甲苯咪唑与曙红Y相互作用的共振瑞利散射、倍频散射和荧光光谱及其分析应用

在pH值3.4~3.9的Britton-Robinson(BR)缓冲介质中,甲苯咪唑(MBZ)与曙红Y(EY)反应形成1:1的离子缔合物,体系反应不仅导致荧光光谱的猝灭,还使共振瑞利散射(RRS)和倍频散射(FDS)显著增强,最大的RRS峰位于326 nm处。 荧光猝灭法、RRS法、FDS法的检出限分别为32.31、7.24和11.65 μg/L,其中RRS法的灵敏度最高。 实验讨论了反应的最佳条件以及共存物质的影响。 该方法用于甲苯咪唑片剂以及尿样中MBZ的测定,结果令人满意。     

氯霉素、甲砜霉素与曙红Y的共振瑞利散射光谱及应用

在pH 1.30的酸性介质中,曙红Y(EOSY)分别与氯霉素(CHP)、甲砜霉素(TAP)相互作用形成离子缔合物,使共振瑞利散射(RRS)显著增强并产生新的RRS光谱。CHP–EOSY体系的最大RRS峰位于313nm,线性范围为0.015～0.32 mg.L-1,检出限为0.013 mg.L-1;TAP–EOSY体系的最大RRS峰位于314nm,线性范围为0.018～0.39 mg.L-1,检出限为0.012 mg.L-1。据此发展了以曙红Y为探针,用共振瑞利散射法测定氯霉素、甲砜霉素的方法。方法简便快速,有较高灵敏度,可用于实际样品中氯霉素、甲砜霉素的测定。     

阳离子表面活性剂与曙红Y的荧光反应及其分析应用

研究阳离子表面活性剂(CSAA)在水溶液中与曙红Y的荧光反应,发现当CSAA单体与曙红Y形成离子缔合物时,荧光发生猝灭,而CSAA胶束与曙红Y作用又会出现一个新的、更强的荧光.荧光猝灭反应具有很高的灵敏度,对于不同的CSAA,其检测限在6.6～12.0ng/mL之间,可用于痕量CSAA的测定.此外,荧光猝灭和新荧光的产生也为研究表面活性剂和荧光染料在溶液中的存在状态提供了新的途径.还研究了反应体系的荧光特征、适宜条件并讨论了反应机理.     

苯海拉明与赤藓红相互作用的吸收、荧光和共振瑞利散射光谱及其分析应用

在pH 4.5的Britton-Robinson(BR)缓冲溶液中, 赤藓红(ET)与苯海拉明(DP)形成1: 1的离子缔合物, 不仅引起吸收光谱的变化和荧光猝灭, 更导致共振瑞利散射(RRS)的显著增强并产生新的RRS光谱, 最大RRS峰位于580 nm附近. 研究了反应产物的吸收、荧光和RRS光谱特征, 适宜的反应条件及分析化学性质, 据此发展了以赤藓红为光谱探针的灵敏、简便、快速测定DP的新方法. RRS法、分光光度法和荧光猝灭法对DP的检出限依次为0.0020, 0.088和0.094 μg/mL, 线性范围分别是0.0067 ~ 2.0, 0.29 ~ 6.4和0.31~3.2 μg/mL. 研究了苯海拉明与赤藓红相互作用对吸收、荧光和RRS光谱的影响. 散射光偏振实验显示结合产物在最大散射波长处的偏振度为0.9779, 表明DP-ET体系的共振散射光谱主要由散射光构成, 基本不含共振荧光成分. 还采用量子化学AM1法计算了反应前后生成焓和平均极化率的变化, 讨论了RRS光谱产生及增强的原因及光吸收、荧光和RRS之间的能量转换关系.     

