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101.
Matiide Angulo Mercedes Ruiz Montoya Rafael Marin Galvin José Miguel Rodriguez Mellado 《Electroanalysis》1997,9(4):345-349
The electroreductions of the NAD+ model compounds nicotinamide (I), N1-methyl nicotinamide (II), N′-methyl nicotinamide (III) and isonicotinamide (IV) on carbon electrodes have been studied in aqueous media in the pH range 0–12 by linear-sweep cyclic voltammetry (Scheme 1, I-IV). Logarithmic analyses of the reduction peaks were performed by computing the convolution of the current with time as a function of the potential. On the basis of the experimental results it was concluded that the irreversibility of the electron transfers increased when a glassy carbon electrode was used, and this irreversibility being more marked when a plastic formed carbon electrode was employed. The reduction processes occurred with more difficulty on carbon electrodes than on mercury electrodes. Both the reduction and the reoxidation (when occurred) processes changed with respect to those observed on mercury electrodes, being irreversible electron transfers the rate-determining steps in most cases. Thus, for compounds I, II and III at pH < 2 the reductions occurred by the uptake of two electrons and two H+ ions, and the rate determining step was found to be the first one-electron transfer, for I and III, and the irreversible second electron transfer, preceded by the uptake of an H+ ion, for II. At pH>3 the processes consisted of electrodimerization reactions, preceded by the protonation of the heterocyclic nitrogen in cases I and III. The second electron transfer of the electroreduction of IV always appeared irreversible, in contrast with that found for mercury electrodes. 相似文献
102.
微分倒数示波计时电位法的研究—定量测试及滴定分析 总被引:3,自引:0,他引:3
首次利用微分倒数示波图定量测试微量金属离子并滴定分析药物,结果满意。 相似文献
103.
A differential microcalorimetric study of whey proteins and their behaviour in oil-in-water emulsions 总被引:1,自引:0,他引:1
Oil-in-water emulsions (20% soya oil, 1% protein) have been prepared containing lysozyme or isolates of -lactalbumin and β-lactoglobulin from whey protein. The structural characteristics of these proteins adsorbed at an oil/water interface were determined by following their thermal transitions using differential scanning microcalorimetry. Thermograms of the proteins in the adsorbed state differed markedly from the corresponding transitions seen for the proteins in solution. This suggests that the proteins underwent substantial changes in secondary and tertiary structure upon adsorption. In general, for all the proteins studied, a net decrease in the total energy absorbed during denaturation was found when the proteins were in an adsorbed state. Both lysozyme and -lactalbumin were in part “surface denatured”, and they showed a certain degree of reversibility between solution and the adsorbed state. β-Lactoglobulin showed the highest degree of denaturation upon adsorption and the conformational change was irreversible. 相似文献
104.
《Electroanalysis》2004,16(12):1051-1058
The voltammetric behavior of α‐ketoglutarate (α‐KG) at the hanging mercury drop electrode (HMDE) has been investigated in acetate buffer solution. Under the optimum experimental conditions (pH 4.5, 0.2 M NaAc‐HAc buffer solution), a sensitive reductive wave of α‐KG was obtained by linear scan voltammetry (LSV) and the peak potential was ?1.18 V (vs. SCE), which was an irreversible adsorption wave. The kinetic parameters of the electrode process were α=0.3 and ks=0.72 1/s. There was a linear relationship between peak current ip, α‐KG and α‐KG concentration in the range of 2×10?6–8×10?4 M α‐KG. The detection limit was 8×10?7 M and the relative standard deviation was 2.0% (Cα‐KG=8×10?4 M, n=10). Applications of the reductive wave of α‐KG for practical analysis were addressed as follows: (1) It can be used for the quantitative analysis of α‐KG in biological samples and the results agree well with those obtained from the established ultraviolet spectrophotometric method. (2) Utilizing the complexing effect between α‐KG and aluminum, a linear relationship holds between the decrease of peak current of α‐KG Δip and the added Al concentration Cequation/tex2gif-inf-5.gif in the range of 5.0×10?6–2.5×10?4 M. The detection limit was 2.2×10?6 M and the relative standard deviation was 3.1% (Cequation/tex2gif-inf-6.gif=4×10?5 M, n=10). It was successfully applied to the detection of aluminum in water and synthetic biological samples with satisfactory results, which were consistent with those of ICP‐AES. (3) It was also applied to study the effect of AlIII on the glutamate dehydrogenase (GDH) activity in the catalytically reaction of α‐KG+NH +NADH?L ‐glutamate+NAD++H2O by differential pulse polarography (DPP) technique. By monitoring DPP reductive currents of NAD+ and α‐KG, an elementary important result was found that Al could greatly affect the activity of GDH. This study could be attributed to intrinsic understanding of the aluminum's toxicity in enzyme reaction processes. 相似文献
105.
