Absorption Spectra and Resonance Rayleigh Scattering Spectra of Cu(Ⅱ)-Fluoroquinolone Chelates with Tetrachlorotetraiodo-fluoresceindisodium Salt System and Their Analytical Applications

在pH 4.2～4.8的B-R缓冲介质中,莫西沙星(MXFX)和加替沙星(GTF)等氟喹诺酮类抗生素(FLQs)能与铜(Ⅱ)形成螯合阳离子,进一步与虎红(Tf)阴离子通过静电引力和疏水作用形成FLQs∶Cu(Ⅱ)∶Tf为1∶1∶1的离子缔合物,体系反应导致共振瑞利散射(RRS)显著增强并出现新的RRS光谱.两种药物的反应产物具有相似的光谱特征,最大RRS峰位于373 nm处,并在590 nm处有1个较小的散射峰.在373 nm处一定浓度的抗生素与散射增强(△I)成正比,MXFX和GTF的线性范围分别为0.031 ～7.8 mg/L和0.029～9.0 mg/L.据此建立了测定氟喹诺酮类药物的新方法,方法用于胶囊和人尿液中FLQs的测定并取得满意结果.同时对反应机理及RRS增强原因进行了讨论.     

钯(Ⅱ)-泛昔洛韦螯合物与铬天青S相互作用的共振瑞利散射光谱及其分析应用

在pH值为2.5～3.5的Britton-Robinson缓冲溶液中,泛昔洛韦与钯(Ⅱ)相互作用形成1∶1的螯合阳离子,并进一步与铬天青S反应形成1∶1的离子缔合物。该反应可引起共振瑞利散射(RRS)光谱的显著增强并产生新的RRS光谱,最大RRS波长位于367 nm。在一定范围内,共振瑞利散射增强(ΔIRRS)与泛昔洛韦的质量浓度成正比,其线性范围为0.02～2.4 mg/L。该方法的灵敏度高,对泛昔洛韦的检出限为3.6μg/L。实验考察了适宜的反应条件以及共存物质的影响。应用计算化学软件Gaussview3.07和Gaussian03W,采用密度泛函法,在B3LYP/6-31G基组水平上计算了泛昔洛韦的电荷分布,对反应机理和RRS增强的原因进行了讨论。基于Pd(Ⅱ)-泛昔洛韦-铬天青S体系三元离子缔合物的RRS光谱,发展了一种简便、快速、灵敏测定泛昔洛韦的新方法。此方法用于胶囊和尿样中泛昔洛韦的测定,结果满意。     

钯(Ⅱ)-甲氨蝶呤螯合物与亚甲蓝相互作用的共振瑞利散射光谱及其分析应用

在pH为4.1~7.0的Britton-Robinson缓冲溶液中, 甲氨蝶呤与钯(Ⅱ)相互作用形成1∶1的螯合阴离子, 并进一步与亚甲蓝(MB)反应形成1∶1的离子缔合物. 该反应可引起共振瑞利散射(RRS)的显著增强并产生新的RRS光谱, 最大RRS波长位于342 nm. 在一定条件下, 散射增强(ΔI)与甲氨蝶呤的浓度成正比, 其线性范围为0.008~2.0 μg/mL. 此方法具有高灵敏度, 对于甲氨蝶呤的检出限为2 ng/mL. 考察了适宜的反应条件和影响因素, 研究了共存物质的影响, 基于Pd(Ⅱ)-甲氨蝶呤-亚甲蓝体系三元离子缔合物的RRS光谱, 发展了一种高灵敏、简便快速测定甲氨蝶呤的新方法. 此方法用于人血清和尿样中的甲氨蝶呤的测定获得满意的结果. 同时, 对三元离子缔合物的结构和反应机理进行了讨论.     

