铜（Ⅱ)-氟喹诺酮类抗生素螯合物与虎红体系的吸收和共振瑞利散射光谱及其分析应用研究

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（ΔI)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。     

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.     

氟喹诺酮类抗生素与赤藓红的共振瑞利散射光谱研究及其分析应用

在Ph4.0～5.0的BR缓冲介质中,赤藓红(Ery)与莫西沙星(MXFX)和加替沙星(GTF)等氟喹诺酮类抗生素(FLQs)相互作用形成1:1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,最大散射波长位于568nm处,并在342nm和378nm处有2个较小的散射峰.在342nm处一定浓度的抗生素与散射增强成正比,两种氟喹诺酮类药物的线性范围分别是0.02～2.7μg/mL(MXFX)和0.06～10.2μg/mL(GTF).据此建立了测定氟喹诺酮类药物的新方法,已用于胶囊和人尿液中的FLQs测定,并对反应机理和RRS增强的原因作了讨论.     

氟喹诺酮类抗生素与钴(Ⅱ)和刚果红三元配合物的共振瑞利散射光谱研究及其分析应用

在pH 4.5～6.5的Bdtton-Robinson缓冲溶液中,钴(Ⅱ)与环丙沙星(CIP)、诺氟沙星(NOR)、氧氟沙星(OF)和左氧氟沙星(LEV)等氟喹诺酮类抗生素(FLQs)能形成螯合阳离子,它们能通过静电引力和疏水作用与刚果红(CR)阴离子反应,形成1:2:1(Co2 :FLQs:CR)三元离了缔合配合物.此时将引起溶液的共振瑞利散射(RRS)显著增强,并出现新的RRS光谱.不同抗生素具有相似的光谱特征,其最大散射波长均位于560 nm处,并在382和278 nm处有2个较小的散射峰.一定浓度的抗生素与散射增强(△成正比,对不同氟喹诺酮类药物的线性范围和检出限(3σ)分别是0.026～2.64 μg·mL-1和7.68 μg·mL-1(CIP),0.045～3.20 μg·mL-1和13.00 ng·mL-1(NOR),0.037～4.00μg·mL-1和11.24 ng·mL-1(OF),0.039～4.00 μg·mL-1和11.80 ng·mL-1(LEV),据此提出了一种以RRS技术测定氟喹诺酮抗牛素的新方法.方法不仅灵敏度高,而且简单、快速,并有良好的选择性和重复性,可用于片剂、针剂、滴眼液和人尿液中氟喹诺酮类药物的测定.文中还对反应机理和RRS增强的原因作了讨论.     

铈(Ⅳ)与氟喹诺酮类抗生素相互作用的共振瑞利散射光谱及其分析应用

在pH4.0～5.0的弱酸性介质中,Ce(Ⅳ)能与诺氟沙星(NOR)、环丙沙星(CIP)、培氟沙星(PE)、洛美沙星(LOM)和司帕沙星(SPA)等氟喹诺酮类抗生素(FLQs)反应,并最终形成Ce(HL)(OH)4型的三元混配络合物.此时,仅能引起吸收光谱的微小变化和摩尔吸光系数(ε)的少量提高,但是却能导致共振瑞利散射(RRS)的显著增强,5种体系的最大散射波长均位于381nm附近,并在534nm处出现一个较小的散射峰,散射增强(ΔI)在一定范围内与FLQs的浓度成正比,方法有高灵敏度,对不同的FLQ其检出限(3σ)除SPA(16.0μgmL-1)之外,其余FLQs在1.9～5.3ngmL-1之间.研究了Ce(Ⅳ)与FLQs相互作用对RRS光谱的影响,反应的适宜条件和影响因素,考察了共存物质的影响,表明方法有良好的选择性,可用于某些样品中FLQs的测定.还结合吸收光谱的变化和量子化学计算,讨论了反应机理及散射增强的原因.     

氟喹诺酮类抗生素与钴(II)和刚果红三元配合物的共振瑞利散射光谱研究及其分析应用

在pH 4.5～6.5的Britton-Robinson缓冲溶液中, 钴(II)与环丙沙星(CIP)、诺氟沙星(NOR)、氧氟沙星(OF)和左氧氟沙星(LEV)等氟喹诺酮类抗生素(FLQs)能形成螯合阳离子, 它们能通过静电引力和疏水作用与刚果红(CR)阴离子反应, 形成1∶2∶1 (Co^2＋∶FLQs∶CR)三元离子缔合配合物. 此时将引起溶液的共振瑞利散射(RRS)显著增强, 并出现新的RRS光谱. 不同抗生素具有相似的光谱特征, 其最大散射波长均位于560 nm处, 并在382和278 nm处有2个较小的散射峰. 一定浓度的抗生素与散射增强(ΔI)成正比, 对不同氟喹诺酮类药物的线性范围和检出限(3s)分别是0.026～2.64 μg•mL^－1和7.68 ng•mL^－1 (CIP), 0.045～3.20 μg•mL^－1和13.00 ng• mL^－1 (NOR), 0.037～4.00 μg•mL^－1和11.24 ng• mL^－1 (OF), 0.039～4.00 μg•mL^－1和11.80 ng•mL^－1 (LEV), 据此提出了一种以RRS技术测定氟喹诺酮抗生素的新方法. 方法不仅灵敏度高, 而且简单、快速, 并有良好的选择性和重复性, 可用于片剂、针剂、滴眼液和人尿液中氟喹诺酮类药物的测定. 文中还对反应机理和RRS增强的原因作了讨论.     

