无筛板型固相萃取柱的制备及其在食品中苯甲酸的测定研究

结合固相萃取(SPE)盘与含支撑物的SPE柱技术,制备了一种新型的无筛板型固相萃取柱.以C18填料为例,以话梅样品为介质对其中的苯甲酸进行分析,并用传统固相萃取小柱平行比较;将SPE与HPLC-UV结合,考察了填料对简单介质中苯甲酸的最大吸附量及洗脱曲线,研究了新型SPE柱在实际应用中的分离纯化效果.结果表明,新型SPE柱对样品的吸附效果更好,规格为200 mg/3 mL的SPE柱对苯甲酸的吸附量达到0.951 mg,超过了传统柱的吸附量0.908 mg;其洗脱曲线与传统柱几乎重合;苯甲酸在1～100 mg/L浓度范围内线性关系良好, r=0.9999,用此SPE柱纯化后的样品加标回收率和相对误差分别在88.4%～102.3%和1.4%～2.9%之间.     

固相萃取技术在食品痕量残留和污染分析中的应用

食品痕量残留和污染分析中,样品的前处理极为重要,也是其难点所在。由于食品和农产品样品的多样性和复杂性,目前还没有一种前处理技术能够适合所有情况下的所有样品。本文对近年来发展起来的新型固相萃取技术如固相微萃取、搅拌棒吸附萃取、基质固相分散萃取、分子印迹固相萃取、免疫亲和固相萃取、整体柱固相萃取、碳纳米管固相萃取等在食品痕量残留和污染分析中的应用进行了综述,对未来的发展前景作了展望。     

基于磁固相萃取-自动前处理分离和富集动物肝脏中的β-受体激动剂

基于磁固相萃取-自动前处理分离和富集动物肝脏中的β-受体激动剂,建立了动物肝脏中3种β-受体激动剂（沙丁胺醇、克伦特罗和莱克多巴胺）残留的液相色谱-串联质谱（LC-MS/MS）分析方法。样品溶液经提取后,采用磁性阳离子吸附剂（M-MCX）结合自动前处理装置进行净化,使用LC-MS/MS检测,同位素内标法进行定量。结果显示,M-MCX较传统混合阳离子固相萃取（MCX）柱的吸附容量高34%,而且节约了吸附材料。结合自动磁固相萃取装置,30 min内可完成8个样品的净化,方法检出限为0.01～0.1μg/kg,平均回收率为88.2%～110.5%,相对标准偏差为2.9%～10.3%。与传统柱填充式固相萃取法相比,本方法具有操作简单、快速、高效等优点,能够满足动物组织样品前处理的批量、自动化处理的需求。     

亲水性邻苯二甲酸二丁酯分子印迹聚合物的研制及应用

采用溶胶-凝胶技术,制备了邻苯二甲酸二丁酯(DBP)亲水性分子印迹聚合物(HYM IP)。静态吸附和选择性吸附实验表明,聚合物对DBP具有较高的吸附量与良好的特异吸附性。将其作为固相萃取填料,对水相样品中DBP的净化和富集效果优于C18柱。建立了亲水性分子印迹固相萃取结合高效液相色谱法检测化妆水中DBP的方法,检出限为4.46μg/kg,加标回收率在97.8%~98.7%之间,RSD小于2.4%。     

同时亚临界水萃取与固相萃取从河流沉积物中分离有机氯化合物

静态亚临界水萃取中加入固相萃取剂对河流沉积物中4种有机氯化合物(2-氯酚、2,4,6-三氯酚、五氯酚、六氯苯)进行了同时萃取。与离线亚临界水萃取-固相萃取方法相比,分析物的萃取回收率均有提高,且受亚临界水萃取罐冷却程度的影响较小。以活性炭纤维(ACF)为固相萃取剂,在160℃时,0.050 g的ACF和4.0 mL水对0.500 g的加标沉积物样品中的2-氯酚(2-CP),2,4,6-三氯酚(246-TCP),五氯酚(PCP)和六氯苯(HCB)的萃取效率比离线亚临界水萃取-固相萃取的回收率均有所提高,萃取回收率受萃取罐冷却温度影响较小。方法特别适合于高含量的沉积物样品萃取。该方法与气相色谱检测联用,分析了长江镇江段沉积物中4种有机氯化合物的含量,结果与美国环保署(USEPA)标准方法所得的结果吻合。     