Resonance Rayleigh Scattering Spectra of Thorium(IV)-bisazo Dye of Chromotropic Acidprotein Systems and Their Analytical Applications

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｄｅｔｅｒｍｉｎａｔｉｏｎｏｆｐｒｏｔｅｉｎｓｉｓｉｍｐｏｒｔａｎｔｉｎｂｉｏｃｈｅｍｉｃａｌｓｔｕｄｙ ,ｃｌｉｎｉｃａｌｔｒｅａｔｍｅｎｔａｎｄｆｏｏｄａｎａｌｙｓｉｓ .Ａｓｉｔｉｓｋｎｏｗｎ ,ｔｈｅｃｏｍｍｏｎｍｅｔｈｏｄｓｕｓｅｄｔｏｄｅｔｅｒｍｉｎｅｔｈｅｐｒｏｔｅｉｎｑｕａｎｔｉｔａ ｔｉｖｅｌｙａｔｐｒｅｓｅｎｔａｒｅｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｒｙａｎｄｆｌｕｏｒｏｓｐｅｃ ｔｒｏｐｈｏｔｏｍｅｔｒｙ.1Ｒｅｃｅｎｔｌｙ ,ｒｅｓｏｎａｎｃｅＲａｙｌｅｉｇ…     

钴(Ⅱ)-2-(5-溴-2-吡啶偶氮)-5-二乙氨基酚体系共振瑞利散射法测定环境水样中十二烷基苯磺酸钠

在pH 1.8～3.0的Britton-Robinson(BR)缓冲溶液中,钴(Ⅱ)与2-(5-溴-2-吡啶偶氮)-5-二乙氨基酚(5-Br-PADAP)(HL)反应形成紫红色螯合阳离子,此时仅能引起吸收光谱的变化,不能导致共振瑞利散射(RRS)的增强.当钴(ID-5-Br-PADAP螯合阳离子与阴离子表面活性剂十二烷基苯磺酸钠(SDBS)、十二烷基磺酸钠(SLS)和十二烷基硫酸钠(SDS)作用时,仅能与SDBS进一步反应形成三元离子缔合物并引起RRS的显著增强,而不与SDS和SLS产生类似反应.离子缔合物的RRS峰分别位于306,370和650 nm处,在一定范围内RRS增强(△I)与SDBS浓度成正比,当用650 nm处测量时,其检出限为0.043 μg·mL1,线性范围为0.14～6.0 μg·mL-1.文中研究了反应产物的RRS光谱特征,适宜的反应条件及分析化学性质,据此发展了一种在一定量SDS和SLS等阴离子表面活性剂存在下选择性测定SDBS的新方法,方法灵敏、简便、快速,用于天然水和污水中SDBS的测定,获得满意结果.文中还对反应机理进行了讨论.     

Study on the Supramolecular Interaction of β-Cyclodextrin with Gemfibrozil by Spectrofluorimetry and Its Analytical Application

The supramolecular interaction of gemfibrozil with β-cyclodextrin （β-CD） was studied by spectrofluorimetry. The mechanism of the inclusion was discussed by spectrofluoremetry, infrared spectrum and ^1H NMR spectrum. The results showed that a 1 ： 1 （β-CD ： gemfibrozil） complex was formed with an apparent association constant of 3.844 × 10^3 L·mol^-1. Based on the enhancement of the fluorescent intensity of gemfibrozil, a spectrofluorimetric method for the determination of gemfibrozil in bulk aqueous solution in the presence of β-CD was developed. The linear range was 3.30 ng·mL^- 1 -6.00 ug·mL^-1 with the detection limit of 0.980 ng·mL^-1. There was no interference from the excipients normally used in tablet composition and the serum main compositions. The proposed method was then successfully applied to the determination of gemfibrozil in capsules and serum.     

