固相萃取-高效液相色谱法同时测定牛奶中残留的9种磺胺类药物

建立了同时测定牛奶中残留的9种磺胺类药物的固相萃取-高效液相色谱分析方法。牛奶样品经磷酸盐缓冲液稀释后高速离心去除脂肪,过C18小柱,用水淋洗,甲醇洗脱,洗脱液经氮气吹干后用乙酸乙酯溶解,并过氨基固相萃取小柱净化,用正己烷及水淋洗,以甲醇-乙腈-水（含1%乙酸）(体积比为1∶1∶8)洗脱,洗脱液用于高效液相色谱分析。采用Inertsil ODS-3 C18柱分离,以水-乙酸和甲醇-乙腈为流动相进行梯度洗脱,二极管阵列检测器检测,外标法定量。9种磺胺类药物标准曲线的线性回归系数均在 0.9999 以上,线性范围为25～5000 μg/L,检出限为1.7～2.8 μg/L,定量限为5.7～9.2 μg/L。在10,20,40 μg/L 添加水平下的添加回收率为72.1%~88.3%,相对标准偏差为2.3%～5.0%。该方法具有快速、灵敏的特点,符合现行兽药残留分析的要求。     

固相萃取/高效液相色谱法测定化妆品中5种抗组胺药物残留

建立了固相萃取/高效液相色谱(SPE/HPLC)测定化妆品中5种抗组胺药物(多西拉敏、曲吡那敏、溴苯那敏、苯海拉明、氯苯沙明)残留的分析方法。试样经三氯乙酸溶液超声提取,PCX柱净化后,以甲醇-磷酸盐缓冲溶液为流动相,经C18柱分离后进行HPLC检测。5种抗组胺药物在5.0～100 mg/L范围内均呈良好的线性关系,线性系数均大于0.999。在5.0、10.0、25.0 mg/kg 3个加标水平下的平均回收率为92%～108%,相对标准偏差(RSD,n=6)为2.1%～4.2%,检出限为0.5～1.0 mg/L。该方法灵敏度高、重现性好、定量准确。     

固相萃取-高效液相色谱法测定地表水中的苯并三唑和苯并噻唑

建立了固相萃取-高效液相色谱分析地表水中苯并噻唑、苯并三唑、5-甲基-苯并三唑、5-氯-苯并三唑及5,6-二甲基-苯并三唑的方法。地表水样品采用HLB固相萃取柱富集净化后,在甲醇-水(55:45, v/v)流动相中用ZORBAX SB-C18色谱柱(250 mm×4.6 mm, 5 μm)分离,紫外检测,外标法定量。结果表明,5种目标化合物在0.064～80 mg/L范围内均呈良好的线性关系,线性相关系数均大于0.9999,仪器检出限为1.9～3.2 μg/L。空白自来水样中的加标回收率为87.8%～125.6%,相对标准偏差(n=3)为0.4%～9.4%。应用该方法测定了大连自来水及辽河入海口水样,在辽河入海口地表水中检出苯并噻唑、苯并三唑、5-甲基-苯并三唑、5-氯-苯并三唑。     

基于十八烷基三甲基溴化铵修饰的磁性粒子在线磁性固相萃取-高效液相色谱法测定水样中磺酰脲类农药

采用溶胶-凝胶法制备表面修饰了十八烷基三甲基溴化铵的磁性粒子作为萃取剂，研制了一种在线磁性固相萃取（on-line MSPE）装置，建立了on-line MSPE与高效液相色谱联用测定水样中两种磺酰脲类农药（氯磺隆、苄嘧磺隆）的方法。实验优化了在线磁性固相萃取条件并进行方法学考察，证明该方法具有良好的线性关系（两种目标物的线性相关系数均≥ 0.9997）和较低的检出限（两种目标物的检出限分别为0.32和1.12 μg/L）。将此法用于3种环境水样中两种磺酰脲类农药的检测，水样中均检出氯磺隆，均未检出苄嘧磺隆。两种目标物加标回收率为70.0%~113.4%。该方法高效、简便，在分离富集环境水样中磺酰脲类农药方面有一定的应用前景。     

Polyamide as an efficient sorbent for simultaneous interference-free determination of three Sudan dyes in saffron and urine using high-performance liquid chromatography-ultra violet detection北大核心CSCD

