现代分析技术在痕量物质分析中的应用
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摘要
“痕量组分”一般是指其样本含量小于万分之一的物质,如药物中的某些活性较强的成分、环境中药物或毒素污染物或者药物金属离子污染等,这些物质的浓度极低,但都有很强的生理活性,或者在体内后有很强的蓄积能力,进而产生对肌体的产生毒害作用,其一直是药物分析及分析化学家的研究的焦点。这些物质含量较低,采用常规的分析方法(如高效液相色谱法、紫外光谱法)检测困难。提高分析方法的灵敏度或开发高灵敏度的新的分析方法是解决这一问题的主要途径,然而,对于极其痕量的物质,尤其是某些pg级以下的物质,即使使用了高灵敏度的现代分析方法(如MS等),其检测分析仍然困难,因此,采用适当的样品前处理方法,提纯富集这些痕量样品,使其达到可分析的灵敏度水平,是现代分析技术解决这一问题的另一途径,也是现代分析技术的研究热点;这些新的样品前处理技术同时也为解决某些难监测物质(如样品MS检测离子化效率低)的分析检测提供了新的分析手段。
本课题研究了磷钼杂多酸-罗丹明B络合物共振瑞利散射(RRS)体系,建立了更加灵敏的唑来膦酸分析方法,解决了唑来膦酸输注液中唑来膦酸检测困难的问题,考察了体系中硫酸浓度、过硫酸钾溶液浓度、钼酸铵溶液浓度、罗丹明B(RDB)溶液浓度、煮沸时间、反应温度及反应时间对RRS的影响,优化了分析条件,提高了检测灵敏度,其唑来膦酸的检测限达了1.55 ng/ml,成功应用于唑来膦酸输注液中唑来膦酸的测定。课题研究了石墨炉原子吸收光谱法分析药物注射剂中铝离子污染的检测中的背景和分析条件,通过塞曼背景校正和基底改进技术成功解决了样品背景的干扰问题,通过优化干燥、灰化、原子化温度和时间,提高了方法灵敏度,检出限达0.14 ng/ml,所建分析方法可不经样品消化处理直接进行分析,满足了唑来膦酸注射液铝离子污染的检测要求。课题采用新型的中空纤维液相微萃取技术,建立了环境水中痕量雌二醇的富集和纯化方法,解决了传统的液液萃取和固相萃取方式富集率低、有机溶剂使用量大、分析成本高以及交叉污染等难题,研究了萃取效率的影响因素,在优化的萃取条件下,环境水中痕量雌二醇的富集倍数可达300倍,采用HPLC-UV检测,其分析灵敏度可达0.1 ng/ml,该方法成功应用于环境水样中雌二醇的检测。
一共振瑞利散射法测定唑来膦酸
目的:利用共振瑞利散射技术(RRS),建立灵敏、快速、简便的唑来膦酸输注液中唑来膦酸的测定方法。
方法:精密量取供试品1ml,加1%过硫酸钾煮沸破坏10min,在0.125 mol/L酸性条件下,依次与0.25 mg/ml钼酸铵和7×10-6 mol/L罗丹明B(RDB)反应,静置45 min。在λex=λem=370 nm,狭缝宽度5 nm的条件下,测定RRS强度,用同样的方法测定空白值强度,以共振散射信号的增加值(ΔI)计算样品浓度。
结果:在优化的条件下,共振散射信号的增加值(ΔI)与唑来膦酸的浓度成正比。唑来膦酸在6.25~100 ng/ml的浓度范围内线性关系良好,最低检出限1.55 ng/ml,RSD小于2.1%,回收率为100~101%。磷酸盐、亚磷酸盐和其他常见共存物质(金属离子、非金属离子和无机酸根)等均不干扰测定。
结论:所建立的共振瑞利散射光谱法分析测定唑来膦酸,方法简便快速,其灵敏度高达1.55 ng/ml,较传统钼蓝法提高了近500倍。该方法为唑来膦酸输注液提供新的分析手段,可用于唑来膦酸输注液的质量控制。
二GF-AAS研究唑来膦酸注射剂中铝离子的污染
目的:采用石墨炉原子吸收光谱法(GF-AAS),建立唑来膦酸注射剂中痕量铝离子的分析方法,用于考察唑来膦酸注射液中铝离子污染的来源和水平。
方法:取样品溶液100μl,加入50μl 5 mg/ml基底改性剂硝酸镁,1%硝酸定稀释至2.5 ml,直接进样,注入石墨炉中。AAS分析采用热解涂层石墨管,铝空心阴极灯检测波长309.3 nm,灯电流10 mA,狭缝宽度0.4 nm,干燥温度80℃和220℃,灰化温度700℃和1200℃,原子化温度2600℃,采用塞曼偏振背景校正的原子吸收光谱法,标准曲线法测定唑来膦酸注射剂中铝的含量。
结果:所建立的方法能有效降低唑来膦酸注射液基底效应。铝离子在4.00~20.0 ng/ml的浓度范围内线性关系良好,相关系数r为0.9995。检出限为0.14 ng/ml,加样回收率为99% ~104%,RSD为2.7% ~3.5%。唑来膦酸注射液中铝离子30天检测结果表明,随着放置时间的延长,铝离子浓度显著提高。
结论:本文建立了塞曼-石墨炉原子吸收法分析唑来膦酸注射液中痕量铝离子,方法灵敏度高,其检出限达0.14 ng/ml,样品未经复杂的消化处理,直接进样,且加入基底改进剂能有效降低样品基底效应。唑来膦酸注射液稳定性试验结果表明,唑来膦酸注射液中铝离子主要来源于安瓿瓶。
三中空纤维液相微萃取-高效液相色谱测定环境水样中雌二醇
目的:以新型的中空纤维液相微萃取技术(HF-LPME)为富集和纯化手段,建立HPLC-UV法分析环境水中痕量雌二醇(E2)的方法。
方法:采用聚偏氟乙烯中空纤维,以正辛醇为萃取溶剂,将正辛醇装入11 cm的中空纤维膜内,将中空纤维两端密封后首尾连接,放入140 ml水样中,于室温、搅拌速度为500 rpm条件下萃取60 min,萃取后,中空纤维用100μl甲醇冲洗中空纤维内壁,合并萃取物在90℃经氮气流吹干后用甲醇溶解,进样20μl,进行HPLC分析,采用KROMASIL C18色谱柱(150 mm×4.6 mm, 5μm),流动相为甲醇-水(75:25),检测波长280 nm,流速1 ml/min,柱温室温。
结果:在优化的实验条件下,样品中雌二醇的富集因子可达300,雌二醇在1~1000 ng/ml的浓度范围内线性关系良好,相关系数r为0.9995,最低检出限为0.1 ng/ml。回收率为97.5% ~120.5%,RSD为4.7% ~7.3%。
结论:本文建立的中空纤维液相微萃取方法较文献报道的液液萃取方法富集率高,达300倍,提高了分析灵敏度;与固相萃取、固相微萃取等相比,方法简单,结果准确可靠,分析成本低,有机溶剂使用量少,且不存在交叉污染,为痕量雌激素的分析提供了可靠的富集手段。
"Trace Elements" generally refers to samples less than 0.01%, such as active ingredients in drugs, drugs or toxins pollutants in environment, metal ion contamination in drugs. The concentration of these substances is low, but the physiological activity is strong. In addition, high accumulation accured gives toxic effect to human body. These problems, people paid more and more attention, have become the focuses of their research. However, it is difficult to analyze trace substances with conventional analytical methods, such as high-performance liquid chromatography, UV spectroscopy. The main method to solve the problem is to improve the sensitivity of analytical methods or develop more sensitive methods. However, it is difficult to detect some of substances which are below pg level, even if sensitive method is performed (such as MS, etc.). Therefore, appropriate sample pre-treatment method to enrich trace substances is introduced to solve this problem. New sample pre-treatment techniques provide new analytical tools to analyze substances which are difficult to monitor (such as substances with low ionization efficiency by MS detection).
In this project, a sensitive method has been developed to solve the difficulty in the detection of zoledronic acid. Phosphorusmolybdenum heteropoly acid-rhodamin B produced high RRS, and greatly improved the sensitivity. The detection limit was 1.55ng/ml. The parameters affecting the reaction such as sulfuric acid concentration, potassium persulfate concentration, ammonium molybdate concentration, Rhodamine B concentration, as well as the boiling time, reaction temperature, reaction time were investigated. The method was successfully applied for the determination of zoledronic acid infusion solution. A GF-AAS was established for the determination of aluminum in zoledronic acid injection, and the resource of aluminum in zoledronic acid injection was discussed. The background interference was eliminated by Zeeman background correction. The sensitivity of the method was improved by optimizing the drying, ashing, atomization temperature and time, as well as choice of base modifier. The detection limit was 0.14ng/ml. The method supports direct analysis without digestion and was successfully applied to explore the sources of aluminum in zoledronic acid injection. Another job established in our project is to show the application of Hollow fiber liquid-phase micro-extraction. Hollow fiber liquid-phase micro-extraction, a new enrichment and purified pre-treatment technique, has been applied for the analysis of trace substances in environmental water. Compared with the reported sample preparation techniques, the proposed method seems to be more preferred for its high enrichment, cost effectiveness, minimization of organic waste, and absence of memory effect. Meanwhile, it earned many merits such as extraction and concentration in one set, outstanding purification, no cross-contamination and suitable for various analytes in different matrix. Under optimizing conditions, the enrichment efficiency was 300 and the detection limit was 0.1ng/ml.
PART 1 Determination of Trace Zoledronic Acid by Resonance Rayleigh Scattering Method
Objective: To establish a sensitive, fast and simple resonance Rayleigh scattering method for the determination of trace zoledronic acid.
Methods: In acid medium, ammonium molybdate of 0.25 mg/ml and inorganic phosphorus which is produced from 1 ml sample solution reacting with KPs of 1% for 10 min, reacts with rhodamin B of 7×10-6 mol/L to form an associated complex of phosphorusmolybdenum heteropoly acid- rhodamin B. The RRS(I) of complex was detected atλex=λem=370 nm with slit width of 5 nm. The same procedure was carried out to measure the blank signal(I0). Sample concentration was calculated by the enhancement of RRS (ΔI= I﹣I0).
Results: Under the optimized conditions, the enhancement of RRS (ΔI) is proportional to the concentration of zoledronic acid in solution. The linear relationship was obtained in the range of 6.25 to 100ng/ml. The limit of detection is 1.55 ng/ml with RSD 2.1% and the recovery was 100~101%. Phosphate, phosphate and other coexistence substance (metal ion and mineral acid radical ion) did not interfere the determination of zoledronic acid.