盐酸吡格列酮与曙红Y相互作用的荧光和共振光散射光谱研究

在HCl-NaOAc酸性缓冲介质中,曙红Y(EY)与盐酸吡格列酮(PGH)反应形成1∶1的离子缔合物,不仅引起曙红Y的荧光猝灭(FLU),更能导致共振散射(RRS)的显著增强。荧光猝灭的激发和发射波长分别为λex=524nm和λem=544nm;最大共振散射波长为308nm,并在540nm处产生一共振峰。方法的线性范围分别为9.04×10-7～2.05×10-5mol/L(FLU)和1.6×10-7～5.1×10-6mol/L(RRS),检出限分别为1.88×10-7mol/L(FLU)和4.82×10-8mol/L(RRS)。研究了荧光和共振散射的光谱特征、适宜的反应条件及影响因素,据此建立了灵敏、简便、快速测定抗糖尿病药物盐酸吡格列酮的新方法。     

阳离子表面活性剂与曙红Y的荧光反应及其分析应用

研究阳离子表面活性剂(CSAA)在水溶液中与曙红Y的荧光反应, 发现当CSAA单体与曙红Y形成离子缔合物时, 荧光发生猝灭, 而CSAA胶束与曙红Y作用又会出现一个新的、更强的荧光。荧光猝灭反应具有很高的灵敏度, 对于不同的CSAA, 其检测限在6.6-12.0ng/mL之间, 可用于痕量CSAA的测定。此外, 荧光猝灭和新荧光的产生也为研究表面活性剂和荧光染料在溶液中的存在状态提供了新的途径。还研究了反应体系的荧光特征、适宜条件并讨论了反应机理。     

分子光谱法研究曙红Y与马来酸罗格列酮相互作用及其分析应用

在HCl-NaAc酸性缓冲介质中,曙红Y(EY)与马来酸罗格列酮(ROM)反应形成1∶1的离子缔合物,不仅引起吸收光谱(UV)的变化和EY的荧光猝灭(FS),更能导致共振瑞利散射(RRS)的显著增强,并产生新的RRS光谱。以试剂为参比,吸收光谱的最大褪色波长为510nm;荧光猝灭的激发波长λex和发射波长λem分别为521和544nm;最大共振散射波长λRRS为307nm,并在532nm处形成较强的散射峰。各方法的线性范围分别为4.98×10-7～7.5×10-6 mol/L(UV)、8.34×10-8～1.79×10-5 mol/L(FS)和4.66×10-9～1.25×10-5 mol/L(RRS),检出限分别为1.49×10-7 mol/L(UV)、2.50×10-8 mol/L(FS)和1.40×10-9 mol/L(RRS)。文中研究了吸收、荧光和共振散射的光谱特征、适宜的反应条件及影响因素,并对荧光猝灭机制及RRS的增强进行了讨论,据此建立了灵敏、简便、快速测定抗糖尿病药物马来酸罗格列酮的新方法。     

荧光红-曙红Y能量转移荧光猝灭法测定痕量铜(Ⅱ)的研究

探讨了荧光红与曙红Y之间的荧光能量转移,研究了Cu(Ⅱ)-荧光红-曙红Y-邻菲罗啉能量转移荧光猝灭体系的最佳条件,建立了荧光分析测定痕量铜的新方法.实验结果表明,在λex/λem=404.7 nm/545 nm,乳化剂0P存在下,荧光红的荧光光谱(λem=524 nm)和曙红Y的吸收光谱(λmax=520 nm)能有效重叠.当荧光红和曙红Y单独存在时,其最大发射波长分别为524 nm和545 nm;当荧光红和曙红Y同时存在时,曙红Y的最大发射波长不变,但其荧光强度明显增大,可见,荧光红和曙红Y分别作为能量给予体和能量接受体发生能量转移,使曙红Y荧光光谱灵敏度增大.在pH 6.5～7.6的KH2PO4-NaOH缓冲溶液中,Cu(Ⅱ)与曙红Y和邻菲罗啉形成配合物使曙红Y的荧光猝灭,加入荧光红后,体系的荧光猝灭值大大增加.利用荧光红-曙红Y能量转移荧光猝灭法测定痕量铜,提高了测定铜的灵敏度和选择性.铜含量在0～250μg/L范围内与曙红Y的荧光猝灭程度成良好的线性关系.方法的检出限为0.082μg/L;测定100μg/L铜溶液,其相对标准偏差为4.6%;样品加标回收率为101%～107.7%.方法已应用于人发、茶叶中痕量铜的测定.     