With polyamide( PA)as an efficient sorbent for solid phase extraction( SPE)of Sudan dyes II,III and Red 7B from saffron and urine,their determination by HPLC was performed. The optimum conditions for SPE were achieved using 7 mL methanol/water( 1:9,v/v,pH 7)as the washing solvent and 3 mL tetrahydrofu-ran for elution. Good clean-up and high( above 90%)recoveries were observed for all the analytes. The opti-mized mobile phase composition for HPLC analysis of these compounds was methanol-water( 70:30,v/v). The SPE parameters,such as the maximum loading capacity and breakthrough volume,were also determined for each analyte. The limits of detection( LODs),limits of quantification( LOQs),linear ranges and recoveries for the analytes were 4. 6-6. 6 μg/L,13. 0-19. 8 μg/L,13. 0-5 000 μg/L( r2> 0. 99)and 92. 5% -113. 4%,respec-tively. The precisions( RSDs)of the overall analytical procedure,estimated by five replicate measurements for Sudan II,III and Red 7B in saffron and urine samples were 2. 3%,1. 8% and 3. 6%,respectively. The developed method is simple and successful in the application to the determination of Sudan dyes in saffron and urine sam-ples with HPLC coupled with UV detection.     

Sensitive Analysis of Idarubicin in Human Urine and Plasma by Liquid Chromatography with Fluorescence Detection: An Application in Drug Monitoring

A new approach for the sensitive, robust and rapid determination of idarubicin (IDA) in human plasma and urine samples based on liquid chromatography with fluorescence detection (LC-FL) was developed. Satisfactory chromatographic separation of the analyte after solid-phase extraction (SPE) was performed on a Discovery HS C18 analytical column using a mixture of acetonitrile and 0.1% formic acid in water as the mobile phase in isocratic mode. IDA and daunorubicin hydrochloride used as an internal standard (I.S.) were monitored at the excitation and emission wavelengths of 487 and 547 nm, respectively. The method was validated according to the FDA and ICH guidelines. The linearity was confirmed in the range of 0.1–50 ng/mL and 0.25–200 ng/mL, while the limit of detection (LOD) was 0.05 and 0.125 ng/mL in plasma and urine samples, respectively. The developed LC-FL method was successfully applied for drug determinations in human plasma and urine after oral administration of IDA at a dose of 10 mg to a patient with highly advanced alveolar rhabdomyosarcoma (RMA). Moreover, the potential exposure to IDA present in both fluids for healthcare workers and the caregivers of patients has been evaluated. The present LC-FL method can be a useful tool in pharmacokinetic and clinical investigations, in the monitoring of chemotherapy containing IDA, as well as for sensitive and reliable IDA quantitation in biological fluids.     

高效液相色谱法同时测定蔬菜水果中的12种农药残留

建立了同时测定蔬菜水果中12种农药残留的反相高效液相色谱分析方法。将样品捣碎,用乙酸乙酯超声提取,经Florisil固相萃取柱净化、正己烷-二氯甲烷(体积比为1∶1)洗脱、氮气吹干、甲醇溶解并定容后,采用高效液相色谱柱分离、紫外检测,以外标法定量。结果表明：12种农药标准曲线的线性相关系数范围为0.9985~0.9999;检测限为0.14~2.65 ng;在水果中的平均加标回收率为62.2%~118.2%,相对标准偏差(RSD)为0.56%~11.8%;在蔬菜中的平均加标回收率为52.1%~124.6%,RSD为0.89%~18.4%。用所建立的方法成功地测定了白菜、莲白、黄瓜、苹果、梨等40份样品中的农药残留。方法具有快速、简便、准确、灵敏、重现性较好的特点,适合于蔬菜水果样品中多种微量农药残留的测定。     

固相萃取-高效液相色谱法对罗汉果及其提取物中甲基托布津与多菌灵的同时测定

应用固相萃取及高效液相色谱技术,建立了同时测定罗汉果及其提取物中甲基托布津和多菌灵残留的方法。罗汉果及其提取物样品经乙腈超声提取后,由弗罗里硅土固相萃取小柱净化,以Zorbax extend-C18(150 mm×4.6 mm,5μm)色谱柱为分析柱,乙酸铵水溶液(含乙酸0.5%)-甲醇为流动相,线性梯度淋洗,紫外二极管矩阵检测器检测,波长为270 nm。结果表明,甲基托布津和多菌灵在0.5~15.0 mg.L-1范围内有良好的线性关系,方法的定量下限(S/N=10)分别为0.06、0.1 mg.kg-1,加标回收率为77%~96%,相对标准偏差不大于7.1%。     

