Ionic liquid based dispersive liquid-liquid microextraction of aromatic amines in water samples

In this work, a new microextraction method termed ionic liquid based dispersive liquid-liquid microextraction （IL-DLLME） was demonstrated for the extraction of 2-methylaniline, 4-chloroaniline, 1-naphthylamine and 4-aminobiphenyl in aqueous matrices. After extraction the ionic liquid （IL） phase was injected directly into the high performance liquid chromatography （HPLC） system for determination. Some parameters that might affect the extraction efficiency were optimized. Under the optimum conditions, good linear relationship, sensitivity and reproducibility were obtained. The limits of detection （LOD, S/N = 3） for the four analytes were in the range of 0.45-2.6 μg L^-1. The relative standard deviations （R.S.D., n = 6） were in the range of 6.2-9.8%. This method was applied for the analysis of the real water samples. The recoveries ranged from 93.4 to 106.4%. The main advantages of the method are high speed, high recovery, good repeatability and volatile organic solvent-free.

Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

A novel method for the determination of five carbamate pesticides （metolcarb, carbofuran, carbaryl, isoprocard and diethofencard） in water samples was developed by dispersive liquid-liquid microextraction （DLLME） coupled with high performance liquid chromatography-diode array detector （HPLC-DAD）. Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results. Under the optimum conditions for the method, the calibration curve was linear in the concentration range from 5 to 1000 ng mL^-1 for all the five carbamate pesticides, with the correlation coefficients （r^2） varying from 0.9984 to 0.9994. Good enrichment factors were achieved ranging from 80 to 177- fold, depending on the compound. The limits of detection （LODs） （S/N = 3） were ranged from 0.1 to 0.5 ng mL^-1. The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

Dispersive liquid-liquid microextraction,an effective tool for the determination of synthetic cannabinoids in oral fluid by liquid chromatography-tandem mass spectrometry

In the present work,dispersive liquid-liquid microextraction(DLLME)was used to extract six synthetic cannabinoids(JWH-018,JWH-019,JWH-073,JWH-200,or WIN 55,225,JWH-250,and AM-694)from oral fluids.A rapid baseline separation of the analytes was achieved on a bidentate octadecyl silica hydride phase(Cogent Bidentate C18;4.6 mm×250 mm,4μm)maintained at 37℃,by eluting in isocratic conditions(water:acetonitrile(25:75,V/V)).Detection was performed using positive electrospray ionization-tandem mass spectrometry.The parameters affecting DLLME(pH and ionic strength of the aqueous phase,type and volume of the extractant and dispersive solvent,vortex and centrifugation time)were optimized for maximizing yields.In particular,using 0.5 mL of oral fluid,acetonitrile(1 mL),was identified as the best option,both as a solvent to precipitate proteins and as a dispersing solvent in the DLLME procedure.To select an extraction solvent,a low transition temperature mixture(LTTM;composed of sesamol and chlorine chloride with a molar ratio of 1:3)and dichloromethane were compared;the latter(100μL)was proved to be a better extractant,with recoveries ranging from 73%to 101%by vortexing for 2 min.The method was validated according to the guidelines of Food and Drug Administration bioanalytical methods:intra-day and inter-day precisions ranged between 4%and 18%depending on the spike level and analyte;limits of detection spanned from 2 to 18 ng/mL;matrixmatched calibration curves were characterized by determination coefficients greater than 0.9914.Finally,the extraction procedure was compared with previous methods and with innovative techniques,presenting superior reliability,rapidity,simplicity,inexpensiveness,and efficiency.

Dispersive Liquid-liquid Microextraction Combined with High-performance Liquid Chromatography for the Determination of Clozapine and Chlorpromazine in Urine

A simple method has been proposed for the determination of clozapine （CLZ） and chlorpromazine （CPZ） in human urine by dispersive liquid-liquid microextraction （DLLME） in combination with high-performance liquid chromatography-ultraviolet detector （HPLC-UV）. All important variables influencing the extraction efficiency, such as pH, types of the extraction solvent and the disperser solvent and their volume, ionic strength and centrifugation time were investigated and optimized. Under the optimal conditions, the limit of detection （LODs） and quantification （LOQs） of the method were 13 and 39 ng/mL for CLZ, and 2 and 6 ng/mL for CPZ, respectively. The relative standard deviations （RSDs） of the targets were less than 5.1% （C=0.100 μg/mL, n=9）. Good linear behaviors over the tested concentration ranges were obtained with the values of R20.999 for the targets. The absolute extraction efficiencies of CLZ and CPZ from the spiked blank urine samples were 98.3% and 97.8%, respectively. The applicability of the technique was validated by analyzing urine samples and the mean recoveries for spiked urine samples ranged from 93.3% to 105.0%. The method was successfully applied for the determination of CLZ and CPZ in real human urine.