Conclusion: A simple and rapid RRS method for the determination of zoledronic acid has been developed. Compared with traditional molybdenum blue spectrophotometry method, it is 500 times more sensitive with limit of detection at 1.55 ng/ml. It provides a new method for the determination of zoledronic acid. The method was successfully applied to the quality control of zoledronic acid infusion solution.
PART 2 Pollution of Aluminium in Zoledronic Acid Injection by Graphite Furnace Atomic Absorption Spectrometry
Objective: A graphite furnace atomic absorption spectrometry was established for the study of the source of aluminium and the pollution in zoledronic acid injection.
Methods: Sample solution of 100μl, adding 50μl 5 mg/ml of magnesium nitrate, diluted to 2.5 ml with 1% nitric acid, and then injected directly into the graphite furnace. Pyrolysis coating graphite tube and aluminium hollow cathode lamp with wavelength of 309.3 nm and lamp current of 10 mA were employed. 80℃and 220℃for drying, 700℃and 1200℃for ashing, 2600℃for atomizing were optimized for temperature program. The aluminium ion in zoledronic acid injection was determined directly by graphite furnace atomic absorption spectrometry with polarized Zeeman background correction.
Results: Matrix effect in zoledronic acid injection was cut down in this condition. There was a good linear relationship in the concentration range of 4.00~20.0 ng/ml (r = 0.9995). The detection limit was 0.14 ng/ml, the relative standard deviation were 99% ~104%, and the RSD were 2.7% ~3.5%. The result of zoledronic acid injection of 30 days showed that concentration of aluminium increased with increasing the staying time.
Conclusion: A graphite furnace atomic absorption spectrometry was established for the determination of aluminium in zoledronic acid injection. The method was sensitive with the detection limit of 0.14ng/ml. The sample was injected directly instead of complex digestive process. Basal modifier added can reduce the effects of the sample substrate effectively. The result of zoledronic acid injection stability test showed that aluminum ions came from ampoule.
PART 3 Enrichment and determination of trace estradiol in environmental water samples by hollow fiber liquid phase microextraction prior to high performance liquid chromatography
Objective: A novel and simple cleanup procedure, based on hollow-fiber liquid-phase microextraction (HF-LPME) is described here, and HPLC-UV was used for the determination of trace estradiol in environmental water samples.
Methods: For HF-LPME, the polyvinylidene difluoride hollow fiber membrane was used. N-octyl alcohol was used as n-octyl alcohol. The n-octyl alcohol was injected into the fiber of 11 cm. Then, the two ends of the fiber were enveloped, and then were introduced into a 140ml glass bottle with screw cap. The extraction was performed by agitation at 500 rpm at 25℃for 60 min. After that, 100μl methanol was slowly flushed through the lumen. The whole elution solution was evaporated to dryness at 90℃under nitrogen gas. To the dried sample, 100μl methanol was added before HPLC analysis. The analysis was performed on a KROMASIL C18 column (150 mm×4.6 mm, 5μm), with the mobile phase of methanol-water (75:25) at 25℃and detected at 280nm using UV detector. The flow rate was 1 ml/min.
Results: Under the optimized experimental conditions, the enrichment factor was 300. The proposed method was found to be linear in the concentration 1-1000ng/ml for estradiol and the limit of detection for an S/N = 3 was 0.1ng/ml. The recovery of esdradiol was 97.5% ~120.5% with RSD of 4.7% ~7.3%.
Conclusion: A hollow-fiber liquid-phase microextraction has been established for the analysis of estradiol. It takes a serial of advantages over liquid-liquid extraction such as high sensitivity with high enrichment factor of 300. Compared with the reported sample preparation techniques, such as solid phase extraction and solid phase microextraction , the proposed method seems to be more preferred for its cost effectiveness, minimization of organic waste, absence of memory effect, accuraty and reliability. It provides a new reliable means for the analysis of estradiol.
本课题研究了磷钼杂多酸-罗丹明B络合物共振瑞利散射(RRS)体系,建立了更加灵敏的唑来膦酸分析方法,解决了唑来膦酸输注液中唑来膦酸检测困难的问题,考察了体系中硫酸浓度、过硫酸钾溶液浓度、钼酸铵溶液浓度、罗丹明B(RDB)溶液浓度、煮沸时间、反应温度及反应时间对RRS的影响,优化了分析条件,提高了检测灵敏度,其唑来膦酸的检测限达了1.55 ng/ml,成功应用于唑来膦酸输注液中唑来膦酸的测定。课题研究了石墨炉原子吸收光谱法分析药物注射剂中铝离子污染的检测中的背景和分析条件,通过塞曼背景校正和基底改进技术成功解决了样品背景的干扰问题,通过优化干燥、灰化、原子化温度和时间,提高了方法灵敏度,检出限达0.14 ng/ml,所建分析方法可不经样品消化处理直接进行分析,满足了唑来膦酸注射液铝离子污染的检测要求。课题采用新型的中空纤维液相微萃取技术,建立了环境水中痕量雌二醇的富集和纯化方法,解决了传统的液液萃取和固相萃取方式富集率低、有机溶剂使用量大、分析成本高以及交叉污染等难题,研究了萃取效率的影响因素,在优化的萃取条件下,环境水中痕量雌二醇的富集倍数可达300倍,采用HPLC-UV检测,其分析灵敏度可达0.1 ng/ml,该方法成功应用于环境水样中雌二醇的检测。
一共振瑞利散射法测定唑来膦酸
目的:利用共振瑞利散射技术(RRS),建立灵敏、快速、简便的唑来膦酸输注液中唑来膦酸的测定方法。
方法:精密量取供试品1ml,加1%过硫酸钾煮沸破坏10min,在0.125 mol/L酸性条件下,依次与0.25 mg/ml钼酸铵和7×10-6 mol/L罗丹明B(RDB)反应,静置45 min。在λex=λem=370 nm,狭缝宽度5 nm的条件下,测定RRS强度,用同样的方法测定空白值强度,以共振散射信号的增加值(ΔI)计算样品浓度。
结果:在优化的条件下,共振散射信号的增加值(ΔI)与唑来膦酸的浓度成正比。唑来膦酸在6.25~100 ng/ml的浓度范围内线性关系良好,最低检出限1.55 ng/ml,RSD小于2.1%,回收率为100~101%。磷酸盐、亚磷酸盐和其他常见共存物质(金属离子、非金属离子和无机酸根)等均不干扰测定。
结论:所建立的共振瑞利散射光谱法分析测定唑来膦酸,方法简便快速,其灵敏度高达1.55 ng/ml,较传统钼蓝法提高了近500倍。该方法为唑来膦酸输注液提供新的分析手段,可用于唑来膦酸输注液的质量控制。
二GF-AAS研究唑来膦酸注射剂中铝离子的污染
目的:采用石墨炉原子吸收光谱法(GF-AAS),建立唑来膦酸注射剂中痕量铝离子的分析方法,用于考察唑来膦酸注射液中铝离子污染的来源和水平。
方法:取样品溶液100μl,加入50μl 5 mg/ml基底改性剂硝酸镁,1%硝酸定稀释至2.5 ml,直接进样,注入石墨炉中。AAS分析采用热解涂层石墨管,铝空心阴极灯检测波长309.3 nm,灯电流10 mA,狭缝宽度0.4 nm,干燥温度80℃和220℃,灰化温度700℃和1200℃,原子化温度2600℃,采用塞曼偏振背景校正的原子吸收光谱法,标准曲线法测定唑来膦酸注射剂中铝的含量。
结果:所建立的方法能有效降低唑来膦酸注射液基底效应。铝离子在4.00~20.0 ng/ml的浓度范围内线性关系良好,相关系数r为0.9995。检出限为0.14 ng/ml,加样回收率为99% ~104%,RSD为2.7% ~3.5%。唑来膦酸注射液中铝离子30天检测结果表明,随着放置时间的延长,铝离子浓度显著提高。
结论:本文建立了塞曼-石墨炉原子吸收法分析唑来膦酸注射液中痕量铝离子,方法灵敏度高,其检出限达0.14 ng/ml,样品未经复杂的消化处理,直接进样,且加入基底改进剂能有效降低样品基底效应。唑来膦酸注射液稳定性试验结果表明,唑来膦酸注射液中铝离子主要来源于安瓿瓶。
三中空纤维液相微萃取-高效液相色谱测定环境水样中雌二醇
目的:以新型的中空纤维液相微萃取技术(HF-LPME)为富集和纯化手段,建立HPLC-UV法分析环境水中痕量雌二醇(E2)的方法。
方法:采用聚偏氟乙烯中空纤维,以正辛醇为萃取溶剂,将正辛醇装入11 cm的中空纤维膜内,将中空纤维两端密封后首尾连接,放入140 ml水样中,于室温、搅拌速度为500 rpm条件下萃取60 min,萃取后,中空纤维用100μl甲醇冲洗中空纤维内壁,合并萃取物在90℃经氮气流吹干后用甲醇溶解,进样20μl,进行HPLC分析,采用KROMASIL C18色谱柱(150 mm×4.6 mm, 5μm),流动相为甲醇-水(75:25),检测波长280 nm,流速1 ml/min,柱温室温。
结果:在优化的实验条件下,样品中雌二醇的富集因子可达300,雌二醇在1~1000 ng/ml的浓度范围内线性关系良好,相关系数r为0.9995,最低检出限为0.1 ng/ml。回收率为97.5% ~120.5%,RSD为4.7% ~7.3%。
结论:本文建立的中空纤维液相微萃取方法较文献报道的液液萃取方法富集率高,达300倍,提高了分析灵敏度;与固相萃取、固相微萃取等相比,方法简单,结果准确可靠,分析成本低,有机溶剂使用量少,且不存在交叉污染,为痕量雌激素的分析提供了可靠的富集手段。
"Trace Elements" generally refers to samples less than 0.01%, such as active ingredients in drugs, drugs or toxins pollutants in environment, metal ion contamination in drugs. The concentration of these substances is low, but the physiological activity is strong. In addition, high accumulation accured gives toxic effect to human body. These problems, people paid more and more attention, have become the focuses of their research. However, it is difficult to analyze trace substances with conventional analytical methods, such as high-performance liquid chromatography, UV spectroscopy. The main method to solve the problem is to improve the sensitivity of analytical methods or develop more sensitive methods. However, it is difficult to detect some of substances which are below pg level, even if sensitive method is performed (such as MS, etc.). Therefore, appropriate sample pre-treatment method to enrich trace substances is introduced to solve this problem. New sample pre-treatment techniques provide new analytical tools to analyze substances which are difficult to monitor (such as substances with low ionization efficiency by MS detection).
