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本文讨论用分光光度法求多核络合物的各级稳定常数和克分子消光系数的一般处理。如果只有单核络合物存在,则本文归结为Ядимирский所得到的结果。 相似文献
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本文测定了CAS,Sc-CAS和Sc-CAS-CTMAB体系的吸收光谱,三元络合物组成比为Sc:CAS∶CTMAB=1∶2∶2,用动力学方法获得经验速率方程R=k[Sc(h)][CAS][CTMAB]-2,参照Eigen-Tamm机理提出了一种“胶束-溶剂笼”机理,此机理用平衡浓度法处理后,其速率方程与实验结果一致,对三元络合物的几何构型和反应模式也进行了讨论。 相似文献
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卡尔曼滤波法解析严重重叠的荧光峰 总被引:2,自引:2,他引:2
锌、铝同7-碘-8羟基喹啉-5-磺酸-溴化十六烷基三甲铵形成的络合物荧光光谱严重重叠,分离度仅为0.26。本文以该体系为例,着重考察了卡尔曼滤波法解析谱峰严重重叠体系的潜力。结果表明,在锌、铝络合物峰值处,当铝络合物的荧光强度小于锌络合物的荧光强度时,二者均可得到满意的分析结果,当铝络合物的荧光强度大于锌络合物的荧光强度时,锌的分析结果显著变差。在此情况下,用卡尔曼滤波法处理同步荧光光谱数据,分析 相似文献
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5-CI-PADAB和钯的络合物萃取性能及萃取机构的初步研究 总被引:5,自引:1,他引:5
5-C1-PADAB是广泛用于测定钴的灵敏试剂,Shibata等曾用于测定纯溶液中的钯。国内结合试金分析用于矿石中钯的测定,但尚未见到研究Pd-5-C1-PADAB络合物的萃取性能。本文研究了5-C1-PADAB与钯形成络合物的萃取性能及其用于光度测定钯的可能性。实践证明:5-C1-PADAB与钯形成紫红色络合物,可为正戊醇萃取,络合物形成后,在强酸介质中极为稳定;经萃取后最 相似文献
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担载液相催化剂的研究——Ⅳ.催化剂的原位红外光谱表征 总被引:1,自引:0,他引:1
本文利用原位红外光谱方法对铑基担载液相催化剂(SLPC)在接近于实际反应条件下进行了表征。结果表明,新鲜催化剂上,铑膦络合物主要以二聚物的形式存在,如Rh_2(CO)_2(PPh_3)_4而在合成气或反应气氛中,催化剂铑膦络合物以单核络合物HRh(CO)_2(PPh_3)_2的形式存在。文中还对SLPC在CO,H_2,C_2-H_4,空气和HCl中处理时铑络合物种的变化进行了原位观察。实验结果表明,SLPC上活性铑络合物与对应的均相过程完全一致,进一步证实了SLPC催化在微观上就是一个均相催化过程。 相似文献
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3, 4-Bis (trifluoromethyl)-perfluorohexene-(3) (1) reacted with diethylamine to give the 1-N, N-diethylamino-2-pentafluoroethyl -3-trifluoromethyl-perfluoropentene-(1)(2), which was easily hydrolyzed to the corresponding N, N-diethyl-2-penta-fluoroethyl- 3-trifluoromethyl-perfluoropenteno-(2)-amide (3). When compound 1 was allowed to react with n-butyl amine at 40-50`C, the 2,3,4-tris(trifluoromethyl)-4-pentafluoroethyl-1-n-butyl-aza- cyclobutene-(2) (5) was obtained as the main product and at-30-40`C, 3,4-bis(trifluoromethyl)-4-n-butylamino-perfluorohexene-(2) (4) as the main product. The isomers 3, 4-bis(trifluoromethyl)-4-allyloxy-perfluoro-hexen-(2) (6) and 2-pentafluoroethyl-3-trifluoromethyl-3-allyloxy-perfluoropentene-(1)(7) were formed when 1 was reacted with sodium allyl alcoholate. 相似文献
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The electronic structure of BeAl was investigated by laser induced fluorescence and resonance enhanced multiphoton ionization spectroscopy. BeAl was formed by pulsed laser ablation of a Be/Al alloy in the presence of helium carrier gas, followed by a free jet expansion into vacuum. In agreement with recent ab initio studies, the molecule was found to have a (2)Pi(1/2) ground state. Transitions to two low lying electronic states, (2)(2)Pi(1/2)(v') <-- X (2)Pi(1/2) (v' = 0) and (1)(2)Delta(v') <-- X (2)Pi(1/2) (v' = 0,1), were observed and rotationally analyzed. An additional band system, identified as (4)(2)Sigma(+)(v') <-- X (2)Pi(1/2), was found in the 28 000-30 100 cm(-1) energy range. This transition exhibited an unusual pattern of vibrational levels resulting from an avoided crossing with the (5)(2)Sigma(+) electronic state. New multi-reference configuration interaction calculations were carried out to facilitate the interpretation of the UV bands.An ionization energy of 48 124(80) cm(-1) was determined for BeAl from photoionization efficiency (PIE) measurements. Fine structure in the PIE curve was attributed to resonances with Rydberg series correlating with vibrationally excited states of the BeAl(+) ion. Analysis of this structure yielded a vibrational frequency of 240(20) cm(-1) for the cation. 相似文献
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中心为氨基、末端为硝基的苯乙炔树枝状分子的合成 总被引:1,自引:0,他引:1
将固定相合成与“收敛/发散”方法相结合,合成了第一、二代苯乙炔树枝状分子.通过Heck-Cassar-Sonogashira-Hagihara偶联反应,将其中心和末端分别修饰上供电子的氨基和拉电子的硝基,得到第一、二代中心为氨基、末端为硝基的苯乙炔树枝状分子NH2-G1-(NO2)2和NH2-G2-(NO2)4.用傅里叶变换红外光谱跟踪了整个固定相合成过程.苯乙炔树枝状分子的紫外-可见吸收光谱呈现出规律性变化. 相似文献