分散固相萃取净化/高效液相色谱法测定婴幼儿奶粉与米粉中15种多环芳烃

建立了高效液相色谱-荧光检测法同时测定婴幼儿奶粉和米粉中15种多环芳烃的检测方法。样品经乙腈提取,PSA分散固相萃取净化;乙腈-水梯度洗脱,Waters PAH专用柱分离,荧光检测器检测,外标法定量。在最优条件下,15种多环芳烃均得到有效分离,线性范围为1.0~50μg/L,相关系数均大于0.995,方法检出限(LODs,S/N=3)为0.05~0.3μg/kg,回收率为86.5%~106.8%,精密度(RSD,n=6)为0.7%~7.5%。该方法操作简单、灵敏度高,适用于婴幼儿奶粉和米粉中多环芳烃的检测。     

一种亲水-亲油复合固相萃取填料的制备及其在食品安全检测中的应用

合成了一种以二乙烯苯和N-乙烯吡咯烷酮为单体的高分子聚合物固相萃取填料(DVB-NVP),以6种不同极性的化合物为模型化合物,结合高效液相色谱法(HPLC)对该填料进行了系统的评价,并与传统的C18填料及商品化同类型填料做对比;对填料进行了磺酸化修饰(DVB-NVP-SO₃H),并将合成的填料应用于复杂基质中化合物的分析。结果表明:该填料对不同极性化合物的回收率在95.55%~101.08%之间,优于商品化C18填料,与商品化同类型填料相当。DVB-NVP对于白酒中邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯的分析回收率分别为102.55%、102.99%、102.11%,相对标准偏差分别为2.11%、1.69%、0.79%; DVB-NVP-SO₃H用于对猪肉中的可乐定和赛庚啶进行分析,回收率分别为89.23%和91.42%,相对标准偏差分别为8.21%和8.86%,符合生物样品分析要求。所合成的填料具有普适性,并具有较高的回收率,应用前景广泛。     

沉淀聚合法制备3-吲哚乙酸印迹聚合物微粒及其固相萃取应用

以3-吲哚乙酸(IAA)为模板分子、丙烯酰胺(AA)为功能单体,采用沉淀聚合法制备了IAA印迹聚合物微粒,研究了致孔剂乙腈的用量及IAA的加入量对印迹聚合物结合性能的影响,采用色谱法对其进行评价。结果表明,当乙腈为37.5 m L,IAA为2 mmol(与AA物质的量比为1∶1)时,制得印迹聚合物P7对IAA的亲和力最大(k=4.24),印迹因子(IF)为14.1,其对IAA展示了最显著的特异识别能力。将P7作为固相萃取柱的填料,研究了分子印迹固相萃取IAA的方法,测得绿豆芽样品的加标回收率为90.6%~92.6%。结果表明,以AA为功能单体沉淀聚合法制备的IAA印迹聚合物颗粒适合作为固相萃取柱填料,可实现实际样品中IAA的选择性分离净化。该文提出的采用适当增大模板分子加入量的方法是制备高亲和力与高选择性印迹聚合物的一条新途径。     

Application of carbon nanotubes in extraction and chromatographic analysis: A review

Carbon nanotube (CNT), a well-known carbon-based nanomaterial has drawn much attention in many application fields including chemistry in the last few decades. Many researchers and scientists have shown huge interest to improve the extraction methodologies and adopt their applications in combination with chromatography technique. With respect to this, the exceptional applications of CNTs have been introduced as extraction sorbent due to their excellent inborn physical and chemical properties. In particular, CNTs have consistently been used as adsorbents in various techniques including solid-phase micro-extraction, solid-phase extraction, micro dispersive slid phase extraction, magnetic dispersive solid phase extraction, analytes enrichment, sample fractionation and clean-up as well as support for many derivatization reactions. Many research papers have discussed the successful use of CNTs to overcome the limitations of the extraction techniques due to their excellent sorbent capacity. In addition, considering the clear need to make chromatographic technique more successful, the applications of CNTs have been reported in the literatures in details as stationary and pseudo-stationary phases for the separation and extraction of challenging compounds. Because of the higher thermal and chemical stability, CNTs have been anticipated as stationary phase modifier for chromatographic applications to avoid bleeding of the columns and enable the analysis even at very high temperature (1200 °C). In liquid chromatography CNTs have primarily been used in combination with other packing materials (silica) and sometimes incorporated in a porous polymeric monolith. Therefore, the recent utilizations of CNTs as extraction materials and stationary phases have been illustrated in the current review and a table listing the details applications of CNTs in aforementioned field is provided as well. We believe that the review will help researcher to gain vast knowledge about application of carbon nanotubes in the field of separation chemistry.     