In this project, a sensitive method has been developed to solve the difficulty in the detection of zoledronic acid. Phosphorusmolybdenum heteropoly acid-rhodamin B produced high RRS, and greatly improved the sensitivity. The detection limit was 1.55ng/ml. The parameters affecting the reaction such as sulfuric acid concentration, potassium persulfate concentration, ammonium molybdate concentration, Rhodamine B concentration, as well as the boiling time, reaction temperature, reaction time were investigated. The method was successfully applied for the determination of zoledronic acid infusion solution. A GF-AAS was established for the determination of aluminum in zoledronic acid injection, and the resource of aluminum in zoledronic acid injection was discussed. The background interference was eliminated by Zeeman background correction. The sensitivity of the method was improved by optimizing the drying, ashing, atomization temperature and time, as well as choice of base modifier. The detection limit was 0.14ng/ml. The method supports direct analysis without digestion and was successfully applied to explore the sources of aluminum in zoledronic acid injection. Another job established in our project is to show the application of Hollow fiber liquid-phase micro-extraction. Hollow fiber liquid-phase micro-extraction, a new enrichment and purified pre-treatment technique, has been applied for the analysis of trace substances in environmental water. Compared with the reported sample preparation techniques, the proposed method seems to be more preferred for its high enrichment, cost effectiveness, minimization of organic waste, and absence of memory effect. Meanwhile, it earned many merits such as extraction and concentration in one set, outstanding purification, no cross-contamination and suitable for various analytes in different matrix. Under optimizing conditions, the enrichment efficiency was 300 and the detection limit was 0.1ng/ml.
PART 1 Determination of Trace Zoledronic Acid by Resonance Rayleigh Scattering Method
Objective: To establish a sensitive, fast and simple resonance Rayleigh scattering method for the determination of trace zoledronic acid.
Methods: In acid medium, ammonium molybdate of 0.25 mg/ml and inorganic phosphorus which is produced from 1 ml sample solution reacting with KPs of 1% for 10 min, reacts with rhodamin B of 7×10-6 mol/L to form an associated complex of phosphorusmolybdenum heteropoly acid- rhodamin B. The RRS(I) of complex was detected atλex=λem=370 nm with slit width of 5 nm. The same procedure was carried out to measure the blank signal(I0). Sample concentration was calculated by the enhancement of RRS (ΔI= I﹣I0).
Results: Under the optimized conditions, the enhancement of RRS (ΔI) is proportional to the concentration of zoledronic acid in solution. The linear relationship was obtained in the range of 6.25 to 100ng/ml. The limit of detection is 1.55 ng/ml with RSD 2.1% and the recovery was 100~101%. Phosphate, phosphate and other coexistence substance (metal ion and mineral acid radical ion) did not interfere the determination of zoledronic acid.
Conclusion: A simple and rapid RRS method for the determination of zoledronic acid has been developed. Compared with traditional molybdenum blue spectrophotometry method, it is 500 times more sensitive with limit of detection at 1.55 ng/ml. It provides a new method for the determination of zoledronic acid. The method was successfully applied to the quality control of zoledronic acid infusion solution.
PART 2 Pollution of Aluminium in Zoledronic Acid Injection by Graphite Furnace Atomic Absorption Spectrometry
Objective: A graphite furnace atomic absorption spectrometry was established for the study of the source of aluminium and the pollution in zoledronic acid injection.
Methods: Sample solution of 100μl, adding 50μl 5 mg/ml of magnesium nitrate, diluted to 2.5 ml with 1% nitric acid, and then injected directly into the graphite furnace. Pyrolysis coating graphite tube and aluminium hollow cathode lamp with wavelength of 309.3 nm and lamp current of 10 mA were employed. 80℃and 220℃for drying, 700℃and 1200℃for ashing, 2600℃for atomizing were optimized for temperature program. The aluminium ion in zoledronic acid injection was determined directly by graphite furnace atomic absorption spectrometry with polarized Zeeman background correction.
Results: Matrix effect in zoledronic acid injection was cut down in this condition. There was a good linear relationship in the concentration range of 4.00~20.0 ng/ml (r = 0.9995). The detection limit was 0.14 ng/ml, the relative standard deviation were 99% ~104%, and the RSD were 2.7% ~3.5%. The result of zoledronic acid injection of 30 days showed that concentration of aluminium increased with increasing the staying time.
Conclusion: A graphite furnace atomic absorption spectrometry was established for the determination of aluminium in zoledronic acid injection. The method was sensitive with the detection limit of 0.14ng/ml. The sample was injected directly instead of complex digestive process. Basal modifier added can reduce the effects of the sample substrate effectively. The result of zoledronic acid injection stability test showed that aluminum ions came from ampoule.
PART 3 Enrichment and determination of trace estradiol in environmental water samples by hollow fiber liquid phase microextraction prior to high performance liquid chromatography
Objective: A novel and simple cleanup procedure, based on hollow-fiber liquid-phase microextraction (HF-LPME) is described here, and HPLC-UV was used for the determination of trace estradiol in environmental water samples.
Methods: For HF-LPME, the polyvinylidene difluoride hollow fiber membrane was used. N-octyl alcohol was used as n-octyl alcohol. The n-octyl alcohol was injected into the fiber of 11 cm. Then, the two ends of the fiber were enveloped, and then were introduced into a 140ml glass bottle with screw cap. The extraction was performed by agitation at 500 rpm at 25℃for 60 min. After that, 100μl methanol was slowly flushed through the lumen. The whole elution solution was evaporated to dryness at 90℃under nitrogen gas. To the dried sample, 100μl methanol was added before HPLC analysis. The analysis was performed on a KROMASIL C18 column (150 mm×4.6 mm, 5μm), with the mobile phase of methanol-water (75:25) at 25℃and detected at 280nm using UV detector. The flow rate was 1 ml/min.
Results: Under the optimized experimental conditions, the enrichment factor was 300. The proposed method was found to be linear in the concentration 1-1000ng/ml for estradiol and the limit of detection for an S/N = 3 was 0.1ng/ml. The recovery of esdradiol was 97.5% ~120.5% with RSD of 4.7% ~7.3%.
Conclusion: A hollow-fiber liquid-phase microextraction has been established for the analysis of estradiol. It takes a serial of advantages over liquid-liquid extraction such as high sensitivity with high enrichment factor of 300. Compared with the reported sample preparation techniques, such as solid phase extraction and solid phase microextraction , the proposed method seems to be more preferred for its cost effectiveness, minimization of organic waste, absence of memory effect, accuraty and reliability. It provides a new reliable means for the analysis of estradiol.
引文
1彭六保,崔巍.唑来膦酸的临床应用研究进展.中国新药与临床杂志, 2007, 26(3): 237-240
2 Paul W. Physicians’Desk Reference. 56th ed. Montvale: Dikran NB, 2001: 3621-3623
3蒋晔,张晓青,徐智儒,等.唑来膦酸的电位滴定法测定.中国医药工业杂志, 2005, 36(1): 37-38
4 Legay F, Gauron S, Deckert F, et al. Development and validation of a highly sensitive RIA for zoledronic acid, a new potent heterocyclic bisphosphonate, in human serum, plasma and urine. J Pharma Biomed Anal, 2002, 30(4): 897-911
5蒋晔,张晓青,徐智儒.反相高效液相色谱法测定唑来膦酸及其制剂含量.中国药学杂志, 2005, 40(7): 543-545
6蒋晔,张晓青,徐智儒.高效液相色谱法测定唑来瞵酸及其制剂含量.药物分析杂志, 2005, 25(4): 406-408
7唐克慧,王宇驰,朱群彬,等.离子交换HPLC法测定唑来膦酸的含量及有关物质.中国抗生素杂志, 2005, 30(2): 88-90
8龙明立,黄红林,闫锋,等.钼蓝比色法测定复方阿仑膦酸钠片中阿仑膦酸钠的含量.解放军药学学报, 2006, 22(6): 434-436
9 Luo H Q, Liu S P, Liu Z F, et al. Resonance Rayleigh scattering spectra for studying the interaction of heparin with some basicphenothiazine dyes and their analytical applications. Analytica Chimica Acta, 2001, 449(1-2): 261-270
1张加玲,刘桂英.铝对人体的危害、铝的来源及测定方法研究进展.临床医药实践, 2005, 14(1): 3
2 Yokel R A, Rhineheimer S S, Brauer R D, et al. Aluminum bioavailability from drinking water is very low and is not appreciably influenced by stomach contents or water hardness. Toxicology, 2001, 161: 93-101
3 Yokel R A, Hicks C L, Florence R L. Aluminum bioavailability from basic sodium aluminum phosphate, an approved food additive emulsifying agent, incorporated in cheese. Food and Chemical Toxicology, 2008, 46: 2261-2266
4宋慧坚.石墨炉原子吸收光谱法测定面制品中铝.中国卫生检验杂志, 2006, 16(3): 316
5桂保松,姜生礼,闰喜荣,等.西安地区尿毒症患者血清、透析液及饮用水铝含量的检测.西安医科大学学报, 1996, 17(2): 198
6桂保松,朱建民,薛蕴玉.尿毒症患者血清及腹膜透析液铝含量分析.陕西医学杂志, 1994, 23(2): 89
7 Heller W, Pichler B, Winter G, et al. Stable injection solutions containing diphosphonic acids. WO: 4228552, 1994-04-27
8胡珊玲,赖晓绮,张小联,等.电感耦合等离子体-原子发射光谱法测定稀土萃取液中的铝.光谱实验室, 2008, 25(2): 92
9李敏娇,罗祎,张述林.示波极谱法测定易拉罐啤酒中的微量铝.饮料工业, 2008, 2(6): 31
10 Denise B, Morgana B D, Rosilene K, et al. Tissue digestion for aluminum determination in experimental animal studies. Anal Biochem, 2008, 377(2): 120
1 Herman GE. The Termination of a case of recurrent mammary cancer treated by oophorectomy. The Lancet 1904, 163: 145-146
