Determination of 4-Hydroxyphenyllactic Acid in Human Urine by Magnetic Solid-Phase Extraction and High-Performance Anion-Exchange Chromatography with Fluorescence Detection

A novel, simple, rapid, and accurate method is reported for the determination of 4-hydroxyphenyllactic acid in human urine by high-performance anion-exchange chromatography with fluorescence detection and magnetic solid-phase extraction. The separation and pretreatment conditions for urine were optimized. The isolation of 4-hydroxyphenyllactic acid was performed with isocratic elution with 4?mmol?L^?1 sodium hydroxide at 0.45?mL min^?1. Fluorescence detection was performed at an excitation wavelength of 277?nm and an emission wavelength of 340?nm. Under the optimized conditions, the linear dynamic range and the limit of detection for 4-hydroxyphenyllactic acid were 0.05–10 and 0.020?mg?L^?1, respectively. The recovery for the analyte was from 86.5 to 105.5%, with relative standard derivations less than 4.12%. The method was used for the determination of 4-hydroxyphenyllactic acid in human urine. Statistically significant differences in the 4-hydroxyphenyllactic acid concentration in urine were obtained between healthy control and individuals with breast cancer.     

固相萃取-毛细管气相色谱法测定中草药中13种有机氯农药的残留量

建立了中草药中有机氯类农药残留量的固相萃取-毛细管气相色谱(SPE-CGC)分析方法。对丹参、黄芩、射干、白芍、白芷、天南星、牛蒡子、知母、桔梗共9种中草药中六六六的4种异构体、滴滴涕的4种异构体、七氯、艾氏剂、环氧七氯、狄氏剂、异狄氏剂共13种有机氯农药的残留量进行了测定。以丙酮-正己烷混合物作提取剂,采用超声波提取样品,然后用Florisil固相萃取小柱快速净化提取物。采用SPB-5弹性石英毛细管气相色谱柱分离样品,电化学检测器进行检测。13种农药的峰面积与其质量浓度均有良好的线性关系,相关系数均大于0.998。最小检测量为0.064～0.61 μg/L;样品的加标回收率为87.3%～102.3%(相对标准偏差为1.3%～6.8%)。该法简便快速、灵敏准确,具有广泛的应用前景。     

Facile Fabrication of Diatomite-Supported ZIF-8 Composite for Solid-Phase Extraction of Benzodiazepines in Urine Samples Prior to High-Performance Liquid Chromatography

A novel diatomite-supported zeolitic imidazolate framework-8 sorbent (ZIF-8@Dt-COOH) was in situ fabricated and developed for solid-phase extraction of three benzodiazepines (triazolam, midazolam and diazepam) in urine followed by high-performance liquid chromatography. ZIF-8@Dt-COOH was easily prepared by coating ZIF-8 on the surface of Dt-COOH and characterized by Fourier transform infrared spectra, X-ray powder diffractometry and scanning electron microscopy. Compared with bare Dt-COOH, the extraction efficiency of ZIF-8@Dt-COOH for the target was significantly increased from 20.1–39.0% to 100%. Main extraction parameters, including ionic strength and pH of solution, loading volume, washing solution, elution solvent and elution volume, were optimized in detail. Under optimum conditions, the developed method gave linearity of three BZDs in 2–500 ng/mL (r ≥ 0.9995). Limits of detection (S/N = 3), and limits of quantification (S/N = 10) were 0.3–0.4 ng/mL and 1.0–1.3 ng/mL, respectively. In addition, the average recoveries at three spiked levels (5, 10 and 20 ng/mL) varied from 80.0% to 98.7%, with the intra-day and inter-day precisions of 1.4–5.2% and 1.5–8.2%, respectively. The proposed method provided an effective purification performance and gave the enrichment factors of 24.0–29.6. The proposed method was successfully employed for the accurate and sensitive determination of benzodiazepines in urine.     

A New Molecularly Imprinted Polymer for Solid-phase Extraction of Cotinine from Human Urine

A molecularly imprinted polymer （MIP）, prepared around a cotinine template, has been synthesized. The feasibility of using the polymer for solid-phase extraction （SPE） of cotinine from biological samples has been investigated. The results show that cotinine can be quantitatively retained and eluted from the polymer. Experiments with human urine samples indicate that clean target analyte is obtained for HPLC with UV detection using the protocol.     

