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.     

氟喹诺酮类抗生素与磷钨酸体系的共振瑞利散射光谱研究及其分析应用

在5.0 mol/L的HCl缓冲介质中,磷钨酸（Pwa）与莫西沙星(MXFX)和加替沙星（GTF）等氟喹诺酮类抗生素(FLQs)相互作用形成摩尔比1∶1离子缔合物,导致体系的共振瑞利散射(RRS)显著增强并出现新的RRS光谱。 MXFX和GTF的反应产物具有相似的光谱特征,最大散射波长位于320 nm附近,且药物浓度与散射增强(ΔI)成正比,2种氟喹诺酮类药物的线性范围分别为0.025~6.0 mg/L（MXFX）和0.023~9.0 mg/L（GTF）。 据此可建立用于测定氟喹诺酮类药物的简捷快速灵敏的新方法,方法用于胶囊和人尿液中的FLQs测定并取得满意结果。 并对反应机理和RRS增强的原因进行了讨论。     

Study on the ternary mixed ligand complex of palladium(II)-aminophylline-fluorescein sodium by resonance Rayleigh scattering, second-order scattering and frequency doubling scattering spectrum and its analytical application

The interaction between palladium(II)-aminophylline and fluorescein sodium was investigated by resonance Rayleigh scattering, second-order scattering and frequency doubling scattering spectrum. In pH 4.4 Britton-Robinson (BR) buffer medium, aminophylline (Ami) reacted with palladium(II) to form chelate cation([Pd(Ami)]2+), which further reacted with fluorescein sodium (FS) to form ternary mixed ligand complex [Pd(Ami)(FS)2]. As a result, resonance Rayleigh scattering (RRS), second-order scattering (SOS) and frequency doubling scattering spectrum (FDS) were enhanced. The maximum scattering wavelengths of [Pd(Ami)(FS)2] were located at 300 nm (RRS), 650 nm (SOS) and 304 nm (FDS). The scattering intensities were proportional to the Ami concentration in a certain range and the detection limits were 7.3 ng mL(-1) (RRS), 32.9 ng mL(-1) (SOS) and 79.1 ng mL(-1) (FDS), respectively. Based on it, the new simple, rapid, and sensitive scattering methods have been proposed to determine Ami in urine and serum samples. Moreover, the formation mechanism of [Pd(Ami)(FS)2] and the reasons for enhancement of RRS were fully discussed.     

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.     

Determination of Indole Alkaloids by High-Performance Liquid Chromatography with Resonance Rayleigh Scattering Detection

A novel resonance Rayleigh scattering (RRS) detection approach combined with high–performance liquid chromatography (HPLC) was developed for the determination of reserpine, deserpidine, and ajmalicine. The resonance Rayleigh scattering signal increased when the analytes were bound to diiodofluorescein in Britton–Robinson buffer (pH 4.2). Separation was performed using a C18 column with a mobile phase consisting of acetonitrile–5 millimolar ammonium acetate buffer at pH 4.2 (44:56, volume by volume). Resonance Rayleigh scattering was measured at excitation and emission wavelengths of 320 nanometers. The experimental parameters affecting the separation and the scattering intensity were carefully optimized. Possible mechanisms for the resonance Rayleigh scattering enhancement of the indole alkaloid–diiodofluorescein system were explored by scanning electron microscopy, nuclear magnetic resonance, and ultraviolet-visible absorption spectroscopy. The method was employed for the determination of the analytes in human urine and pharmaceutical tablets.     

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。     

固绿FCF共振瑞利散射法测定食品中的Al(Ⅲ)

在酸性Tris-HCl缓冲介质中,溴化十六烷基三甲基铵(CTMAB)增敏固绿FCF,与Al(Ⅲ)结合生成三元络合物使共振瑞利散射(RRS)显著增强并产生新的RRS光谱,其最大共振瑞利散射峰位于330 nm,RRS增强程度(△IRRS)与Al(Ⅲ)的质量浓度在0.02～0.49 mg/L成正比,方法有很高的灵敏度,检出限是0.0096 mg/L.方法用于面制食品中Al(Ⅲ)的测定,结果满意.     