Ag~+-Cl~--多取代荧光素体系的RRS和RNLS光谱及其分析应用

在pH 3.2~5.7的HAc-Na Ac缓冲溶液中,Ag+与Cl-反应形成Ag Cl.当Ag+适当过量时,Ag Cl与Ag+结合形成[Ag Cl·Ag]+阳离子,它能进一步借静电引力和疏水作用力与曙红B(二溴二硝基荧光素)、曙红Y(四溴荧光素)、乙基曙红(四溴荧光素乙酯)、荧光桃红(四氯四溴荧光素)和虎红(四氯四碘荧光素)等多取代荧光素阴离子(HL-)反应生成离子缔合物[(Ag Cl·Ag)HL].该疏水性离子缔合物可在水相的挤压作用和范德华力的作用下,进一步聚集形成平均粒径约为20 nm的纳米微粒.此时仅引起吸收光谱和荧光光谱的微小变化,但能导致共振瑞利散射(RRS)以及倍频散射(FDS)和二级散射(SOS)等共振非线性散射(RNLS)的显著增强,其中以曙红B体系最灵敏.曙红B体系的最大RRS、FDS和SOS波长分别位于315 nm、350 nm和560 nm处,3种散射增强(ΔIRRS、ΔIFDS和ΔISOS)在一定范围内均与氯离子浓度成正比,均可用于氯离子的测定.其中以FDS法最灵敏,RRS法次之.3种方法(RRS、FDS和SOS法)对于氯离子的检测,曙红B体系的线性范围分别是0.005~1.22μg/m L、0.004~2.92μg/m L和0.01~1.94μg/m L,检出限分别为1.50 ng/m L、1.20 ng/m L和3.90 ng/m L.本文研究了[(Ag Cl·Ag)HL]n纳米微粒的形成、散射强度的提高、适宜的反应条件及影响因素,考察了共存物质的影响,表明方法具有良好的选择性.据此利用上述反应,发展一种RRS、SOS和FDS技术高灵敏、高选择性和简便、快速测定环境空气和废气中HCl及环境水样中氯化物的新方法.文中还对反应机理和散射增强的原因进行了讨论.     

钯（II）-克林霉素-卤代荧光素体系的共振瑞丽散射光谱及其分析应用

在pH为5.0-5.4的乙酸-乙酸钠缓冲溶液中,克林霉素（Clin）与钯(Ⅱ)形成螯合阳离子,它能进一步与二碘荧光素（DIF）,赤藓红（Ery）,曙红Y（EY）等卤代荧光素类染料反应形成1：1：1的三元离子缔合物,此时将引起吸收光谱变化和荧光猝灭,同时还导致共振瑞利散射(RRS)的急剧增强并产生新的RRS光谱,钯(Ⅱ)-克林霉素与DIF,Ery和EY形成产物的最大散射波长分别位于285,287,32 1nm处,另外还有些较弱的散射峰存在。散射增强（ΔI）与克林霉素浓度在一定范围内成正比,可用于克林霉素的定量测定。对于DIF,Ery和EY体系的线性范围和检出限分别为0.025-2.1μg•mL-1和7.8 ng•mL-1,0.053-2.4μg•mL-1和16.0 ng•mL-1;以及0.038-2.4μg•mL-1和11.0 ng•mL-1。本文研究了适宜的反应条件,考察了共存物质的影响,表明方法有较好的选择性,基于三元离子缔合物的RRS光谱,发展了一种高灵敏、简便快速测定克林霉素的新方法。文中还对离子缔合物的组成,结构和反应机理,以及离子缔合物对吸收,荧光和RRS光谱的影响进行了讨论。     

Absorption, fluorescence and resonance Rayleigh scattering spectra of hydrophobic hydrogen bonding of eosin Y/Triton X-100 nanoparticles and their analytical applications

