聚电解质──壳聚糖浓溶液流变学性质研究：浓度、温度、溶剂pH值和外加盐对粘度及流动性的影响

本工作用日本岩本ＲＰＸ－７０５多功能流变仪测定了在不同浓度、温度、溶剂ｐＨ值和外加盐浓度对壳聚糖在甲酸水溶液中其浓溶液粘度η随剪切速率γ的变化关系．讨论了浓度、温度等对溶液粘度、流动活化能Ｅ_γ和流动指数ｎ的影响．发现溶剂ｐＨ值减小或溶液中外加盐浓度增加，溶液粘度变小，ｎ增大，表明非牛顿流动性减弱，并且进一步讨论了零剪切粘度η_０和外加盐浓度Ｃ_ｓ的依赖关系．

LUMINESCENCE OF BI(3+) AND THE ENERGY-TRANSFER FROM BI(3+) TO R(3+) (R=EU,DY,SM,TB) IN ALKALINE-EARTH BORATES

At room temperature, the Bi3+ ion shows broad band characters of its luminescence in Ca2B2O5, M3B2O6 ( M=Ca,Sr ) and SrB4O7. The maxima of the Bi3+ S-1(0)-->P-3(1) absorption bands are located in the range of 240-300nm, but the energy variation of the corresponding P-3(1)-->S-1(0) emissions is very large. The maxima of these emission bands change from 350nm in Ca3B2O6;Bi3+ to 586nm in SrB4O7:Bi3+. The Stokes shift of the Bi3+ luminescence increases from 6118 cm-1, in Ca2B2O5:Bi3+, to 24439 cm-1, in SrB4O7:Bi3+. The emission intensity of the Bi3+ luminescence increases with the decreasing Stokes shift. It has been found that in Ca2B2O5, the Bi3+ ion could transfer its excitation energy to the R3+ ions ( R=Eu, Dy, Sm, Tb ) , but in, Ca3B2O6 and Sr3B2O6, only Bi3+-->Eu3+ was observed. No energy transfer from Bi3+ to R3+ was detected in SrB4O7.

REDOX THERMODYNAMICS OF CYTOCHROME-C AT THE BARE GLASSY-CARBON ELECTRODE

Investigation of the redox thermodynamics of horse heart cytochrome c at bare glassy carbon electrodes has been performed using cyclic voltammetry with a nonisothermal electrochemical cell. The thermodynamic parameters of the electron-transfer reaction of cytochrome c have been estimated in different component buffer solutions. The change DELTAS(re)-degrees in reaction center entropy and the formal potential E-degrees' (at 25-degrees-C, vs. standard hydrogen electrode (SHE)) for cytochrome c are found to be -64.1 J K-1 mol-1 and 0.251 V in phosphate buffer, -64.8 J K-1 mol-1 and 0.257 V in Tris + HCl buffer, -65.6 J K-1 mol-1 and 0.261 V in Tris+CH3COOH buffer (pH 7.0, ionic strength 100 mM). The temperature dependence of the formal potential obtained in phosphate buffer with or without NaCl in the range 5-55-degrees-C shows biphase characteristics in an alkaline solution with an intersection point at ca. 44-degrees-C or 42-degrees-C, which should be due to a structural change in the protein moiety of cytochrome c. However, in acidic and neutral solutions only a monotonic relationship between E-degrees' and temperature is observed. The effect of the buffer component on E-degrees' for cytochrome c is also discussed.

ALKALI AND ALKALINE-EARTH METAL-ION TRANSFER ACROSS THE LIQUID-LIQUID INTERFACE FACILITATED BY IONOPHORE ETH157

The H+, Li+, Na+, K+, Mg2+, Ca2+ and Ba2+ ion transfer across the water/nitrobenzene (NB) and water/1,2-dichloroethane (DCE) interfaces, facilitated by the ionophore ETH157, has been investigated by cyclic voltammetry (CV). The mechanism of the transfer process has been discussed, and the diffusion coefficients and the stability constants of the complexes formed in the nitrobenzene phase have been determined.

溶剂聚合膜pH电极作内电极的气敏电极的研究

研究了以中性载体为活性物的石墨内导平头溶剂聚合膜(SPM)pH电极作内电极的二氧化碳和氨气敏电极。电极的性能取决于中性载体的特性,其中以菸酸十八酯为内电极膜活性物的二氧化碳气敏电极和以二辛基十八胺为活性物的氨气敏电极性能较佳。二氧化碳气敏电极用作丙酮酸脱羧酶酶电极的原电极,其性能院于传统的以玻璃pH电极作内电极的二氧化碳气敏电极。

pH电位法研究稀土与N—乙酰基—DL—缬氨酸的配位作用

本文以pH电位法在25.0±0.1℃及0.10mol/dm_3(NaClO_4)离子强度下测定了N—乙酰基—DL—缬氨酸的质子化常数,并系统地研究了该配体与十五种稀土元素的配应作用。发现在所研究的pH范围内,生成1:1配合物。稀土与N—乙酰基—DL—缬氨酸配合物的稳定性呈现明显的“钆断效应”。

EFFECT OF PH ON THE ELECTRON-TRANSFER OF CYTOCHROME-C ON A GOLD ELECTRODE MODIFIED WITH BIS(4-PYRIDYL)DISULPHIDE

The adsorption of bis(4-pyridyl)disulphide (PySSPy) and 4.4'-bipyridyl (PyPy) on a gold electrode was studied using cyclic voltammetry. The adsorption isotherms and equilibrium constants (1 X 10(6) mol-1 l for PyPy and 6 x 10(6) Mol-1 l for PySSPy) were determined. The effect of pH on the electrochemical behaviour of cytochrome c was studied on the PySSPy-modified gold electrode. The results show that cytochrome c can only transfer electrons on a deprotonated electrode surface. When the pH is decreased, the standard heterogeneous rate constant of cytochrome c on the modified gold electrode decreases and the electrochemical behaviour changes from a quasi-reversible to an irreversible process.

