamic voltammetry were used. Cyclic voltammetry was used to
investigate the redox properties of the modified electrode at various scan rates. The diffusion coefficient (D, cm2 s−1 = 3.05 × 10−5) and the kinetic parameters such as the electron transfer coefficient (α = 0.51) and the rate constant (k, cm3 mol−1 s−1 = 1.8 × 103) for DA were determined using electrochemical approaches. By using differential pulse voltammetry for simultaneous measurements,
we obtained two peaks for DA and UA in the same solution, with the peak separation approximately 136 mV. The average recovery
was measured at 102.45% for DA injection. 相似文献
10.
Liang Wang Jun Yue Bai Peng Fei Huang Hong Jing Wang Xiao Wei Wu Yu Qing Zhao 《Mikrochimica acta》2007,158(1-2):73-78
The electrochemical behaviors of uric acid (UA) at the penicillamine (Pen) self-assembled monolayers modified gold electrode
(Pen/Au) have been studied. The Pen/Au electrode is demonstrated to promote the electrochemical response of UA by cyclic voltammetry
(CV). The diffusion coefficient D of UA is 6.97 × 10−6 cm2 s−1. In differential pulse voltammetric (DPV) measurements, the Pen/Au electrode can separate the UA and ascorbic acid (AA) oxidation
potentials by about 120 mV and can be used for the selective determination of UA in the presence of AA. The detection limit
was 1 × 10−6 mol L−1. The modified electrode shows excellent sensitivity, good selectivity and antifouling properties. 相似文献
11.
Mohammad Ali Kamyabi Z. Asgari H. Hosseini Monfared 《Journal of Solid State Electrochemistry》2010,14(9):1547-1553
A carbon past electrode modified with [Mn(H2O)(N3)(NO3)(pyterpy)],
( \textpyterpy = 4¢- ( 4 - \textpyridyl ) - 2,2¢:\text6¢,\text2¢¢- \textterpyridine ) \left( {{\text{pyterpy}} = 4\prime - \left( {4 - {\text{pyridyl}}} \right) - 2,2\prime:{\text{6}}\prime,{\text{2}}\prime\prime - {\text{terpyridine}}} \right) complex have been applied to the electrocatalytic oxidation of nitrite which reduced the overpotential by about 120 mV with
obviously increasing the current response. Relative standard deviations for nitrite determination was less than 2.0%, and
nitrite can be determined in the ranges of 5.00 × 10−6 to 1.55 × 10−2 mol L−1, with a detection limit of 8 × 10−7 mol L−1. The treatment of the voltammetric data showed that it is a pure diffusion-controlled reaction, which involves one electron
in the rate-determining step. The rate constant k′, transfer coefficient α for the catalytic reaction, and diffusion coefficient of nitrite in the solution, D, were found to be 1.4 × 10−2, 0.56× 10−6, and 7.99 × 10−6 cm2 s−1, respectively. The mechanism for the interaction of nitrite with the Mn(II) complex modified carbon past electrode is proposed.
This work provides a simple and easy approach to detection of nitrite ion. The modified electrode indicated reproducible behavior,
anti-fouling properties, and stability during electrochemical experiments, making it particularly suitable for the analytical
purposes. 相似文献
12.
The electrocatalytic oxidation of quinine sulfate (QS) was investigated at a glassy carbon electrode, modified by a gel containing
multiwall carbon nanotubes (MWCNTs) and room-temperature ionic liquid of 1-Butyl-3-methylimidazolium hexafluorophate (BMIMPF6) in 0.10 M of phosphate buffer solution (PBS, pH 6.8). It was found that an irreversible anodic oxidation peak of QS with
E
pa as 0.99 V appeared at MWCNTs-RTIL/glassy carbon electrode (GCE). The electrode reaction process was a diffusion-controlled
one and the electrochemical oxidation involved two electrons transferring and two protons participation. Furthermore, the
charge-transfer coefficient (α), diffusion coefficient (D), and electrode reaction rate constant (k
f) of QS were found to be 0.87, 7.89 × 10−3 cm2⋅s−1 and 3.43 × 10−2 s−1, respectively. Under optimized conditions, linear calibration curves were obtained over the QS concentration range 3.0 × 10−6 to 1.0 × 10−4 M by square wave voltammetry, and the detection limit was found to be 0.44 μM based on the signal-to-noise ratio of 3. In
addition, the novel MWCNTs-RTIL/GCE was characterized by the electrochemical impedance spectroscopy and the proposed method
has been successfully applied in the electrochemical quantitative determination of quinine content in commercial injection
samples and the determination results could meet the requirement. 相似文献
13.