In a weak acidic medium (pH 2.4–2.8), eosin Y molecules (H₂L) could replace water molecules to associate with Triton X-100 to form hydrophobic hydrogen bonding complexes. These complexes could further aggregate to form nanoparticles through the squeezing action of the water phase and Van Der Waals force, resulting in changes in the absorption spectrum and fluorescence quenching of EY as well as the significant enhancement of resonance Rayleigh scattering. This enables the sensitive determination of Triton X-100 using the fading spectrophotometry, fluorescence quenching method and RRS method. Among them, the RRS method shows the highest sensitivity with a detection limit of 20.6 ng mL^?1 for Triton X-100. The optimum experimental conditions and factors that affect the absorption, fluorescence and RRS spectra were tested. The effects of coexisting substances were investigated and the results showed good selectivity. Based on these results, new spectrophotometric methods, fluorescence quenching method and RRS method for the determination of Triton X-100, were established. The hydrogen bonding association of eosin Y with Triton X-100 and the formation of nanoparticles as well as their effects on related spectral characteristics were discussed utilizing infrared, transmission electron microscope technique and quantum chemical method.     

A new method for the determination of the critical micelle concentration of Triton X-100 in the absence and presence of beta-cyclodextrin by resonance Rayleigh scattering technology

A new method for the determination of the critical micelle concentration (CMC) of Triton X-100 in aqueous solution and beta-cyclodextrin solution by resonance Rayleigh scattering (RRS) has been developed. The method is based on the measurement of the RRS intensity of different concentration of Triton X-100 in aqueous solution and beta-cyclodextrin solution (6.0 x 10(-4) mol l(-1)). When the RRS intensities were plotted against the concentration of Triton X-100, an inflection point appeared at the Triton X-100 concentration of 5.0 x 10(-4) mol l(-1) in aqueous solution and 1.1 x 10(-3) mol l(-1) in beta-cyclodextrin solution, respectively. These values of concentration corresponded to the CMC of Triton X-100 in aqueous solution and beta-cyclodextrin solution, which also agreed closely with the results reported by surface tension and UV-Vis absorption spectrophotometry. Therefore, the present RRS method is very convenient, rapid and accurate and can be used as a new technology for the determination of CMC values of surfactants without any probe. The relationship between the RRS intensity and the concentration, aggregate state and the aggregate molecular size of Triton X-100 has been primarily discussed.     

钯(Ⅱ)与法莫替丁和卤代荧光素染料三元离子缔合物纳米微粒的共振瑞利散射光谱及其分析应用

在pH3.5～4.7NaAc-HAc的缓冲溶液中,法莫替丁(FMTD)与Pd(Ⅱ)形成五元环螯合阳离子([Pd(FMTD)]2+),再与二氯荧光素(DCF)、二溴荧光素(DBF)、二碘荧光素(DIF)、赤鲜红(ER)、曙红Y(EY)、乙基曙红(EE)等卤代荧光素(HF)反应形成1:1:2的三元离子缔合物([Pd(FMTD)]·(HF)2).[Pd(FMTD)]·(HF)2在疏水作用和范德华力的作用下进一步聚集形成平均粒径为9nm左右的纳米微粒,此时将引起体系吸收光谱变化、荧光猝灭和共振瑞利散射(RRS)急剧增强.[Pd(FMTD)]·(HF)2的最大吸收峰位于476nm(DCF体系)、540nm(DBF体系)、553nm(DIF体系)、560nm(ER体系)、547nm(EY体系)和549nm(EE体系),最大RRS散射波长位于302～361nm,散射增强程度(ΔI)在一定的范围内与FMTD的浓度成良好的线性关系,检出限为1.0～2.6ng/mL.据此提出了灵敏度高、选择性好、快速准确测定FMTD的分子光谱新方法.适用于片剂、胶囊和注射液等药物制剂的测定.研究了反应的适宜条件、影响因素和分析化学特性,并结合吸...     