酸性铬兰K-OP-牛血清白蛋白体系的共振瑞利散射及共振非线性散射光谱研究及应用

在pH 3.2的邻苯二甲酸氢钾-HCl缓冲液中,酸性铬兰K(ACBK)-OP与牛血清白蛋白(BSA)形成三元离子缔合物,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,光谱最大散射波长分别位于420,678和340nm。体系的光散射强度与BSA浓度在一定范围内呈线性增强,RRS在0~3.5 mg/L,SOS在0~3 mg/L,FDS在0~3 mg/L范围内对BSA的检出限分别为0.3,0.7和0.8μg/L,据此建立了测定BSA的共振线性(RRS)和共振非线性光散射(RNLS)分析法。以RRS法考察了酸性铬兰K-OP与白蛋白形成三元缔合物的适宜条件、影响因素等。方法可用于合成样品及血清样品中蛋白含量的测定。     

乙基紫探针共振瑞利散射法测定头孢硫脒

建立了测定痕量头孢硫脒(CEFA)的共振瑞利散射(RRS)法。在稀NaOH溶液中,头孢硫脒与乙基紫(EV)结合,使体系的RRS急剧增强并产生新的RRS光谱,最大共振光散射峰位于波长341nm处,头孢硫脒的质量浓度在0.094~0.70mg/L范围与散射强度(△IRRS)呈良好的线性关系,检出限(3Sb/K)为0.075mg/L。该方法可用于人体血液及市售药物中头孢硫脒的测定。     

铜(II)-氟喹诺酮类抗生素螯合物与赤藓红体系的吸收、荧光和共振Rayleigh散射光谱及其分析应用研究

在pH 4.2~5.0的Britton-Robinson 缓冲溶液中, 环丙沙星(CIP), 诺氟沙星(NOR), 氧氟沙星(OF), 左氧氟沙星(LEV), 洛美沙星(LOM)和司帕沙星(SPA)等氟喹诺酮类抗生素(FLQs) 能与铜(II)形成螯合阳离子, 它们能进一步与赤藓红(Ery)阴离子通过静电引力和疏水作用形成FLQs:Cu(II): Ery为1:1:1的离子缔合物. 此时, 能引起吸收光谱的变化, 并发生明显的褪色作用, 最大褪色波长均位于526 nm处, 反应具有较高的灵敏度, 除NOR的摩尔吸光系数(ε)较低外, 其余5种抗生素的ε值均大于1.0×10⁵ L·mol^-1·cm^-1, 而且LOM和OF体系的ε值均大于3×10⁵ L·mol^-1·cm^-1, 而SPA的e 值高达7.22×10⁵ L·mol^-1·cm^-1, 可用于这类药物的分光光度测定. 离子缔合反应还导致赤藓红的荧光猝灭, 反应也具有高灵敏度, 上述6种FLQs药物的检出限在7.1~12.2 μg·L^-1之间, 为荧光猝灭法测定μg·L^-1级FLQs创造了条件. 离子缔合反应更能导致共振瑞利散射(RRS)的显著增强, 并产生新的RRS光谱. 六种药物的反应产物具有相似的光谱特征, 最大散射波长均位于566 nm处, 并在333 nm和287 nm处有2个较小的散射峰. 在一定条件下散射增强(ΔI)与药物浓度成正比. RRS法较褪色分光光度法和荧光猝灭法具有更高的灵敏度, 对不同的FLQs药物的检出限在1.7 μg·L^-1至3.1 μg·L^-1之间, 更适于痕量的FLQs测定. 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, 结合量子化学计算方法讨论了离子缔合反应的历程及对光谱特征的影响, 并研究了RRS法 的选择性及分析应用.     

