氯化铁-铁氰化钾体系共振瑞利散射法测定白藜芦醇

在pH 1.8的B-R缓冲溶液中,白藜芦醇(RES)使[Fe(CN)6]3-还原为[Fe(CN)6]4-,后者与铁(Ⅲ)反应生成普鲁士蓝,其共振瑞利散射(RRS)急剧增强。于最大RRS峰314nm处测定其散射强度IRRS,扣除空白溶液的散射强度,RES的质量浓度在0.05~5.0mg·L-1范围内与散射强度差ΔI呈线性关系。RES的检出限(3s/k)为15μg·L-1。应用此方法测定了葡萄叶和虎杖中RES的含量。所得结果与高效液相色谱法测得的结果相符。用标准加入法进行回收试验,测得回收率在96.0%~104%之间。测定值的相对标准偏差(n=5)在1.7%~4.3%之间。对反应体系的RRS增强的机理也进行了探讨。     

苯唑西林与维多利亚蓝B的共振瑞利散射光谱及应用

在pH 9.54时,苯唑西林的水解产物与维多利亚蓝B形成紫红色的离子缔合物,使体系的共振瑞利散射(RRS)急剧增强并产生新的RRS光谱,在最大散射波长366 nm处,苯唑西林的浓度在0~6.0μg/mL范围内与散射强度(△IRRS)成良好的线性关系,据此建立了测定苯唑西林的共振瑞利散射法,检出限为0.039μg/mL。该方法可用于苯唑西林药物及人体尿液中苯唑西林含量的测定。     

钯(II)与阿莫西林和氨苄西林相互作用的共振瑞利散射光谱及其分析应用

在酸性介质中加热, 使阿莫西林(AMO)和氨苄西林(AMP)等侧链含苄氨基的青霉素类抗生素发生降解, 其降解产物青霉胺和苄氨基青霉醛在pH 5左右的弱酸性介质中能进一步与钯(II)反应形成物质的量比为1∶1∶1的混配型三元配合物, 此时将引起共振瑞利散射(RRS)的显著增强, 并出现新的RRS光谱. 钯(II)与两种药物的反应产物具有相似的RRS光谱特征, 最大散射波长均位于370 nm. 在一定范围内散射增强(ΔI)与药物的浓度成正比. 该方法具有较高的灵敏度, 对于AMO和AMP的检出限(3δ)分别为18.0和15.4 ng•mL^－1. 此时侧链不含苄氨基的其他青霉素不产生类似反应, 并且也允许一定量的其它物质存在, 因此, 方法有较好的选择性, 可用于胶囊、片剂及血清、尿样中阿莫西林和氨苄西林的测定, 能获得较满意的结果.     

共振光散射法测定对乙酰氨基酚

在酸性介质中,对乙酰氨基酚将铁氰酸根离子还原成亚铁氰酸根离子,后者与硫酸锌反应生成K2Zn3[Fe(CN)6]2粒子引起体系的共振光散射信号显著增强,且波长345 nm处增强的散射信号强度△IRLS与对乙酰氨基酚的浓度在0.01～1.0 μg/mL范围内呈良好线性关系.其线性回归方程为△IRLS=-15.01+4214...     

共振瑞利散射光谱法对盐酸异丙嗪与盐酸氯丙嗪的同时测定

钼酸铵(AM)与盐酸氯丙嗪(CPZ)及盐酸异丙嗪(PZ)均能反应形成离子缔合物,引起共振瑞利散射(RRS)的显著增强,并出现新RRS光谱.2种反应产物具有相似的RRS光谱特征,其最大散射峰均在365 nm处,且在一定范围内散射增强(Δ_(IRRS))与药物的质量浓度成正比,但RRS强度随药物质量浓度的线性增幅存在显著差异.结合两组分RRS光谱强度的加和性,可建立双组分信号响应的两条同原射线的计量分析法.方法对CPZ 和PZ的检出限分别为4.5、7.7 μg/L,线性范围均为0.03～2.4 mg/L.将该方法用于血清、尿样和非那根止咳糖浆中CPZ和PZ的同时测定,取得满意结果.     