加替沙星分子印迹聚合物的制备及其应用

以加替沙星为模板分子,采用溶胶-凝胶分子印迹技术,合成具有分子识别作用的新型有机-无机杂化分子印迹聚合物,对其进行吸附性能研究证明了印迹聚合物对加替沙星的专一吸附性能。以该印迹聚合物为固相萃取材料填充固相萃取柱,优化固相萃取条件,结合超高效液相色谱法,对牛奶样品进行检测。建立了分子印迹固相萃取方法,分离富集并检测牛奶中的加替沙星,其回收率为79.87%,富集倍数为38,高于市售C18柱,具有一定的实际应用价值。     

移液枪头式整体柱直接固相微萃取-高效液相色谱法测定尿液中苯二氮卓类药物

本文采用甲基丙烯酸2-羟乙酯(HEMA)与乙二醇二甲基丙烯酸酯在移液器枪头中共聚制备固相微萃取整体柱，用于直接处理尿液中3种苯二氮卓类药物(BZDs)。实验考察了单体用量、聚合时间及固相微萃取条件对BZDs萃取效率的影响，评价了其吸附性能。当HEMA用量为40 mg,聚合温度60℃时，固相微萃取整体柱对目标物吸附效率达98.9%～100%,且对尿液中杂质的吸附率低于10%。取3 mL尿液样品，无需处理，直接上样至该柱，经4 mL纯净水冲洗，1 mL乙腈洗脱，得到的样品结合高效液相色谱仪分析。方法对3种BZDs在2.5～1 000 ng/mL浓度范围呈现良好线性关系(r=0.999),检出限(S/N=3)和定量限(S/N=10)为0.8～1.5 ng/mL和2.5～5.0 ng/mL,回收率为86.2%～107%。本方法构筑的萃取柱制备简单，能实现对原始尿液的直接、高效萃取，操作便捷。     

固相微萃取新技术

 固相微萃取是基于萃取涂层与样品之间的吸附 /溶解 解吸平衡而建立起来的集进样、萃取、浓缩功能于一体的技术。综述了固相微萃取技术的最新发展动态 ,介绍了管内 (in tube)固相微萃取、新型萃取头以及固相微萃取与其他分析技术的联用情况。     

固相萃取-高效液相色谱法测定水中BPA、NP和OP含量

采用国产新型D4020大孔吸附树脂自制固相萃取柱,研究了柱长、上样速度、样品溶液的pH、盐浓度等因素对壬基酚、辛基酚和双酚A吸附率的影响,确定了最佳固相萃取条件,建立了固相萃取-高效液相色谱测定水中痕量壬基酚、辛基酚和双酚A的分析方法.该法双酚A、壬基酚和辛基酚的检出限分别为0.432 μg/L、0.998 μg/L和1.336 μg/L,回收率为91%～96%,相对标准偏差(RSD)为1.5%～5.6%.方法简便快速、成本低廉,灵敏度高,准确度好,用于实际水样分析,取得满意结果.     

罗丹明B分子印迹固相萃取小柱的研制及应用

研制一种对罗丹明B具有特异性识别性能的分子印迹固相萃取小柱。用沉淀聚合法制备罗丹明B分子印迹聚合物,通过静态平衡吸附实验及固相萃取实验表征其性能,并对市售辣椒样品中的罗丹明B进行测量。罗丹明B模板聚合物的吸附能力明显优于空白聚合物;印迹固相萃取小柱对罗丹明B标准溶液(0.05 mmol/L)一次性萃取率为98.24%,实际样品测量的回收率为90.0%~95.0%,测定结果的相对标准偏差为0.9%~1.7%(n=3)。罗丹明B分子印迹固相萃取小柱选择性好、萃取率高,可应用于食品、化妆品检测等相关领域。     

高效液相色谱法和固相萃取法用于环境中农药残留物分析的研究进展

农药是一类被广泛使用的毒药 ,由于它们在现代农业中的广泛使用及其毒性 ,越来越引起人们对水、食品、农产品以及环境中的农药残留分析的重视 ,高效液相色谱法 (HPLC)和固相萃取法 (SPE)由于其具有分析速度快、灵敏度高的特点 ,特别适合于农药残留物分析 .本文对近年来用于环境中农药残留物的分析和有关的研究进展做了较全面的评述     