2 Colditz GA. Relationship between estrogen levels, use of hormone replacement therapy, and breast cancer. J Natl Cancer Inst. 1998, 90: 814-823
3 Rogan EG, Badawi AF, Devanesan PD. Relative imbalances in estrogen metabolism and conjugation in breast tissue of women with carcinoma: potential biomarkers of susceptibility to cancer. Carcinogenesis 2003, 24: 697-702
4 Cavalieri E, Chakravarti D, Guttenplan J, et al. Catechol estrogen quinones as initiators of breast and other human cancers: Implications for biomarkers of susceptibility and cancer prevention. BBA 2006, 1776: 63-78
5 Bedding ND, McIntyre AE, Lester JN. Organic contaminants in the aquatic environment. Sci. Total Environ. 1983, 27: 163-200
6 Snyder EM, Snyder SA, Giesy JP, et al. SCRAM: A scoring and ranking system for persistent, bioaccumulative, and toxic substances for the North American Great Lakes: Part I: Structure of the scoring and ranking system [ESPR 7 (1) 51-61 (2000)] Part II: Bioaccumulation potential and persistence [ESPR 7 (2) 115-121 (2000)] Part III: Acute and subchronic orchronic toxicity Part IV: Results from representative chemicals, sensitivity analysis, and discriminatory power. Environ. Sci. Pollut. Res. Int. 2000, 7: 116-121
7 Servos MR, Bennie DT, Burnison BK, et al. Distribution of estrogens, 17β-estradiol and estrone, in Canadian municipal wastewater treatment plants. Sci. Total Environ. 2005, 336: 155-170
8 Auriol M, Filali-Meknassi Y, Tyagi RD, et al. Endocrine disrupting compounds removal from wastewater, a new challenge. Process Biochem. 2006, 41: 525-539
9 Lai KM, Scrimshaw MD, Lester JN. Biotransformation and bioconcentration of steroid estrogens by Chlorella vulgaris. Appl. Environ. Microbiol. 2002, 68: 859-864
10 Gomes RL, Deacon HE, Lai KM, et al. An assessment of the bioaccumulation of estrone in Daphnia magna. Environ. Toxicol. Chem. 2004, 23: 105-108
11 Wei HB, Lin JM, Wu DN, et al. Chin. J. Anal. Chem. 2007, 35: 319-324
12 Geisler J, Ekse D, Helle H, et al. An optimised, highly sensitive radioimmunoassay for the simultaneous measurement of estrone, estradiol and estrone sulfate in the ultra-low range in human plasma samples. J. Steroid Biochem. Mol. Biol. 2008, 109: 90-95
13 Zhao HX, Sun ZW, Xia L, et al. A novel fluorescence reagent for the analysis of trace free oestradiol and oestriol in urine by reversed-phase high performance liquid chromatography with fluorescence detection and mass spectrometry identification. Chin. J. Chromatogra 2009, 27: 164-168
14 Yamashita K, Okuyama M, Watanabe Y, et al. Highly sensitive determination of estrone and estradiol in human serum by liquid chromatography-electrospray ionization tandem mass spectrometry. Steroids 2007, 72: 819-827
15 Zacharia LC, Dubey RK, Jackson EK. A gas chromatography/mass spectrometry assay to measure estradiol, catecholestradiols, and methoxyestradiols in plasma. Steroids 2004, 69: 255-261
16 Hendriks L, Gielen B, Pottie G, et al. Matrix effects in the radioimmunoassay of estradiol and testosterone in plasma of veal calves and how to avoid them. Anal. Chim. Acta 1993, 275: 113-122
17 Jimenez JJ, Bernal JL, Nozal MJ, et al. Use of SPE-GC/EIMS for residue analysis in wine elaborated from musts spiked with formulations of chlorpyriphos-methyl, methiocarb, dicofol, and cyproconazol. J. Sep. Sci. 2007, 30: 547-556
18 Molina-Mayo C, Hernández-Borges J, Borges-Miquel TM, et al. Determination of pesticides in wine using micellar electrokinetic chromatography with UV detection and sample stacking. J. Chromatogr. A 2007, 1150: 348-355
19 Romero MT, Ferrer N. Determination of oil and grease by solid phase extraction and infrared spectroscopy. Anal. Chim. Acta 1999, 395: 77-84
20 Prosen H, Zupancic-Kralj L. Solid-phase microextraction. Trends Anal. Chem. 1999, 18: 272-282
21 Tat L, Comuzzo P, Stolfo I, et al. Optimization of wine headspace analysis by solid-phase microextraction capillary gas chromatography with mass spectrometric and flame ionization detection. Food Chem. 2005, 93: 361-369
22 Sandahl M, Mathiasson L, Jonsson JA. Determination of thiophanate-methyl and its metabolites at trace level in spiked natural water using the supported liquid membrane extraction and the microporous membrane liquid-liquid extraction techniques combined on-line with high-performance liquid chromatography. J. Chromatogr. A 2000, 893: 123-131
23 Khrolenko M, Dzygiel P, Wieczorek P. Combination of supported liquid membrane and solid-phase extraction for sample pretreatment of triazine herbicides in juice prior to capillary electrophoresis determination. J. Chromatogr. A 2002, 975: 219-227
24 Shariati S, Yamini Y, Esrafili A. Carrier mediated hollow fiber liquid phase microextraction combined with HPLC-UV for preconcentration anddetermination of some tetracycline antibiotics. J. Chromatogr. B 2009, 877: 393-400
25 Hawthorne SB, Miller DJ, Pawliszyn J, et al. Solventless determination of caffeine in beverages using solid-phase microextraction with fused-silica fibers. J. Chromatogr. 1992, 603: 185-191
26 Penalver A, Pocurull E, Borrull F, et al. Trends in solid-phase microextraction for determining organic pollutants in environmental samples. Trends Anal. Chem. 1999, 18: 557-568
27 Lord H, Pawliszyn J. Evolution of solid-phase microextraction technology. J. Chromatogr. A 2000, 885: 153-193
28 Ulrich S. Solid-phase microextraction in biomedical analysis. J. Chromatogr. A 2000, 902: 167-194
29 Cruz-Vera M, Lucena R, Cárdenas S, et al. Ionic liquid-based dynamic liquid-phase microextraction: application to the determination of anti-inflammatory drugs in urine samples. J. Chromatogr. A 2008, 1202: 1-7
30 Bolanos PP, Romero-González R, Frenich AG, et al. Application of hollow fibre liquid phase microextraction for the multiresidue determination of pesticides in alcoholic beverages by ultra-high pressure liquid chromatography coupled to tandem mass spectrometry. J. Chromatogr. A 2008, 1208: 16-24
31 Sarafraz-Yazdia A, Mofazzeli F, Eshaghic Z. A new high-speed hollow fiber based liquid phase microextract method using volatile organic solvent for determination of aromatic amines in environmental water samples prior to high-performance liquid chromatography. Talanta 2009, 79: 472-478
32 Jiang HM, Hu B, Chen BB, et al. Hollow fiber liquid phase microextract combined with graphite furnace atomic absorption spectrometry for the determination of methylmercury in human hair and sludge sample. Spectrochim. Acta. B 2008, 63: 770-776
33 Es’haghi Z. Determination of widely used non-steroidal anti-inflammatorydrugs in water samples by in situ derivatization, continuous hollow fiber liquid-phase microextraction and gas chromatography-flame ionization detector. Anal. Chim. Acta 2009, 641: 83-88
34 Kawaguchi M, Ito R, Honda H, et al. Miniaturized hollow fiber assisted liquid-phase microextraction and gas chromatography-mass spectrometry for determination of benzophenone and derivates in human urine sample. J. Chromatogr. B 2009, 877: 298-302
35 Liu MH, Qiu B, Jin X, et al. Determination of estrogens in wastewater using three-phase hollow fiber-mediated liquid-phase microextraction followed by HPLC. J. Sep. Sci. 2008, 31: 622-628
36 Psillakis E, Kalogerakis N. Developments in liquid-phase microextraction. Trends Anal. Chem. 2003, 22: 565-574
37 Basheer C, Balasubramanian R, Lee HK. Determination of organic micropollutants in rainwater using hollow fiber membrane/liquid-phase microextraction combined with gas chromatography-mass spectrometry. J. Chromatogr. A 2003, 1016: 11-20
38 Charalabaki M, Psillakis E, Mantzavinos D, et al. Analysis of polycyclic aromatic hydrocarbons in wastewater treatment plant effluents using hollow fibre liquid-phase microextraction. Chemosphere 2005, 60: 690-698
39 Liu JF, Cai XQ, Li ZF, et al. Development of negligible depletion hollow fiber membrane-protected liquid-phase microextraction for simultaneous determination of partitioning coefficients and acid dissociation constants. J. Chromatogr. A 2009, 1216: 2583-2586
40 Xu X, Roman JM, Issaq HJ, et al. Quantitative Measurement of Endogenous Estrogens and Estrogen Metabolites in Human Serum by Liquid Chromatography-Tandem Mass Spectrometry. Anal Chem 2007, 79: 7813-7821
41 Xu X, Roman JM, Veenstra TD, et al. Analysis of Fifteen Estrogen Metabolites Using Packed Column Supercritical Fluid Chromatography- Mass Spectrometry. Anal Chem. 2006, 79: 1553-1558
42 Mao LS, Sun CJ, Zhang H, et al. Determination of environmental estrogens in human urine by high performance liquid chromatography after fluorescent derivatization with p-nitrobenzoyl chloride. Anal. Chim. Acta 2004, 522: 241-246
43 Long Z, Hong L, Jie J. Determination ofβ-Estradiol Residues in Fish/Shellfish Muscle by Gas Chromatography-Mass Spectrometry. Chin J Anal Chem 2007, 35: 983-987
44 Wei HB, Lin JM, Wu DN, et al. Detection of 17β-Estradiol in River and Human Urine by Highly Sensitive Chemiluminescent Enzyme Immunoassay. Chin J Anal Chem 2007, 35: 320-324
45 Li XJ, Chen GL, Xu YJ. Determination of Sex Hormones by Capillary Micellar Electrokinetic Chromatography. Guangxi. J. Aca. Sci. 2006, 22: 463-465
46 Xiao XH, Yin Y, Hu YL, et al. Determination of Trace Estrogens in Cosmetic Water by Liquid-Phase Microextraction Coupled with High Performance Liquid Chromatography. Chin J Chromatogr 2007, 25: 234-237
