Chiral Separation of Rosiglitazone Sodium by Aqueous/Nonaqueous Capillary Electrophoresis

以环糊精及其衍生物为手性选择剂,通过优化缓冲液的浓度、酸度以及采用环糊精的种类和浓度等,建立了罗格列酮钠对映体的水介质和非水介质两种毛细管电泳拆分方法。最佳条件为:150 mmol/LTris-H3PO4缓冲液,pH=2.0,含有1 mmol/Lβ_CD或DM_β_CD,10%(φ)甲醇的运行液,分离电压为25 kV,检测波长215 nm。也可以使用含有9 mmol/L HDMS_β_CD,20 mmol/L磷酸和10 mmol/L NaOH的甲醇电泳液。两种拆分体系均实现了罗格列酮钠对映体的基线分离,而且拆分效率基本相当。方法简便、快速,可作为罗格列酮钠的手性分离方法。HPCE methods for separating and determining the rosiglitazone sodium enantiomers were estabˉlished.The effects of buffer concentration,pH,and the type and concentrations of CDs in the chiral separaˉtion of rosiglitazone sodium were investigated.The buffer solution used in aqueous capillary electrophoresis(ACE)was150mmol/L Tris-H 3 PO 4 solution,pH=2.0,containing1mmol/Lβ-CD or DM-β-CD,and10%(φ)methanol.The voltage applied was25kV,and the detective wavelength was215nm.In addiˉtion,a simple method for the separation of rosiglitazone sodiumenantiomers was described by nonaqueous capˉillary electrophoresis(NACE)after establishing suitable separation conditions.Under the experiment condiˉtions adopted,the baseline separation of rosiglitazone sodium enantiomers was obtained by the two methods.The proposed methods were simple,rapid and accurate,and could be used for the chiral separation of rosiglitaˉzone sodium

Sensitized Room-Temperature Phosphorescence of Biacetyl by Naphthalene in Micellar Systems

研究了SdS胶束介质中萘敏化双乙酰的室温磷光，认为SdS增强了萘与双乙酰的能量转移效率，敏化磷光强度与POISSOn分布有关，并由胶团中含较少给（受）体的决定。选择了最佳实验条件，该法简便、快速，萘的检出限达6.5x10（-8）MOl/l。Micelle organizes the donor and acceptor molecules into a discrete volume region,Facilitates the energy transFer and enhances the intensity of sensitized RTP.This paper reports the sensitized RTP of biacetyl by naphthalene in SDS micellar solution, and indicates that the intensity of sensitized RTP was correlative with the Poisson distribution and determined by values of which is the probability of less donor and less acceptor occurred in the same micelle.The linear range of detection is 0-8.0×10(-5)mol/L.Typically,the limit of detection For naphthalene in SDS is 6.5×10(-8)mol/L

胶束介质中猝灭α─溴代萘敏化双乙酰室温磷光法测定溴离子的研究

胶束介质中猝灭α─溴代萘敏化双乙酰室温磷光法测定溴离子的研究谢剑炜，许金钩，陈国珍（厦门大学化学系现代分析化学研究所，厦门，361005）淬灭/敏化室温磷光法最先是由dOnkCrbrOCk等人在1981年提出的，它是基于T─T能量转移为基础的间接分析..

Studies on Solubilization Site of the Triplet Energy Acceptor Biacetyl in Normal Micelles by Using Quenched RTP Method

采用丁二酮室温光猝灭法研究了胶束介质中丁二酮的增溶位点，通过研究4种不同荷电和不同亲水亲脂性的光猝灭剂以及盐效应等对STErn-VOlMEr常数的影响，表明了二酮在SdS、CTAb的胶束中是增溶在胶团的栏栅并靠近离子头基一侧和头基/水界面附近，而在CTAb胶束中更加趋向于胶团外部头基附近.The solubilization site of the triplet energy acceptor biacetyl in normal micelles isstudied by quenched RTP.Ethyl iodide, butyl bromide were used as hydrophobic quenchers.Potassium bromide, copper chloride were the hydrophilic quenchers.The results indicatethat biacetyl is located in the head group-water interFace and likely to be lined up along thealkyl chains of the surFactant's aggregates but its carbonyl group is close to the head group ofsurFactant.So, iF donor is located in the head group-water interFace where biacetyl issolubilitized, enhanced energy transFer is observed