Semi-automated disk-type solid-phase extraction method for polychlorinated dibenzo-p-dioxins and dibenzofurans in aqueous samples and its application to natural water

A disk-type solid-phase extraction (SPE) method was used for the extraction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in natural water and tap water. Since this SPE system comprised airtight glass covers with a decompression pump, it enabled continuous extraction with semi-automation. The disk-type SPE method was validated by comparing its recovery rates of spiked internal standards with those of the liquid-liquid extraction (LLE). The recovery ranges of both methods were similar in terms of (13)C-labeled internal standards: 64.3-99.2% for the LLE and 52.4-93.6% for the SPE. For the native spike of 1,3,6,8-tetrachlorinated dibenzo-p-dioxin (TCDD) and octachlorinated dibenzo-p-dioxin (OCDD), the recoveries in the SPE were in the normal range of 77.9-101.1%. However, in the LLE, the recoveries of 1,3,6,8-TCDD decreased significantly. One of the reasons for the low recovery is that the solubility of this congener is high. The semi-automated SPE method was applied to the analysis of different types of water: river water, snow, sea water, raw water for drinking purposes, and tap water. PCDD/F congeners were found in some sea water and snow samples, while their concentrations in the other samples were below the limits of detection (LODs). This SPE system is appropriate for the routine analysis of water samples below 50L.     

Solid-phase extraction versus solid-phase microextraction for the determination of chlorinated paraffins in water using gas chromatography-negative chemical ionisation mass spectrometry

Solid-phase extraction (SPE) and solid-phase microextraction (SPME) were evaluated for the analysis of short-chain chlorinated paraffins (SCCPs) in water samples using gas chromatography coupled to negative chemical ionisation mass spectrometry (GC-NCI-MS). For SPE optimisation, four commercially available SPE cartridges were tested and several SPE parameters, such as the elution solvent, elution volume and breakthrough volume were studied. The best results were obtained with Varian Bond Elut-C18. In order to achieve a high selectivity in the determination of SCCPs, GC-NCI-MS was used. Quality parameters of the optimised SPE and SPME procedures were determined, and the best results were obtained for the SPE/GC-NCI-MS method with LODs of 5 and 20 ng l(-1) for tap and river water, respectively. This method was successfully applied to the analysis of SCCPs in river water samples at concentrations below the microg l(-1) level.     

Determination of estrogens and their metabolites in water using C30 SPE-LC-MS

Triacontyl bonded silica (C(30)) material was applied as solid-phase extraction (SPE) sorbent and an SPE-LC-MS method was established for the determination of eight estrogens and their metabolites in water samples. Compared to commercial C(18) SPE cartridge, the performance of C(30) was evaluated in various important SPE conditions, such as sorbent mass, elution solvent and its volume, loading flow rate, and sample loading volume. The results showed a superior performance of C(30)-C(18) by the shorter treatment time and fewer required elution solvent. In the optimum conditions, the results showed good recoveries (80.5-109.4%), excellent linear relationships (0.02-1 ng/mL, except 2-MeO-E(2)), high precisions (lower than 10.0% RSD for both low and high spiked concentration), and low LODs (1-16 ng/L). Method validation using C(30) packed cartridge was also testified with spiked real water samples, including tap water and river water. Satisfy results demonstrated the feasibility of C(30) SPE to the analysis for real environmental waters.     

Simple and rapid extraction, separation, and detection of alkaloids in beverages

Implementation of an uncomplicated SPE process for the rapid extraction and preconcentration of the alkaloids, colchicine, strychnine, aconitine, and nicotine, from water, apple juice, and nonfat milk samples is presented. When coupled to analysis via micellar EKC (MEKC), the total analysis time per sample was less than 15 min for the water and juice samples and less than 20 min for the milk. The SPE process allowed for anywhere from a three to a fourteen-fold improvement in the LOD for each alkaloid when compared to detecting the alkaloids in a nontreated water sample matrix. Following SPE, the LODs for colchicine, strychnine, and nicotine were sufficient to meet levels from 150 to 5000 times more dilute than the LD(50) for a 50 kg individual drinking 12 oz of a contaminated beverage. Aconitine, on the other hand, was detected at approximately the LD(50) level. The percent recoveries for the SPE ranged from 37% to as high as 99%. Nicotine attained the highest recovery efficiencies, followed by colchicine, and finally, aconitine and strychnine, which were nearly identical. The greatest recovery efficiencies were achieved from apple juice and water, whereas nonfat milk yielded the lowest.     

