β—型过渡元素三取代钨锗杂多配合物的合成,表征和催化活性

报道Ａ－β－Ｍ＇ｘＨｙ－［ＧｅＷＯＭ３（Ｈ２Ｏ）３Ｏ３７］．ｎＨ２Ｏ（Ｍ＝Ｃｒ＾３＾＋，Ｃｏ＾２＾＋，Ｎｉ＾２＾＋，Ｃｕ＾２＾＋；Ｍ＇＝Ｂｕ４Ｎ＾＋，Ｋ＾＋）的立体有择合成法制备及红外和远红外光谱，紫外和可见光谱和循环伏安，磁化率和磁矩，ＸＰＳ，ＥＳＲ以及催化活性等研究结果。     

碳基铁—硫醇（硫酚）—格氏试剂体系与芳酰氯反应的研究：…

通过Ｆｅ３（ＣＯ）１２、硫醇（硫酚）和ＥｔＭｇＢｒ所形成的络盐［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ６）》－Ｍｇ＾＋Ｂｒ与氯代芳酰氯的原位反应，合成了通式为（μ－ＲＳ）（μ－ｏ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ６）和（μ－ＲＳ）（μ－ｍ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ）６（Ｒ＝ｎ－Ｂｕ，ｔ－Ｂｕ，Ｐｈ）的６个新桥芳酰基铁硫配合物，并用Ｃ／Ｈ分析、ＩＲ和＾１ＨＮＭＲ表征了它们的结构。     

苯二甲酰基桥联铁硫配合物［（μ－RS）Fe_2（CO）_6］_2（μ－OCC_6

通过由Ｆｅ３（ＣＯ）１２、ＲＳＨ和Ｅｔ３Ｎ所形成的［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ）６］Ｅｔ３ＮＨ于室温下分别与对或间苯二甲酰氯的原位反应，首次合成６个结构新颖的苯二甲酰基桥联铁硫配合物［（μ－ＲＳ）·Ｆｅ２（ＣＯ）６］２（μ－ｐ－ＯＣＣ６Ｈ４ＣＯ－ｐ－μ）（Ｒ＝Ｅｔ，ｎ－Ｂｕ，ｔ－Ｂｕ）以及［（μ－ＲＳ）Ｆｅ２（ＣＯ）６］２（μ－ｍ－ＯＣＣ６Ｈ４ＣＯ－ｍ－μ）（Ｒ＝ｎ－Ｐｒ，ｎ－Ｂｕ，ｔ－Ｂｕ）。经元素分析、ＩＲ光谱及１ＨＮＭＲ表征了它们的结构，并讨论了产物的生成过程。此外，还提出了合成对苯二甲酰氯的一种新方法。     

SR—生物丙烯菊酯极谱行为及应用的研究

本报道了ＳＲ－生物丙烯菊酷的极谱行为。在乙醇－ＢＲ缓冲溶液中，ＥＢＴ在－１．０４Ｖ有一还原峰，峰高与ＥＢＴ浓度在４×１０＾－＾７－６×１０＾－＾５ｇ／ｍＬ范围内有良好的线性关系。该极谱波受扩散控制电子转移数２的还原波。应用此法对卫生杀虫剂进行监测，结果令人满意。回收率为１００．９ ±１．６％。     

烯土—铌（钽）复合溴氧化物的结构与光谱特性

用高温固相法合成了系列化合物ＲＥ０．０６Ｌａ０．９４Ｍ２Ｏ６Ｂｒ（Ｍ＝Ｎｂ，Ｔａ；ＲＥ＝Ｅｕ，Ｔｂ，Ｐｒ，Ｓｍ），并测定了其激发和发射光谱。室温下Ｅｕ＾３＋，Ｔｂ＾３＋，Ｐｒ＾３＋，Ｓｍ＾３＋在稀土－铌（钽）复合溴氧化物中呈现特征激发谱线，但Ｎｂ和Ｔａ的光谱特性稍有不同。     

羰基铁－硫醇（硫酚）－格氏试剂体系与芳酰氯反应的研究──某些μ－芳酰基铁硫配合物的合成及结构

通过Ｆｅ３（ＣＯ）（１２）、硫醇（硫酚）和ＥｔＭｇＢｒ所形成的络盐［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ）６］－Ｍｇ＋Ｂｒ与氯代芳酰氯的原位反应，合成了通式为（μ－ＲＳ）（μ－ｏ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ）６和（μ－ＲＳ）（μ－ｍ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ）６（Ｒ＝ｎ－Ｒｕ，ｔ－Ｂｕ，Ｐｈ）的６个新桥芳酰基铁硫配合物，并用Ｃ／Ｈ分析、ＩＲ和１ＨＮＭＲ表征了它们的结构。     