茜素红-镧-左氧氟沙星体系的共振瑞利散射及共振非线性散射光谱研究及应用

在pH6.0的HAc-NaAc缓冲液中,茜素红-镧与左氧氟沙星(LVFX)形成三元配合物,导致共振瑞利散射(RRS)、二级散射(SOS)和倍频散射(FDS)均增强,光谱最大散射波长分别位于314 nm、570 nm和285 nm,对于RRS在0.02～1.2 mg/L、SOS在0.01～1.0 mg/L和FDS在0.01～1.0 mg/L范围内呈良好的线性关系,LVFX的检出限分别为4.00μg/L(RRS法)、9.16μg/L(SOS法)和4.42μg/L(FDS法),据此建立了灵敏的测定左氧氟沙星的共振线性和非线性光散射分析法。并以RRS法考察了茜素红-镧-左氧氟沙星体系的反应条件、影响因素等。方法可用于片剂、胶囊中左氧氟沙星的测定,同时以标准加入法对尿样和血样进行了分析。     

Resonance Rayleigh scattering, second-order scattering and frequency doubling scattering spectra for studying the interaction of erythrosine with Fe(phen)3(2+) and its analytical application

In a weak alkaline Britton-Robinson buffer medium, erythrosine (Ery) can react with Fe(phen)(3)(2+) to form 1:1 ion-association complex, which will cause not only the changes of the absorption spectra, but also the remarkable enhancement of resonance Rayleigh scattering (RRS), second-order scattering (SOS) and frequency doubling scattering (FDS) spectra, and the appearance of new spectra of RRS, SOS and FDS. The maximum RRS, SOS and FDS wavelengths (λ(ex)/λ(em)) of the ion-association complex are located at 358/358 nm, 290/580 nm and 780/390 nm, respectively. The increments of scattering intensities (ΔI) are directly proportional to the concentration of Ery in a certain range. The detection limits for Ery are 0.028 μg mL(-1) for RRS method, 0.068 μg mL(-1) for SOS method and 0.11 μg mL(-1) for FDS method, respectively. Among them, the RRS method has the highest sensitivity. Based on the above researches, a new highly sensitive and simple method for the determination of Ery has been developed. In this work, the spectral characteristics of absorption, RRS, SOS and FDS spectra, the optimum conditions of the reaction and influencing factors for the RRS, SOS and FDS intensities were investigated. In addition, the reaction mechanism was discussed.     

Resonance Rayleigh scattering spectra for studying the interaction of aminoglycoside antibiotics with pontamine sky blue and their analytical applications

In a weakly acid medium, some aminoglycoside antibiotics, such as kanamycin (KANA), gentamicin (GEN), tobramycin (TOB), and neomycin (NEO), or acid bisazo dye pontamine sky blue (PSB) can only produce very weak resonance Rayleigh scattering (RRS) signals. However, when the two agents react with each other to form the ion association complexes, the RRS intensity can be enhanced greatly and a new RRS spectrum and a significant enhancement of the RRS intensity in the wavelength range 350-600 nm can be observed. The maximum scattering peak is at 580 nm. There is a linear relationship between the RRS intensity and the antibiotic concentration in the range 0.01-6.0 microg mL(-1) at 580 nm. This RRS method has therefore been developed for the determination of trace levels of aminoglycoside antibiotics. The detection limits (3 sigma) of the four antibiotics, whose order of sensitivity is KANA>NEO>TOB>GEN, are 5.8-6.9 ng mL(-1). This method has a good selectivity and has been successfully applied to the quick determination of antibiotics not only for injections and ear drops, but clinic serum samples as well. In addition, quantum chemistry-based analysis of the reaction mechanism, the factors influencing the RRS spectra, and the reasons for the enhancement of RRS are discussed.     

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。     

Study on the interaction between diphenhydramine and erythrosin by absorption,fluorescence and resonance Rayleigh scattering spectra

In pH 4.5 Britton-Robinson(BR)buffer solution,erythrosin(ET)can react with diphenhydramine(DP)to form a 1:1 ion-association complex,which not only results in the change of the absorption spectra,but also results in the great enhancement of resonance Rayleigh scattering(RRS)and the quenching of fluorescence.Furthermore,a new RRS spectrum will appear,and the maximum RRS wavelength was located at about 580 nm.In this work,the spectral characteristics of the absorption,fluorescence and RRS,the optimum conditions of the reaction and the properties of an analytical chemistry were inves- tigated.A sensitive,simple and new method for the determination of DP by using erythrosin as a probe has been developed.The detection limits for DP were 0.0020μg/mL for RRS method,0.088μg/mL for absorption method and 0.094μg/mL for fluorophotometry.There was a linear relationship between the absorbance,RRS and fluorescence intensities and the drug concentration in the range of 0.0067-2.0, 0.29-6.4 and 0.31-3.2μg/mL,respectively.The effects of the interaction of diphenhydramine and erythrosin on the absorption,fluorescence and resonance Rayleigh scattering spectra were discussed. In light polarization experiment,the polarization of RRS at maximum wavelength was measured to be P =0.9779,and it revealed that the RRS spectrum of DP-ET complex consists mostly of resonance scat- tering and few resonance fluorescence.In this study,enthalpy of formation and mean polarizability were calculated by AM1 quantum chemistry method.In addition,the reaction mechanism and the rea- sons for the enhancement of scattering spectra and the energy transfer between absorption,fluores- cence and RRS were discussed.     