固相萃取柱上衍生气相色谱-质谱法测定水中烷基酚

以烷基酚(APs)主要降解产物辛基酚(4-t-OP)、壬基酚(4-n-NP)为研究对象,建立了固相萃取(SPE)柱上衍生化、气相色谱-质谱(GC-MS)法测定水中APs的分析方法。以C18柱为固相萃取柱、N,O-(三甲基硅)三氟乙酰胺(BSTFA)为硅烷化试剂,设计五因素四水平正交实验L16(45),对衍生化影响因素、衍生化溶剂、衍生化时间以及SPE主要影响因素pH值、盐度和洗脱剂进行优化;在优化条件下,方法的回收率(高于80%)和重现性(RSD低于10%)结果令人满意,4-t-OP和4-n-NP的仪器检出限分别为3.35ng/L和6.38ng/L。采用建立的方法,回收率略高于传统的SPE萃取衍生法,具有有机溶剂用量少,方法简单快速、灵敏度高的特点,适用于河水和海水中痕量烷基酚的快速测定。     

Simultaneous determination of endocrine disrupting phenolic compounds and steroids in water by solid-phase extraction-gas chromatography-mass spectrometry

A solid-phase extraction (SPE)-gas chromatography (GC)-mass spectrometry (MS) analytical method for the simultaneous separation and determination of endocrine disrupting chemicals (EDCs) from water samples is described in detail. Important and contrasting EDCs including estrone, 17beta-estradiol, 17beta-ethynylestradiol, 16beta-hydroxyestrone, 4-nonylphenol, bisphenol A and 4-tert-octylphenol were selected as the target compounds. The SPE technique, followed by the derivatisation with bis (trimethylsilyl) trifluoroacetamide was used for the extraction recoveries of target compounds from water samples. A number of parameters that may affect the recovery of EDCs, such as the type of SPE cartridges, eluents, as well as water properties including pH value, and concentration of salts and humic substances were investigated. It is shown that the Oasis cartridges produced the best recoveries of target EDCs while ethyl acetate was efficient in eluting EDCs from SPE cartridges. The recovery of some EDCs was enhanced by the addition of salt, but reduced by the increase in pH value and humic acid concentration. The optimised method was further verified by performing spiking experiments in natural river water and seawater matrices, with good recovery and reproducibility for all the selected compounds. The established method was successfully applied to environmental water samples from East and West Sussex, UK, for the determination of the target EDCs.     

Fifty years of solid-phase extraction in water analysis--historical development and overview

The use of an appropriate sample handling technique is a must in an analysis of organic micropollutants in water. The efforts to use a solid phase for the recovery of analytes from a water matrix prior to their detection have a long history. Since the first experimental trials using activated carbon filters that were performed 50 years ago, solid-phase extraction (SPE) has become an established sample preparation technique. The initial experimental applications of SPE resulted in widespread use of this technique in current water analysis and also to adoption of SPE into standardized analytical methods. During the decades of its evolution, chromatographers became aware of the advantages of SPE and, despite many innovations that appeared in the last decade, new SPE developments are still expected in the future. A brief overview of 50 years of the history of the use of SPE in organic trace analysis of water is given in presented paper.     

Comparison of solvent extraction and solid-phase extraction for the determination of organochlorine pesticide residues in water.

Solid-phase extraction (SPE) of organochlorine pesticide residues from environmental water samples was evaluated using octadecyl (C18)-bonded porous silica. The efficiency of SPE of these pesticide residues from reagent water samples at 1-5 micrograms dm-3 levels was compared with those obtained by solvent extraction with hexane and Freon TF (trichlorotrifluoroethane). Average recoveries exceeding 80% for these organochlorine pesticides were obtained via the SPE method using small cartridges containing 100 mg of 40 microns C18-bonded porous silica. The average recovery by solvent extraction with hexane and Freon TF exceeded 90% in both instances. It was concluded that the recoveries and precision for the SPE of organochlorine pesticides were poorer than those for the solvent extraction method. Organochlorine pesticide residue levels in environmental water samples from two major rivers flowing through predominantly rice-growing areas were monitored by gas chromatography using the solvent extraction method with hexane. Exceptionally high levels of organochlorine pesticide residues such as BHC, DDT, heptachlor, endosulfan and dieldrin were found in these water samples.