A laccase has been purified from the liquid culture growth medium containing bagasse particles of Fomes durissimus. The method involved concentration of the culture filtrate by ultrafiltration and anion exchange chromatography on diethyl
aminoethyl cellulose. The sodium dodecyl sulphate–polyacrylamide gel electrophoresis (SDS-PAGE) and native polyacrylamide
gel electrophoresis both gave single protein band indicating that the enzyme preparation was pure. The molecular mass of the
purified laccase determined from SDS-PAGE analysis was 75 kDa. Using 2,6-dimethoxyphenol as the substrate, the determined
K
m and k
cat values of the laccase are 182 μM and 0.35 s−1, respectively, giving a k
cat/K
m value of 1.92 × 103 M−1 s−1. The pH and temperature optimum were 4.0 and 35 °C, respectively. The purified laccase has yellow colour and does not show
absorption band around 610 nm found in blue laccases. Moreover, it transformed methylbenzene to benzaldehyde in the absence
of mediator molecules, property exhibited by yellow laccases. 相似文献
14.
Razika Brahimi Mohamed Trari Aïssa Bouguelia Yassine Bessekhouad 《Journal of Solid State Electrochemistry》2010,14(7):1333-1338
The delafossite CuAlO2 single crystal, prepared by the flux method, is a low mobility p-type semiconductor with a hole mobility of 1.2 × 10−5 cm−2 V−1 s−1. The chronoamperometry showed an electrochemical O2− insertion with a diffusion coefficient D
303K of 3.3 × 10−18 cm2 s−1. The thermal variation of D in the range 293–353 K gave an enthalpy of diffusion (ΔH) of 44.7 kJ mol−1. CuAlO2 is photoactive, and the Mott–Schottky plot indicates a flat band potential of +0.42 V vs saturated calomel electrode and
a holes density (N
A) of 1016 cm−3. The photocurrent spectra have been analyzed by using the Gartner model from which the absorption coefficients and diffusion
lengths were determined. An optical transition at 1.66 eV, indirectly allowed, has been obtained. The spectral photoresponse
provides a high absorption at 480 nm. The low quantum yield (η) is attributed to a small depletion length (440 nm) and a hole diffusion width (271 nm) compared to a very large penetration
depth (12 μm). 相似文献
15.
This paper describes the use of an aluminum electrode plated by metallic palladium and modified by Prussian blue (PB/Pd-Al)
in the electrocatalytic reduction of hydrogen peroxide (H2O2). The effect of pH on the electroreduction of H2O2 on the modified electrode is investigated and a simple irreversible reduction pathway is suggested. The electroreduction
kinetics including transfer coefficient α, potential-dependent charge transfer rate constants k
f, and diffusion coefficient D are estimated by means of forced hydrodynamic voltammetry using a rotating disk PB/Pd-Al electrode. The mean values obtained
for kinetics are 0.38, 10−2 cm−1, and 7.6 × 10−6 cm2 s−1, respectively. The long-term stability of the modifying layers on the Al substrate was studied. 相似文献
16.
N. Hattori H. Hirata H. Okabayashi M. Furusaka C. J. O'Connor R. Zana 《Colloid and polymer science》1999,277(1):95-100
The microstructure of the normal micelles formed by dimeric surfactants with long spacers, [Br−(CH3)2N+(C
m
H2
m
+1)-(CH2)
S
-(C
m
H2
m
+1)N+(CH3)2Br−, m = 10 and s = 8, 10 and 12], has been investigated by small-angle neutron scattering and compared with previously reported results for
micelles of the same dimeric surfactants with shorter spacers (m = 10 and s = 2, 3, 4 and 6). It was found that for dimeric surfactants with long spacers (s = 8 and 10), both micellar growth and variation in shape occur to only a small extent, if at all, compared with dimeric surfactants
with short spacers. However, for the dimeric surfactant with the longest spacer, s = 12, the extent of micellar growth and shape variation is also large. These results are due to the differences in conformation
of dimeric surfactants with short spacers (s = 2–6) compared with that of the surfactants with long spacers (s = 8–12).
Received: 15 June 1998 Accepted: 22 July 1998 相似文献
17.
Zhao Yang Gao-Shao Cao Jian Xie Xin-Bing Zhao 《Journal of Solid State Electrochemistry》2012,16(3):1271-1277
LiMnPO4, with a particle size of 50–150 nm, was prepared by oleic acid-assisted solid-state reaction. The materials were characterized
by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. The electrochemical
properties of the materials were investigated by galvanostatic cycling. It was found that the introduction of oleic acid in
the precursor led to smaller particle size and more homogeneous size distribution in the final products, resulting in improved
electrochemical performance. The electrochemical performance of the sample could be further enhanced by Co doping. The mechanism
for the improvement of the electrochemical performance was investigated by Li-ion chemical diffusion coefficient
( [(D)\tilde]\textLi ) \left( {{{\tilde{D}}_{\text{Li}}}} \right) and electrochemical impedance spectroscopy measurements. The results revealed that the
[(D)\tilde]\textLi {\tilde{D}_{\text{Li}}} values of LiMnPO4 measured by cyclic voltammetry method increase from 9.2 × 10−18 to 3.0 × 10−17 cm2 s−1 after Co doping, while the charge transfer resistance (R
ct) can be decreased by Co doping. 相似文献
18.