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 enhanced 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 conditions 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 determination of STSⅡA in the synthesis samples and Nuoxinkang injection. Combined with infrared absorption and NMR spectra, the structure of the chelate and the reasons of RRS enhancement are also discussed.     

Resonance Rayleigh scattering spectra, non-linear scattering spectra of tetracaine hydrochloride-erythrosin system and its analytical application

The interaction between erythrosine (ET) and tetracaine hydrochloride (TA) was studied by resonance Rayleigh scattering (RRS), frequency doubling scattering (FDS) and second-order scattering (SOS) combining with absorption spectrum. In a weak acidic medium of Britton-Robinson (BR) buffer solution of pH 4.5, erythrosine reacted with tetracaine hydrochloride to form 1:1 ion-association complex. As a result, the new spectra of RRS, SOS and FDS appeared and their intensities enhanced greatly. The maximum peaks of RRS, SOS and FDS were at 342 nm, 680 nm and 380 nm, respectively. The intensities of the three scattering were directly proportional to the concentration of TA in the range of 0.008-4.2 microg mL(-1) for RRS, 0.027-4.2 microg mL(-1) for SOS and 0.041-4.2 microg mL(-1) for FDS. The methods had very high sensitivities and good selectivities, and the detection limits were 0.003 microg mL(-1) for RRS, 0.008 microg mL(-1) for SOS and 0.012 microg mL(-1) for FDS, respectively. Therefore, a new method was developed to determinate trace amounts of TA. The recovery for the determination of TA in blood serum and urine samples was between 97.0% and 103.8%. In this study, mean polarizability was calculated by AM1 quantum chemistry method. In addition, the reasons for the enhancement of scattering spectra and the energy transfer between absorption, fluorescence and RRS were discussed.     

曲利本红与氨基糖苷类抗生素相互作用的共振瑞利散射光谱及其分析应用

在弱酸条件下，酸性双偶氮染料曲利本红（TR）或硫酸卡那霉（KANA）、硫酸 新霉素（NEO）、硫酸庆大霉素（GEN）和硫酸妥布霉素（TOB）等氨基糖苷类抗生 素的各自共振瑞利散射（RRS）十分微弱，但两者相互作用形成离子缔合物时能使 RRS急剧提高并产生新的RRS光谱，在400～535nm之间有一个强的散射带，最大散射 峰位于400nm处，在0.013～6.0μg·mL~(-1)范围内RRS强度与抗生素浓度成正比， 可用于氨基糖苷类抗生素的测定，对不同抗生素的检出限（3σ）在12.9～17.6ng ·mL~(-1)之间，其灵敏度的顺序是KANA＞NEO＞TOB＞GEN,方法有较好的选择性， 可用于市售抗生素注射液或滴耳液中药物含量和临床血药浓度的快速测定，中还用 量子化学方法对反应机理进行探讨，并讨论了的RRS光谱特性的影响因素和RRS增强 的原因。     

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。     

Achievements in resonance Raman spectroscopy review of a technique with a distinct analytical chemistry potential

In an extended introduction, key aspects of resonance Raman spectroscopy (RRS) such as enhanced sensitivity and selectivity are briefly discussed in comparison with normal RS. The analytical potential is outlined. Then achievements in different fields of research are highlighted in four sections, with emphasis on recent breakthroughs: (1) The use of visible RRS for analyzing carotenoids in biological matrices, for pigments and dyes as dealt with in art and forensics, and for characterizing carbon nanotubes. (2) The use of RRS in the deep UV (excitation below 260 nm) in the bioanalytical and life sciences fields, including nucleic acids, proteins and protein-drug interactions. Metalloproteins can be studied by visible RRS in resonance with their chromophoric absorption. (3) Progress in theoretical calculations of RRS excitation profiles and enhancement factors, which ultimately might facilitate analytical RRS. (4) Instrumental and methodological achievements including fiber-optic UV-RRS, coupling of RRS to liquid chromatography and capillary electrophoresis. Sensitivities can approach the single-molecule level with surface-enhanced RRS or tip-enhanced RRS. Last but not least, promising fluorescence background rejection techniques based on time-gated detection will be presented. This review ends with a concluding section on future expectations for RRS, in particular its potential as an analytical technique.     

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 enhanced 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 conditions 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 determination of STSIIA in the synthesis samples and Nuoxinkang injection. Combined with infrared absorption and NMR spectra, the structure of the chelate and the reasons of RRS enhancement are also discussed.