Sensitized Biacetyl Room Temperature Phosphorescence in AOT Reversed Micelles

本文报道了AOT-C_6H_(12)-H_2O反相胶束介质中α-萘乙酸(α-nAA)敏化双乙酰(bIAC)的室温燐光.详细讨论了琥珀酸二(2-乙基己基)酯磺酸钠(AOT)浓度和水泡大小(W值)对敏化燐光的影响.吸收、发光性质和微粘度性质的实验表明AOT浓度对敏化燐光强度的影响由敏化燐光寿命、能量转移效率和POISSOn分布决定;一定范围内,随着水浓度增大,由于粘度下降和内腔半径增大作用的相互抵销,水泡大小仅有微弱影响.当W([H_2O]/[AOT])大于20后,内腔半径增大起主要作用,敏化燐光强度快速下降.与普通SdS胶束相比,燐光强度约增强13倍,检出限约下降一个数量级.建立了灵敏的测定α-萘乙酸和双乙酰的敏化室温燐光法,检出限分别达2.0x10--(-8)MOl·dM--(-3)(α-nAA)和8.5x10--(-9)MOl·dM--(-3)(bIAC).Sensitized biacetyl Room Temperature Phosphorescence by a-Naphthylacetic acid in reversed micelles of AOT-C6H12-H2O is presented.The intensity of biacetyl RTP is enhanced about 13 times than the intensity observed in aqueous SDS micelles.Parameters including the concentrations of AOT, solubilized water as well as donor and accepter concentration that may inFluence the sensitized biacetyl phosphorescence are also examined.The absorption spectra and characteristics of luminescence as well as micro viscosity data are used to elucidate the Factors that aFFect sensitized phosphorescence.The intensity of sensitized biacetyl phosphorescence in AOT reversed micelles is determined by the liFetime of sensitized biacetyl, energy transFer eFFiciency and the Poisson distribution.No remarkable inFluence of water content on the intensity of sensitized biacetyl phosphorescence is observed at W([H2O] / [AOT]) less than 20 because the eFFects of both decreasing in micro viscosity and increasing in radius of inner core of reversed micelles ofFset each other.The decreasing in sensitized biacetyl RTP is observed at W more than 20.The detection limits For α-naphthylacetic acid and biacetyl are 2.0 ×10-8mol·dm-3 and 8.5 x 10-9mol·dm-3, respectively

Quenching of Room Temperature Phosphorescence of Biacetyl Sensitized by α-Bromonaphthalene in CTAB Micelles

本文首次报道了将敏化和猝灭同时偶合在同一体系中的敏化/猝灭室温烘燐新方法.体系中,CTAb胶束一方面增强α-溴代萘的室温燐光发射、α-溴代萘和联乙酰的三重态-三重态能量转移效率,另一方面起到猝灭α-溴代萘敏化联乙酰发射的室温燐光的作用.CTAb对联乙酰的猝灭反应由三重态-三重态能量转移速率限制,求得α-溴代萘敏化联乙酰的三重态-三重态能量转移速率常数为1.76x10--9(MOl·dM--(-3)--(-1)S--(-1),CTAb对联乙酰的猝灭常数为7.82x10--7(MOl·dM--(-3)--(-1)S--(-1).详细研究了实验条件,实现了猝灭法测定联乙酰,检测限达2.8x10--(-8)MOl·dM--(-3).A new method of determining biacetyl in aqueous solutions by quenching its room temperature phosphorescence sensitized by α-bromonaphthalene in CTAB micelles is presented.CTAB micelles Facilitate the triplet-triplet state energy transFer between α-bromonaphthalene and biacetyl and enhance the phosphorescence emission of α-bromonaphthalene; CTAB micelles act also as a quencher of quenching the phosphorescence of biacetyl sensitized by α-bromonaphthalene.The rate constant of triplet-triplet energy transFer between α-bromonaphthalene and biacetyl is 1.76×109 (mol ·dm-3)-1s-1 and the quenched rate constant of biacetyl phosphorescence by CTAB is 7.82 ×107 (mol·dm-3)-1s-1.The detection limit of biacetyl is 2.8×10-8mol·dm-3

Sensitized Lanthanide Luminescence in AOT Reversed Micelles——Purine Compounds as Energy Donor