Complexation of serum albumins and triton X-100: Quenching of tryptophan fluorescence and analysis of the rotational diffusion of complexes

The polarized and nonpolarized fluorescence of bovine serum albumin and human serum albumin in Triton X-100 solutions is studied at different pH values. Analysis of the constants of fluorescence quenching for BSA and HSA after adding Triton X-100 and the hydrodynamic radii of BSA/HSA–detergent complexes show that the most effective complexation between both serum albumins and Triton X-100 occurs at pH 5.0, which lies near the isoelectric points of the proteins. Complexation between albumin and Triton X-100 affects the fluorescence of the Trp-214 residing in the hydrophobic pockets of both BSA and HSA.     

博莱霉素铜配合物-DNA体系的共振瑞利散射及分析应用

用共振瑞利散射(resonance Rayleigh scattering,RRS)光谱和紫外吸收光谱及荧光光谱研究了博莱霉素(bleomycinA2,BLMA2)-Cu(Ⅱ)配合物的形成及其与DNA的反应.在水溶液中,BLMA2和Cu(Ⅱ)能形成1:1的配合物,产生新的吸收光谱,并能观察到BLMA2的荧光猝灭.该配合物能与DNA作用生成三元离子缔合物,引起RRS的显著增强.讨论了BLMA2-Cu(Ⅱ)配合物的形成条件及影响因素;对该配合物与DNA的结合模式和反应机理进行了讨论;探讨了博莱霉素荧光猝灭的类型,并建立了一种用BLMA2-Cu(Ⅱ)配合物作探针RRS法测定DNA的高灵敏度、简单、快捷的分析方法.该方法的检出限(3σ)分别为7.2ng·mL-1(ctDNA)、7.1ng·mL-1(sDNA)、18ng·mL-1(hsDNA),能用于痕量DNA的测定.     

Absorption,Fluorescence and Resonance Rayleigh Scattering Spectra of Interaction of Papain with Calf Thymus DNA

In weak acidic medium, interaction between papain and calf thymus DNA (ctDNA) resulted in absorption spectral change, fluorescence quenching of papain and remarkable enhancement of resonance Rayleigh scattering (RRS). The interaction types and binding modes were discussed by characteristics of RRS, absorption, fluorescence and circular dichroism spectra combining thermodynamic data. Four interaction types include electrostatic attraction, hydrophobic force, hydrogen bonding and aromatic stacking interaction. Papain interacted with the major groove of ctDNA. Aromatic stacking interaction is the main reason of change of absorption spectrum and fluorescence quenching of papain. Surface enhanced scattering effect, resonance energy transfer effect, increase of molecular volume and conformational change make contribution to RRS enhancement. The enhanced RRS intensity (ΔI) is directly proportional to the concentration of ctDNA or papain. The detection limit (3σ) is 5.2 ng·mL^?1 for ctDNA and 5.6 ng·mL^?1 for papain. This creates conditions for determination of papain and ctDNA.     

酪氨酸猝灭Eosin Y的荧光

氨基酸残基对探针分子的荧光猝灭行为可以为生物大分子的结构及构象动力学研究提供重要的信息.本文运用飞秒瞬态吸收光谱和时间相关单光子计数实验系统研究了在水(H₂O)和氘代水(D₂O)溶液中乙酰基取代酪氨酸(AcTyr)对Eosin Y的超快荧光猝灭动力学过程.发现导致AcTyr对Eosin Y荧光猝灭的主要原因是由于它们之间形成了短寿命的基态复合物.我们还发现Eosin Y与AcTyr形成的基态复合物的激发态寿命具有明显的动力学同位素效应,表明AcTyr对Eosin Y的荧光猝灭是通过质子耦合电子转移过程发生的.     