氟喹诺酮类抗菌素-钯(Ⅱ)-曙红Y体系的共振瑞利散射光谱及其分析应用

在pH值为4.1~5.0的Britton-Robinson(BR)缓冲溶液中,环丙沙星(ciprofloxacin,CPF)、诺氟沙星(norfloxacin,NRF)、氧氟沙星(ofloxacin,OFL)、左氧氟沙星(levofloxacin,LVF)等氟喹诺酮类抗菌素(fluoro-quinolone derivatives,FQs)与Pd(Ⅱ)反应形成无色阳离子螯合物,当其与曙红Y反应形成三元离子缔合物,共振瑞利散射(RRS)均显著增强,并产生新的RRS光谱,最大RRS峰均位于368nm处。在一定范围内FQNs的浓度与RRS强度(ΔI)成正比,4种抗菌素的线性范围和检出限分别为0~2.4×10-6g/mL和9.4×10-9g/mL(CPF);0~2.4×10-6g/mL和12.8×10-9g/mL(NRF);0~2.2×10-6g/mL和16.2×10-9g/mL(LVF);0~2.8×10-6g/mL和15.6×10-9g/mL(OFL)。并具有较好的选择性,用于针剂、鸡血清中诺氟沙星的测定时,其回收率在95.0%~101.5%。建立了一种灵敏、简便、快速测定喹诺酮类抗菌素的新方法。     

锌(Ⅱ)-硫氰酸盐-中性红体系共振瑞利散射法测定痕量锌

在pH 5.1的HAc-NaAc缓冲溶液中,聚乙烯醇存在下,Zn(Ⅱ)和硫氰酸盐形成的配阴离子[Zn(SCN)4]2-与中性红阳离子结合形成的离子缔合物具有共振瑞利散射光谱,其最强共振瑞利散射峰位于594.5 nm处。基于共振瑞利散射峰的增强,建立了测定痕量Zn(Ⅱ)的共振瑞利散射方法。Zn2+质量浓度在0~0.5μg/mL范围内呈良好的线性关系,检出限为1.9×10-5μg/mL。方法已用于水样中Zn2+的测定。     

Resonance Rayleigh scattering spectrum for the chelate of lanthanum(Ⅲ) with sodium tanshinon ⅡA silate and its analytical application

In a pH 3.6―5.0 HAc-NaAc buffer solution, when sodium tanshinon ⅡA silate (STSⅡA) reacts with La(Ⅲ) to form a chelate, the resonance Rayleigh scattering (RRS) intensity can be en-hanced greatly and a new RRS spectrum will appear. The maximum RRS peak is located at 306 nm and the RRS intensity is proportional to the concentration of STSⅡA in a certain range. The method is very sensitive and the detection limit for STSⅡA (3σ/K) is 82.12 ng·mL?1. The optimum reaction condi-tions and the effect of coexisting substances have been investigated. A new, simple and fast method for the determination of STSⅡA based on RRS method is developed. It can be applied to the deter-mination of STSⅡA in the synthesis samples and Nuoxinkang injection. Combined with infrared ab-sorption and NMR spectra, the structure of the chelate and the reasons of RRS enhancement are also discussed.     

汞(Ⅱ)-槲皮素螯合物共振瑞利散射光谱法测定槲皮素

在pH4.8~6.1的BR缓冲溶液中,槲皮素(QT)和汞(Ⅱ)形成螯合物时,将引起溶液共振瑞利散射(RRS)显著增强,并产生新的RRS光谱,其最大RRS波长位于320nm,另在450nm处有一小的散射峰。槲皮素在0.98~7.0mg/L范围内与散射强度(ΔI)成正比;反应具有较高的灵敏度,对槲皮素的检出限为29.5μg/L。研究了适宜的反应条件和影响因素,考察了共存物质的影响,表明方法有良好的选择性。基于上述研究,建立了一种灵敏、简便、快速测定槲皮素的新方法,并用于天然药物槐米中槲皮素的测定。     

A novel method for Co(Ⅱ) and Cu(Ⅱ) analysis by capillary electrophoresis with chemiluminescence detection