用某些双电荷三氨基三苯甲烷染料共振瑞利散射法测定食品中的亚铁氰化钾

在pH 1左右的酸性介质中，甲基绿（MeG）和碘绿（IG）双电荷三氨基三苯甲烷染料与亚铁氰根阴离子能借助静电引力和疏水作用而形成2：1的离子缔合物，在引起吸收光谱变化的同时，能导致共振瑞利散射（RRS）的显著增强，并出现新的RRS光谱，两体系有相似的RRS光谱特征，最大RRS波长位于276 nm，并在332 nm，457 nm有强度较低的散射峰，K₄[Fe(CN)₆]分别为0.03~5.7μg•mL^-1(MeG体系)和0.04~5.9μg•mL^-1(IG体系)范围内，K₄[Fe(CN)₆]浓度与散射强度(ΔI_RRS)成正比。方法具有高灵敏度，对K₄[Fe(CN)₆]的检出限(3σ)分别为9.3 ng•mL^-1和11.2ng•mL^-1。本文实验了适宜的反应条件和影响因素，考察了共存物质的影响，表明方法有较好的选择性，可用于盐渍食品和食盐中痕量亚铁氰化钾的测定。     

钯(II)与阿莫西林和氨苄西林相互作用的共振瑞利散射光谱及其分析应用

在酸性介质中加热, 使阿莫西林(AMO)和氨苄西林(AMP)等侧链含苄氨基的青霉素类抗生素发生降解, 其降解产物青霉胺和苄氨基青霉醛在pH 5左右的弱酸性介质中能进一步与钯(II)反应形成物质的量比为1∶1∶1的混配型三元配合物, 此时将引起共振瑞利散射(RRS)的显著增强, 并出现新的RRS光谱. 钯(II)与两种药物的反应产物具有相似的RRS光谱特征, 最大散射波长均位于370 nm. 在一定范围内散射增强(ΔI)与药物的浓度成正比. 该方法具有较高的灵敏度, 对于AMO和AMP的检出限(3δ)分别为18.0和15.4 ng•mL^－1. 此时侧链不含苄氨基的其他青霉素不产生类似反应, 并且也允许一定量的其它物质存在, 因此, 方法有较好的选择性, 可用于胶囊、片剂及血清、尿样中阿莫西林和氨苄西林的测定, 能获得较满意的结果.     

利福霉素类抗生素-Cu(II)-核酸体系的RRS光谱研究

在Britton-Robinson (B-R)缓冲溶液中, 利福霉素类药物与ctDNA反应的适宜的pH范围是1.9～2.1. 此类药物本身有微弱RRS峰, 它们具有相似的光谱特征, 其散射峰均在290和370 nm附近; 而ctDNA的RRS峰在310 nm处. 两者反应形成结合产物后其RRS明显增强, 并在375 nm左右出现最大散射峰, 且有不同程度的红移和散射增强, 说明两者结合成新的产物; 加入Cu2＋离子后, Cu2＋与利福霉素抗生素及DNA形成三元复合物, 此时将导致RRS进一步剧增, 而且RRS光谱增强值与DNA浓度呈正比, 因而可用于DNA测定具有较高的灵敏度, 实验对ctDNA的检出限为9.7 ng/mL (RFSV-Cu2＋- ctDNA体系). 文中研究了三元配合物反应的适宜条件和影响因素, 基于此反应发展了一种用RRS技术测定DNA的新方法.     

健那绿作光谱探针共振瑞利散射法测定藻酸钠

本文提出了共振瑞利散射法测定藻酸钠的新方法。研究发现在pH=4.0的Britton-Robinson缓冲溶液中,藻酸钠或健那绿单独存在时共振瑞利散射(RRS)强度非常弱,当两者反应形成复合物时,RRS大大增强并产生新的RRS光谱,其最大RRS峰位于560nm,另在328nm和397nm处产生两个强度较低的散射峰。在560nm处,藻酸钠的浓度在0.015～1.0μg/mL范围内与RRS强度有良好的线性关系,检出限(3σ/k)为5ng/mL。方法灵敏度高,选择性好,可用于面条和海带提取液中的藻酸钠测定。     

利福霉素类抗生素-Cu（Ⅱ）-核酸体系的RRS光谱研究

在Britton-Robinson(B-R)缓冲溶液中,利福霉素类药物与ctDNA反应的适宜的pH范围是1.9～2.1.此类药物本身有微弱RRS峰,它们具有相似的光谱特征,其散射峰均在290和370 nm附近;而ctDNA的RRS峰在310 nm处.两者反应形成结合产物后其RRS明显增强,并在375nm左右出现最大散射峰,且有不同程度的红移和散射增强,说明两者结合成新的产物;加入Cu2 离子后,Cu2 与利福霉素抗生素及DNA形成三元复合物,此时将导致RRS进一步剧增,而且RRS光谱增强值与DNA浓度呈正比,因而可用于DNA测定具有较高的灵敏度,实验对ctDNA的检出限为9.7ng/mL(RFSV-Cu2 -ctDNA体系).文中研究了三元配合物反应的适宜条件和影响因素,基于此反应发展了一种用RRS技术测定DNA的新方法.     

