首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
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   

2.
The spectra and kinetic behavior of solvated electrons (esol) in alkyl ammonium ionic liquids (ILs), i.e. N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMMA-BF4), N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13-TFSI), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13-TFSI), and N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P14-TFSI) were investigated by the pulse radiolysis method. The esol in each of the ammonium ILs has an absorption peak at 1100 nm, with molar absorption coefficients of 1.5–2.3×104 dm3 mol−1 cm−1. The esol decayed by first order with a rate constant of 1.4–6.4×106 s−1. The reaction rate constant of the solvated electron with pyrene (Py) was 1.5–3.5×108 dm3 mol−1 s−1 in the various ILs. These values were about one order of magnitude higher than the diffusion-controlled limits calculated from measured viscosities. The radiolytic yields (G-value) of the esol were 0.8–1.7×10−7 mol J−1. The formation rate constant of esol in DEMMA-TFSI was 3.9×1010 s−1. The dry electron (edry) in DEMMA-TFSI reacts with Py with a rate constant of 7.9×1011 dm3 mol−1 s−1, three orders of magnitude higher than that of the esol reactions. The G-value of the esol in the picosecond time region is 1.2×10−7 mol J−1. The capture of edry by scavengers was found to be very fast in ILs.  相似文献   

3.
Dynamic interfacial tension between aqueous solutions of 3-dodecyloxy-2-hydroxypropyl trimethyl ammonium bromide (R12HTAB) and n-hexane were measured using the spinning drop method. The effects of the R12HTAB concentration (the concentration below the CMC) and temperature on the dynamic interfacial tension have been investigated; the reason of the change of dynamic interfacial tension with time has been discussed. The effective diffusion coefficient, Da, and the adsorption barrier, a, have been obtained from the experimental data using the extended Word–Tordai equation. The results show that the dynamic interfacial tension becomes smaller while a becomes higher with increasing R12HTAB concentration in the bulk aqueous phase. Da decreases from 5.56 × 10−12 m−2 s−1 to 0.87 × 10−12 m−2 s−1 while a increases from 5.41 kJ mol−1 to 7.74 kJ mol−1 with the increase of concentration in the bulk solution of R12HTAB from 0.5 × 10−3 mol dm−3 to 4 × 10−3 mol dm−3. Change of temperature affects the adsorption rate through altering Da and a. The value of Da increases from 5.56 × 10−12 m−2 s−1 to 13.98 × 10−12 m−2 s−1 while that of a decreases from 5.41 kJ mol−1 to 5.07 kJ mol−1 with temperature ascending from 303 K to 323 K. The adsorption of surfactant from the bulk phase into the interface follows a mixed diffusion–activation mechanism, which has been discussed in the light of interaction between surfactant molecules, diffusion and thermo-motion of molecules.  相似文献   

4.
The preparation and electrochemical characterization of a carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) as well as its behavior as electrocatalyst toward the oxidation of N-acetylcysteine were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of N-acetylcysteine were explored using sweep linear voltammetry. The best voltammetric response was observed for a paste composition of 20% (w/w) copper(II) hexacyanoferrate(III) complex, acetate buffer solution at pH of 6.0 as the electrolyte and scan rate of 10 mV s− 1. A linear voltammetric response for N-acetylcysteine was obtained in the concentration range from 1.2 × 10− 4 to 8.3 × 10− 4 mol L− 1, with a detection limit of 6.3 × 10− 5 mol L− 1. The proposed electrode is useful for the quality control and routine analysis of N-acetylcysteine in pharmaceutical formulations.  相似文献   