M. H. Pournaghi-Azar H. Dastangoo M. Ziaei 《Journal of Solid State Electrochemistry》2007,11(9):1221-1227
The electrocatalytic activity of a Prussian blue (PB) film on the aluminum electrode by taking advantage of the metallic palladium
characteristic as an electron-transfer bridge (PB/Pd–Al) for electrooxidation of 2-methyl-3-hydroxy-4,5-bis (hydroxyl–methyl)
pyridine (pyridoxine) is described. The catalytic activity of PB was explored in terms of FeIII [FeIII (CN)6]/FeIII [FeII (CN)6]1− system. The best mediated oxidation of pyridoxine (PN) on the PB/Pd–Al-modified electrode was achieved in 0.5 M KNO3 + 0.2 M potassium acetate of pH 6 at scan rate of 20 mV s−1. The mechanism and kinetics of the catalytic oxidation reaction of PN were monitored by cyclic voltammetry and chronoamperometry.
The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. The charge transfer-rate
limiting reaction step is found to be a one-electron abstraction, whereas a two-electron charge transfer reaction is the overall
oxidation reaction of PN by forming pyridoxal. The value of α, k, and D are 0.5, 1.2 × 102 M−1 s−1, and 1.4 × 10−5 cm2 s−1, respectively. Further examination of the modified electrodes shows that the modifying layers (PB) on the Pd–Al substrate
have reproducible behavior and a high level of stability after posing it in the electrolyte or Pyridoxine solutions for a
long time. 相似文献
19.
J. Aupiais 《Journal of solution chemistry》2011,40(9):1629-1644
The electrophoretic mobilities of a few halide isotopes in aqueous solution have been evaluated at 25 °C and infinite dilution
by analyzing a combination of data obtained by capillary electrophoresis (CE) and conductance data extracted from the literature.
The effect of the temperature on the electrophoretic mobility has been thoroughly re-investigated to give the following temperature
dependence for the chloride ion at 25 °C: 1.565%/ °C in 5×10−3 mol⋅L−1 sodium chromate + 3×10−3 mol⋅L−1 sodium borate buffer. The precise determination of the electrophoretic mobility of chloride and bromide ions, including the
evaluation of their associated uncertainties, has been performed from conductance data spanning over 75 years. The electrophoretic
mobilities are found to be −(79.124±0.020)×10−9 m2⋅V−1⋅s−1 for Cl− and −(80.99±0.04)×10−9 m2⋅V−1⋅s−1 for Br−. Thanks to the precise determination of the temperature contribution and the re-evaluation of conductance data, the following
values have been found for 35Cl−, 37Cl−, 79Br−, and 81Br− (in 10−9 m2⋅V−1⋅s−1): −(79.18±0.02), −(78.95±0.06), −(81.04±0.04), and −(80.94±0.04). 相似文献
20.
A new modified electrode was prepared by electrodeposition of caffeic acid (CFA) at the surface of an activated glassy carbon
electrode. Cyclic voltammetry was used to investigate the redox properties of this electrode at various solution pH values
and at various scan rates. The pH dependence of the electrode response was found to be 58.5 mV/pH, which is very close to
the expected Nernstian value. The electrode was also employed to study electrocatalytic oxidation of reduced nicotinamide
adenine dinucleotide (NADH), using cyclic voltammetry, chronoamperometry and rotating disk voltammetry as diagnostic techniques.
It was found that the modified electrode exhibits potent and persistent electrocatalytic properties toward NADH oxidation
in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 450 mV compared to the process at an
unmodified electrode. The electrocatalytic current increases linearly with NADH concentration in the range tested from 0.05
to 1.0 mM. The apparent charge transfer rate constant and transfer coefficient for electron transfer between the electrode
surface and immobilized CFA were calculated as 11.2 s−1 and 0.43, respectively. The heterogeneous rate constant for oxidation of NADH at the CFA-modified electrode surface was also
determined and found to be about 3 × 103 M−1 s−1. Finally, the diffusion coefficient of NADH was calculated as 3.24 × 10−6 cm2 s−1 for the experimental conditions, using chronoamperometric results.
Received: 6 January 1999 / Accepted: 11 May 1999 相似文献