Resonance Rayleigh scattering measurement of aminoglycoside antibiotics with Evans Blue.

In a weak acid medium, some aminoglycoside antibiotics, such as kanamycin (KANA), gentamicin (GEN), tobramycin (TOB) and neomycin (NEO), or acid bisazo dye Evans Blue (EB) can only produce very weak resonance Rayleigh scattering (RRS) signals. However, when two agents react with each other to form ion-association complexes, the RRS intensity can be greatly enhanced and a new RRS spectrum with a significant enhancement of the RRS intensity in the wavelength range from 350 nm to 600 nm can be observed. The maximum scattering peak is at 570 nm. There is a linear relationship between the RRS intensity and the antibiotic concentration in the range of 0.01-6.0 microg mL(-1) at 570 nm. This RRS method for the determination of aminoglycoside antibiotics at trace-amount levels has been developed. The detection limits (3sigma) of the four antibiotics, whose order of sensitivity from high to low ranks as KANA > NEO > TOB > GEN, are 5.2-6.9 ng mL(-1). This method has good selectivity and has been successfully applied to the quick determination of antibiotics not only for injections and ear drops, but for clinic serum samples as well. In addition, the reaction mechanism by using a quantum chemistry method and the influencing factors of the RRS spectra and the enhancement reasons of RRS have been 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。     

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.     

胰蛋白酶与DNA相互作用的共振瑞利散射光谱及其分析应用研究

当胰蛋白酶与鲱鱼精DNA(hsDNA)、 鲑鱼精DNA(sDNA)以及小牛胸腺DNA(ctDNA)之间发生相互作用时,共振瑞利散射(RRS)会显著增强,并产生新的RRS光谱. 三者有近似的光谱特征,其最大RRS峰分别位于307 nm(hsDNA和sDNA体系)和290 nm处(ctDNA体系),另一散射峰位于350 nm处,其散射强度(ΔI)与DNA或者胰蛋白酶的浓度成正比,因此可用于蛋白质和DNA的相互测定. 当用胰蛋白酶测定DNA时,hsDNA,sDNA和ctDNA的检测范围分别为1.4×10^-3～2.3, 2.1×10^-3～2.5和3.5×10^-3～1.9 μg/mL(ctDNA),它们的检出限分别为0.4,0.7和1.1 ng/mL. 当用hsDNA测定胰蛋白酶时,其线性范围为0.1～30.0 μg/mL,检出限为39.0 ng/mL. 研究了最佳的反应条件、 影响因素和结合产物的化学性质,考察了胰蛋白酶与DNA的结合比,推测了它们的结合方式,并以胰蛋白酶作RRS探针,发展了一种高灵敏、 简便和快速测定痕量DNA的新方法.     

金纳米微粒作探针共振瑞利散射光谱法测定盐酸异丙嗪

在pH 1.8～3.0的酸性介质中,质子化的盐酸异丙嗪(PMZ)可与带负电荷的金纳米微粒依靠静电和疏水作用相互结合,导致共振瑞利散射(RRS)强度显著增强,其最大散射峰位于368 nm,并在284,440,498 nm处有明显的散射峰,在选定的测量波长下,盐酸异丙嗪在0.04～0.10μg/mL的浓度范围内与RRS强度成正比,该法具有高的灵敏度,其检出限为1.34 ng/mL。考察了体系的RRS光谱特征,研究了适宜的反应条件、影响因素,研究了共存物质的影响,据此建立了金纳米微粒作探针RRS法测定盐酸异丙嗪的新方法。     

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.     

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。     

Determination of Matrine and Oxymatrine in Radix Sophorae Flavescentis by Resonance Rayleigh Scattering,Second-order Scattering and Frequency Doubling Scattering Technique

In 0.1 mol/L HCl medium, 12-tungstophosphoric(TP) acid reacted with matrine(Mat) and oxymatrine(Oxy) to form an ion-association complex. As a result, the new spectra of resonance Rayleigh scattering(RRS), second-order scattering(SOS) and frequency doubling scattering(FDS) appeared and their intensities were enhanced greatly. The maximum scattering wavelengths of RRS, SOS and FDS were located at 370, 670 and 390 nm, respectively. The increments of scattering intensity were directly proportional to the concentration of Mat and Oxy in a certain range. Based on this, the method for the determination of matrine and oxymatrine has been established. It has been applied to the determination of matrine and oxymatrine in samples of Radix sophorae flavescentis with satisfactory result. The reaction mechanism and reasons of RRS enhancement were discussed.     