Determination of Amitraz in the Honey Samples by Dispersive Liquid-Liquid Microextraction Followed by Gas Chromatography—Flame Ionization Detection

Dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography–flame ionization detection (GC-FID), as a simple, rapid and efficient method, was developed for the determination of amitraz in honey samples. This method involves the use of an appropriate mixture of the extraction and disperser solvents for the formation of a cloudy solution in 5.0 mL aqueous sample containing amitraz. After extraction, phase separation was performed by centrifugation and the concentrated amitraz in the sedimented phase was determined by gas chromatography—flame ionization detection (GC-FID). Some important parameters such as the type and volume of extraction and disperser solvents, and the effect of pH and salt on the extraction recovery of amitraz were investigated. Under the optimum conditions (13 μL of carbon tetrachloride as an extraction solvent, 1 mL of acetonitrile as a disperser solvent, no salt addition and pH 6) preconcentration factor and the extraction recovery were 955 and 95.5%, respectively. The linear range was 0.01 - 1.0 mg?kg–1 and the limit of detection was 0.0015 mg?kg–1. The relative standard deviation (RSD, n = 4) for 0.1 mg?kg–1 of amitraz was 3.2%. The recoveries of amitraz from honey samples at the spiking levels of 0.1 mg?kg-1 were 78.8 and 98.2%. The results indicated that DLLME is an efficient technique for the extraction of amitraz in honey samples.

Utilization of Dispersive Liquid-Liquid Microextraction Coupled with HPLC-UV as a Sensitive and Efficient Method for the Extraction and Determination of Oleanolic Acid and Ursolic Acid in Chinese Medicinal Herbs

Isomeric triterpenic acids of oleanolic acid (OA) and ursolic acid (UA) both have very low ultraviolet absorption and always exist in the same plant, so the separation and simultaneous determination of them have been a difficult task. In this study, a sensitive method combining dispersive liquid-liquid microextraction (DLLME) with HPLC-UV was developed for the extraction and determination of OA and UA in traditional Chinese medicinal herbs (CMHs). Variables influencing DLLME such as type and volume of extraction solvent, volume of dispersive solvent, ionic strength, aqueous phase pH, extraction time, centrifugation speed and time, and sample volume were investigated and optimized. Under the optimum conditions, both OA and UA attained favorable extraction efficiencies with enrichment factors 1378 and 933, respectively. The linear dynamic ranges of 0.07 - 30.4 μg?mL–1 for OA and 0.08 - 33.6 μg?mL–1 for UA were obtained with square correlation coefficients of 0.9963. The detection limits of OA and UA were both 0.02 μg?mL–1. The method recoveries ranged between 88.2% - 116.2% for OA and 85.7% - 108.2% for UA with the RSDs (n = 5) lower than 8.6%. The proposed method was successfully applied to concentrate and simultaneously determine these two triterpenic acids in Hedyotis diffusa and Eriobotrya japonica samples.

Determination of Cobalt in Food, Environmental and Water Samples with Preconcentration by Dispersive Liquid-Liquid Microextraction

A new method for the determination of cobalt was developed by dispersive liquid-liquid microextraction preconcentra-tion and flame atomic absorption spectrometry. In the proposed approach, 1,5-bis(di-2-pyridyl) methylene thiocarbohydrazide (DPTH) was used as a chelating agent, and chloroform and ethanol were selected as extraction and dispersive solvents. Some factors influencing the extraction efficiency of cobalt and its subsequent determination, including extraction and dispersive solvent type and volume, pH of sample solution, concentration of the chelating agent, and extraction time, were studied and optimized. Under the optimum conditions, a preconcentration factor of 8 was reached. The detection limit for cobalt was 12.4 ng?mL–1, and the relative standard deviation (RSD) was 3.42% (n = 7, c = 100 ng?mL–1). The method was successfully applied to the determination of cobalt in food, environmental and water samples.

Evaluation of Response Surface Methodology in Dispersive Liquid-Liquid Microextraction for Lead Determination Using Ionic Liquids

This paper describes a dispersive liquid–liquid microextraction (DLLME) procedure using room temperature ionic liquids (RTILs) coupled with flame atomic absorption spectrometry detection with microsample intro-duction system capable of quantifying trace amounts of lead. In the proposed approach, ammonium pyr-rolidine dithiocarbamate (APDC) was used as a chelating agent and 1-hexyl-3-methylimmidazolium bis (trifluormethylsulfonyl)imid as an extraction solvent was dissolved in acetone as the disperser solvent. The binary solution was then rapidly injected by a syringe into the water sample containing Pb2+ complex. Some factors influencing the extraction efficiency of Pb2+ and its subsequent determination, including extraction and dispersive solvent type, pH of sample solution, concentration of the chelating agent and salt effect were inspected by a full factorial design to identify important parameters and their interactions. Next, a central composite design was applied to obtain the optimum points of the important parameters. Under the optimum conditions, the limit of detection (LOD) was 0.2 μg/L. The relative standard deviation (R.S.D) was 1.4% for 5 μg/L of Pb2+ (n = 7). The relative recovery of lead in seawater, blood, tomato and black tea samples was measured.