SYNTHESIS AND ANTICHOLINERGIC ACTIVITIES OF 6，11－DIHYDRODIBENZ［b，e］OXEPIN AND 6，11－DIHYDRODIBENZO［b，e］THIEPIN HYDROXYCARBOXYLATES

ＳＹＮＴＨＥＳＩＳＡＮＤＡＮＴＩＣＨＯＬＩＮＥＲＧＩＣＡＣＴＩＶＩＴＩＥＳＯＦ６，１１－ＤＩＨＹＤＲＯＤＩＢＥＮＺ［ｂ，ｅ］ＯＸＥＰＩＮＡＮＤ６，１１－ＤＩＨＹＤＲＯＤＩＢＥＮＺＯ［ｂ，ｅ］ＴＨＩＥＰＩＮＨＹＤＲＯＸＹＣＡＲＢＯＸＹＬＡＴＥＳ￥Ｓｈｏ...     

STUDIES ON THE SYNTHESIS AND REACTIONS OF N－（1－OXO－4－CARBONYL－2，6，7－TRIOXA－1－PHOSPHABICYCLO ［2．2．2］ OCTANE）－N＇－ARYL THIOUREAS

ＳＴＵＤＩＥＳＯＮＴＨＥＳＹＮＴＨＥＳＩＳＡＮＤＲＥＡＣＴＩＯＮＳＯＦＮ－（１－ＯＸＯ－４－ＣＡＲＢＯＮＹＬ－２，６，７－ＴＲＩＯＸＡ－１－ＰＨＯＳＰＨＡＢＩＣＹＣＬＯ［２．２．２］ＯＣＴＡＮＥ）－Ｎ’－ＡＲＹＬＴＨＩＯＵＲＥＡＳＹｕＧｕｉＬＩ；Ｘｕ...     

在空气中合成MBPO5：Eu^2＋和MBPO5：Yb^2＋（M=Ca,Sr,Ba）荧…

以含ＲＥ２Ｏ３（ＲＥ＝Ｅｕ，Ｙｂ）为起始物，在空气中成功地合成了ＭＢＰＯ５：ＲＥ＾２＋（Ｍ＝Ｃａ，Ｓｒ，Ｂａ；ＲＥ＾２＋＝Ｅｕ＾２＋，Ｙｂ＾２＋）荧光体，测定了它们的激光发发射光谱峰位以及发射半高宽。     

2,6—二甲酸吡啶氮氧化物与稀土硝酸盐配合物的合成及表征

在无水乙醇介质中合成了２，６－二甲酸吡啶氮氧化物（Ｈ２ＰｄＣＯ）和稀土硝酸盐形成的配合物［ＲＥ（ＰｄＣＯ）·ＮＯ３·２Ｈ２Ｏ］（ＲＥ＝Ｌａ－Ｎａ，Ｓｍ，Ｅｕ，Ｔｂ，Ｈｏ，Ｅｒ，Ｙ）。通过元素分析，摩尔电导，红外光谱，紫外光谱，１Ｈ核磁共振谱及热重－差热分析等对该系列配合物进行了表征，并研究了Ｅｕ（Ⅲ），Ｔｂ（Ⅲ）配合物荧光性质。     

Study by electron paramagnetic resonance and spectrophotometry of absorption of the primary processes in photochemistry of frozen aqueous solutions at 77 degree K of aromatic amino acids and polypeptides

Abstract— Neutral, acidic or basic frozen aqueous solutions of aromatic amino acids undergo photoionisation under u.v. irradiation, at 77°K. In neutral or basic solutions, photo-ejected electrons are trapped in the solvent matrix and exhibit a characteristic absorption band in the visible region. In acidic solutions electrons are trapped by protons and ESR signal spectrum of hydrogen atoms may be observed. Hydrogen atoms are also produced in low yield in neutral or basic frozen aqueous solutions, u.v. irradiated at 77°K. In basic media the ESR spectrum of 0^- radical ions is observed. Kinetic studies as a function of light intensity show that photoionisation takes place after absorption of a second photon by the phosphorescent molecule in its lowest triplet state. Recombination of trapped electrons in neutral or basic solutions may be induced using secondary excitation with visible light. In all instances we could record the absorption spectrum of photolytic products of aromatic amino acids and polypeptides which are u.v. irradiated at 77°K.     

