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21.
The actual mobilities and dissociation constants of acidic and basic pharmaceuticals were determined in methanol. Actual mobilities were derived from the dependence of the effective mobilities of the analytes on the pH of the methanolic background electrolyte solution (pH(MeOH)). The pKa values of the pharmaceuticals in methanol (pK(a,MeOH)) were calculated by non-linear curve fitting to the measured mobility values. It was found that the shift in pKa value (when compounds were transferred from water to methanol) increased with the acidity of the analyte. The average pKa shift for compounds exhibiting acidic properties in water was ca. 5.5 units, and the shift for basic compounds about 2 units. As was shown for a mixture of beta-blockers, the calculated actual mobilities and pKa values can be utilised in the optimisation of pH conditions for separation. The practical value of the method was illustrated by the analysis of urine samples. 相似文献
22.
The dissociation of water adsorbed on the surface of NiO was investigated by using the semi-empirical SCF MO method MSINDO.
Simulations were based on embedded cluster models representing the (100) surface, with and without a monatomic step. The angle
formed between the metal adsorption site and the O–H bond associated with water has been found to be critical to the energetics
of the dissociation process. Based on this criterion, it was shown that water dissociation is favorable on the stepped surface,
but highly unlikely on the planar surface. In addition, the activation energy required for water dissociation in a monatomic
NiO step was considerably lower than for dissociation at the planar surface. The high activation energy associated with water
dissociation on the planar surface is attributed to the rigidity of the NiO lattice.
Dedicated to Prof. K. Jug in honor of his 65th birthday 相似文献
23.
《中国化学快报》2020,31(5):1207-1212
Developing high efficiency and low cost electrocatalysts is critical for the enhancement of oxygen reduction reaction (ORR), which is the fundamental for the development and commercialization of renewable energy conversion technology. Herein, zinc-nitrogen-carbon (Zn-N-C) was prepared by using biomass resource chitosan via a facile carbon bath method. The obtained Zn-N-C delivered a high specific surface area (794.7 cm2/g) together with pore volume (0.49 cm3/g). During the electrochemical evaluation of oxygen reduction reaction (ORR), Zn-N-C displayed high activity for ORR with an onset potential E0 = 0.96 VRHE and a half wave potential E1/2 = 0.86 VRHE, which were more positive than those of the commercial 20 wt% Pt/C benchmark catalyst (E0 = 0.96 VRHE and E1/2 = 0.81 VRHE). In addition, the Zn-N-C catalyst also had a better stability and methanol tolerance than those of the Pt/C catalyst. 相似文献
24.
《Electroanalysis》2003,15(21):1713-1718
The effect of oxygen on the mediated electrocatalytic oxidation of nicotinamide adenine dinucleotide (NADH) by diaphorase from Clostridium kluveri (DI) was studied using cyclic voltammetry, UV‐vis spectrophotometry and NMR spectrometry. The enzyme was found to be able to use molecular oxygen as an electron acceptor. NADH could therefore be oxidized by two competitive electron acceptors: a redox mediator, for istance p‐methylamino‐phenolsulfate (MAP) or ferrocene monocarboxylic acid (FMCA) properly added to the solution, and molecular oxygen. Some considerations on the consequence of the use of diaphorase from Clostridium kluveri in amperometric biosensors were also reported. 相似文献
25.
26.
As bio‐inspired chemical model of the oxygen‐evolving complex (OEC) in photosystem II, a new tyrosine‐modified corrole ligand 3 and its high‐valent copper and manganese complexes 3a and 3b were synthesized and characterized. The copper complexes 1a and 2a of corrole 1 and 2 were also prepared for comparison. The emission property indicates that the emission of ligands 2 and 3 is located at 670 nm, but no emission is observed for their metal complexes due to its suppression by the metal center. The electrochemical study shows that 3a might dimerize at the first two reversible oxidations, a behavior which was not observed in the case of 1a and 2a . The corrolato manganese(IV) complex 3b shows one reversible reduction and one quasireversible oxidation at ?0.17 and 0.77 V vs. Ag/Ag+, respectively. 相似文献
27.
应用改进了的旋转全电极上的电势阶跃计时库仑法,分别测定了不同电极电势下氧还原过程中电极吸附中间物和溶解中间物氧化所需的电量,实验证明,在此过程中电极上确有吸附中间物存在,而且是电极电势的函数,但其分子属性尚需进一步鉴别。 相似文献
28.
29.
LaxBa1—xCoO3系导电陶瓷导电性研究 总被引:1,自引:1,他引:1
对LaxBa1-xCoO导电陶瓷的导电性及其导电机制进行了研究,在x=0.5mol处,导电陶瓷具有金属态导是性,在La0.5Ba0.5CoO3陶瓷中,存在着氧缺位和导电电子,并且此种导电陶瓷具有较高的电子和氧离子混合导电特性。 相似文献
30.
本文报道测钪新试剂均三溴氯磺酚在水溶液中的离解与质子化作用,用电位法和光度法测得了它的逐级离解常数与质子化常数,以及热力学参数,并由分布函数获得试剂主要存在形式和pH值的关系。 相似文献