47 Mitani K, Fujioka M, Kataoka H. Fully automated analysis of estrogens in environmental waters by in-tube solid-phase microextraction coupled with liquid chromatography–tandem mass spectrometry. J. Chromatogr. A 2005, 1081: 218-224
48 Wen Y, Zhou BS, Xu Y, et al. Analysis of estrogens in environmental waters using polymer monolith in-polyether ether ketone tube solid-phase microextraction combined with high-performance liquid chromatography. J. Chromatogr. A 2006, 1133: 21-28
49 Carpinteiro J, Quintana JB, Rodríguez I, et al. Applicability of solid-phase microextraction followed by on-fiber silylation for the determination of estrogens in water samples by gas chromatography-tandem mass spectrometry. J. Chromatogr. A 2004, 1056: 179-185
1 Long X F, Li D S, Wang N, et al. A novel and sensitive method for recognition and indirect determination of AlIII in biological fluid based on the quenching of resonance Rayleigh scattering intensities of“AlIII-EV-DNA”complexing system. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2008, 69(1): 142-147
2 Liu S P, Yang Z, Liu Z F. Resonance Rayleigh scattering method for the determination of proteins with gold nano-particle probe. Analytical Biochemistry, 2006, 53(1): 108-116
3 Zhang M L, Sheng G P, Yu H Q. Determination of proteins and carbohydrates in the effluents from wastewater treatment bioreactors using resonance light-scattering method. Water Research, 2008, 42(13): 3464-3472
4 Long X F, Bi S P. Ni H Y. Resonance Rayleigh scattering determination of trace amounts of Al in natural waters and biological samples based on the formation of an Al(III)–morin–surfactant complex. Analytica Chimica Acta, 2004, 501(1): 89-97
5 Yang H R, Hu Y, Jiang Y Y, et al. Resonance Rayleigh Scattering Spectra of Interaction of Netilmicin Sulfate and Etimicin Sulfate with Trypan Blue and Their Analytical Applications. Chinese Journal of Spectroscopy Laboratory, 2006, 23(4): 797-799
6 Hu Q H, Jiang B, Zhou X M. Resonance Scattering Method for Determination of Netilmicin Using Ponceau Gas Probe. Guizhou Medical Journal, 2008, 32(5):387-389
7 Qian M Y, Liu S P, Liu Z F, et al. Resonance Rayleigh scattering spectra, non-linear scattering spectra of tetracaine hydrochloride-erythrosin system and its analytical application. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2009, 71(5): 2063-2068
8 Liu J T, Liu Z F, Hu X L. A highly sensitive resonance Rayleigh scattering method for the determination of bleomycinA5 and bleomycin A2 withsome halofluorescein dyes. Journal of Pharmaceutical and Biomedical Analysis, 2007, 43(4): 1452-1459
9 Tang X L, Liu Z F, Liu S P. Study on the interaction between diphenhydramine and erythrosin by absorption, fluorescence and resonance Rayleigh scattering spectra. science in China Series B: Chemistry, 2007, 50(1): 54-62
10 Wang J, Liu Z F, Liu J T, et al. Study on the interaction between fluoroquinolones and erythrosine by absorption, fluorescence and resonance Rayleigh scattering spectra and their application. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2008, 69(3): 956-963
11 Qin M Y, Liu S P, Liu Z F, et al. Resonance Rayleigh scattering spectra, non-linear scattering spectra of tetracaine hydrochloride-erythrosin system and its analytical application. Spectrochimica Acta Part A, 2009, 71(5): 2063-2068
12 Hu X L, Liu S P, Luo H Q, et al. Progress in Research on Analytical Methods of Aminoglycoside Antibiotic. Journal of Analytical Science, 2005, 21(3): 316-321
13 Wang M X, Liu Z F, Hu X L, et al. Study of the Resonance Rayleigh Scattering Spectra produced by the Interaction of Aminoglycosidic Antibiotics with Titan yellow and its Analytical Application. PTCA PartB:Chem.Anal., 2005, 30(2): 304-307
14 Lu Q M, He Y Q, Liu S P, et al. Resonance Rayleigh Scattering Spectra Method for Determination of Methylene Blue with Gold Nanoparticle as Prob. Chemical Journal of Chinese Universities, 2006, 27(5):849-852
15 Zhou Y, Yang G S, Liu Y M. Resonance Rayleigh Scattering Spectra of Interaction of Etimicin Sulfate and Netilmicin Sulfate with Evans Blue and Their Analysis Application. Ludong University Journal Natural Science Edition, 2006, 22(4): 321-325
16 Wang F, Liu Z F, Liu S P. Study on the Interaction between Three Anthracycline Anticancer Drugs and Congo Red by Absorption,Fluorescence and Resonance Rayleigh Scattering Spectra. Acta Chinaca Sinica, 2005, 63(21): 1991-1998
17 Liu S P, Hu X L, Liu Z F. Study on the resonance Rayleigh scattering spectra and resonance non-linear spectra of congo red-amikacin system and its analytical application. Science in China Series B: Chemistry, 2006, 49(6): 507-516
18 Li S D, Meng J H, Li M Q, et al. Determination of chlorophenol environmental estrogens by resonance right-scattering. Chinese Journal of Analysis Laboratory, 2007, 26(10): 34-36
19 Hao X L, Li N B, Luo H Q. Determination of dextran sulfate sodium with crystal violet by triple-wavelength overlapping resonance Rayleigh scattering. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2009, 71(5): 1673-1677
20 Wei X Q, Liu Z F, Liu S P. Resonance Rayleigh Scattering Spectra of Tetracycline Antibiotics-Sodium Tungstate-Ethyl Violet System and Their Analytical Application. Acta Chinaca Sinica, 2006, 64(6): 521-526
21 Luo H Q, Li N B, Liu S P. Resonance Rayleigh scattering study of interaction of hyaluronic acid with ethyl violet dye and its analytical application. Biosensors and Bioeletronics, 2006, 21(7): 1186-1194
22 Ma Y, Li N B, Luo H Q. Novel and sensitive methods for the determination of dopamine based on the resonance Rayleigh scattering, second-order scattering and frequency doubling scattering quenching effects. Spectrochimica Acta Part A , 2009, 73(4): 747-751
23 Liu S P, Zhang Z Y, Hu X L, et al. Resonance Rayleigh Scattering Spectra of the Interaction between Some Basic Phenazine Dyes and Heparin. Chinese Journal of Analytical Chemistry, 2005, 33(7) : 989-992
24 Guo X Q. Resonance rayleigh scattering method for the determinaion of heparin with methyl red. Chemical Research and Application, 2006, 18(10): 1242-1244
25 Chen H L, Luo H Q, Liu S P, et al. Determination of Sodium Hyaluronate with Victoria Blue B by Resonance Rayleigh Scattering Method. ChineseJournal of Spectroscopy Laborator, 2005, 22(3): 547-550
26 Chen H L, Luo H Q, Liu S P, et al. Determination of Sodium Hyaluronate with Night Blue by Resonance Rayleigh Scattering Method. Jounal of Analytical Science, 2005, 2l(3): 304-306
27 Hu QD, Jiang B, Li KY. Resonance light scattering method for determination of the trace heparin sodium with Nile Blue A sulphate as probe. Acta academiae medicinae zunyi, 2008, 31(3): 225-230
28 Heng Y Y, Jiang Z L, Liang A H. A new Spectral Method for the Determination of Cationic Surfactant Based on the Resonance Scattering Effect of AgI2- Association Particles. Spectroscopy and Spectral Analysis, 2006, 26(10): 1888-1890
29 Yan J, Liu Z F, Liu S P. Resonance Rayleigh Scattering Method for the Determination of Quercetin with Hg(Ⅱ)-Quercetin Chelate. Chinese Journal of Analytical Chemistry, 2007, 35(1): 123-126
30 Peng J D, Liu S P, Liu Z F. Resonance Rayleigh scattering spectrum for the chelate of anthanum(III) with sodium tanshinon IIA silate and its analytical application. Science in China Series B: Chemistry, 2006, 49(5): 423-429
31 Wei X Q, Liu Z F, Liu S P. Resonance Rayleigh scattering spectra of tetracycline antibiotic–Cu (II)–titan yellow systems and their applications in analytical chemistry. Analytical and Bioanalytical Chemistry, 2006, 385(6): 1039-1044
32 Fu S H, Liu Z F, Liu S P, et al. Study on the resonance Rayleigh scattering, second-order scattering and frequency doubling scattering spectra of the interactions of palladium(II)–ceftriaxone chelate with anionic surfactants and their analytical applications. Talanta, 2008, 75(2): 528-535
33 Fu S H, Liu Z F, Liu S P, et al. Study on the resonance Rayleigh scattering spectra of the interactions of palladium (II)–cephalosporins chelates with 4,5-dibromofluorescein and their analytical applications. Analytica Chimica Acta, 2007, 599(2): 271-278
34 Duan H, Liu Z F, Liu S P, et al. 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. Talanta, 2008, 75(5): 1253-1259
35 Xi C X, Liu Z F, Kong L, et al. Effects of Interaction of Folic Acid with Uranium (VI) and Basic Triphenylmethane Dyes on Resonance Rayleigh Scattering Spectra and Their Analytical Applications. Analytica Chimica Acta, 2008, 613(1): 83-90
36 Liu S P, He Y Q, Liu Z F, et al. Resonance Rayleigh scattering spectral method for the determination of raloxifene using gold nanoparticle as a probe. Analytica Chimica Acta, 2007, 598(2): 304-311
37 Liu S P, Yang Z, Liu Z F. Resonance Rayleigh scattering study on the interaction of gold nanoparticles with berberine hydrochloride and its analytical application. Analytica Chimica Acta, 2006, 572(2): 283-289
38 He Y Q, Liu S P, Liu Z F et al. Resonance Rayleigh Scattering Spectral Method for the Determination of Kanamycin with Gold Nanoparticle as Probe. Acta Chinaca Sinica, 2005, 63(11): 997-1002
39 Lu Q M,, Liu Z F, Liu S P. Resonance Rayleigh Scattering Method for the Determination of Some Anthracycline Anticancer Drugs with Gold Nanoparticle as Probe. Acta Chinaca Sinica, 2007, 65(9): 821-828
