希土-HEDTA-蛋氨酸三元配合物研究

用pH电位法测定了希土与N-羟乙基乙二胺三乙酸(HEDTA)、蛋氨酸(Met)三元配合物在25℃和0.15mol/L(NaCl)离子强度下的稳定常数。以荧光光谱法研究了TbCl_3、Tb-Met、Tb-HEDTA以及Tb-HEDTA-Met体系,Tb~(3+)的三元配合物发射被两个配体同时敏化的Tb~(3+)特征荧光。讨论了三元体系中的配位作用以及能量传递特点。

稀土与L-苏氨酸配合物的热力学性质

在25℃和0.15mol/L(NaCl)离子强度下,用pH电位法和量热滴定法系统地测定了十五种稀土元素(除钷外)与L-苏氨酸配合物的稳定常数及其热力学参数,也得到配体L-苏氨酸的质子化常数及相应的热力学参数。考察了稀土与L-苏氨酸配合物的稳定性及其热力学参数的变化规律,详细地讨论L-苏氨酸与稀土配位作用的特点。

STUDY ON DEPOSITION POTENTIALS OF LITHIUM AND SODIUM-IONS AND DEPOLARIZATION IN BINARY CHLORIDE

Deposition potentials of Lithium and Sodium ions have been measured in binary chloride systems (LiCl-KCl, NaCl-KCl) by I-V curve method, to provide a theoretical base for preparing high purity Al-Li alloy by electrolysis in molten salt. The changes of free energy and enthalpy were calculated in terms of depolarization values on Al cathode. Thermodynamic meaning of depolarization was discussed in details and the empirical relation between binary alloy type and depolarization type was proposed. It is shown for the first time that the presence of a third element in Al-Li alloy can strengthen depolarization of Li ion at Al alloy cathode and give foundation for preparing high purity Al-Li-M ternary alloy. The effect of LiCl concentration on deposition potentials of Li ion at Al cathode in KCl-LiCl melt was studied and average active coefficient of LiCl was obtained.

STUDY ON RARE EARTH-HEDTA-SERINE TERNARY SYSTEM BY POTENTIOMETRY AND FLUORESCENCE SPECTROSCOPY

In this pare earth-HEDTA-serine (Ser) ternary system has been studied by potentiometric titration at 25 degrees C with an ionic strength of 0.15 mol.L-1 (NaCl). The excitation and fluorescence spectra of TbCl3, Tb-Ser, Tb-HEDTA and Tb-HEDTA-Ser have hem determined at room temperature. The stability constants of these ternary complexes have been obtained, It lieu been found that Tb-HEDTA-Ser ternary system exhibit characteriatic fluorescence spectrum of Tb3+ sensitized by two ligands,The results mean that the chemical hood between the control ion and the ligand in this ternary system is predominantly ionic in character,and the energy transfer from ligand to Tb8+ is performed by a kind of abort-range electron exchange action.

用透明电解槽研究镧、钕在氯化物熔盐中的溶解过程

采用透明电解槽技术首次观察了金属镧、钕分别在LaCl_3_KCl、NdCl_3+KCl以及KCl+NaCl熔盐中的溶解过程。实验发现镧、钕在各自熔盐中溶解时均产生黑色的金属雾。在电解条件下,镧、钕的溶解扩散受到很小的抑制。金属钕的溶解扩散明显快于金属镧的溶解扩散。形成的镧、钕金属雾主要由低价离子和部分金屈粒子(或原子)组成。

稀土-蛋氨酸配合物的热力学

在25℃和μ=0.15mol·L~(-1)[NaCl]条件下,用pH电位法测定了L-蛋氨酸的质子化常数、15个稀土元素与该配体生成配合物的稳定常数。表明稀土与L-蛋氨酸可生成1:1配合物。讨论了“四分组效应”及钇的位置。用量热滴定法直接测定了稀土与L-蛋氨酸生成1:1配合物的△H_(101)值,计算了△S_(101)和△G_(101)值。

衬钽管石墨炉中分子背景的调查

调查了钾、钠、钙的化合物在热解管(PGT)和衬钽管(TaT)中的分子背景。结果表明,衬钽管对NaCl、KCl、CaCl_2、Ca(NO_3)_2的背景吸收均具有明显抑制作用。