用钼酸盐高灵敏共振瑞利散射法测定米托蒽醌

在盐酸和硝酸介质中用共振瑞利散射法测定了血清和尿液中的米托蒽醌, 结果表明, 该方法的灵敏度高, 对米托蒽醌的检出限为6 ng/mL(硝酸介质)和8 ng/mL(盐酸介质), 可用于血清和尿样中米托蒽醌的测定.     

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.     

Resonance Rayleigh-scattering method for the determination of vitamin B1 with methyl orange.

In a pH 2.3-3.0 acid medium, the resonance Rayleigh scattering (RRS) intensity is greatly enhanced when vitamin B, reacts with Methyl Orange to form an ion-association complex. The maximum RRS peak appears at 588 nm, another higher peak is at 403 nm and there are two smaller RRS peaks at 800 nm and 288 nm. The RRS intensity is directly proportional to the concentration of vitamin B, in the range of 0-400 ng ml(-1). The method has high sensitivity and the detection limit (3sigma) for vitamin B1 is 7.2 ng ml(-1). The effects of coexisting substances on the determination of vitamin B, were investigated, and the results show that this method has good selectivity and can be applied to the direct determination of vitamin B1 in composite vitamin B tablets and multivitamin tablet samples.     

Resonance Rayleigh scattering spectra for studying the interaction of anthracycline antineoplastic antibiotics with some anionic surfactants and their analytical applications

In pH 5.8 acidic medium, the anionic surfactants such as sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS) or sodium dodecyl sulfonate (SLS) can react with anthracycline antibiotics such as epirubicin (EPI), daunorubicin (DNR) or mitoxantrone (MXT) to form ion-association complexes, which lead to a great enhancement of resonance Rayleigh scattering (RRS) intensity and appearances of new RRS spectra. The maximum RRS peaks are situated at 313 nm for SDS-DNR and SDS-EPI system, 296 nm for SDS-MXT system. The linear ranges and detection limits for EPI, DNR and MXT are 0.26-20.0, 0.25-20.0, 0.14-10.0 and 0.074, 0.078, 0.042 μg mL⁻¹, respectively. In this paper, the characteristics of the absorption, fluorescence and RRS spectra of the reaction products are studied as well as the optimum reaction conditions and analytical chemistry properties. A sensitive, simple and rapid RRS method for the determination of anthracycline anticancer antibiotics has been developed.     

Resonance Rayleigh-scattering method for the determination of sildenafil citrate in a pharmaceutical formulation using Evans blue.

A highly sensitive resonance Rayleigh-scattering (RRS) method for the determination of sildenafil citrate has been developed, based on the fact that sildenafil (Sild) reacted with Evans Blue (EB) to form an ion-association complex in pH 1.1 - 4.6 aqueous solution. This resulted in a significant enhancement of the RRS intensity, and a new spectrum appeared. The wavelength of the maximum RRS was at 365 nm, and other scattering peaks were at 400, 442, 470 and 534 nm, respectively. The intensity of RRS was directly proportional to the concentration of Sild in the range 0 - 11.5 microg ml(-1), and the detection limit for Sild (3 sigma) was 30.3 ng ml(-1). The composition of the ion-association complex was Sild:EB = 1:1, as established by Job's method. The method had good selectivity and could be applied to the determination of Sild in the aqueous phase without using organic solvent extraction. The method was simple and rapid. In addition, the reaction mechanism and the reason for RRS enhancement were considered.     

Resonance Rayleigh scattering spectra, non-linear scattering spectra of malachite green-12-tungstophosphoric acid system and its analytical application in fish

In 0.1 molL(-1) (pH 1.0) HCl medium, 12-tungstophosphoric acid (TP) reacted with malachite green (MG) to form an ion-association complex. As a result, the new spectra of RRS, SOS and FDS appeared and their intensities were enhanced greatly. The maximum wavelengths of RRS, SOS and FDS were located at 334 nm, 586 nm and 330 nm, and the scattering intensities were proportional to the concentration of MG. Based on it a new method for the determination of MG has been established. The detection limits (3σ) of these methods were in the range of 3.7-27 ng mL(-1). The RRS, SOS, and FDS characteristics, absorption spectrum characteristics and optimum reaction conditions of the system were discussed. Effects of coexistent substances were tested, and the results demonstrated that this method had good selectivity. It has been applied to the determination of malachite green residues in fish flesh with satisfactory results. The reaction mechanism and reasons of RRS enhancement are 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.     