40 Wang N, Dong Z Z, Xu S K, et al. Resonance Rayleigh Scattering Spectral Method for the Determination of Procaine Hydrochloride with Nanogold as Probe. Chinese Journal of Analytical Chemistry, 2008, 36(7): 995-998
41 Wang Q, Liu Z F, Liu S P. Resonance Rayleigh Scatter ing Spectra Method for the Determination of Anthracycline Anticancer Drugs with CdS Nanoparticles as Probe. Chemical Journal of Chinese Universities, 2007, 28(5): 837-842
42 Liu Z W, Liu S P, Wang L. Resonance Rayleigh scattering and resonance non-linear scattering method for the determination of aminoglycoside antibiotics with water solubility CdS quantum dots as probe. Spectrochimica Acta Part A, 2009, 74(1): 36-41
43 Liu S P, Luo H Q, Xu H. Resonance Rayleigh scattering study of interaction of heparin with some cationic surfactants and their analytical application. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2005, 61(5): 861-867
44 Liu S P, Wang F, Liu Z F, et al. Resonance Rayleigh scattering spectra for studying the interaction of anthracycline antineoplastic antibiotics with some anionic surfactants and their analytical applications. Analytica Chimica Acta, 2007, 601(1): 101-107
45 Xiao X L, Wang Y S, Chen Z M, et al. Resonance light scattering method for the determination of anionic surfactant with acridine orange. Spectrochimica Acta Part A: Molecular and Biomolecular pectroscopy, 2008, 71(2): 398-402
46 Jiang Z L, Huang W X. Determination of Trace Gentamycin by Resonance Scattering Spectral Method. Journal of Sichuan NormalUniversity, 2008, 31(1):118-121
47 Yang Q L, Lu Q M, Liu Z F, et al. Resonance Rayleigh scattering spectra of ion-association nanoparticles of [Co(4-[(5-Chloro-2-pyridyl) azo]-1, 3-diaminobenzene)2]2+-sodium dodecyl benzene sulfonate system and its analytical application. Analytica Chimica Acta, 2009, 632(1):115-121
48 Li N B, Luo H Q, Liu S P. A new method for the determination of the critical micelle concentration of Triton X-100 in the absence and presence ofβ-cyclodextrin by resonance Rayleigh scattering technology. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy, 2004, 60(8-9): 1811-1815
49 Li N B, Luo H Q, Liu S P. Resonance Rayleigh scattering study of the inclusion complexation of chloramphenicol withβ-cyclodextrin. Analysis of Phosphorus in Environmental and Agricultural Samples, 2005, 66(2): 495-500
50 Peng J D, Liu S P, Liu Z F. Interaction between Chloroauric Acid and Berberine Hydrochloride Investigated by Resonance Rayleigh Scattering Spectrum and its Analytical Appl ications. Acta Chinaca Sinica, 2005,63(8): 745-751
51 Wang F, Liu Z F, Liu S P, et al. Determination of Mitoxantrone via Ammonium Molybdate Using High Sensitive Resonance Rayleigh Scattering Method. Chemical Journal of Chinese Universities, 2006, 27(8): 1459-1461
52 Li H X, Wang W H, Jiang Y. Determination of Trace Zoledronic Acid by Resonance Rayleigh Scattering Method. Chinese Journal of Pharmaceuticals, 2008, 39(12):930-932
53 Wen G Q, Liang A H, Wu B L, et al. Antimonphosphomolybdate Blue-anogold Resonance Scattering Spectral Method for Determination of Ascorbic Acid. Journal of Guangxi Normal University:Natural Science Edition, 2008, 26(4): 95-98
54 Liang L N, Ge G H, Do C Z. Determination of sulfonamides using resonance light scattering method. Chinese Journal ofHealth Laboratory Technology, 2008, 18(8): 1561-1562
55 Wang F, Peng J D, Liu L M. A reversed-phase high performance liquid chromatography coupled with resonance Rayleigh scattering detection for the determination of four tetracycline antibiotics. analytica chimica acta, 2008, 630(1): 101-106
56 Nan H J, Liu Z F, Liu S P. Resonance Rayleigh Scattering Spectra of Self-aggregation for Bile Salts in Acidic Media and Their Analytical Application. Acta Chinaca Sinica, 2006, 64(12): 1253-1259
2 Paul W. Physicians’Desk Reference. 56th ed. Montvale: Dikran NB, 2001: 3621-3623
3蒋晔,张晓青,徐智儒,等.唑来膦酸的电位滴定法测定.中国医药工业杂志, 2005, 36(1): 37-38
4 Legay F, Gauron S, Deckert F, et al. Development and validation of a highly sensitive RIA for zoledronic acid, a new potent heterocyclic bisphosphonate, in human serum, plasma and urine. J Pharma Biomed Anal, 2002, 30(4): 897-911
5蒋晔,张晓青,徐智儒.反相高效液相色谱法测定唑来膦酸及其制剂含量.中国药学杂志, 2005, 40(7): 543-545
6蒋晔,张晓青,徐智儒.高效液相色谱法测定唑来瞵酸及其制剂含量.药物分析杂志, 2005, 25(4): 406-408
7唐克慧,王宇驰,朱群彬,等.离子交换HPLC法测定唑来膦酸的含量及有关物质.中国抗生素杂志, 2005, 30(2): 88-90
8龙明立,黄红林,闫锋,等.钼蓝比色法测定复方阿仑膦酸钠片中阿仑膦酸钠的含量.解放军药学学报, 2006, 22(6): 434-436
9 Luo H Q, Liu S P, Liu Z F, et al. Resonance Rayleigh scattering spectra for studying the interaction of heparin with some basicphenothiazine dyes and their analytical applications. Analytica Chimica Acta, 2001, 449(1-2): 261-270
1张加玲,刘桂英.铝对人体的危害、铝的来源及测定方法研究进展.临床医药实践, 2005, 14(1): 3
2 Yokel R A, Rhineheimer S S, Brauer R D, et al. Aluminum bioavailability from drinking water is very low and is not appreciably influenced by stomach contents or water hardness. Toxicology, 2001, 161: 93-101
3 Yokel R A, Hicks C L, Florence R L. Aluminum bioavailability from basic sodium aluminum phosphate, an approved food additive emulsifying agent, incorporated in cheese. Food and Chemical Toxicology, 2008, 46: 2261-2266
4宋慧坚.石墨炉原子吸收光谱法测定面制品中铝.中国卫生检验杂志, 2006, 16(3): 316
5桂保松,姜生礼,闰喜荣,等.西安地区尿毒症患者血清、透析液及饮用水铝含量的检测.西安医科大学学报, 1996, 17(2): 198
6桂保松,朱建民,薛蕴玉.尿毒症患者血清及腹膜透析液铝含量分析.陕西医学杂志, 1994, 23(2): 89
7 Heller W, Pichler B, Winter G, et al. Stable injection solutions containing diphosphonic acids. WO: 4228552, 1994-04-27
8胡珊玲,赖晓绮,张小联,等.电感耦合等离子体-原子发射光谱法测定稀土萃取液中的铝.光谱实验室, 2008, 25(2): 92
9李敏娇,罗祎,张述林.示波极谱法测定易拉罐啤酒中的微量铝.饮料工业, 2008, 2(6): 31
10 Denise B, Morgana B D, Rosilene K, et al. Tissue digestion for aluminum determination in experimental animal studies. Anal Biochem, 2008, 377(2): 120
1 Herman GE. The Termination of a case of recurrent mammary cancer treated by oophorectomy. The Lancet 1904, 163: 145-146
2 Colditz GA. Relationship between estrogen levels, use of hormone replacement therapy, and breast cancer. J Natl Cancer Inst. 1998, 90: 814-823
3 Rogan EG, Badawi AF, Devanesan PD. Relative imbalances in estrogen metabolism and conjugation in breast tissue of women with carcinoma: potential biomarkers of susceptibility to cancer. Carcinogenesis 2003, 24: 697-702
4 Cavalieri E, Chakravarti D, Guttenplan J, et al. Catechol estrogen quinones as initiators of breast and other human cancers: Implications for biomarkers of susceptibility and cancer prevention. BBA 2006, 1776: 63-78
5 Bedding ND, McIntyre AE, Lester JN. Organic contaminants in the aquatic environment. Sci. Total Environ. 1983, 27: 163-200
6 Snyder EM, Snyder SA, Giesy JP, et al. SCRAM: A scoring and ranking system for persistent, bioaccumulative, and toxic substances for the North American Great Lakes: Part I: Structure of the scoring and ranking system [ESPR 7 (1) 51-61 (2000)] Part II: Bioaccumulation potential and persistence [ESPR 7 (2) 115-121 (2000)] Part III: Acute and subchronic orchronic toxicity Part IV: Results from representative chemicals, sensitivity analysis, and discriminatory power. Environ. Sci. Pollut. Res. Int. 2000, 7: 116-121
7 Servos MR, Bennie DT, Burnison BK, et al. Distribution of estrogens, 17β-estradiol and estrone, in Canadian municipal wastewater treatment plants. Sci. Total Environ. 2005, 336: 155-170
8 Auriol M, Filali-Meknassi Y, Tyagi RD, et al. Endocrine disrupting compounds removal from wastewater, a new challenge. Process Biochem. 2006, 41: 525-539
9 Lai KM, Scrimshaw MD, Lester JN. Biotransformation and bioconcentration of steroid estrogens by Chlorella vulgaris. Appl. Environ. Microbiol. 2002, 68: 859-864
10 Gomes RL, Deacon HE, Lai KM, et al. An assessment of the bioaccumulation of estrone in Daphnia magna. Environ. Toxicol. Chem. 2004, 23: 105-108
11 Wei HB, Lin JM, Wu DN, et al. Chin. J. Anal. Chem. 2007, 35: 319-324
12 Geisler J, Ekse D, Helle H, et al. An optimised, highly sensitive radioimmunoassay for the simultaneous measurement of estrone, estradiol and estrone sulfate in the ultra-low range in human plasma samples. J. Steroid Biochem. Mol. Biol. 2008, 109: 90-95
13 Zhao HX, Sun ZW, Xia L, et al. A novel fluorescence reagent for the analysis of trace free oestradiol and oestriol in urine by reversed-phase high performance liquid chromatography with fluorescence detection and mass spectrometry identification. Chin. J. Chromatogra 2009, 27: 164-168
14 Yamashita K, Okuyama M, Watanabe Y, et al. Highly sensitive determination of estrone and estradiol in human serum by liquid chromatography-electrospray ionization tandem mass spectrometry. Steroids 2007, 72: 819-827
15 Zacharia LC, Dubey RK, Jackson EK. A gas chromatography/mass spectrometry assay to measure estradiol, catecholestradiols, and methoxyestradiols in plasma. Steroids 2004, 69: 255-261
16 Hendriks L, Gielen B, Pottie G, et al. Matrix effects in the radioimmunoassay of estradiol and testosterone in plasma of veal calves and how to avoid them. Anal. Chim. Acta 1993, 275: 113-122
17 Jimenez JJ, Bernal JL, Nozal MJ, et al. Use of SPE-GC/EIMS for residue analysis in wine elaborated from musts spiked with formulations of chlorpyriphos-methyl, methiocarb, dicofol, and cyproconazol. J. Sep. Sci. 2007, 30: 547-556
18 Molina-Mayo C, Hernández-Borges J, Borges-Miquel TM, et al. Determination of pesticides in wine using micellar electrokinetic chromatography with UV detection and sample stacking. J. Chromatogr. A 2007, 1150: 348-355
19 Romero MT, Ferrer N. Determination of oil and grease by solid phase extraction and infrared spectroscopy. Anal. Chim. Acta 1999, 395: 77-84