同多钨酸-阿米卡星相互作用的共振瑞利散射光谱及其分析应用

在pH 0.65~1.10的HCl-NaAc缓冲溶液中,当同多钨酸(IPT)与阿米卡星(AMK)形成离子缔合物,能引起共振瑞利散射 (RRS)显著增强,并产生新的RRS光谱,其最大散射峰位于340 nm,AMK浓度在0.001~0.08 µg•mL-1范围内与散射增强程度呈线性关系,据此建立测定AMK的RRS新方法。方法具有较高的灵敏度,检出限(3σ)为0.4 ng•mL-1。考察了体系的RRS和吸收光谱特征,优化了适宜的反应条件,试验了常见共存物质的影响,表明方法具有良好的选择性。方法用于人血清中AMK的测定,结果满意。文中对离子缔合反应机理和RRS增强的原因进行了讨论。     

聚乙烯醇增敏藏红T为探针的共振瑞利散射法测定阴离子表面活性剂

在pH=4.0的柠檬酸-柠檬酸钠缓冲体系中,藏红T(ST)与十二烷基苯磺酸钠(SDBS)通过静电引力和疏水作用结合形成离子缔合物,再进一步与聚乙烯醇(PVA)形成三元复合物后,可使体系的共振瑞利散射强度显著提高,其最大散射强度位于340nm处。SDBS含量在0.15~5.0μg/mL范围内与共振瑞利散射强度增强值ΔI呈良好线性关系(R2=0.9969),检出限为8.6ng/mL,据此建立一种定量分析阴离子表面活性剂的共振瑞利散射新方法。探讨了影响因素和最佳实验条件,并将建立的方法应用于环境水样中阴离子表面活性剂的检测。该方法测得结果与国家标准方法相比较无显著性差异。     

十二烷基苯磺酸钠-硫酸耐而蓝体系的共振瑞利散射光谱及其分析应用

提出了共振瑞利散射法(RRS)测定十二烷基苯磺酸钠(SDBS)的新方法。在pH为1.98～3.29的B-R缓冲溶液中,硫酸耐而蓝与SDBS结合生成离子缔合物,使溶液共振瑞利散射(RRS)增强,其最大散射峰位于760 nm,另在533 nm、400 nm有两个较弱的散射峰。SDBS的浓度在0.04～1.6 mg/L范围内,与RRS强度有良好的线性关系,对SDBS的检出限(3σ)达0.018 mg/L。研究了适宜的反应条件和影响因素,表明该方法灵敏、稳定。用于环境水样中阴离子表面活性剂含量的测定,回收率为95.9%～106.7%。     

金纳米微粒作探针共振瑞利散射光谱法测定卡那霉素

在一种含柠檬酸盐的溶液中, 柠檬酸根阴离子自组装于带正电荷的金纳米微粒表面, 使金纳米微粒成为一种被柠檬酸根包裹的带负电荷的超分子化合物. 在pH 4.4～6.8的弱酸性介质中, 它可与质子化的卡那霉素(KANA)阳离子借静电引力、疏水作用力结合, 形成粒径更大的聚集体(平均粒径从12增至20 nm), 这种聚集体的形成在引起金纳米的等离子体吸收带明显红移(Δλ＝102 nm)的同时, 共振瑞利散射(RRS)显著增强并且倍频散射(FDS)和二级散射(SOS)等共振非线性散射也有较大的增强, 最大散射峰分别位于280 nm (RRS), 310 nm (FDS)和480 nm (SOS)处. 在适当条件下, 散射强度(ΔI)与卡那霉素的浓度成正比, 其中RRS法灵敏度最高, 因此金纳米微粒可作为测定卡那霉素的高灵敏RRS探针, 它对卡那霉素的检出限为10.52 ng•mL^－1, 方法有较好的选择性, 可用于血液中卡那霉素的测定, 文中还讨论了有关反应机理和RRS增强的原因.     

共振瑞利散射光谱法测定饮料中日落黄

日落黄与壳聚糖盐酸盐发生缔合反应形成离子缔合物可使体系共振光显著增强。在1.0 mL pH 5.5的BR缓冲溶液中,该体系共振散射强度最大,反应可在室温5 min内迅速完成。在0.6～9μg.mL-1范围内散射强度(ΔI)与日落黄的浓度成正比,检出限为0.395μg.mL-1(n=5)。建立了一种简便、快速测定日落黄的方法,并成功用于饮料样品中日落黄含量的测定.加标回收率为93.0～101.8%,RSD为1.8～3.4%。     