钴(II)-2-(5-溴-2-吡啶偶氮)-5-二乙氨基酚体系共振瑞利散射法测定环境 水样中十二烷基苯磺酸钠

在pH 1.8～3.0的Britton-Robinson (BR)缓冲溶液中, 钴(II)与2-(5-溴-2-吡啶偶氮)-5-二乙氨基酚(5-Br-PADAP)(HL)反应形成紫红色螯合阳离子, 此时仅能引起吸收光谱的变化, 不能导致共振瑞利散射(RRS)的增强. 当钴(II)-5-Br-PADAP螯合阳离子与阴离子表面活性剂十二烷基苯磺酸钠(SDBS)、十二烷基磺酸钠(SLS)和十二烷基硫酸钠(SDS)作用时, 仅能与SDBS进一步反应形成三元离子缔合物并引起RRS的显著增强, 而不与SDS和SLS产生类似反应. 离子缔合物的RRS峰分别位于306, 370和650 nm处, 在一定范围内RRS增强(ΔI)与SDBS浓度成正比, 当用650 nm处测量时, 其检出限为0.043 μg•mL－1, 线性范围为0.14～6.0 μg•mL－1. 文中研究了反应产物的RRS光谱特征, 适宜的反应条件及分析化学性质, 据此发展了一种在一定量SDS和SLS等阴离子表面活性剂存在下选择性测定SDBS的新方法, 方法灵敏、简便、快速,用于天然水和污水中SDBS的测定, 获得满意结果. 文中还对反应机理进行了讨论.     

共振瑞利散射法测定微量硒

在稀HCl中硒(Ⅳ)与抗坏血酸(Vc)反应生成单质硒Se(0),并在液相中以纳米粒子的形式存在。利用此纳米粒子在470nm处的共振瑞利散射峰可对硒进行测定。在0.028~5.640μg/mL范围内,共振瑞利散射强度与硒(Ⅳ)的质量浓度成线性关系,检出限为0.00789μg/mL,相对标准偏差为4.7%。应用此法测定了茶叶、螺旋藻、黄芪样品中的总硒量,通过与例行方法DAN荧光法对照、干扰实验、回收率实验及质量控制对本方法进行了评价。     

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.     

流动注射-共振瑞利散射法测定某些局部麻醉药物

在稀盐酸介质中, 12-钨磷酸(TP)分别与丁卡因(TC)、普鲁卡因(PC)和利多卡因(LC)等局部麻醉药反应形成离子缔合物, 导致溶液的共振瑞利散射(RRS)显著增强. 它们的最大RRS峰位于345 nm(TP-TC), 368 nm(TP-PC)和379 nm(TP-LC), 并且在一定范围内, 麻醉药的浓度与散射强度呈线性关系, 据此建立流动注射-共振瑞利散射联用技术测定丁卡因、普鲁卡因和利多卡因的新方法, 不同麻醉药的检出限在0.5~9.5 ng/mL之间. 以灵敏度最高的丁卡因为例, 试验了共存物质的影响及分析应用, 表明方法具有良好的选择性和较高的重复性; 用于尿样中TC的测定, 加标回收率为98.8%~103.2%; 对于质量浓度为2.0 μg/mL的TC进行9次平行测定的相对标准偏差为1.7%; 进样频率为60 h-1. 采用量子化学AM1法计算了3种药物的电荷分布, 并从药物结构差异上讨论了反应机理.     

Ag(Ⅰ)-呋塞米相互作用的共振瑞利散射、二级散射和倍频散射光谱及其分析应用

在pH=3.5的HAc-NaAc介质中,呋塞米(FUR)与Ag(Ⅰ)形成1:1(摩尔比)的螯合物,从而引起共振瑞利散射(RRS)、二级散射(SOS)和倍频散射(FDS)光谱显著增强,其最大RRS,SOS和FDS波长分别位于310,584和330 nm.在一定范围内,3种散射信号的增强(△ⅠRRs,△ⅠSOS和△ⅠFDS...