二元氯化物熔体中锂和钠离子析出电位的测定及去极化作用的研究

本文利用Ⅰ-Ⅴ曲线法测定了锂和钠离子在二元混合氯化物体系(LiCl-KCl;NaCl-KCl)中的析出电位,为利用熔盐电解法制备低钠高纯铝-锂合金提供了理论依据.根据锂离子在铝阴极上产生的去极化值求出铝和锂发生合金化反应的热力学意义,提出二元合金类型与极化类型之间的经验关系.首次通过研究锂离子在铝合金电极上的去极化行为,发现某些第三合金元素的存在可以加强锂离子的去极化作用,为进一步制取低钠高纯三元铝-锂-M合金系列提供了参考.还研究了在氯化钾-氯化锂体系中,氯化锂浓度对锂离子在铝阴极上析出电位的影响,求出了氯化锂的平均活度系数.

A NOVEL DESIGN OF LIGHT-TRANSPARENT GOLD-MINIGRID THIN-LAYER FTIR SPECTROELECTROCHEMICAL CELL WITH VERTICAL CONFIGURATION

A Teflon bridge/edge-eliminator is designed to connect a glass container and a light-transparent gold-minigrid NaCl thin-layer cell to form a vertically configured in-situ FTIR spectroelectrochemical cell. The bridge/edge-eliminator sets an internal reference point for accurate potential control. The size of the thin-layer chamber is 5 X 5 X 0.11mm. A 1900-omega formal resistance of the thin-layer cell was measured in CH2Cl2/0.1 M TBAP solution. Well defined thin-layer cyclic voltammograms and IR spectral changes for ferrocene oxidation were obtained.

氯化物熔盐中钕离子在铂电极上的电化学还原

利用极谱,Ⅲ利用电位阶跃研究了轻稀土离子在碱金属氯化物熔盐中的阴极还原。本文作者研究过Sm~(3+)在NaCl-KCl熔盐中的电还原。上述工作分别提出了稀土离子一步还原和分步还原的结论。本文采用线性扫描伏安法和恒电位电解,并配以扫描电子显微镜X射线能谱分析,对Nd~(3+)在Pt电极上的阴极还原过程进行了研究,利

直接氯化法测定LiCl熔盐体系相图的研究及LiCl-KCl-LiF三元相图的制作

首次成功地将NH_4Cl直接氯化Li_2CO_3的反应引入热分析,制作含LiCl的二元、三元体系溶盐相图,避免LiCl吸水性给相图绘制带来的困难,三个二元体系LiCl-KCl、NaCl-LiCl和LiCI-LiF的测定结果与文献吻合很好.并在此基础上制作了LiCl-KCl-LiF三元相图。

稀土-丝氨酸配合物的热力学研究

在25℃和μ=0.15mol[NaCl]条件下,用电位法测定了L-丝氨酸的质子化常数、15个稀土元素与该配体生成配合物的稳定常数,表明稀土与L-丝氨酸可生成1:1及1:2配合物。讨论了“四分组效应”及钇的位置。用量热滴定法直接测定了稀土与L-丝氨酸生成1:1配合物的△H_(101)值,计算了△S_(101)和△G_(101)值。

石墨炉原子吸收光谱法测铝时氯化物的干扰及硝酸钙的增感作用

本文研究了石墨炉原子吸收光谱法测铝时各种氯化物的干扰及硝酸钙的增感作用。NaCl、KCl、FeCl_3、CuCl_2对铝的测定产生负干扰,这种干扰来自气相中铝和氯的结合;MgCl_2和CaCl_2对铝产生正干扰,其干扰来自它们分解出的氧物化对铝的增感作用。硝酸钙不仅对铝产生增感作用,而且也提高铝的最高允许灰化温度,降低原子化温度,同时也增强抗干扰能力。本文还利用钙的增感作用直接测定了河水及地下水中的痕量铝,结果满意。

Molecular cloning and stress-dependent expression of a gene encoding Delta(12)-fatty acid desaturase in the Antarctic microalga Chlorella vulgaris NJ-7