固相萃取结合毛细管气相色谱法分析血浆中5种氨基甲酸酯

报道了用Ｘ－５树脂固相萃取分离纯化、气相色谱法（ＧＣ）定性和定量同时测定血浆中５种氨基甲酸酯杀虫剂的方法。含药物的血浆可直接用萃取柱处理,用甲醇－乙酸乙酯作为洗脱剂。不同药物的回收率在８０．０％～９２．５％之间,最低检测浓度为１ｍｇ／Ｌ,检测灵敏度及线性范围（０～４０ｍｇ／Ｌ）适合临床中毒急救分析的需要。     

固相萃取-毛细管气相色谱法测定人参制品中19种有机氯农药的残留量

毛细管气相色谱法;有机氯农药;固相萃取;人参制品     

固相萃取和气相-质谱法测定主流烟气中苯并[a]芘的研究

 提出了一种用于测定主流烟气中痕量苯并 [a]芘的方法。以甲醇 正庚烷萃取体系初步处理主流烟气中的总粒相物 (TPM) ,接着以KOH甲醇溶液数毫升洗涤正庚烷萃取液 ,再将正庚烷萃取液适当浓缩后经过酸化的硅胶固相萃取小柱 ,流出液用N2 吹干后以乙酸乙酯 2 0 0 μL定容 ,对苯并 [a]芘进行选择离子监测方式下的气相 质谱法定量测定。方法的分离效果及重现性好 ,可用于复杂体系中痕量组分苯并 [a]芘的定量测定。     

固相萃取-气相色谱/质谱法分析水果和蔬菜中残留的嘧菌酯

建立了多种水果和蔬菜中嘧菌酯残留的气相色谱/质谱分析方法。首先用乙酸乙酯-环己烷(体积比为1∶1)对样品中的嘧菌酯进行超声波提取,经硅胶固相萃取小柱对样品提取液进行净化、富集,采用气相色谱/质谱法以选择离子监测模式(m/z 344,372,388,403定性,m/z 344定量)进行检测。实验结果表明,嘧菌酯在0.01～1.0 mg/kg浓度范围内呈线性,其相关系数r>0.99。在低、中、高3个添加水平,嘧菌酯的回收率为85.2%～98.2%,相对标准偏差为5.8%～21.5%。方法的检测限不大于0.01 mg/kg,定量限不大于0.05 mg/kg。     

固相萃取-气相色谱/质谱联用测定环境水中噻唑硫磷农药残留

建立了对环境水中噻唑硫磷农药残留进行检测的离线固相萃取-气相色谱/质谱联用(SPE-GC/MS)的方法。固相萃取采用C18柱,用甲醇洗脱;GC/MS采用选择离子监测模式。该方法具有较高的灵敏度和选择性,对环境水中噻唑硫磷的最低检测质量浓度为56.4 ng/L(S/N=3);在0.282~141 μg/L时,响应值与样品浓度呈良好的线性关系;加样回收率大于85.5%,相对标准偏差（RSD）小于4.42%。方法操作简便、快速,可用于施用噻唑硫磷后环境水中痕量农药的监测。     

Response Surface Optimization of Dispersive Solid-Phase Extraction Combined with HPLC for the Rapid Analysis of Multiple Coccidiostats in Feed

Since antimicrobials were banned as feed additives, coccidiostats with favorable anticoccidial action and growth promotion have been widely used in the breeding industry. The monitoring of coccidiostats in feed is necessary, while the current methods based on mass-spectrometer analysis have limited applicability and matrix effects could interfere with the results. Accordingly, in the present paper, a rapid analytical strategy for the simultaneous determination of six synthetic coccidiostats in feed using high-performance liquid chromatography coupled with diode-array detection was developed. Coccidiostats in chicken feeds were extracted with the trichloroacetic acid–acetonitrile solution. The cleanup was performed by dispersive solid-phase extraction after the optimization of the response surface methodology. The method exhibited good linearity for target coccidiostats within the range of 0.05~20 µg/mL. Recoveries for six compounds in fortified feed samples were from 67.2% to 107.2% with relative standard deviations less than 9.6%. The limit of detection was 0.2~0.3 mg/kg. The successful application of the method in commercial feed verified that it is effective and sensitive for the rapid determination of multiple coccidiostats in chicken feeds.     