20 Prosen H, Zupancic-Kralj L. Solid-phase microextraction. Trends Anal. Chem. 1999, 18: 272-282
21 Tat L, Comuzzo P, Stolfo I, et al. Optimization of wine headspace analysis by solid-phase microextraction capillary gas chromatography with mass spectrometric and flame ionization detection. Food Chem. 2005, 93: 361-369
22 Sandahl M, Mathiasson L, Jonsson JA. Determination of thiophanate-methyl and its metabolites at trace level in spiked natural water using the supported liquid membrane extraction and the microporous membrane liquid-liquid extraction techniques combined on-line with high-performance liquid chromatography. J. Chromatogr. A 2000, 893: 123-131
23 Khrolenko M, Dzygiel P, Wieczorek P. Combination of supported liquid membrane and solid-phase extraction for sample pretreatment of triazine herbicides in juice prior to capillary electrophoresis determination. J. Chromatogr. A 2002, 975: 219-227
24 Shariati S, Yamini Y, Esrafili A. Carrier mediated hollow fiber liquid phase microextraction combined with HPLC-UV for preconcentration anddetermination of some tetracycline antibiotics. J. Chromatogr. B 2009, 877: 393-400
25 Hawthorne SB, Miller DJ, Pawliszyn J, et al. Solventless determination of caffeine in beverages using solid-phase microextraction with fused-silica fibers. J. Chromatogr. 1992, 603: 185-191
26 Penalver A, Pocurull E, Borrull F, et al. Trends in solid-phase microextraction for determining organic pollutants in environmental samples. Trends Anal. Chem. 1999, 18: 557-568
27 Lord H, Pawliszyn J. Evolution of solid-phase microextraction technology. J. Chromatogr. A 2000, 885: 153-193
28 Ulrich S. Solid-phase microextraction in biomedical analysis. J. Chromatogr. A 2000, 902: 167-194
29 Cruz-Vera M, Lucena R, Cárdenas S, et al. Ionic liquid-based dynamic liquid-phase microextraction: application to the determination of anti-inflammatory drugs in urine samples. J. Chromatogr. A 2008, 1202: 1-7
30 Bolanos PP, Romero-González R, Frenich AG, et al. Application of hollow fibre liquid phase microextraction for the multiresidue determination of pesticides in alcoholic beverages by ultra-high pressure liquid chromatography coupled to tandem mass spectrometry. J. Chromatogr. A 2008, 1208: 16-24
31 Sarafraz-Yazdia A, Mofazzeli F, Eshaghic Z. A new high-speed hollow fiber based liquid phase microextract method using volatile organic solvent for determination of aromatic amines in environmental water samples prior to high-performance liquid chromatography. Talanta 2009, 79: 472-478
32 Jiang HM, Hu B, Chen BB, et al. Hollow fiber liquid phase microextract combined with graphite furnace atomic absorption spectrometry for the determination of methylmercury in human hair and sludge sample. Spectrochim. Acta. B 2008, 63: 770-776
33 Es’haghi Z. Determination of widely used non-steroidal anti-inflammatorydrugs in water samples by in situ derivatization, continuous hollow fiber liquid-phase microextraction and gas chromatography-flame ionization detector. Anal. Chim. Acta 2009, 641: 83-88
34 Kawaguchi M, Ito R, Honda H, et al. Miniaturized hollow fiber assisted liquid-phase microextraction and gas chromatography-mass spectrometry for determination of benzophenone and derivates in human urine sample. J. Chromatogr. B 2009, 877: 298-302
35 Liu MH, Qiu B, Jin X, et al. Determination of estrogens in wastewater using three-phase hollow fiber-mediated liquid-phase microextraction followed by HPLC. J. Sep. Sci. 2008, 31: 622-628
36 Psillakis E, Kalogerakis N. Developments in liquid-phase microextraction. Trends Anal. Chem. 2003, 22: 565-574
37 Basheer C, Balasubramanian R, Lee HK. Determination of organic micropollutants in rainwater using hollow fiber membrane/liquid-phase microextraction combined with gas chromatography-mass spectrometry. J. Chromatogr. A 2003, 1016: 11-20
38 Charalabaki M, Psillakis E, Mantzavinos D, et al. Analysis of polycyclic aromatic hydrocarbons in wastewater treatment plant effluents using hollow fibre liquid-phase microextraction. Chemosphere 2005, 60: 690-698
39 Liu JF, Cai XQ, Li ZF, et al. Development of negligible depletion hollow fiber membrane-protected liquid-phase microextraction for simultaneous determination of partitioning coefficients and acid dissociation constants. J. Chromatogr. A 2009, 1216: 2583-2586
40 Xu X, Roman JM, Issaq HJ, et al. Quantitative Measurement of Endogenous Estrogens and Estrogen Metabolites in Human Serum by Liquid Chromatography-Tandem Mass Spectrometry. Anal Chem 2007, 79: 7813-7821
41 Xu X, Roman JM, Veenstra TD, et al. Analysis of Fifteen Estrogen Metabolites Using Packed Column Supercritical Fluid Chromatography- Mass Spectrometry. Anal Chem. 2006, 79: 1553-1558
42 Mao LS, Sun CJ, Zhang H, et al. Determination of environmental estrogens in human urine by high performance liquid chromatography after fluorescent derivatization with p-nitrobenzoyl chloride. Anal. Chim. Acta 2004, 522: 241-246
43 Long Z, Hong L, Jie J. Determination ofβ-Estradiol Residues in Fish/Shellfish Muscle by Gas Chromatography-Mass Spectrometry. Chin J Anal Chem 2007, 35: 983-987
44 Wei HB, Lin JM, Wu DN, et al. Detection of 17β-Estradiol in River and Human Urine by Highly Sensitive Chemiluminescent Enzyme Immunoassay. Chin J Anal Chem 2007, 35: 320-324
45 Li XJ, Chen GL, Xu YJ. Determination of Sex Hormones by Capillary Micellar Electrokinetic Chromatography. Guangxi. J. Aca. Sci. 2006, 22: 463-465
46 Xiao XH, Yin Y, Hu YL, et al. Determination of Trace Estrogens in Cosmetic Water by Liquid-Phase Microextraction Coupled with High Performance Liquid Chromatography. Chin J Chromatogr 2007, 25: 234-237
47 Mitani K, Fujioka M, Kataoka H. Fully automated analysis of estrogens in environmental waters by in-tube solid-phase microextraction coupled with liquid chromatography–tandem mass spectrometry. J. Chromatogr. A 2005, 1081: 218-224
48 Wen Y, Zhou BS, Xu Y, et al. Analysis of estrogens in environmental waters using polymer monolith in-polyether ether ketone tube solid-phase microextraction combined with high-performance liquid chromatography. J. Chromatogr. A 2006, 1133: 21-28
49 Carpinteiro J, Quintana JB, Rodríguez I, et al. Applicability of solid-phase microextraction followed by on-fiber silylation for the determination of estrogens in water samples by gas chromatography-tandem mass spectrometry. J. Chromatogr. A 2004, 1056: 179-185
1 Long X F, Li D S, Wang N, et al. A novel and sensitive method for recognition and indirect determination of AlIII in biological fluid based on the quenching of resonance Rayleigh scattering intensities of“AlIII-EV-DNA”complexing system. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2008, 69(1): 142-147
2 Liu S P, Yang Z, Liu Z F. Resonance Rayleigh scattering method for the determination of proteins with gold nano-particle probe. Analytical Biochemistry, 2006, 53(1): 108-116
3 Zhang M L, Sheng G P, Yu H Q. Determination of proteins and carbohydrates in the effluents from wastewater treatment bioreactors using resonance light-scattering method. Water Research, 2008, 42(13): 3464-3472
4 Long X F, Bi S P. Ni H Y. Resonance Rayleigh scattering determination of trace amounts of Al in natural waters and biological samples based on the formation of an Al(III)–morin–surfactant complex. Analytica Chimica Acta, 2004, 501(1): 89-97
5 Yang H R, Hu Y, Jiang Y Y, et al. Resonance Rayleigh Scattering Spectra of Interaction of Netilmicin Sulfate and Etimicin Sulfate with Trypan Blue and Their Analytical Applications. Chinese Journal of Spectroscopy Laboratory, 2006, 23(4): 797-799
6 Hu Q H, Jiang B, Zhou X M. Resonance Scattering Method for Determination of Netilmicin Using Ponceau Gas Probe. Guizhou Medical Journal, 2008, 32(5):387-389
7 Qian M Y, Liu S P, Liu Z F, et al. Resonance Rayleigh scattering spectra, non-linear scattering spectra of tetracaine hydrochloride-erythrosin system and its analytical application. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2009, 71(5): 2063-2068
8 Liu J T, Liu Z F, Hu X L. A highly sensitive resonance Rayleigh scattering method for the determination of bleomycinA5 and bleomycin A2 withsome halofluorescein dyes. Journal of Pharmaceutical and Biomedical Analysis, 2007, 43(4): 1452-1459
9 Tang X L, Liu Z F, Liu S P. Study on the interaction between diphenhydramine and erythrosin by absorption, fluorescence and resonance Rayleigh scattering spectra. science in China Series B: Chemistry, 2007, 50(1): 54-62
10 Wang J, Liu Z F, Liu J T, et al. Study on the interaction between fluoroquinolones and erythrosine by absorption, fluorescence and resonance Rayleigh scattering spectra and their application. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2008, 69(3): 956-963
11 Qin M Y, Liu S P, Liu Z F, et al. Resonance Rayleigh scattering spectra, non-linear scattering spectra of tetracaine hydrochloride-erythrosin system and its analytical application. Spectrochimica Acta Part A, 2009, 71(5): 2063-2068
12 Hu X L, Liu S P, Luo H Q, et al. Progress in Research on Analytical Methods of Aminoglycoside Antibiotic. Journal of Analytical Science, 2005, 21(3): 316-321
13 Wang M X, Liu Z F, Hu X L, et al. Study of the Resonance Rayleigh Scattering Spectra produced by the Interaction of Aminoglycosidic Antibiotics with Titan yellow and its Analytical Application. PTCA PartB:Chem.Anal., 2005, 30(2): 304-307