Absolute quantification of superoxide dismutase in cytosol and mitochondria of mice hepatic cells exposed to mercury by a novel metallomic approach

In the last years, the development of new methods for analyzing accurate and precise individual metalloproteins is of increasing importance, since numerous metalloproteins are excellent biomarkers of oxidative stress and diseases. In that way, methods based on the use of post column isotopic dilution analysis (IDA) or enriched protein standards are required to obtain a sufficient degree of accuracy, precision and high limits of detection. This paper reports the identification and absolute quantification of Cu,Zn-superoxide dismutase (Cu,Zn-SOD) in cytosol and mitochondria from mice hepatic cells using a innovative column switching analytical approach. The method consisted of orthogonal chromatographic systems coupled to inductively coupling plasma-mass spectrometry equipped with a octopole reaction systems (ICP-ORS-MS) and UV detectors: size exclusion fractionation (SEC) of the cytosolic and mitochondrial extracts followed by online anion exchange chromatographic (AEC) separation of Cu/Zn containing species. After purification, Cu,Zn-SOD was identified after tryptic digestion by molecular mass spectrometry (MS). The MS/MS spectrum of a doubly charged peptide was used to obtain the sequence of the protein using the MASCOT searching engine. This optimized methodology reduces the time of analysis and avoids the use of sample preconcentration and clean-up procedures, such as cut-off centrifuged filters, solid phase extraction (SPE), precipitation procedures, off-line fractions insolates, etc. In this sense, the method is robust, reliable and fast with typical chromatographic run time less than 20 min. Precision in terms of relative standard deviation (n = 5) is of 3–5% and detection limits is 0.21 ng Cu g⁻¹.     

Analytical techniques for wine analysis: An African perspective; a review

Analytical chemistry is playing an ever-increasingly important role in the global wine industry. Chemical analysis of wine is essential in ensuring product safety and conformity to regulatory laws governing the international market, as well as understanding the fundamental aspects of grape and wine production to improve manufacturing processes. Within this field, advanced instrumental analysis methods have been exploited more extensively in recent years. Important advances in instrumental analytical techniques have also found application in the wine industry. This review aims to highlight the most important developments in the field of instrumental wine and grape analysis in the African context. The focus of this overview is specifically on the application of advanced instrumental techniques, including spectroscopic and chromatographic methods. Recent developments in wine and grape analysis and their application in the African context are highlighted, and future trends are discussed in terms of their potential contribution to the industry.     

Pesticides in water and the performance of the liquid-phase microextraction based techniques. A review

The control of pesticides in surface, drinking and groundwater is nowadays a real necessity. In the European Community, their concentration must comply with the established parametric and environmental quality standards (EQSs). Regarding the new legislation, this article updates the information concerning the monitoring of pesticides and the technical specifications for their measurement in water samples where ultra-sensitive analytical methods are required. For some compounds, like pesticides, there is still a need to improve the performance of the existing methods. High sensitive techniques like gas chromatography tandem mass spectrometry (GC–MS/MS) and liquid chromatography coupled with mass spectrometry (LC–MS) have been developed. However, for most of the substances present at trace and ultra-trace levels the extraction and preconcentration steps are so far essential for their detection. Advances at a micro scale have been made and different types of microextractions are being developed. Liquid-phase microextraction (LPME) is an example. The study of this technique has increased in the last years and some innovations have been recently reported for pesticides water analysis. This article reviews the new developed LPME-based techniques and compares its performance with the analytical specifications established for pesticides water monitoring. The results show that LPME-based techniques can be a promising tool to improve the nowadays performance of methods used in pesticides water control.     

Evolution of dispersive liquid–liquid microextraction method

Dispersive liquid–liquid microextraction (DLLME) has become a very popular environmentally benign sample-preparation technique, because it is fast, inexpensive, easy to operate with a high enrichment factor and consumes low volume of organic solvent. DLLME is a modified solvent extraction method in which acceptor-to-donor phase ratio is greatly reduced compared with other methods. In this review, in order to encourage further development of DLLME, its combination with different analytical techniques such as gas chromatography (GC), high-performance liquid chromatography (HPLC), inductively coupled plasma-optical emission spectrometry (ICP-OES) and electrothermal atomic absorption spectrometry (ET AAS) will be discussed. Also, its applications in conjunction with different extraction techniques such as solid-phase extraction (SPE), solidification of floating organic drop (SFO) and supercritical fluid extraction (SFE) are summarized. This review focuses on the extra steps in sample preparation for application of DLLME in different matrixes such as food, biological fluids and solid samples. Further, the recent developments in DLLME are presented. DLLME does have some limitations, which will also be discussed in detail. Finally, an outlook on the future of the technique will be given.     