Determination of Aromatic Amines in Urine using Extraction and Chromatographic Analysis: A Minireview

Abstract

Aromatic amines found in tobacco smoke are carcinogenic to humans. There are no doubts that they cause of cancers in the lungs, bladder, kidneys, pancreas, esophagus, larynx, pharynx, and oral cavities associated with public health. Therefore, monitoring, control, and awareness toward the smoking effects are important subjects to be conveyed. Thus, rapid, sensitive, simple and accurate analytical methods for the identification of aromatic amines and their metabolites are required to provide a clear and complete visualization for the occurrence of aromatic amines by investigating the urine of smokers and nonsmokers. This comprehensive review serves to give an overview of the previous and recent studies about the analytical trends for the determination of urinary aromatic amines. This review covers the sampling methodologies and sample preparation techniques such as solvent extraction, solid phase extraction, magnetic solid phase extraction, and solid phase microextraction couple with different separation methods including gas chromatography and liquid chromatography. To add more value to this review paper, the advantages, disadvantages, challenges, and the future prospects of these methods are discussed as well. This review is hopefully beneficial for researchers to access and monitor the level of potentially carcinogenic aromatic amines in human urine.     

固相微萃取和同时蒸馏萃取与气相色谱/质谱法分析芥末膏制品的风味成分

采用固相微萃取和同时蒸馏萃取技术分离芥末膏制品的挥发性成分，用ＧＣ／ＭＳ分析鉴定，对总离子流色谱的峰面积进行归一化定量。共鉴定了２２种化学成分，占总峰面积的９９％以上，其中含硫化合物８种，含氮化物３种，含氧化合物１１种。最主要的成分是异硫氰酸烯丙酯，其次是丙二醇，其他主要成分还有对羟基二叔丁基甲苯、油酸、９－十六烯酸、棕榈酸、５－甲基甲氢噻吩－２酮、二烯丙基二硫化物，异硫氰酸苯乙酯等。比较了各种萃取技术对分析结果的影响，同时蒸馏萃取法不能分离出水溶性成分如丙二醇等，在固相微萃取方法中，聚二甲基硅氧烷纤维头对极性较强的成分的取样效果不理想，聚乙二醇－二乙烯苯纤维头顶空取样的萃取效果最好。     

Combination of Sea Sand Disruption Method and Ion-Pair Solid-Phase Extraction for Effective Isolation and Purification of Chlorogenic Acid from Plants Prior to the HPLC Determination

Chlorogenic acid (CQA) is one of phenolics commonly found in higher plants, possessing numerous health-promoting effects on humans. Unfortunately, it is easily degraded/transformed into other substances during extraction. Therefore, its reliable analysis requires a special approach that does not involve high temperatures. This paper presents a very simple method of CQA isolation using the sea sand disruption method with subsequent purification of the extract using the ion-pair solid-phase extraction process, followed by HPLC–DAD detection. It was found that control of the ion pairing reagent concentration and sample pH is crucial to improve purification, and that the best results, with recovery exceeding 98%, were obtained for 0.05 M tetrabutylammonium bisulfate at pH 7 when the ion pairs were formed directly in the extract and eluted from the C18 sorbent using an acidified methanol–water mixture. The practical potential of the developed procedure was verified by using it for CQA isolation from different plants. The approach represents one of the contemporary analytical trends and current advances in the solid phase extraction, in which several sorption extraction techniques are combined to ensure high-quality analytical results.     

A New Procedure for the Extraction of Unconjugated Steroids from Plasma and Urine

Abstract

A procedure is described for the extraction of nanogram quantities of steroids from plasma and urine. The method involves saturation of a diluted plasma or urine sample with ammonium carbonate and extraction with an organic solvent. The application of this method to the analysis of cortisol and unconjugated estriol in plasma and to the analysis of unconjugated steroids in the urine of the newborn infant is described.     

固相萃取-高效液相色谱法测定蔬菜水果中的氨基甲酸酯杀虫剂及其代谢物残留

采用乙腈提取-固相萃取浓缩 高效液相色谱分离 柱后衍生-荧光检测法测定了蔬菜 水果中8种氨基甲酸酯类杀虫剂及其代谢物残留量。采用加标法(添加水平为0.10,0.50mg/kg)测定了氨基甲酸酯杀虫剂及其代谢物的回收率,其平均回收率为70%-120%,相对标准偏差(RSD)小于20%(n=3),最低检出限范围为0.0042-0.0106 mg/kg。该方法的测定结果满足多残留农残的检测要求。     

A Comparison of Solid-Phase Extraction Techniques for Assay of Drugs in Aqueous and Human Plasma Samples

Abstract

Six commercially available solid adsorbent materials were evaluated for their applicability as effective tools for extraction of drugs from aqueous and human plasma samples. Ten model compounds were selected as representative of the acidic, basic, amphoteric, hydrophobic, and hydrophilic drug classes. Percent recovery and precision data for each model drug on each solid adsorbent material were calculated using spiked water and/or plasma samples. Octadecylsilane materials were the best overall choice for extraction of the different chemical classes of drugs from water and plasma samples, giving both highest recovery and best reproducibility data for a majority of the drugs studied. It was also determined that good extractability for basic drugs could be obtained using either XAD-2, Clin-eht® or cyanopropyl columns. In addition, XAD-2 gave good recoveries of amphoteric compounds and Clin-elut® was good for hydrophobic drugs.     