Based on the fact that some metal ions can catalyze the chemiluminescence(CL)reaction of luminol with K_3Fe(CN)_6,a novel capillary electrophoresis CL method was developed for the determination of Co(Ⅱ)and Cu(Ⅱ).The separation was carried out with a 10 mmol/L sodium acetate solution containing 0.8 mmol/L luminol and 2.0 mmol/Lα-HIBA(adjusted to pH 4.8 by HAc solution).The post-capillary reagent was 2.0 mmol/L K_3Fe(CN)_6 which was adjusted to pH 13.0 by NaOH solution.Under the optimum conditions,the detection limits(S/N=3)for Co(Ⅱ)and Cu(Ⅱ)were 7.5×10~(-11)mol/L and 7.5×10~(-9)mol/L,with the linear range of 7.5×10~(-9)mol/L to 1.0×10~(-6)mol/L and 7.5×10~(-8)mol/L to 5.0×10~(-5)mol/L, respectively.     

Spectral Study on the Interactions Among Cu(Ⅱ), Doxorubicin and CopC

Interactions among Cu(Ⅱ),doxorubicin and copper operon C(CopC)have been investigated in detail by means of fluorescence,UV-Vis,IR spectra,isothermal titration calorimetry(ITC)and molecular docking in Tris-HCl buffer(50 mmol/L,pH=7.4,25℃).The results suggest that Cu(Ⅱ)-doxorubicin is formed in a Cu(Ⅱ)to doxorubicin molar ratio of 1:2,and the conditional stability constant,K[Cu(Ⅱ)-doxorubicin]is 1.90×10^9 L^2/mol^2,CopC and doxorubicin can form a 1:1 complex,the conditional stability constant is greater than 10^5 L/mol.Binding of doxorabicin causes a conformational change in CopC with the reduction of β-sheet and increase of random coil,and the stability of CopC is decreased.Cu(Ⅱ),doxorubicin and CopC can form a CopC-Cu(Ⅱ)-doxorubicin ternary complex.The formation of CopC-Cu(Ⅱ)-doxorubicin reduced greatly the reduction rate of Cu(Ⅱ)by ascorbate(Vc),i.e.,the binding of doxorubicin affects the action of CopC as redox switch.     

Complex Pd( Ⅱ ) with Vinyiphosphine and Its Application in Sonograshira Cross Coupling Reaction

合成了含有大位阻和富电子膦配体的1,2-二苯基乙烯基膦配体,并研究了以1,2-二苯基乙烯基膦配体和二氯化二苯腈合钯(Ⅱ)为催化剂催化的Sonograshira交叉偶联反应.     

Studies on synthesis and kinetics of thermodecomposition of the nickel(Ⅱ) compounds with Schiff base derived from amino acids

Monoaqua salicylaldehyde-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp1) and monoaqua o-vanillin-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp2) were synthesized. The composition and structures of these two compounds were analyzed. Their thermal stability and non-isothermal kinetics were also investigated by use of TG and DTG curves. The possible reaction mechanisms in their first steps of thermal decomposition reactions were deduced by means of integral and differential methods. Thermodecomposition kinetic equations of the compounds are as follows:Cp1: da/At = A . exp(-E/RT) . 3/2(1 - a)4/3 . [1/(1 - a)1/3 -1]-1 Cp2 : da/At = A . exp(-E/RT) . (1 - a)     

Synthesis and characterization of μ-oxamido copper(Ⅱ)-iron(Ⅱ) heterobinuclear complexes with an antiferromagnetic exchange interaction

Four new u-oxamido heterobinuclear complexes have been synthesized and identified as [Cu(oxap)Fe(L)2]SO4, where oxap denotes the N, N'-bis(2-aminopropyl)oxamido dianion and L represents diaminoethane (en); 1,3-diaminopropane (pn); 1,2-diaminopropane (ap) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen). Based on the elemental analyses, spectroscopic studies, magnetic moments (at room temperature) and molar conductivity measurements, extended oxamido-bridged structures consisting of a copper(Ⅱ) and an iron(Ⅱ) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. Complexes [Cu(oxap)Fe(en)2]SO4 (1) and [Cu(oxap)Fe(pn)2]SO4 (2) have been characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(Ⅱ) ion, H=-2JS1.S2-DSzl2, giving the exchange integrals J=-2     