A STUDY ABOUT PH CHEMICALLY MODIFIED ELECTRODES BASED ON AMINO-DERIVATIVES OF NAPHTHALENE

The electrochemical polymerization of amino-derivatives of naphthalene has been studied on the platinum wire electrodes. The effects of acidity of the modifying media and the potential scan rate on the cyclic voltammograms are verified. As potentiometric pH sensors, the electrodes prepared from 1-naphthylamine and 2,3-diaminonaphthalene showed performance characteristics superior to some other electrodes tested. The electrode modified with 1-naphthylamine in the optimum medium showed a nearly Nernstian response of 4.20-13.70 pH and a slope of -54.8 mV/pH, while the linear range of the electrode prepared by 2,3-diaminonaphthalene was 4.00-13.60 pH, with a slope of -52.4 mV/pH.

CYCLIC VOLTAMMETRIC AND SPECTROELECTROCHEMICAL STUDIES OF COPPER IN ALKALINE-SOLUTION

The behaviour of the electroplated copper film electrode on tin oxide/glass or glassy carbon surface was studied in potassium hydroxide medium by cyclic voltammetry and in situ transmission spectroelectrochemistry. The results indicate that the electroplated copper film electrode is similar to a copper electrode and cyclic voltammetry with this electrode affords more resolution. The anodic peaks were found to correspond successively to the adsorption of oxygen, the formation of a surface layer of Cu2O, the formation of a surface layer of Cu(OH)2 or CuO and formation of a thick multilayer film of CuO. This is the first time it has been proposed that a surface layer of Cu(OH)2 or CuO is formed from the oxidation of the surface layer of Cu2O. Similarly, a clear interpretation is presented that the cathodic peaks correspond successively to the reduction of CuO to Cu2O, the reductions of Cu2O to Cu and the soluble Cu(II) species to Cu. On the other hand, a shoulder peak related to the chemical transformation of Cu(OH)2 to CuO was first observed.

稀土与L-苯丙氨酸配合物的pH电位法及量热滴定法研究

本文在25℃和0.15mol·dm~(-3)(NaCl)离子强度下,用pH电位法和量热滴定法测定了十五个稀土元素(Y和除Pm外的镧系元素)与L-苯丙氨酸1∶1配合物的稳定常数及热力学函数。L-苯丙氨酸通过—CO_2~-和—NH_2与稀土离子配位,生成较稳定的1∶1配合物。配合物稳定性呈“四分组效应”。配合物稳定性顺序中Y的位置向轻稀土方向移动。体系的熵变是配位反应驱动力。离子的去水化在配位反应中超重要作用。

INVESTIGATION ON THE LUMINESCENCE PROPERTIES OF DY-3+ AND EU-3+ IN ALKALINE-EARTH BORATES

In this paper, the yellow-to-blue intensity ratio of Dy3+ (Y/B) and the red-to-orange intensity ratio of Eu3+ (R/O) were studied in relation to the compositions and structures of alkaline-earth borates. The dependence of the energy of the Eu3+ charge-transfer band (CTB) and of the emission intensity of Dy3+ on the alkaline-earth ions and the boron content of the hosts is discussed.

ANODIC-OXIDATION OF HYDRAZINE ON GLASSY-CARBON MODIFIED BY MACROCYCLIC TRANSITION-METAL COMPLEXES .1. COBALT PROTOPORPHYRIN DIMETHYL ESTER MODIFIED ELECTRODE

The electrocatalytic oxidation of hydrazine (N2H4) on a glassy carbon electrode (GC) modified by monolayer and polymer films of cobalt protoporphyrin dimethyl ester (CoPP) has been studied. Both the monolayer and polymer films of CoPP are very active to the anodic oxidation of N2H4. The activity of CoPP for the anodic oxidation of N2H4 is dependent on the pH of the solution, and the thickness of polymerized CoPP film. The oxidation kinetics were examined by methods of cyclic voltammetry, rotating disc electrodes and steady-state polarization measurement.

稀土-HEDTA-丝氨酸三元体系的pH电位法和荧光光谱研究

氨基多羧酸是镧、锕系元素促排剂,氨基酸是重要的生物配体。稀土-氨基多羧酸-氨基酸三元体系的研究对探索稀土在人体内代谢及其生物效应具有重要意义,其次,多元配位体系荧光研究亦是令人感兴趣的课题。有关稀土-氨基多羧酸-氨基酸三元体系研究不多,稀土-N-羟乙基乙二胺三乙酸(HEDTA)-丝氨酸(Ser)三元体系研究尚未见报导。本文用pH电位法和荧光光谱研究了稀土(除钷外镧系元素及钇)-HEDTA-Ser三元体系的配位作用,考察了铽配合物配体敏化荧光光谱特点。