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Micellar inhibition effect of gangliosides on a degradation of drug was investigated, where ganglioside G(M1) (GM1), G(D1a) (GD1a) and G(T1b) (GTlb) whose sialic acid residue is one, two and three, respectively, were used. The base-catalyzed isomerization of prostaglandin A(2) (PGA(2)) to prostaglandin B(2) (PGB(2)) was chosen as a model experiment. The rate for the isomerization of PGA(2) was determined by measuring the concentration of PGA(2) (and PGB(2)) with a high-performance liquid chromatography. Gangliosides micelles inhibited the isomerization of PGA(2). The inhibition effect of GT1b micelles was larger than that of GD1a micelles. This result would be due to the larger absolute value of surface potential of GT1b micelles, which brings about a larger electrostatic repulsion between micellar surface and OH(-). The terminal sialic acid residue of ganglioside was effective to inhibit the isomerization of PGA(2). GM1 micelles without terminal sialic acid residue but with large aggregation number exhibited a superior steric shielding effect rather than an electrostatically repulsive effect. The inhibition effect of GM1 micelles was enhanced by the mixed micellization with the other ganglioside with a terminal sialic acid residue. GM1-GD1a or GM1-GT1b mixed micelles remarkably inhibited the isomerization of PGA(2). The physiological activity of PGs in the biological membranes containing gangliosides was also discussed. 相似文献
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A hydroxyl substituted phenolic Schiff base 1, used as sensor for detection of Zn^2+, was synthesized and investigated. It was found that a strong fluorescence emission was observed when 1 bound to Zn^2+ in acetonitrile, whereas no fluorescence emission was detected when 1 bound to other metal ions (Fe^2+, Co^2+, Ni^2+, Cu^2+, Cd^2+, Hg^2+, Mg^2+, Pb^2+, Ca^2+, Ba^2+, Sr^2+) except for Mg^2+, for which a weak fluorescence emission was detected in the same condition. Competition experiment showed that no obvious interference was observed in its fluorescence while 1 performed the titration with Zn^2+ in the different mixtures of metal ions. To understand the site where Zn^2+ coordinated to the ligand and the mechanism of binding, three other hydroxyl substituted phenolic Schiff bases 2-4 were synthesized and their binding reactions with Zn^2+were also investigated. 相似文献
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1, 2-Dimethyl-5-nitroimidazole( 1 )and N,N-dimethylformamide dicyclohexylacetal gave the 2-(β-dimethylaminovinyl) analog 2 and with iodine and pyridine gave the 2-(1-pyridinium)methyl compound 3 . Benzoyl chloride-triethylamine and 1 led to benzoylation of the 2-methyl group to give ketone 9 as the enol benzoate. Nitrous acid or nitrosylsulfuric acid with 9 or its enol ester afforded the oximinoketone 10 which was cleaved with thionyl chloride to give 2-cyano-1-methyl-5-nitroimidazole ( 11 ) in high overall yield. 1-Ethyl-2-methylbenzimidazole ( 22 ) was converted to 2-cyano-1-ethylbenzimidazole ( 25 ) similarly. Reaction of 1 with ethyl oxalyl chloride and triethylamine afforded ethyl 1-methyl-5-nitro-2-imidazolepyruvate ( 19 ) as the enol oxalate. Nitrous acid and 19 gave the oximino pyruvate 20 which effervesced on mild heating to give 2-cyano-1-methyl-5-nitroimidazole ( 11 ). The preparation of 1-methyl-5-nitro-2-imidazoleacetonitrile ( 39 ) is reported. 相似文献
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1,1,3,3-四(全氟己基乙基)二锡氧烷二聚体在环氧化合物开环反应中的催化作用 总被引:2,自引:0,他引:2
采用氟碳-有机溶剂两相催化体系,考察了1,1,3,3-四(全氟己基乙基)二锡氧烷二聚体(1)在环氧化合物开环反应中的催化作用.结果表明,催化剂(1)在氟碳-有机溶剂两相体系中使环氧苯乙烯和甲醇的开环反应产率高达95%,13CNMR谱表明,开环反应的区域选择性为100%.在氟碳-有机溶剂两相催化体系中以一锅法制备了3-苯基丙酸2-甲氧基-2-苯乙醇酯,收率高,方法简便,催化剂几乎可以定量回收循环使用. 相似文献