Investigations of Thallium(Ⅰ) Underpotential Deposition on the Silver Rotating Disk Electrode and Its Analytical Application

Ｔｈａｌｌｉｕｍｉｓａｔｏｘｉｃｍｅｔａｌ.Ｂｅｃａｕｓｅｉｔｓｃｏｎｃｅｎｔｒａｔｉｏｎｉｎｅｎｖｉｒｏｎｍｅｎｔａｌａｎｄｂｉｏｌｏｇｉｃａｌｓａｍ ｐｌｅｓｉｓｉｎｔｈｅ 1ｎｇ/ｇｒａｎｇｅｏｒｌｅｓｓ[1] ,ｉｔｉｓｄｉｆｆｉｃｕｌｔｔｏｄｅｔｅｒｍｉｎｅｔｈｅｍｅｔａｌｂｙｕｓｉｎｇｃｏｎｖｅｎｔｉｏｎａｌｅｌｅｃｔｒｏａｎａｌｙｓｉｓｍｅｔｈｏｄｓ .Ｄｉｆｆｅｒｅｎｔｉａｌｐｕｌｓｅａｎｏｄｉｃｓｔｒｉｐｐｉｎｇｖｏｌｔａｍｍｅｔｒｙ(ＤＰＡＳＶ )ｉｓａｓｅｎｓｉｔｉｖｅｍｅｔｈｏｄｆｏｒ…     

Kinetics and Mechanism of the Oxidation of Glycol by Dihydroxyditelluratoargentate(Ⅲ) with Spectrophotometry

The kinetics of the oxidation of glycol by dihydroxyditelluratoargentate (Ⅲ) complex(DDA) was studied in alkaline medium with spectrophotometry(in a temperature range of 16.6-40 ℃).The first-order rates with respect to glycol and Ag(Ⅲ) were all found.The rates increased with the increase in [OH-] and decreased with the increase in [TeO2-4].No effect was found with the addition of KNO3 and no free radical was detected.In view of this,the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can explain all experimental observations.Activation parameters of the rate-determining step and constants are evaluated.     

~(99)Ru and ~(13)C-NMR Spectra for the Tris Chelates of 5-Substituted 1,10-Phenanthrolines with Ruthenium (Ⅱ)

Ru(5-X-Phen),' complexes(whereX=H,CH3,Ph,Cl,andNO2)havebeenfoundtohaveextensiveapplicationascatalystsinphotoinducedelectron-transferprocessesand,especially,asphotosensitizersinsolarenergyconversionbywaterphotoreductionprocesses.Someresearchersincludingthepresentauthorhavefound1Handl3CNMRspectroscopyusefultostudytheinteractionsthatdevelopincoordinationofpolypyridineligandstotransitionmetalsl-3.Sincethe99Ru-NMRchendcalshiftcansensitivelyreflecttheelectronicandgeometricalchangesaroundtheme…     

Dimerization of Propylene by Nickel (Ⅱ) and Cobalt (Ⅱ) Catalysts Based on Bidentate Nitrogen-phosphino Chelating Ligands

The catalytic property of propylene dimerization by several nickel (Ⅱ), cobalt (Ⅱ) complexes containing N-P bidentate ligands was studied in combination with organoaluminum co-catalysts. The effects of the type of aluminum co-catalysts and its relative amount, the nature of precursors in terms of ligand backbone and metal center were investigated. The results indicated that precursor I (N,N-dimethyl-2-(diphenylphosphino)aniline nickel (Ⅱ) dichloride) exhibited high activity in propylene dimerization in the presence of the strong Lewis acid Et3Al2Cl3, whereas low productivity by its cobalt analogues was observed under identical reaction conditions.