The psychrotrophic Antarctic alga, Chlorella vulgaris NJ-7, grows under an extreme environment of low temperature and high salinity. In an effort to better understand the correlation between fatty acid metabolism and acclimation to Antarctic environment, we analyzed its fatty acid compositions. An extremely high amount of Delta(12) unsaturated fatty acids was identified which prompted us to speculate about the involvement of Delta(12) fatty acid desaturase in the process of acclimation. A full-length cDNA sequence, designated CvFAD2, was isolated from C. vulgaris NJ-7 via reverse transcription polymerase chain reaction (RT-PCR) and RACE methods. Sequence alignment and phylogenetic analysis showed that the gene was homologous to known microsomal Delta(12)-FADs with the conserved histidine motifs. Heterologous expression in yeast was used to confirm the regioselectivity and the function of CvFAD2. Linoleic acid (18:2), normally not present in wild-type yeast cells, was detected in transformants of CvFAD2. The induction of CvFAD2 at an mRNA level under cold stress and high salinity is detected by real-time PCR. The results showed that both temperature and salinity motivated the upregulation of CvFAD2 expression. The accumulation of CvFAD2 increased 2.2-fold at 15A degrees C and 3.9-fold at 4A degrees C compared to the alga at 25A degrees C. Meanwhile a 1.7- and 8.5-fold increase at 3 and 6% NaCl was detected. These data suggest that CvFAD2 is the enzyme responsible for the Delta(12) fatty acids desaturation involved in the adaption to cold and high salinity for Antarctic C. vugaris NJ-7.

琼脂分级产物的研究

琼脂（agar，又称琼胶）作为世界三大工业海藻胶之一，被广泛应用于食品、医药、生物技术、造纸等领域。本文首先研究了琼脂的分级方法，用DEAE-Cellulose将石花菜琼脂分级，得到四个级分，即水级分、0.5mol/L NaCl级分、1.0mol/L NaCl级分、2.5mol/L NaCl级分。分析了各级分的理化性质，并通过IR和~（13）C-NMR光谱研究其化学结构。石花菜琼脂分级得到的四个级分中，水级分的硫酸基含量为0.16%，凝胶强度为1130 g/cm~2（1%浓度），电内渗（EEO）为0.12，主要质量标准为Sigma公司的低电内渗琼脂糖(agarose）产品接近，符合低电内渗琼脂糖产品的质量要求。1.0mol/L NaCl级分和2.5mol/L NaCl级分的硫酸基含量较高，分别为22.8%和32.5%，合称为硫琼脂(agaropectin）。在琼脂糖的应用中，特别是现代生物技术研究中，需要低凝固温度琼脂糖。本文以石花菜琼脂分级得到的水级分为原料，采用甲基化反应制备低凝固温度琼脂糖。实验产品的凝固温度为30.1 ℃(1.5%浓度），融化温度为64.8 ℃（1.5%浓度），凝胶强度为264 g/cm~2(1%浓度），主要质量标准与Sigma公司的低凝固温度琼脂糖产品接近，符合低凝固温度琼脂糖产品的质量要求。随着对多糖生物学功能的深入，海藻硫酸多糖表现出多种生物活性，其活性研究已经成为目前新药研究的一个热点。到目前为止，有关琼脂分级产物的生物活性研究较少。本文在研究石菜硫琼脂的组成和主要理化特性的基础上，对基体内外抗凝血活性进行了较系统的研究。新西兰兔腹主动脉血体外抗凝实验结果表明，石花菜硫琼脂具有明显的体外抗凝血活性，在3.125mg/ml ～ 25mg/ml剂量范围内呈现量效关系；大鼠体内抗凝血实验的结果表明其口服可以吸收，在体内产生抗凝血作用，在100 mg/kg·d ～ 400 mg/kg·d剂量范围内，与全血凝血时间(CT）、凝血酶时间（TT）、凝血酶原时间（PT）、部分凝血活酶时间（KPTT）的延长及血浆纤维蛋白原（Fib）含量的降低均呈剂量依赖关系。就其抗凝血机制而言，石花菜硫琼脂的抗凝血作用既影响凝血系统，又影响纤溶系统。