贮氢合金的吸放氢性能测定

贮氢合金的吸放氢量，压力组成等温线，以及吸放氢过程的热力学函数变化诸性能的测定，离不开一套适宜的高压一真空实验装置．不少研究者曾报导过较简单的仪器装置[1-4]．还有将吸氢装置配以色谱仪和质谱仪来研究合金的吸氢与中毒问．为测定各类贮氢合金的吸氢性能本实验室研制并装配了一种准确实用的实验装置，可在-196℃至＋500℃和16MPa－0．0001MPa氢压范围内获得准确的平衡数据．1实验装置与仪器实验装置由阀件、压力表、压力传感数字低压计、真空泵和反应器组成（图1）．全部管路为外径rk3mm的不锈钢管．阀件是自行设计的高压微型阀…     

烷基芳基磺酸盐结构对微乳液热力学性质的影响

用稀释法研究了自制的6种不同结构的烷基芳基磺酸盐(AAS)在多组分体系中形成微乳液的标准热力学函数,并考察了分子结构、温度、短链醇、含水量和无机盐含量对其的影响。 结果表明,随着烷基芳基磺酸盐分子长烷基链碳原子数的增加,导致表面活性剂/正丁醇/正癸烷/水形成的微乳液体系中醇由油相转移到界面相的标准自由能ΔG0o→i减小,有利于微乳液的形成;ΔH0o→i无明显变化,ΔS0o→i增大,且与烷基链碳原子数呈线性关系。 ΔS0o→i=1.7975n+71.538。 随着表面活性剂分子芳环向烷基链中间位置移动,导致表面活性剂/正丁醇/正癸烷/水形成的微乳液体系中醇由油相转移到界面相的标准自由能ΔG0o→i减小,有利于微乳液的形成;ΔS0o→i增大,ΔH0o→i减小;温度的升高导致微乳液体系的ΔG0o→i减小,微乳液的形成更容易。随醇碳链上碳原子数增加,ΔG0o→i减小,有利于微乳液的形成,且ΔG0o→i与碳原子数n呈线性关系,ΔG0o→i=-2790.8n+7286.4(328 K);含水量的增加导致ΔG0o→i增大,不利于微乳液的形成,且ΔG0o→i与含水量V也呈线性关系。 ΔG0o→i=6697.8V-7170.4(318 K);无机盐浓度的增加导致ΔG0o→i减小,有利于微乳液的形成。     

铁卟啉与氟尿嘧啶轴向配位热力学性质研究

氟尿嘧啶(Fu)是一种常用的抗代谢药物,在体内可转变为脱氧尿嘧啶核苷酸,抑制胸腺嘧啶核苷酸合成酶,从而阻止尿嘧啶脱氧核苷酸转变成胸腺嘧啶脱氧核苷酸,它的结构与肿瘤细胞所必需的尿嘧啶相类似,在同一系统酶中互相竞争,阻断代谢环节,影响DNA的生物合成,从而抑制了肿瘤细胞的生长.它对多种癌症都有较好的疗效,但具有一定的毒副作用^[1].这些毒副作用产生的机理目前尚不清楚.卟啉类化合物是人体中不可缺少的物质,具有许多特殊的生物效应^[2～11].若它们的含量异常,则会引发多种病变.     

TRIPLET ESR IN l-TYROSINE

Abstract— Triplet state electron spin resonances have been observed from L-tyrosine in low temperature glasses at 77° K on irradiation by u.v. light in the band between 220 and 300 millimicrons. Two different resonances have been observed. and ESR spectra and optical absorption spectra as a function of degree of ionization show that the resonances are due to the ionized and un-ionized forms of tyrosine respectively. Solvent composition and temperature affect the ratio of the concentrations of the two forms but not their resonant fields. The resonances have half lives of from two to three seconds at 77° K.     

In situ Synthesis of Rosin Derived Chiral Derivatizing Agents for 31P NMR Assays of Amine and Alcohol Enantiomers

Chiral alcohols(3, 5) were synthesized in optically pure forms from easily available rosin acid in short-steps. A comprehensive protocol for the enantiomeric excess assays of mono-or difunctional-grouped chiral secondary amine or alcohol has been established with them used as chiral auxiliary for chiral phosphorus derivatizing agents(CPDAs) in ³¹P NMR tests. Chemical shift difference(Δδ_P) values ranging from 4.5 to 0.15 between two diastereoisomers of the CPDAs and the aryl substrates were obtained. Positive Δδ_R-S was observed for all the tested alcohol P(III) and P(V) derivatives, while negative Δδ_R-S was observed for all the amines.     