A sensitive cathodic stripping voltammetric method is developed for determination of lead(II), with adsorptive collection of complexes with Pyrogallol red (PGR) on to a hanging mercury drop electrode. After accumulation of the complex at −0.80 V vs. Ag/AgCl reference electrode, the potential is scanned in a negative direction from −0.20 to −0.50 V with differential pulse method. Then the reduction peak current for the lead(II)-PGR complex is measured at −0.39 V. The influence of reagent and instrumental variables was completely studied by factorial design analysis. The optimum analytical conditions for the determination of lead(II) were established. Under optimum conditions, lead(II) determined in the range of 0.1-30.0 ng ml−1 with a limit of detection of 0.06 ng ml−1. The method is successfully applied to determination of lead(II) in water sample. 相似文献
106.
冻干保护剂溶液低温退火特性的研究 总被引:3,自引:0,他引:3
利用差示扫描量热仪(DSC)研究了10%叔丁醇/10%蔗糖/水溶液的冻结特性, 退火温度及退火时间, 分析了溶液的退火行为. 实验结果表明, 溶液降温时, 蔗糖的存在阻碍了叔丁醇析出, 最大冻结浓缩溶液玻璃化转变温度Tg′由-32.5 ℃降低到-42.0 ℃, 升温时在-30 ℃叔丁醇发生反玻璃化. 在反玻璃化峰附近的温度进行退火可使叔丁醇充分析出, Tg′由-42.0 ℃上升到-34.9 ℃. 所需的退火时间与退火温度有关, 退火温度越接近Tg′, 所需的退火时间越长. 在-37 ℃时, 退火20 min可完全消除反玻璃化. 相似文献
107.
Mixtures of dioctadecyldimethylammonium chloride (DODAC) cationic vesicle dispersions with aqueous micelle solutions of the anionic sodium cholate (NaC) were investigated by differential scanning calorimetry, DSC, turbidity and light scattering. Within the concentration range investigated (constant 1.0 mM DODAC and varying NaC concentration up to 4 mM), vesicle → micelle → aggregate transitions were observed. The turbidity of DODAC/NaC/water depends on time and NaC/DODAB molar concentration ratio R. At equilibrium, turbidity initially decreases smoothly with R to a low value (owing to the vesicle–micelle transition) when R = 0.5–0.8 and then increases steeply to a high value (owing to the micelle–aggregate transition) when R = 0.9–1.0. DSC thermograms exhibit a single and sharp endothermic peak at Tm ≈ 49 °C, characteristic of the melting temperature of neat DODAC vesicles in water. Upon addition of NaC, Tm initially decreases to vanish around R = 0.5, and the main transition peak broadens as R increases. For R > 1.0 two new (endo- and exothermic) peaks appear at lower temperatures indicating the formation of large aggregates since the dispersion is turbid. All samples are non-birefringent. Dynamic light scattering (DLS) data indicate that both DODAC and DODAC/NaC dispersions are highly polydisperse, and that the mean size of the aggregates tends to decrease as R increases. 相似文献
108.
The authors study rotational hypersurfaces with constant Gauss-Kronecker curvature in Rn. They solve the ODE associated with the generating curve of such hypersurface using integral expressions and obtain several geometric properties of such hypersurfaces. In particular, they discover a class of non-compact rotational hypersurfaces with constant and negative Gauss-Kronecker curvature and finite volume, which can be seen as the higher-dimensional generalization of the pseudo-sphere. 相似文献
109.
本文考察了磺胺二甲嘧啶在多种底液中的极谱伏安行为,发现其在BritonRobinson(BR)缓冲溶液(pH2.2)中产生一个良好的还原峰,峰电位为-0.85V(vs.SCE),峰电流与磺胺二甲嘧啶浓度在1×10-73×10-4mol/L范围内呈良好的线性关系,检出限为9×10-8mol/L,大多数金属离子和无机阴离子不干扰测定,可望用于定量测定用多种电化学方法研究了该还原峰电流的性质,结果表明,它是具有吸附性质的不可逆还原峰 相似文献
110.
This paper reports voltammetric sequential determination of Pt(II), Pd(II), and Rh(III), by square-wave adsorption stripping voltammetry (SWAdSV), and Pb(II), by square-wave anodic stripping voltammetry (SWASV), in vegetable environmental matrices. Analytical procedures were verified by the analysis of the standard reference materials: Olive Leaves BCR-CRM 062 and Tomato Leaves NIST-SRM 1573a. Precision and accuracy, expressed as relative standard deviation and relative error, respectively, were always less than 6% and the limits of detection (LOD) for each element were below 0.096 g g–1. Once set up on the standard reference materials, the analytical procedure was transferred and applied to laurel leaves sampled in proximity to a superhighway and in the Po river mouth area. A critical comparison with spectroscopic measurements is discussed. 相似文献