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.     

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。     

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。     

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%。     

Effects of the Interaction of Rifamycin SV with Serum Albumins on the Resonance Rayleigh Scattering Spectra and Their Analytical Application

In pH 4.5–4.8 Britton‐Robinson buffer solution, rifamycin SV (i.e. rifamycin sodium) can react with serum albumin such as human serum albumin (HSA) and bovine serum albumin (BSA) to form macromolecular complexes by electrostatic attraction and hydrophobic force. As a result, the resonance Rayleigh scattering (RRS) of the drug was enhanced remarkably and the RRS peaks were at 374 and 552 nm. The enhancement of RRS (ΔI) is directly proportional to the concentration of HSA or BSA. The linear ranges and the detection limits are 0.03–6.0 µg/mL and 9.0 ng/mL for HSA, and 0.01–8.0 µg/mL and 2.0 ng/mL for BSA, respectively. In this work, a sensitive, selective, simple and fast method for the determination of trace amounts of serum albumin by RRS technique has been developed, which was applied to the determination of serum albumin in the synthesized samples and human urine samples with satisfactory results.     

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.     

甲基紫硫酸软骨素共振瑞利散射光谱及其应用

在Britton-Robinson缓冲介质(pH9.37)中硫酸软骨素与甲基紫反应形成离子缔合物时,共振瑞利散射(RRS)强度会明显增强,其最大RRS峰位于505和661 nm处。本文对反应的最佳条件、影响因素、硫酸软骨素浓度与RRS强度的关系进行了研究,建立起一种快速、简便、灵敏的测定硫酸软骨素的方法。本法在661和505 nm测定波长处的线性范围均为:0.15~0.90 mg/L,其检出限分别为0.019 mg/L(505 nm)和0.043mg/L(661 nm)。该法应用于针剂中硫酸软骨素的测定,结果满意。     

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.     

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.     

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%。     

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。     

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。     

The interaction between furosemide-palladium (II) chelate and basic triphenylmethane dyes by resonance Rayleigh scattering spectra and resonance non-linear scattering spectra and their analytical applications

In pH 4.5–7.0 Britton-Robinson buffer solution, furosemide (FUR) reacted with Pd (II) to form a 1:1 anionic chelate. This chelate could further react with such basic triphenylmethane dyes (BTPMD) as ethyl violet (EV), crystal violet (CV), methyl violet (MV), methyl green (MeG) and brilliant green (BG) to form 1:1 ion-association complexes. This not only resulted in the change of absorption spectra, but also led to the significant enhancement of resonance Rayleigh scattering (RRS), second-order scattering (SOS) and frequency doubling scattering (FDS). The maximum RRS wavelengths were located at 324 nm for the EV, CV and MV system, and 340 nm for the BG and MeG system. The maximum SOS wavelengths were located at 550 nm for the EV, CV, BG and MeG system, and 530 nm for the MV system. The maximum scattering peaks of all the systems were at 392 nm for FDS. The enhanced RRS, SOS and FDS intensities were directly proportional to the concentration of FUR. The detection limits for the different dye systems were 0.3–4.9 ng mL^?1 for the RRS method, 3.2–33.1 ng mL^?1 for the SOS method and 9.0–85.7 ng mL^?1 for the FDS method. These methods could be used for the determination of trace amounts of FUR. The effects of the formation of ternary ion-association complexes on the spectral characteristics and intensities of absorption, RRS, SOS and FDS have been investigated. The optimum conditions of these reactions, the influencing factors and the analytical properties have been tested. The influences of coexisting substances were tested by RRS method and the results showed that this method exhibited a high sensitivity. Based on the aforementioned research, the highly sensitive, simple and rapid methods for the determination of trace amounts of FUR by resonance light scattering technique have been established, which could be applied to the determination of FUR in tablet, injection, human serum and urine samples. The composition and structure of the ternary ion-association complex and the reaction mechanism were discussed.     

A sensitive and rapid method for the determination of protein by the resonance Rayleigh light-scattering technique with Pyrogallol Red

The resonance Rayleigh light-scattering (RRLS) technique was used to develop a simple, sensitive and selective method for the determination of proteins. The method is based on the interaction between proteins and Pyrogallol Red (PR) in the pH range 3.6-4.2, which causes a substantial enhancement of the resonance scattering signal of PR in the wavelength range 300-450 nm with the maximum scattering peak located at 347 nm. With this method, 0.25-13 microg ml(-1) of bovine serum albumin (BSA), 0.25-10 microg ml(-1) of human serum albumin (HSA) and 0.25-13 microg ml(-1) of human immunoglobulin G (IgG) can be determined, and the detection limits, calculated as three times the standard deviation of nine blank measurements, for BSA, HAS and IgG were 51, 48 and 57 microg l(-1), respectively. Moreover, the method shows almost no protein-to-protein variability and is free from interference from many amino acids and metal ions. The method, with high sensitivity, selectivity and reproducibility, was satisfactorily applied to the determination of the total protein in human serum and saliva samples. Mechanism studies indicated that PR can bind to BSA depending mainly on electrostatic forces, and this interaction can encourage the J-aggregation of PR, which results in enhanced Rayleigh light-scattering in the PR-protein system.     

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.     

Resonance Rayleigh Scattering Method for the Determination of Raloxifene with Evans Blue

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Resonance Rayleigh scattering technology as a new method for the determination of the inclusion constant of beta-cyclodextrin

The interaction of procaine hydrochloride and beta-cyclodextrin in aqueous solution was studied using resonance Rayleigh scattering technology. The molar ratio of the inclusion complex was 1:1 established by spectrophotometry. The resonance Rayleigh scattering technology was first applied in the determination of the beta-cyclodextrin inclusion constant. The inclusion constant of procaine hydrochloride beta-cyclodextrin complex Kf is 1.23 x 10(2) and 1.27 x 10(2) l mol(-1) for method I and 1.15 x 10(2) and 1.21 x 10(2) l mol(-1) for method II. These determination results were in correspondence with the results of the spectrophotometric and fluorescence methods. Therefore, the resonance Rayleigh scattering method can be used as a new technology for the determination of the inclusion constant.     

Analytical Application of Resonance Rayleigh Scattering,Frequency Doubling Scattering,and Second-Order Scattering Spectra for the Sodium Alginate-CTAB System

Three new methods for the determination of trace amounts of sodium alginate (SA) based on the reaction of SA with cetyltrimethylammonium bromide (CTAB) by resonance Rayleigh scattering (RRS), frequency doubling scattering (FDS), and second-order scattering (SOS) have been investigated. The SA can react with CTAB in a pH 10.0 Britton–Robinson buffer to form a new product, which can lead to a significant enhancement of RRS, FDS, and SOS intensities and appearance of new spectra. The maximum scattering wavelengths, λex/λem, appear at 351 nm/351 nm for RRS, 240 nm/480 nm for SOS, and 870 nm/435 nm for FDS, respectively. The increments of the scattering intensities (ΔI) are proportional to the concentration of SA in a certain range. The detection limits (3σ) for SA are 3.69 ng mL^?1 for the RRS method, 6.91 ng mL^?1 for the FDS method, and 7.45 ng mL^?1 for the SOS method under optimum conditions. The proposed methods were applied to the determination of SA in real samples with satisfactory results.     

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。     

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。