[HgI4]2－-蛋白质离子缔合物体系共振瑞利散射和共振非线性散射光谱及其分析应用

在0.0035～0.0045 mol/L硫酸介质中, 牛血清白蛋白(BSA)、人血清白蛋白(HSA)、卵白蛋白(OVA)和血红蛋白(HGB)等蛋白质以带正电荷的阳离子存在. 它们能借助于静电引力和疏水作用力与配阴离子[HgI4]2－-反应形成结合产物, 此时将引起共振瑞利散射(RRS)、二级散射(SOS)和倍频散射(FDS)显著增强, 并且出现新的散射光谱. 其最大RRS, SOS和FDS波长分别位于390, 760和390 nm附近. 在一定范围内, 三种散射增强(ΔIRRS, ΔISOS和ΔIFDS)与蛋白质浓度成正比, 方法具有高灵敏度, 三种方法对于不同蛋白质的检出限分别在5.7～15.9 ng/mL (RRS), 8.2～15.4 ng/mL (SOS)和11.2～22.1 ng/mL (FDS)之间, 均可用于痕量蛋白质的测定. 本文研究了[HgI4]2－与蛋白质相互作用对RRS, SOS和FDS光谱特征和强度的影响, 考察了适宜的反应条件, 并以RRS为例考察了共存物质的影响, 表明方法有良好的选择性. 据此, 利用[HgI4]2－与蛋白质的相互作用发展了一种用共振光散射技术、灵敏度高、简便、快速测定蛋白质的新方法. 本方法可用于血清和人尿中总蛋白质的测定.     

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。     

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。     

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.     

多菌灵与Pd（II）体系的共振瑞利散射光谱及分析应用

在pH=10.0的Britton-Robinson（BR）缓冲溶液中,多菌灵与Pd(Ⅱ)反应形成1∶1的六元螯合物,导致共振瑞利散射（RRS）、二级散射（SOS）和倍频散射（FDS）显著增强,并产生新的共振瑞利散射光谱,其最大RRS、SOS和FDS波长分别位于309、606和310 nm。 在一定范围内,3种散射增强（ΔIRRS、ΔISOS和ΔIFDS）均与多菌灵的浓度成正比,反应具有较高的灵敏度,对于多菌灵的检出限分别为7.1×10-9 g/mL（RRS）、7.4×10-9 g/mL（SOS）和10.7×10-9 g/mL（FDS）。 据此提出了测定多菌灵的光散射新方法。 以灵敏度最高的RRS法为例,测定了西芹和市售农药中多菌灵的含量,结果与标准方法一致。 文中还对反应机理和散射增强的原因进行了讨论。     

Study on the interaction between torasemide and 12-tungstophosphoric acid by resonance Rayleigh scattering and resonance nonlinear scattering spectra and its analytical applications

In pH 0.6-1.1 HCl-NaAc buffer solution, torasemide (TOR) reacted with TP to form a 3:1 ion-association complexes. As a result, not only the absorption spectra were changed, but also the intensities of resonance Rayleigh scattering (RRS), second-order scattering (SOS) and frequency doubling scattering (FDS) were enhanced greatly. The maximum RRS, SOS and FDS wavelengths were located at 370, 333, 776 nm, respectively. Under given conditions, the intensities of RRS, SOS and FDS were all directly proportional to the concentration of TOR. The detection limits of RRS, SOS and FDS were 0.7173 ng mL(-1), 7.007 ng mL(-1) and 10.90 ng mL(-1). The optimum conditions and the effects of coexisting substances on the reaction were investigated. The results showed that the method had good selectivity. Therefore, a highly sensitive, simple and quick method has been developed for the determination of TOR. The method can be applied satisfactorily to the determination of TOR in tablets and urine samples.     

藏红T共振瑞利散射光谱法测定保健食品中的透明质酸钠

建立藏红T共振瑞利散射光谱法测定保健食品中透明质酸钠的含量。在p H 5.00的Britton–Robinson缓冲介质中,藏红T与透明质酸钠反应形成化合物,使溶液共振瑞利散射急剧增强并产生相应的散射光谱,其最大散射峰位于335 nm,5.0×10~(–4) mol/L藏红T溶液用量为0.70 m L,反应时间为15 min。透明质酸钠的质量浓度在0.06~3.0mg/L范围内与共振瑞利散射增强程度成良好的线性关系,线性相关系数为0.999 2。方法检出限为19.8μg/L,测定结果的相对标准偏差为3.36%~4.52%(n=6),加标回收率为92.4%~103.0%。该方法灵敏度高、选择性好、操作简便,适用于保健食品中透明质酸钠的测定。     

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.