Sample preparation methods for subsequent determination of metals and non-metals in crude oil—A review

In this review sample preparation strategies used for crude oil digestion in last ten years are discussed focusing on further metals and non-metals determination. One of the main challenges of proposed methods has been to overcome the difficulty to bring crude oil samples into solution, which should be compatible with analytical techniques used for element determination. On this aspect, this review summarizes the sample preparation methods for metals and non metals determination in crude oil including those based on wet digestion, combustion, emulsification, extraction, sample dilution with organic solvents, among others. Conventional methods related to wet digestion with concentrated acids or combustion are also covered, with special emphasis to closed systems. Trends in sample digestion, such as microwave-assisted digestion using diluted acids combined with high-efficiency decomposition systems are discussed. On the other hand, strategies based on sample dilution in organic solvents and procedures recommended for speciation analysis are reported as well as the use of direct analysis in view of the recent importance for crude oil field. A compilation concerning sample preparation for crude oil provided by official methods as well as certified reference materials available for accuracy evaluation is also presented and discussed.     

Application of HPLC to measure vanadium in environmental,biological and clinical matrices

Vanadate and vanadium compounds exist in many environmental, biological and clinical matrices, and despite the need only limited progress has been made on the analysis of vanadium compounds. The vanadium coordination chemistry of different oxidation states is known, and the result of the characterization and speciation analysis depends on the subsequent chemistry and the methods of analysis. Many studies have used a range of methods for the characterization and determination of metal ions in a variety of materials. One successful technique is high performance liquid chromatography (HPLC) that has been used mainly for measuring total vanadium level and metal speciation. Some cases have been reported where complexes of different oxidation states of vanadium have been separated by HPLC. Specifically reversed phase (RP) HPLC has frequently been used for the measurement of vanadium. Other HPLC methods such as normal phase, anion-exchange, cation-exchange, size exclusion and other RP-HPLC modes such as, ion-pair and micellar have been used to separate selected vanadium compounds. We will present a review that summarizes and critically analyzes the reported methods for analysis of vanadium salts and vanadium compounds in different sample matrices. We will compare various HPLC methods and modes including sample preparation, chelating reagents, mobile phase and detection methods. The comparison will allow us to identify the best analytical HPLC method and mode for measuring vanadium levels and what information such methods provide with regard to speciation and quantitation of the vanadium compounds.     

Speciation and detection of arsenic in aqueous samples: A review of recent progress in non-atomic spectrometric methods

Inorganic arsenic (As) displays extreme toxicity and is a class A human carcinogen. It is of interest to both analytical chemists and environmental scientists. Facile and sensitive determination of As and knowledge of the speciation of forms of As in aqueous samples are vitally important. Nearly every nation has relevant official regulations on permissible limits of drinking water As content. The size of the literature on As is therefore formidable. The heart of this review consists of two tables: one is a compilation of principal official documents and major review articles, including the toxicology and chemistry of As. This includes comprehensive official compendia on As speciation, sample treatment, recommended procedures for the determination of As in specific sample matrices with specific analytical instrument(s), procedures for multi-element (including As) speciation and analysis, and prior comprehensive reviews on arsenic analysis. The second table focuses on the recent literature (2005–2013, the coverage for 2013 is incomplete) on As measurement in aqueous matrices. Recent As speciation and analysis methods based on spectrometric and electrochemical methods, inductively coupled plasma-mass spectrometry, neutron activation analysis and biosensors are summarized. We have deliberately excluded atomic optical spectrometric techniques (atomic absorption, atomic fluorescence, inductively coupled plasma-optical emission spectrometry) not because they are not important (in fact the majority of arsenic determinations are possibly carried out by one of these techniques) but because these methods are sufficiently mature and little meaningful innovation has been made beyond what is in the officially prescribed compendia (which are included) and recent reviews are available.     

Common methods for the chiral determination of amphetamine and related compounds I. Gas, liquid and thin-layer chromatography

This article reviews the most common, useful methods for the chiral determination of amphetamine (AM) and AM-derived designer drugs in different of matrix, including blood, hair, urine, medicaments or standard solutions, taking into consideration articles published in the past 15 years. We consider chromatographic methods (e.g., gas, liquid, high-performance liquid, and thin layer). We describe several types of chiral derivatization reagent, mobile-phase additive and chiral stationary phase commonly used in the chromatographic methods. Tables summarize basic information about conditions (e.g., type of column and mobile phase), detection mode and reference data for each procedure.