The use of graphene as an adsorbent for the extraction of permethrin from urine

A nonmagnetically modified graphene was employed as the adsorbent in the dispersive solid-phase extraction (d-SPE) for the isolation of permethrin from urine samples that were further analyzed by the HPLC/UV method. The following four key factors influencing permethrin extraction efficacy were studied: 1. graphene suspension volume, 2. adsorption time, 3. desorbent (acetonitrile) volume, and 4. desorption time. Under the optimized conditions of the d-SPE (graphene) procedure the main validation parameters of the analytical method were determined as follows: extraction recovery (%) 71.2, 63.5, and 95.4; intra-day repeatability (%RSD) 14.7, 11.5, and 15.2; inter-day repeatability (%RSD) 16.2, 11.9, and 19.1 for 0.125, 0.250, and 1.0 µg/mL permethrin concentration levels, respectively. Limits of detection (LOD) and quantification (LOQ) were 0.045 and 0.125 µg mL^?1, respectively. The proposed method may be useful for the monitoring of permethrin in human urine taken from people dressed in uniforms disinfected with this pesticide.     

Micro Salting-Out Assisted Matrix Solid-Phase Dispersion: A Simple and Fast Sample Preparation Method for the Analysis of Bisphenol Contaminants in Bee Pollen

In the present work, a novel sample preparation method, micro salting-out assisted matrix solid-phase dispersion (μ-SOA-MSPD), was developed for the determination of bisphenol A (BPA) and bisphenol B (BPB) contaminants in bee pollen. The proposed method was designed to combine two classical sample preparation methodologies, matrix solid-phase dispersion (MSPD) and homogenous liquid-liquid extraction (HLLE), to simplify and speed-up the preparation process. Parameters of μ-SOA-MSPD were systematically investigated, and results indicated the significant effect of salt and ACN-H₂O extractant on the signal response of analytes. In addition, excellent clean-up ability in removing matrix components was observed when primary secondary amine (PSA) sorbent was introduced into the blending operation. The developed method was fully validated, and the limits of detection for BPA and BPB were 20 μg/kg and 30 μg/kg, respectively. Average recoveries and precisions were ranged from 83.03% to 94.64% and 1.76% to 5.45%, respectively. This is the first report on the analysis of bisphenol contaminants in bee pollen sample, and also on the combination of MSPD and HLLE. The present method might provide a new strategy for simple and fast sample preparation of solid and semi-solid samples.     

超临界CO_2萃取姜油的组成研究

用超临界ＣＯ＿２萃取法从冷冻干燥的姜中萃取出姜油。通过薄层色谱、柱色谱、气相色谱以及色谱。质谱联用等手段进行组成剖析,并与水汽蒸馏法获得的姜油进行一些比较。结果表明超临界ＣＯ＿２萃取法不仅能获得姜中的挥发油组分,而且能同时获得各种姜辣素成分。此法萃取的姜油目前已鉴定出的组分有９７个,占色谱峰总面积的９３％左右。     

Bamboo Charcoal as Solid-Phase Extraction Adsorbent for the Determination of Organophosphorus Pesticides in Water Samples by High-Performance Liquid Chromatography

In this paper, bamboo charcoal was successfully developed for the solid-phase extraction adsorbent for the determination of six organophosphorus pesticides in water samples. After the bamboo charcoal was pretreated and packed in the solid-phase extraction cartridge, the organophosphorus pesticides in water samples were carried out the solid-phase extraction. To establish a perfect solid-phase extraction procedure, the experimental conditions including the eluent, eluent volume, pH of the sample, flow rate of the sample, and loading volume of the sample were all investigated. When 100 mL water samples in the pH range of 6–7 were loaded with the flow rate of 2.5 mL · min^?1 and then eluted with 10 mL acetonitrile, the proposed extraction method was validated by the recovery, correlation coefficient (R²), repeatability (RSD, n = 7) and LODs, which were 69.6–93.4%, 0.9982–0.9998, 2.9–5.6%, and 0.08–1.04 µg · L^?1, respectively. Furthermore, the analysis of the tap, snow, and river water samples demonstrated the feasibility of the proposed SPE method for real water samples. Based on the aforementioned factors, it could be concluded that bamboo charcoal was a good solid-phase extraction adsorbent, and this proposed solid-phase extraction method was suitable for the effective enrichment and determination of the organophosphorus pesticides in water samples.