研究了反相胶束体系中敏化Tb--(3+)的离子荧光.在AOT/C_6H_(12)/H_2O反相胶束溶液中[AOT:琥珀酸二(2-乙基己基)酯磺酸钠]发生了非常有效的从茶碱的三重态到Tb--(3+)的4f能层的能量转移,并敏化稀土离子Tb--(3+)产生离子荧光.而在阳离子表面活性剂CTAb形成的反相胶束体系中,只能观察到较弱的Tb--(3+)的离子荧光.表明在AOT反相胶束中Tb--(3+)是键合在碘酸头基上,有利于能量转移过程,显著增强Tb--(3+)的离子荧光.通过发光光谱和寿命测量,详细讨论了AOT浓度和水泡大小(W值)等对敏化离子荧光的影响,表明与Tb--(3+)离子水合的水分子的高频OH振动猝灭Tb--(3+)的离子发光,该猝灭过程属静态猝灭.在较低的AOT浓度和较小的W值下,可观察到较强的Tb--(3+)离子荧光,并建立了AOT反相胶束中五种嘌呤类化合物的分析方法,检出限在8.0x10--(-9)~8.0x10--(-7)MOl·dM--(-3)之间.Sensitized lanthanide luminescence by purine compounds in AOT reversed micelles has been studied.A signiFicant enhancement of sensitized room temperature luminescence has been observed using lanthanide Tb3+ as energy acceptor in AOT reversed micelles at low AOT concentration and W value, and weak Tb3+ emission has been observed in CTAB reversed micelles.The results indicate that Tb3 + ions are strongly bound to the sulFonate group of the AOT surFactant.Parameters including the concentration of AOT,solubilized water as well as acceptor concentration that may inFluence the sensitized lanthanide luminescence have been examined.The characteristics of luminescence and liFetimes of Tb3+ were used to elucidate the Factors that aFFected sensitized luminescence.The results show that Tb3+ emission is quenched by the high Frequency OH vibrations of the surrounding water molecules, the loss of Tb3 + emission in high AOT concentration and W value suggests that the Tb3+ cation retains water in its coordination sites.The quenching process is static quenching.The low AOT concentration and W value should be reconmmended For obtaining high sensitivity in analytical application.The detection limits For purine and its deriviations are between 8.0×10-9-8.0×10-7mol·dm-3

Enantioseparation of Nateglinide by Micellar Electrokinetic Chromatography

目的:选择合适的环糊精作手性选择剂,建立那格列奈对映体的胶束电动毛细管色谱拆分方法。方法:使用Tris- H3PO4缓冲液研究了运行液pH、背景电解质浓度、表面活性剂浓度、环糊精种类和浓度及有机添加剂对分离的影响,确定了拆分那格列奈的最佳实验条件:200 mmol·L-1Tris-H3PO4缓冲液,pH=7.8,含40 mmol·L-1 SDS,5 mmol·L-1 HP-β-CD, 10%(v/v)正丙醇,检测波长215 nm。结果:在所建立的最佳条件下,那格列奈对映体达到基线分离,分离度为1.68。结论:方法简单、快速,可作为那格列奈的手性分离方法。Objective:To develop a simple, rapid method for enantioseparation of nateglinide by cyclodextrin (CD)-modified micellar electrokinetic chromatography (MEKC), Method:Using Tris-H3PO4 buffer solution, 215 nm as the detective wavelength, the influence of several factors, such as Tris concentration, pH, anionic surfactant sodium dedecyl sulfate (SDS) concentration, CDs types and their concentration, and organic additive, on the enantimeric separation of nateglinide was investigated and the optimal condition for the separation was established. The buffer solution was 200 mmol·L-1 Tris - H3PO4 at pH 7. 8 containing40mmol·L-1 SDS,5 mmol·L-1 HP-P-CD and 10% (v/v)n-propanol. Result:Under the experiment conditions adopted, the baseline separation of nateglinide enantiomers was obtained, with the resolution 1.68. Conclusion:The proposed method is simple and can be used for the chiral separation of nateglinide

Sentisized Biacetyl Room Temperature Phosphorescence by Four Polycyclic Aromatic Hydrocarbons in β-Cyclodextrin System

对β-环糊精（β-Cd）溶液中4种多环芳烃α-溴代萘（α-brn）、β-溴代萘（β-brn）、菲、敏化丁二酮（bIAC）的室温光（rTP）进行了研究，β-Cd能有效地增强敏化光强度，并从三重态能量、主客体分子几何尺寸大小等方面讨论了各种因素的影响。方法的线性动态范围上限受能量受体浓度的限制，其检出限达10-8MOl/l。This paper reports the biacetyl room temperature phosphorescence(RTP) in β-cyclodextrin (β-CD) system, sensitized by the Four polycyclic aromatic hydrocarbons such as a-bromonaphthalene, β－ bromonaphthalene, phenanthrene and chrysene.In this system β-CD can enhance the RTP intensity.Several Factors inFluencing the RTP, e.g., triplet state energy, the size of host and guest, are discussed.The upper Foot of linear range of analytical curve is restricted by the concentration of acceptor.The detection limit is 10-8 mol/L.国家自然科学基金!（No．29575204）;山西省教委基