5.
Recombination rate coefficients of protonated and deuterated ions KrH+, KrD+, XeH+ and XeD+ were measured using Flowing Afterglow with Langmuir Probe (FALP). Helium at 1600 Pa and at temperature 250 K was used as a buffer gas in the experiments. Kr, Xe, H2 and D2 were introduced to a flow tube to form the desired ions. Because of small differences in proton affinities of Kr, D2 and H2 mixtures of ions, KrD+/D3+ and KrH+/H3+ are formed in the afterglow plasma, influencing the plasma decay. To obtain a recombination rate coefficient for a particular ion, the dependencies on partial pressures of gases used in the ion formation were measured. The obtained rate coefficients, αKrD+(250 K) = (0.9 ± 0.3) × 10−8 cm3 s−1 and αXeD+(250 K) = (8 ± 2) × 10−8 cm3 s−1 are compared with αKrH+(250 K) = (2.0 ± 0.6) × 10−8 cm3 s−1 and αXeH+(250 K) = (8 ± 2) × 10−8 cm3 s−1.  相似文献   

6.
The kinetics of phenylalanine (phe) oxidation by permanganate has been investigated in absence and presence of cetlytrimethylammonium bromide (CTAB) using conventional spectrophotometric technique. The rate shows first- and fractional-order dependence on [MnO4] and [phe] in presence of CTAB. At lower values of [CTAB] (≤10.0 × 10−4 mol dm−3), the catalytic ability of CTAB aggregates are strong. In contrast, at higher values of [CTAB] (≥10.0 × 10−4 mol dm−3), the inhibitory effect was observed in absence of H2SO4. We find that anions (Br, Cl and NO3) in the form of sodium salts are strong inhibitors for the CTAB catalyzed oxidation. Kinetic and spectrophotometric evidences for the formation of an intermediate complex and an ion-pair complex between phe and MnO4, CTAB and MnO4, respectively, are presented. A mechanism consistent with kinetic results has been discussed. Complex formation constant (Kc) and micellar binding constant (Ks) were calculated at 30 °C and found to be Kc = 319 mol−1 dm−3 and Ks = 1127 mol−1 dm−3, respectively.  相似文献   

7.
The α-tocopheroxyl radical was generated voltammetrically by one-electron oxidation of the α-tocopherol anion (r1/2=−0.73 V versus Ag|Ag+) that was prepared by reacting α-tocopherol with Et4NOH in acetonitrile (with Bu4NPF6 as the supporting electrolyte). Cyclic voltammograms recorded at variable scan rates (0.05–10 V s−1), temperatures (−20 to 20°C) and concentrations (0.5–10 mM) were modelled using digital simulation techniques to determine the rate of bimolecular self-reaction of α-tocopheroxyl radicals. The k values were calculated to be 3×103 l mol−1 s−1 at 20°C, 2×103 l mol−1 s−1 at 0°C and 1.2×103 l mol−1 s−1 at −20°C. In situ electrochemical-EPR experiments performed at a channel electrode confirmed the existence of the α-tocopheroxyl radical.  相似文献   

8.
Recombination of HCO+ and DCO+ ions with electrons was studied in afterglow plasma. The flowing afterglow with Langmuir probe (FALP) apparatus was used to measure the recombination rate coefficients and their temperature dependencies in the range 150–270 K. To obtain a recombination rate coefficient for a particular ion, the dependencies on partial pressures of gases used in the ion formation were measured. The variations of αHCO+(T) and αDCO+(T) seem to obey the power law: αHCO+(T) = (2.0 ± 0.6) × 10−7 (T/300)−1.3 cm3 s−1 and αDCO+(T) = (1.7 ± 0.5) × 10−7 (T/300)−1.1 cm3 s−1 over the studied temperature range.  相似文献   

9.
Degradation of polyoxyethylene chain of non-ionic surfactant (TritonX-100) by chromium(VI) has been studied spectrophotometrically under different experimental conditions. The reaction rate bears a first-order dependence on the [Cr(VI)] under pseudo-first-order conditions, [TritonX-100]  [Cr(VI)] in presence of 1.16 mol dm−3 perchloric acid. The observed rate constant (kobs) was 3.3 × 10−4 to 3.5 × 10−4 s−1 and the half-life (t1/2) was 33–35 min for chromium(VI). The effects of total [TritonX-100] and [H+] on the reaction rate were determined. Reducing nature of non-ionic TritonX-100 surfactant is found to be due to the presence of –OH group in the polyoxyethylene chain. It was observed that monomeric and non-ionic micelles of TritonX-100 were oxidized by chromium(VI). When [TritonX-100] was less than its critical micelle concentration (cmc) the kobs values increased from 0.76 × 10−4 to 1.5 × 10−4 s−1. As the [TritonX-100] was greater than the cmc, the kobs values increases from 2.1 × 10−4 to 8.2 × 10−4 s−1 in presence of constant [HClO4] (1.16 mol dm−3) at 40 °C. A comparison was made of the oxidative degradation rates of TritonX-100 with different metal ion oxidants. The order of the effectiveness of different oxidants was as follows: permanganate > diperiodatoargentate(III) > chromium(VI) > cerium(IV).  相似文献   