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, second-order scattering and frequency doubling scattering methods for the indirect determination of penicillin antibiotics based on the formation of Fe3[Fe(CN)6]2 nanoparticles

Under the HCl solution and heating condition, penicillin antibiotics such as amoxicillin (AMO), ampicillin (AMP), sodium cloxacillin (CLO), sodium carbenicillin (CAR) and sodium benzylpenicillin (BEN) could react with Fe(III) to produce Fe(II) which further reacted with Fe(CN)₆³⁻ to form a Fe₃[Fe(CN)₆]₂ complex. By virtue of hydrophobic force and Van der Waals force, the complex aggregated to form Fe₃[Fe(CN)₆]₂ nanoparticles with an average diameter of 45 nm. This resulted in a significant enhancement of resonance Rayleigh scattering (RRS) and non-linear scattering such as second-order scattering (SOS) and frequency doubling scattering (FDS). The increments of scattering intensity (ΔI) were directly proportional to the concentrations of the antibiotics in a certain range. The detection limits for the five penicillin antibiotics were 2.9–6.1 ng ml⁻¹ for RRS method, 4.0–6.8 ng ml⁻¹ for SOS method and 7.4–16.2 ng ml⁻¹ for FDS method, respectively. Among them, the RRS method exhibited the highest sensitivity and the AMO system was more sensitive than other antibiotics systems. Based on the above researches, a new highly sensitive and simple method for the indirect determination of penicillin antibiotics has been developed. It can be applied to the determination of penicillin antibiotics in capsule, tablet, human serum and urine samples. In this work, the spectral characteristics of absorption, RRS, SOS and FDS spectra, the optimum conditions of the reaction and the influencing factors were investigated. In addition, the reaction mechanism was discussed.     

Special characteristics of fluorescence and resonance Rayleigh scattering for cadmium telluride nanocrystal aqueous solution and its interactions with aminoglycoside antibiotics

CdTe nanocrystals (CdTe NCs) were achieved by reaction of CdCl₂ with KHTe solution and were capped with sodium mercaptoacetate. The product was detected by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS), fluorescence spectra, ultraviolet-visible spectra and X-ray diffraction (XRD). The CdTe NCs are of cubic structure and the average size is about 5 nm. The fluorescence quantum yield of CdTe NCs aqueous solution increased from 37% to 97% after 20 d under room light. The maximum λ _em of fluorescence changed from 543 nm to 510 nm and the blue shift was 33 nm. CdTe NCs aqueous solution can be steady for at least 10 months at 4 in° a refrigerator. The resonance Rayleigh scattering (RRS) of CdTe NCs in the aqueous solution was investigated. The maximum scattering peak was located at about 554 nm. The interactions of CdTe NCs with amikacin sulfate (AS) and micronomicin sulfate (MS) were investigated respectively. The effects of AS and MS on fluorescence and RRS of CdTe NCs were analyzed. It was found that AS and MS quenched the photoluminescence of CdTe NCs and enhanced RRS of CdTe NCs. Under optimum conditions, there are linear relationships between quenching intensity (F ₀-F), intensity of RRS (I-I ₀) and concentration of AS and MS. The detection limits (3б) of AS and MS are respectively 3.4 ng·mL⁻¹ and 2.6 ng·mL⁻¹ by the fluorescence quenching method, and 15.2 ng·mL⁻¹ and 14.0 ng·mL⁻¹ by the RRS method. The methods have high sensitivity, thus CdTe NCs may be used as fluorescence probes and RRS probes for the detection of aminoglycoside antibiotics. Supported by the National Natural Science Foundation of China (Grant No. 20475045)     