14 Lu Q M, He Y Q, Liu S P, et al. Resonance Rayleigh Scattering Spectra Method for Determination of Methylene Blue with Gold Nanoparticle as Prob. Chemical Journal of Chinese Universities, 2006, 27(5):849-852
15 Zhou Y, Yang G S, Liu Y M. Resonance Rayleigh Scattering Spectra of Interaction of Etimicin Sulfate and Netilmicin Sulfate with Evans Blue and Their Analysis Application. Ludong University Journal Natural Science Edition, 2006, 22(4): 321-325
16 Wang F, Liu Z F, Liu S P. Study on the Interaction between Three Anthracycline Anticancer Drugs and Congo Red by Absorption,Fluorescence and Resonance Rayleigh Scattering Spectra. Acta Chinaca Sinica, 2005, 63(21): 1991-1998
17 Liu S P, Hu X L, Liu Z F. Study on the resonance Rayleigh scattering spectra and resonance non-linear spectra of congo red-amikacin system and its analytical application. Science in China Series B: Chemistry, 2006, 49(6): 507-516
18 Li S D, Meng J H, Li M Q, et al. Determination of chlorophenol environmental estrogens by resonance right-scattering. Chinese Journal of Analysis Laboratory, 2007, 26(10): 34-36
19 Hao X L, Li N B, Luo H Q. Determination of dextran sulfate sodium with crystal violet by triple-wavelength overlapping resonance Rayleigh scattering. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2009, 71(5): 1673-1677
20 Wei X Q, Liu Z F, Liu S P. Resonance Rayleigh Scattering Spectra of Tetracycline Antibiotics-Sodium Tungstate-Ethyl Violet System and Their Analytical Application. Acta Chinaca Sinica, 2006, 64(6): 521-526
21 Luo H Q, Li N B, Liu S P. Resonance Rayleigh scattering study of interaction of hyaluronic acid with ethyl violet dye and its analytical application. Biosensors and Bioeletronics, 2006, 21(7): 1186-1194
22 Ma Y, Li N B, Luo H Q. Novel and sensitive methods for the determination of dopamine based on the resonance Rayleigh scattering, second-order scattering and frequency doubling scattering quenching effects. Spectrochimica Acta Part A , 2009, 73(4): 747-751
23 Liu S P, Zhang Z Y, Hu X L, et al. Resonance Rayleigh Scattering Spectra of the Interaction between Some Basic Phenazine Dyes and Heparin. Chinese Journal of Analytical Chemistry, 2005, 33(7) : 989-992
24 Guo X Q. Resonance rayleigh scattering method for the determinaion of heparin with methyl red. Chemical Research and Application, 2006, 18(10): 1242-1244
25 Chen H L, Luo H Q, Liu S P, et al. Determination of Sodium Hyaluronate with Victoria Blue B by Resonance Rayleigh Scattering Method. ChineseJournal of Spectroscopy Laborator, 2005, 22(3): 547-550
26 Chen H L, Luo H Q, Liu S P, et al. Determination of Sodium Hyaluronate with Night Blue by Resonance Rayleigh Scattering Method. Jounal of Analytical Science, 2005, 2l(3): 304-306
27 Hu QD, Jiang B, Li KY. Resonance light scattering method for determination of the trace heparin sodium with Nile Blue A sulphate as probe. Acta academiae medicinae zunyi, 2008, 31(3): 225-230
28 Heng Y Y, Jiang Z L, Liang A H. A new Spectral Method for the Determination of Cationic Surfactant Based on the Resonance Scattering Effect of AgI2- Association Particles. Spectroscopy and Spectral Analysis, 2006, 26(10): 1888-1890
29 Yan J, Liu Z F, Liu S P. Resonance Rayleigh Scattering Method for the Determination of Quercetin with Hg(Ⅱ)-Quercetin Chelate. Chinese Journal of Analytical Chemistry, 2007, 35(1): 123-126
30 Peng J D, Liu S P, Liu Z F. Resonance Rayleigh scattering spectrum for the chelate of anthanum(III) with sodium tanshinon IIA silate and its analytical application. Science in China Series B: Chemistry, 2006, 49(5): 423-429
31 Wei X Q, Liu Z F, Liu S P. Resonance Rayleigh scattering spectra of tetracycline antibiotic–Cu (II)–titan yellow systems and their applications in analytical chemistry. Analytical and Bioanalytical Chemistry, 2006, 385(6): 1039-1044
32 Fu S H, Liu Z F, Liu S P, et al. Study on the resonance Rayleigh scattering, second-order scattering and frequency doubling scattering spectra of the interactions of palladium(II)–ceftriaxone chelate with anionic surfactants and their analytical applications. Talanta, 2008, 75(2): 528-535
33 Fu S H, Liu Z F, Liu S P, et al. Study on the resonance Rayleigh scattering spectra of the interactions of palladium (II)–cephalosporins chelates with 4,5-dibromofluorescein and their analytical applications. Analytica Chimica Acta, 2007, 599(2): 271-278
34 Duan H, Liu Z F, Liu S P, et al. 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. Talanta, 2008, 75(5): 1253-1259
35 Xi C X, Liu Z F, Kong L, et al. Effects of Interaction of Folic Acid with Uranium (VI) and Basic Triphenylmethane Dyes on Resonance Rayleigh Scattering Spectra and Their Analytical Applications. Analytica Chimica Acta, 2008, 613(1): 83-90
36 Liu S P, He Y Q, Liu Z F, et al. Resonance Rayleigh scattering spectral method for the determination of raloxifene using gold nanoparticle as a probe. Analytica Chimica Acta, 2007, 598(2): 304-311
37 Liu S P, Yang Z, Liu Z F. Resonance Rayleigh scattering study on the interaction of gold nanoparticles with berberine hydrochloride and its analytical application. Analytica Chimica Acta, 2006, 572(2): 283-289
38 He Y Q, Liu S P, Liu Z F et al. Resonance Rayleigh Scattering Spectral Method for the Determination of Kanamycin with Gold Nanoparticle as Probe. Acta Chinaca Sinica, 2005, 63(11): 997-1002
39 Lu Q M,, Liu Z F, Liu S P. Resonance Rayleigh Scattering Method for the Determination of Some Anthracycline Anticancer Drugs with Gold Nanoparticle as Probe. Acta Chinaca Sinica, 2007, 65(9): 821-828
40 Wang N, Dong Z Z, Xu S K, et al. Resonance Rayleigh Scattering Spectral Method for the Determination of Procaine Hydrochloride with Nanogold as Probe. Chinese Journal of Analytical Chemistry, 2008, 36(7): 995-998
41 Wang Q, Liu Z F, Liu S P. Resonance Rayleigh Scatter ing Spectra Method for the Determination of Anthracycline Anticancer Drugs with CdS Nanoparticles as Probe. Chemical Journal of Chinese Universities, 2007, 28(5): 837-842
42 Liu Z W, Liu S P, Wang L. Resonance Rayleigh scattering and resonance non-linear scattering method for the determination of aminoglycoside antibiotics with water solubility CdS quantum dots as probe. Spectrochimica Acta Part A, 2009, 74(1): 36-41
43 Liu S P, Luo H Q, Xu H. Resonance Rayleigh scattering study of interaction of heparin with some cationic surfactants and their analytical application. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2005, 61(5): 861-867
44 Liu S P, Wang F, Liu Z F, et al. Resonance Rayleigh scattering spectra for studying the interaction of anthracycline antineoplastic antibiotics with some anionic surfactants and their analytical applications. Analytica Chimica Acta, 2007, 601(1): 101-107
45 Xiao X L, Wang Y S, Chen Z M, et al. Resonance light scattering method for the determination of anionic surfactant with acridine orange. Spectrochimica Acta Part A: Molecular and Biomolecular pectroscopy, 2008, 71(2): 398-402
46 Jiang Z L, Huang W X. Determination of Trace Gentamycin by Resonance Scattering Spectral Method. Journal of Sichuan NormalUniversity, 2008, 31(1):118-121
47 Yang Q L, Lu Q M, Liu Z F, et al. Resonance Rayleigh scattering spectra of ion-association nanoparticles of [Co(4-[(5-Chloro-2-pyridyl) azo]-1, 3-diaminobenzene)2]2+-sodium dodecyl benzene sulfonate system and its analytical application. Analytica Chimica Acta, 2009, 632(1):115-121
48 Li N B, Luo H Q, Liu S P. A new method for the determination of the critical micelle concentration of Triton X-100 in the absence and presence ofβ-cyclodextrin by resonance Rayleigh scattering technology. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy, 2004, 60(8-9): 1811-1815
49 Li N B, Luo H Q, Liu S P. Resonance Rayleigh scattering study of the inclusion complexation of chloramphenicol withβ-cyclodextrin. Analysis of Phosphorus in Environmental and Agricultural Samples, 2005, 66(2): 495-500
50 Peng J D, Liu S P, Liu Z F. Interaction between Chloroauric Acid and Berberine Hydrochloride Investigated by Resonance Rayleigh Scattering Spectrum and its Analytical Appl ications. Acta Chinaca Sinica, 2005,63(8): 745-751
51 Wang F, Liu Z F, Liu S P, et al. Determination of Mitoxantrone via Ammonium Molybdate Using High Sensitive Resonance Rayleigh Scattering Method. Chemical Journal of Chinese Universities, 2006, 27(8): 1459-1461
52 Li H X, Wang W H, Jiang Y. Determination of Trace Zoledronic Acid by Resonance Rayleigh Scattering Method. Chinese Journal of Pharmaceuticals, 2008, 39(12):930-932
53 Wen G Q, Liang A H, Wu B L, et al. Antimonphosphomolybdate Blue-anogold Resonance Scattering Spectral Method for Determination of Ascorbic Acid. Journal of Guangxi Normal University:Natural Science Edition, 2008, 26(4): 95-98
54 Liang L N, Ge G H, Do C Z. Determination of sulfonamides using resonance light scattering method. Chinese Journal ofHealth Laboratory Technology, 2008, 18(8): 1561-1562
55 Wang F, Peng J D, Liu L M. A reversed-phase high performance liquid chromatography coupled with resonance Rayleigh scattering detection for the determination of four tetracycline antibiotics. analytica chimica acta, 2008, 630(1): 101-106
56 Nan H J, Liu Z F, Liu S P. Resonance Rayleigh Scattering Spectra of Self-aggregation for Bile Salts in Acidic Media and Their Analytical Application. Acta Chinaca Sinica, 2006, 64(12): 1253-1259