10.
The direct electron transfer and electrocatalysis of hemoglobin (Hb) entrapped in polyvinyl alcohol (PVA)–room temperature ionic liquid (i.e., 1-octyl-3-methylimidazolium hexafluorophosphate [OMIM]PF6) composition has been investigated by using cyclic voltammetry and chronocoulometry. It is found that the composition can promote the direct electron transfer of Hb and the heterogeneous electron transfer rate constant (ks) of immobilized Hb is enhanced to 19.9 s−1. The immobilized Hb also shows high electro-catalytic activity towards the redox of oxygen, hydrogen peroxide and nitrite. The Michaelis constants (Km) decrease to 1.2 × 10−4 M (for hydrogen peroxide) and 9.4 × 10−3 M (for nitrite). The surface concentration of electroactive Hb is estimated and it is ca. 1.4 × 10−10 mol cm−2, meaning that several layers of immobilized Hb take part in the electrochemical reaction. When gold nanoparticles (GNP) is introduced into the composition, the resulting PVA–GNP–[OMIM]PF6 composition presents better performance. The electrochemical characteristic of immobilized Hb is improved further. Thus PVA–GNP–[OMIM]PF6 composition is more suitable for the immobilization of Hb. Therefore, it is a good strategy to prepare novel composition for protein immobilization by using several materials with different function.  相似文献   

11.
Four short- and long-alkyl-multiamine ligands L1–L4 have been synthesized and characterized. The catalytic efficiency of complex CuL1 and functional metallomicelles CuL2–CuL4 were comparatively investigated for the hydrolysis of bis(p-nitrophenyl) phosphate (BNPP) in buffered solution at 30 °C. The ternary kinetic model for metallomicellar catalysis was suggested to analyze the experimental data. The kinetic and thermodynamic parameters kN, KT and pKa were obtained. The results indicated that the complexes with 1:1 ratio of ligands L2–L4 to copper(II) ion were the kinetic active catalysts, and the deprotonized Cu(II) complex formed by activated water molecule was the real active species for BNPP catalytic hydrolysis. The real rate constant of the reaction catalyzed by CuL1–CuL4 was 4.00 × 10−6, 7.44 × 10−5, 1.42 × 10−4 and 4.10 × 10−4 s−1, respectively. The effects of ligand and microenvironment on the hydrolytic reaction of BNPP have been discussed in detail.  相似文献   

12.
A model K+ sensor using Prussian blue nanotubes is fabricated by electrochemical deposition of Prussian blue (PB) within the nanochannels of a porous metal-coated membrane with partially covered pore openings. The PB nanotube sensor exhibits excellent stability giving reproducible peak potentials up to 500 measurement cycles, a very low detection limit of 2.0 × 10−8 M and extremely wide logarithmic linear ranges between 5.0 × 10−8–7.0 × 10−4 M and 7.0 × 10−4–1.0 M. Negligible interferences by Na+, Mg2+ and Ca2+ are observed and a rapid analysis time of 30 s is readily achieved. The ease of electrodeposition, high stability of PB nanotubes and outstanding analytical performance which surpasses conventional PB voltammetric and potentiometric sensors demonstrates potential sensing applications including ion sensors and biosensors using PB and other metal hexacyanoferrate nanotubes.  相似文献   