DISTRIBUTIONS OF FREE RADICALS AMONG AMINO ACIDS FROM LYOPHILIZED ULTRAVIOLET-IRRADIATED PROTEINS

Abstract— The effects of u.v.-irradiation at 254 nm upon lyophilized ribonuclease, lysozyme, insulin, and chymotrypsinogen have been investigated by electron spin resonance (ESR). enzymatic assay, and labeling of free radical sites with tritiated hydrogen sulfide (HST). The ESR signal of the irradiated protein diminishes on exposure to HST, and tritium becomes covalently bound to carbon. The distribution of tritium among the amino acids of each protein. studied as an indicator of the carbon free radical distribution, differs markedly from those observed previously to result from exposure to gamma radiation, electrical discharge. or hydrogen atoms. However, the earlier observation that the tritium distribution is influenced by protein conformation holds true as well for u.v.-irradiation. Moreover, the distributions of tritium among the amino acids of u.v.-irradiated proteins indicate a broad scattering of free radicals. Tyrosine and phenylalanine, residues that absorb light energy in the region of the wavelength employed, are not particularly important as radical carriers. Thus, for ribonuclease, these residues incorporated 3.8 and 1.5 per cent of the total tritium, but they absorb 51 and 12 per cent of the light, respectively. These results, together with the observed low recoveries of methionine, an amino acid that does not absorb at 254 nm, add weight to the concept that a migration of energy ensues after the initial absorption of light energy and that photolytic damage may thus be due to destruction of amino acids other than those initially absorbing the u.v.-radiation.     

Pulse radiolysis studies of short-lived species in solid amino acids as precursors of radicals and detected by ESR

The aim of the study was to bring closer solid state radiation chemistry and ESR spectroscopy by looking for precursors of free radicals which give ESR signals. It has been performed using time-resolved spectrophotometry (pulse radiolysis of the solid state) and diffuse reflection spectrophotometry. Alanine has been especially considered as the most investigated amino acid, important for radiation dosimetry. Absorption of the transient (Λ maximum at 460 nm) is identified as the species during deamination. The stable absorption spectrum with the Λ maximum at 345 nm is due to the same radical as the one detected by ESR. Other amino acids: valine, threonine, glutamine and arginine show similar behaviour: microsecond spectrum of the intermediate appears always at longer wavelenghts. The transient spectrum changes into stable absorption in UV of a lower wavelenght. Along with the optical spectrum, the ESR spectrum appears, of similar stability. Also, other features indicate that the same radical is responsible for both the electronic and ESR spectrum. Some amino acids, like methionine give intensive transient absorption in the microsecond range but no ESR signal, after completion of consecutive fast reactions. In that case any optical absorption is due to the stable product of radiolysis, i.e. compounds with paired electrons only.     

乙醇对环糊精葡萄糖基转移酶催化作用的影响

采用紫外吸收光谱法测定了乙醇、环已烷与β-环糊精包合反应稳定常数及自由能变化, 确定乙醇与β-环糊精的包合反应稳定常数K_s=4.71 L/mol, ΔG=-3.84 kJ/mol; 环己烷与β-环糊精包合反应的K_s=19.56 L/mol, ΔG=-7.37 kJ/mol. 环己烷与β-环糊精的结合能力大大高于乙醇, 故用乙醇提高其产率的机理不同于传统工艺中所添加的环己烷. 通过测定乙醇对环糊精葡萄糖基转移酶催化作用的影响进一步探究其作用机理. 结果表明, 乙醇不仅能提高环糊精葡萄糖基转移酶环化作用的活力, 并在一定程度上阻止对转化环糊精有抑制作用的小分子糖的形成, 还可以减轻环糊精葡萄糖基转移酶对环糊精的水解及偶合作用, 从而提高环糊精的产率.     

Investigation of a Cu(II)-poly(gamma-glutamic acid) complex in aqueous solution and its insulin-mimetic activity

The complexation between cupric ions (Cu(II)) and poly(gamma-glutamic acid) (gamma-PGA) in aqueous solutions (pH 3-11) has been studied by UV-visible absorption and electron spin resonance (ESR) techniques. Formation of the Cu(II)-gamma-PGA complex is confirmed by the observation of the blue shift of the absorption band in the visible region, anisotropic line shapes in the ESR spectrum at room temperature, and a computer simulation of the visible absorption spectrum of the complex. The structure of the Cu(II)-gamma-PGA complex, depending on the pH, has been determined. The in vitro insulin-mimetic activity of the Cu(II)-gamma-PGA complex is examined by determining both inhibition of free fatty acid release and glucose uptake in isolated rat adipocytes treated with epinephrine, in which the concentration of the Cu(II)-gamma-PGA complex for 50% inhibition of free fatty acid release is very similar to that of CuSO4. However, it is significantly lower than that of a previously reported insulin-mimetic bis(3-hydroxypicolinato)copper(II), [Cu(3hpic)2], complex.