胆酸盐在酸性介质中自聚集作用的共振瑞利散射光谱及其分析应用研究

研究了牛磺胆酸钠、甘牛胆酸钠、胆酸钠和脱氧胆酸钠等四种胆酸盐在酸性介质中的聚集作用对共振瑞利散射光谱的影响及其分析应用. 结果表明: 在一定浓度的HCl, H₂SO₄或HNO₃溶液中, 四种胆酸盐均能自聚集形成粒径增大的聚集体. 该聚集体能导致溶液RRS显著增强, 并产生了新的RRS光谱. 不同胆酸盐在同种介质中的反应产物具有相似的光谱特征, 最大RRS波长分别位于349 (HNO₃介质), 359 (H₂SO₄介质)和369 nm (HCl介质). 在一定范围内, 胆酸盐的浓度与散射强度(ΔI_RRS)成正比. 对于不同的体系其检出限在12.0～21.8 ng/mL之间. 方法灵敏度高, 选择性较好, 而且十分简便快速. 可用于市售蛇胆川贝液和血清样品中胆酸盐的测定.     

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.     

A Highly Sensitive Resonance Rayleigh Scattering Method for the Determination of Vitamin B1 with Gold Nanoparticles Probe

In weakly acidic buffer medium, vitamin B₁ (VB₁) interacts with gold nanoparticles to form a binding product, which resulted in a significant enhancement of resonance Rayleigh scattering (RRS) intensity and the appearance of a new RRS spectrum. The maximum RRS peak was at 368 nm, and there are three smaller scattering peaks that were at 284 nm, 440 nm and 495 nm, respectively. The enhanced RRS intensity (ΔI) was directly proportional to the concentration of VB₁ in the range of 0–2.8 × 10⁻⁷ mol L⁻¹. The method had high sensitivity and its detection limit (3σ) was 0.9 ng mL⁻¹. The optimum conditions and the influencing factors have been investigated. The method had good selectivity, which could be observed from the influence of coexisting substances. A sensitive, simple and fast RRS method for the determination of VB₁ with gold nanoparticle probe has been developed. In addition, the reasons for RRS enhancement were discussed.     

Resonance Rayleigh scattering and resonance non-linear scattering method for the determination of aminoglycoside antibiotics with water solubility CdS quantum dots as probe

In pH 6.6 Britton–Robinson buffer medium, the CdS quantum dots capped by thioglycolic acid could react with aminoglycoside (AGs) antibiotics such as neomycin sulfate (NEO) and streptomycin sulfate (STP) to form the large aggregates by virtue of electrostatic attraction and the hydrophobic force, which resulted in a great enhancement of resonance Rayleigh scattering (RRS) and resonance non-linear scattering such as second-order scattering (SOS) and frequency doubling scattering (FDS). The maximum scattering peak was located at 310 nm for RRS, 568 nm for SOS and 390 nm for FDS, respectively. The enhancements of scattering intensity (ΔI) were directly proportional to the concentration of AGs in a certain ranges. A new method for the determination of trace NEO and STP using CdS quantum dots probe was developed. The detection limits (3σ) were 1.7 ng mL⁻¹ (NEO) and 4.4 ng mL⁻¹ (STP) by RRS method, were 5.2 ng mL⁻¹ (NEO) and 20.9 ng mL⁻¹ (STP) by SOS method and were 4.4 ng mL⁻¹ (NEO) and 25.7 ng mL⁻¹ (STP) by FDS method, respectively. The sensitivity of RRS method was the highest. The optimum conditions and influence factors were investigated. In addition, the reaction mechanism was discussed.     

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.     

Resonance Rayleigh scattering, frequency doubling scattering and second-order scattering spectra of the heparin-crystal violet system and their analytical application

In pH 6.0-11.2 Britton-Robinson buffer solution, binding of heparin with crystal violet (CV) can result in a significant enhancement of resonance Rayleigh scattering (RRS) and resonance non-linear scattering, such as frequency doubling scattering (FDS) and second-order scattering (SOS). Their maximum scattering wavelengths, λ_ex/λ_em, appear at 492 nm/492 nm for RRS, 984 nm/492 nm for FDS and 492 nm/984 nm for SOS, respectively. The optimum conditions of the reaction, the influencing factors and the relationship between the three scattering intensities and the concentration of heparin have been investigated. New methods for the determination of trace amounts of heparin based on the RRS, FDS and SOS methods have been developed. The methods exhibit high sensitivities, the detection limit for heparin is 2.9 ng ml⁻¹ for the RRS method, 3.5 ng ml⁻¹ for the FDS method and 3.3 ng ml⁻¹ for the SOS method. The methods have good selectivity and were applied to the determination of heparin in heparin sodium injection samples with satisfactory results.