13.
A detailed study of the electrochemical reduction of diacetylbenzene A in aqueous medium between Ho = −5 and pH 14 is presented. The reactants are strongly adsorbed, so that the reactions are of a surface nature. From Ho = −5 to pH 6, a global 2e reduction yielding an enediol-type intermediate occurs. Analysis using the theory of the square schemes with protonations at equilibrium shows that, up to pH 4, the reaction is controlled by the first electron uptake, the paths being successively H+e and eH+. The elementary electrochemical surface rate constants are 9.6 × 107 s and 1.2 × 106 s for AH+ and A respectively. From pH 6 to 14, a le adsorption wave, corresponding to the formation of (a) monoradical(s), appears and is followed by a le wave due to the reduction of the radical(s). A dimerization occurs, due to the coupling A + AH, as in the case of the monocarbonyl compounds. The rate of this surface process, kd = 5 × 1013 cm2 mol−1 s−1, is markedly smaller than the rate of the homogeneous reaction obtained in alkaline ethanol by Savéant et al. for the coupling of the radicals of benzaldehyde, benzophenone and acetophenone.  相似文献   

14.
A rapid, simple and sensitive spectrofluorimetric method for determination of trace amount of bromazepam is developed. In phosphate buffer of pH 7.4. The bromazepam enhance the luminescence intensity of the Eu3+ ion in Eu3+–bromazepam complex at λex = 390 nm. The produced luminescence intensity of Eu3+–bromazepam complex is in proportion to the concentration of bromazepam. The working range for the determination of bromazepam is 2.3 × 10−8 to 6.2 × 10−7 M with detection limit (LoD) and quantitative detection limit (LoQ) of 3 × 10−9 and 1.2 × 10−8 M, respectively. While, the working range, detection limit (LoD) and quantitative detection limit (LoQ) in case of the quantum yield calculations are 3.7 × 10−8 to 3.4 × 10−7 M with of 3.4 × 10−9 and 9.2 × 10−8 M, respectively. The enhancement mechanism of the luminescence intensity in the Eu3+–bromazepam system has been also explained.  相似文献   

15.
Positron lifetime measurements were performed on a series of organic electron acceptors and charge-transfer complexes in solution. The acceptors cause both positronium (Ps) inhibition (with maybe one exception) and quenching, but when an acceptor takes part in a charge-transfer complex the inhibition intensifies and the quenching almost vanishes. The reaction constants between ortho-Ps and the acceptors were determinded to be: 1.5 × 1010 M−1 s−1 for SO2 in dioxane 3.7 × 1010 M−1 s−1 for SO2 in n-heptane, 3.4 × 1010 M−1 s−1 for tetracyanoquinodimethane in tetrahydrofurane and 1.6 × 1010 M−1 s−1 for tetracyanoethylene in dioxane. From the ortho-Ps lifetimes in solutions containing charge-transfer complexes complexity constants were determined that were in reasonable agreement with constants obtained from optical data. The influence of acceptors and charge-transfers complexes on the Ps yield was interpreted in terms of the spur reaction model of Ps formation. Correlation was also made to gas phase reaction between electron acceptors and free electron, as well as to pulse radiolysis data.  相似文献   

16.
Semiautomatic methods are described for the catalytic titrimetric determination of microamounts of silver and mercury(II) using a chloramine-T-selective electrode as monitor. The methods are based on the inhibitory effect of Ag(I) and Hg(II) on the iodide-catalyzed chloramine-T-arsenite and chloramine-T-H2O2 reactions. Microamounts of silver in the range 0.2–200 μg (1 × 10−7−1 × 10−4 M) and of mercury(II) in the range 0.1–200 μg (2.5 × 10−8−5 × 10−5 M) were determined using the chloramine-T-As(III) indicator reaction. Mercury(II) in the range 4–2000 μg (1 × 10−6−5 × 10−4 M) was also determined using the chloramine-T-H2O2 indicator reaction. The accuracy and precision were in the range 0.1–1%.  相似文献   

