SYNTHESIS, SOLUTION DYNAMICS AND X-RAY CRYSTAL-STRUCTURES OF NEODYMIUM-YLIDE COMPLEXES, [(C(5)H(4)R)(3)NDCH2P(ME)PH(2)] (R=H, BU(T))

The interaction of [(C(5)H(4)R)(2)NdCl.2LiCl] (R = H, Bu(t)) with one equivalent of Li[(CH2)(CH2)PPh(2)] in refluxing tetrahydrofuran gave the purplish-blue complex [(C(5)H(4)R)(3)NdCH2P(Me)Ph(2)] in 50% yield. The compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. Variable temperature P-31{H-1} NMR spectroscopy indicated the existence of the following equilibrium: [(C(5)H(4)R)(3)NdCH2P(Me)Ph(2)] + THF reversible arrow (C(5)H(4)R)(3)Nd(THF) + CH2=P(Me)Ph(2). At room temperature, the exchange between the coordinated and free ylide ligand is slow on the NMR time scale.

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．

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.

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。

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。

Spatial and temporal variations in pH and total alkalinity at the beginning of the rainy season in the Changjiang Estuary, China

The results of field observation carried out in May 2003 were used to examine pH and total alkalinity behaviors in the Changjiang Estuary. It was showed that PH and total alkalinity took on clear spatial variations in values with the minima in the low salinity region. Like salinity, transect distributions of PH and total alkalinity (TA) in a downriver direction had a sharp gradient each. These gradients appeared in such a sequence that the TA gradient was earlier than salinity and PH gradients, and the salinity gradient was earlier than the PH gradient. These distribution characteristics seemed to be strongly influenced by the mixing process of freshwater and seawater, for both PH and total alkalinity had significant linear relationships with salinity and temperature. For PH, phytoplankton activities also had a significant impact upon its spatial distribution. During a period of 48 h, PH and total alkalinity changed within wide ranges for every layer of the two anchor stations, namely, Stas 13 and 20, which were located at the mixed water mass and seawater mass, respectively. For both Stas 13 and 20, PH and TA fluctuation of every layer could be very wide during a 4 h period. As a whole, the data of the two anchor stations showed that neither variations in salinity and temperature nor phytoplankton activities were the main factors strongly influencing the total alkalinity temporal variability on a small time scale. The data of Sta. 20 implied that both salinity variation and phytoplankton activities had a significant influence on PH temporal variability, but the same conclusion could not be drawn from the data of Sta. 13.

ICP-MS测定表生水体稀土过程中pH值对酸性膦萃取稀土效率的影响

针对目前最常用的液- 液萃取、ICP- M S 测定法检测表生水体中微量稀土元素方法, 研究了不同pH值条件下, 酸性膦(65%HDEHP 和35%H2M EHP) 自表生水体中萃取稀土元素(REEs) 的回收率。结果表明, 在pH1～ 4 的范围内, 不同性质的水体(湖泊、河流、地下水) 有不同的REEs 回收率。其中湖水在pH 118～ 317 有90% 以上的回收率, 最高回收率为93164%; 河水在pH 211～ 315 范围内有90% 以上的回收率, 最高回收率为95152%; 地下水仅在pH 113～ 115 时回收率超过90% , 最高回收率为97161%。说明在萃取不同表生水体中稀土元素时, 需要调到特定的pH 值才能得到最好的萃取效果。

氢氧化铁胶体/水界面作用与地表水中稀土元素的分异—— pH控制机理的实验研究

实验研究了pH对REE水/粒界面配分行为的影响: 氢氧化铁胶体对REE的作用在胶体形成开始以吸附为主, 然后是解吸, 最后是吸附/解吸趋向平衡; 轻稀土元素(LREE)和重稀土元素(HREE)的吸附率不同, 后者大于前者. 随pH增加, LREE和HREE在氢氧化铁胶体/水之间产生分异, 其配分系数比值(DLREE/DHREE)降低; DREE的分布模式呈现Y的异常(DY/DHo<1)并在低pH条件下呈现明显的四重效应. 实验结果证明自然界中存在REE四重效应. 除pH外, 地表水的化学类型以及离子强度也是控制REE四重效应以及微粒吸附态REE和溶解态REE之间产生分异的重要因素.