Photophysical studies of some dyes in aqueous solution of triton X-100

The spectral (both absorption and fluorescence) and photoelectrochemical studies of a few selective dyes, namely, anionic erythrosin B, neutral riboflavin and cationic safranin O have been carried out in aqueous solution of triton X-100, a neutral surfactant. The results show that the ionic dyes, erythrosin B and safranin O form 1:1 electron donor-acceptor (EDA) or charge-transfer (CT) complexes with triton X-100 both in the ground and excited states, whereas neutral dye riboflavin in its excited state forms 1:1 complex with triton X-100. In these complexes, the dyes act as electron acceptors whereas triton X-100 acts as an electron donor. The fluorescence spectra of erythrosin B and safranin O in presence of triton X-100 show enhancement of fluorescence intensity with red and blue shifts respectively while riboflavin shows normal quenching of fluorescence. A good correlation has been found among photovoltage generation of the systems consisting of these dyes and triton X-100, spectral shift due to complex formation and thermodynamic properties of these complexes.     

Study on the interaction between fluoroquinolones and erythrosine by absorption, fluorescence and resonance Rayleigh scattering spectra and their application

In pH 4.4-4.5 Britton-Robinson (BR) buffer solution, fluoroquinolone antibiotics (FLQs) including ciprofloxacin (CIP), norfloxacin (NOR), levofloxacin (LEV) and lomefloxacin (LOM) could react with erythrosine (Ery) to form 1:1 ion-association complexes, which not only resulted in the changes of the absorption spectra and the quenching of fluorescence, but also resulted in the great enhancement of resonance Rayleigh scattering (RRS). These offered some indications of the determination of fluoroquinolone antibiotics by spectrophotometric, fluorescence and resonance Rayleigh scattering methods. The detection limits for fluoroquinolone antibiotics were in the range of 0.097-0.265 microg/mL for absorption methods, 0.022-0.100 microg/mL for fluorophotometry and 0.014-0.027 microg/mL for RRS method, respectively. Among them, the RRS method had the highest sensitivity. In this work, the spectral characteristics of the absorption, fluorescence and RRS, the optimum conditions of the reactions and the properties of the analytical chemistry were investigated. The methods have been successfully applied to determination of some fluoroquinolone antibiotics in human urine samples and tablets. Taking CIP-Ery system as an example, the charge distribution, the enthalpy of formation and the mean polarizability were calculated by density function theory (DFT) method. In addition, the reasons for the enhancement of scattering spectra were discussed.     

呋塞米-Pd(Ⅱ)螯合物与某些碱性三苯甲烷类染料相互作用的共振瑞利散射和共振非线性散射光谱及其分析应用

在pH4.5～7.0的Britton-Robinson(BR)缓冲溶液中,呋塞米(FUR)与Pd(Ⅱ)形成1:1的螯合阴离子,它能进一步与乙基紫(EV)、结晶紫(CV)、甲基绿(MeG)、亮绿(BG)、甲基紫(MV)等碱性三苯甲烷染料(BTPMD)阳离子通过静电引力和疏水作用形成FUR:Pd(II):BTPMD为1:1:1的离子缔合物.此时,该离子缔合反应不仅能引起吸收光谱的变化,而且更能导致共振瑞利散射(RRS)、二级散射(SOS)和倍频散射(FDS)的显著增强,其最大RRS波长分别位于324nm(EV,CV和MV体系)和340nm(BG和MeG体系),最大SOS波长分别位于550nm(EV,CV,BG和MeG体系)和530nm(MV体系),而最大FDS波长均位于392nm附近.在一定条件下三种散射增强(ΔIRRS,ΔISOS和ΔIFDS)均与呋塞米(FUR)的浓度成正比.对不同染料体系,三种方法对FUR的检出限分别在0.3～4.9ng/mL(RRS),3.2～33.1ng/mL(SOS)和9.0～85.7ng/mL(FDS)之间,均可用于痕量FUR的测定.本文研究了三元离子缔合物的形成对吸收,RRS,SOS和FDS光谱特征和强度的影响,考察了适宜的反应条件、影响因素和分析化学性质,并以RRS法为例考察了共存物质的影响.据此提出了一种高灵敏度、简便、快速测定FUR的共振光散射新方法,将其用于片剂、注射液、人血清和尿样中FUR的测定,结果满意.文中还对三元离子缔合物的组成、结构和反应机理进行了讨论.