17.
Salicylaldehyde rhodamine B hydrazone (SRBH) was developed as a new spectrofluorimetric probe for the selective and sensitive detection of CrO42− in acidic conditions. The proposed method was based on the special oxidation reaction between non-fluorescent SRBH by potassium dichromate to produce a highly fluorescent rhodamine B, as a product. Under the optimum conditions described, the fluorescence enhancement at 591 nm was good linearly related to the concentration of CrO42− from 1.0 × 10−8 to 3.0 × 10−7 M (0.42–12.6 ng mL−1) with a correlation coefficient of R2 = 0.9989 (n = 10) and a detection limit of 1.5 × 10−9 M (0.063 ng mL−1). The relative standard deviation (R.S.D.) was 2.0% (n = 6). The proposed method was also successfully applied to the determination of chromium (VI) in drinking water, river water and synthetic samples.  相似文献   

18.
Pulse radiolysis transient UV–visible absorption spectroscopy was used to study the UV–visible absorption spectrum (225–575 nm) of the phenyl radical, C6H5(), and kinetics of its reaction with NO. Phenyl radicals have a strong broad featureless absorption in the region of 225–340 nm. In the presence of NO phenyl radicals are converted into nitrosobenzene. The phenyl radical spectrum was measured relative to that of nitrosobenzene. Based upon σ(C6H5NO)270 nm=3.82×10−17 cm2 molecule−1 we derive an absorption cross-section for phenyl radicals at 250 nm, σ(C6H5())250 nm=(2.75±0.58)×10−17 cm2 molecule−1. At 295 K in 200–1000 mbar of Ar diluent k(C6H5()+NO)=(2.09±0.15)×10−11 cm3 molecule−1 s−1.  相似文献   

19.
Combining a temperature variable 22-pole ion trap with a cold effusive beam of neutrals, rate coefficients k(T) have been measured for reactions of CO2+ ions with H, H2 and deuterated analogues. The neutral beam which is cooled in an accommodator to TACC, penetrates the trapped ion cloud with a well-characterized velocity distribution. The temperature of the ions, T22PT, has been set to values between 15 and 300 K. Thermalization is accelerated by using helium buffer gas. For reference, some experiments have been performed with thermal target gas. For this purpose hydrogen is leaked directly into the box surrounding the trap. While collisions of CO2+ with H2 lead exclusively to the protonated product HCO2+, collisions with H atoms form mainly HCO+. The electron transfer channel H+ + CO2 could not be detected (<20%). Equivalent studies have been performed for deuterium. The rate coefficients for reactions with atoms are rather small. Within our relative errors of less than 15%, they do not depend on the temperature of the CO2+ ions nor on the velocity of the atoms (k(T) lays between 4.5 and 4.7 × 10−10 cm3 s−1 with H as target, and 2.2 × 10−10 cm3 s−1 with D). For collisions with molecules, the reactivity increases significantly with falling temperature, reaching the Langevin values at 15 K. These results are reported as k = α (T/300 K)β with α = 9.5 × 10−10 cm3 s−1 and β = −0.15 for H2 and α = 4.9 × 10−10 cm3 s−1 and β = −0.30 for D2.  相似文献   

20.
A novel hybrid bifunctional sensing platform for simultaneous determination of NO and O2 has been developed, whereby hematite nanotubes are immobilized into the chitosan matrix onto a gold electrode (labeled as HeNTs-Chi/Au). The HeNTs distributed in porous-structured chitosan matrix not only offer abundant active sites for bifunctional sensing of NO and O2, but also facilitate oxidation of NO and reduction of O2 dramatically. Straight calibration curves are achieved in analyte concentration ranges of 5.0 × 10−8 to 1.25 × 10−6 mol L−1 for NO and 2.5 × 10−7 to 6.0 × 10−6 mol L−1 for O2. Also, the detection limits are low of 8.0 × 10−9 mol L−1 for NO and 5.0 × 10−8 mol L−1 for O2. Such an efficient bifunctional sensor for NO and O2 offers great potential in quantitation of NO levels in biological and medical systems, since NO level is highly regulated by various reactive oxygen species.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号