A novel method for the determination of trace copper in cereals by dispersive liquid-liquid microextraction based on solidification of floating organic drop coupled with flame atomic absorption spectrometry

A novel,simple,rapid,efficient and environment-friendly method for the determination of trace copper in cereal samples was developed by using dispersive liquid-liquid microextraction based on solidification of floating organic drop（DLLME-SFO） followed by flame atomic absorption spectrometry.In the DLLME-SFO,copper was complexed with 8-hydroxy quinoline and extracted into a small volume of 1-dodecanol,which is of low density,low toxicity and proper melting point near room temperature. The experimental parameters affecting the extraction efficiency were investigated and optimized.Under the optimum conditions, the calibration graph exhibited linearity over the range of 0.5—500 ng/mL with the correlation coefficient（r） of 0.9996.The enrichment factor was 122 and the limit of detection was 0.1 ng/mL.The method was applied to the determination of copper in the complex matrix samples such as rice and millet with the recoveries for the spiked samples at 5.0 and 10.0 u,g/g falling in the range of 92.0-98.0%and the relative standard deviation of 3.9-5.7%.

Optimization and Application of Liquid Chromatography Determination of Dispersive Liquid-liquid Microextraction Purified Astaxanthin in Shrimp Waste

A new molecularly imprinted solid-phase extraction（MISPE） monolithic cartridge was synthesized, and MISPE-DLLME（DLLME=dispersive liquid-liquid microextraction） was developed for purification of astaxanthin in shrimp waste. The eluent（methanol） from MISPE was used as the dispersive solvent in subsequent DLLME for further purifying and enriching the analyte prior to high-performance liquid chromatography（HPLC） analysis. The mobile phase was methanol-acetonitrile-water-dichloromethane（85：5：5：5, volume ratio）, flow rate was 0.7 mL/min and UV wavelength was 476 nm. Under optimal conditions, good linearity was obtained in a range of 0.2--200.0 lug/mL（r2=0.9998） with a limit of detection（LOD） of 0.08 Hg/mL, and the extraction recoveries at three spiked levels ranged from 88.3%--92.5% with a relative standard deviation（RSD） less than 4.3%. Moreover, the mean contents of astaxanthin in the three batches of shrimp waste were 95.9, 85.4 and 77.2 μg/g, respectively. This method combining the advantages of MISPE and DLLME results in high selectivity and low cost, which was applied to determining the astaxanthin level in shrimp waste samples.

Dispersive Liquid-liquid Microextraction for Simultaneous Determination of Six Parabens in Aqueous Cosmetics

A simple and rapid sample preparation method of dispersive liquid-liquid microextraction（DLLME） was applied in the simultaneous determination of six parabens in the aqueous cosmetics. The analysis was performed on gas chromatography coupled with a flame ionization detection（GC-FID）. The mixed solution containing 30 μL of chloroform（extraction solvent） and 300 μL of tetrahydrofuran（dispersive solvent） was rapidly injected into the sample solution for the purpose of microextraction. After that, the solution mentioned above was centrifuged at 4000 r/min for 10 min, and then the organic sediment phase was detected by GC-FID. The effects of experimental parameters, such as the extraction solvent and the volume of it, and the dispersive solvent and the volume of it, on the yield of the extraction were studied in detail. Under the optimum conditions, the enrichment factors of the target analytes range from 87 to 214. Linearity ranges are 0.05-10.0μg/mL for methylparaben and 0.025--5.0 μg/mL for the other five parabens. The relative standard deviations（RSDs） are lower than 8.2%（n=6）. The proposed method was applied to the analysis of six parabens in eleven aqueous cosmetics. The recoveries of the target analytes in the spiked real samples are in the range of 81.0%-103%.

Orthogonal array optimization of ionic liquid based dispersive liquid-liquid microextraction for toxic anilines in foods

A simple and rapid method of ionic liquid based dispersive liquid-liquid microextraction(DLLME) combining with high performance liquid chromatography(HPLC) was developed for the analysis of four toxic anilines in flour steamed bread and maize steamed bread.Several possible influential factors such as the type of ionic liquid and disperser solvent,extraction time,sample pH,ionic strength and the volume of ionic liquid and disperser solvent were optimized using single factor experiments and orthogonal array design(OAD) with OA 25(5 4) matrix.Analysis of variance(ANOVA) and percent contribution(PC) were used to investigate the significance of the factors of OAD.Sample pH and ionic strength are statistically demonstrated two chief factors.Under the optimum condition,the method exhibits a good linearity(r 2 > 0.99) over the studied range(50-1000 ng g 1) for anilines.The extraction factors and recoveries for the anilines in two kinds of steamed breads ranged between 34.1%-73.3% and 44.3%-95.3%,respectively.The limit of detections(LODs) and limit of quantitations(LOQs) ranged between 10-15 ng g 1 and 30-45 ng g-1.

Determination of Vanadyl Porphyrins by Liquid-liquid Microextraction and Nano-baskets of p-tert-Calix[4]arene Bearing Di-[N-(X)sulfonye Carboxamide] and Di-(1-propoxy) in Ortho-cone Conformation

Dispersive liquid-liquid microextraction technique was introducd to remove the centrifuging step and conduct inclusion microextraction of charged porphyrins by nano-baskets. For nano-baskets of p-tert-calix[4]arene bearing di-[N-（X）sulfonyl carboxamide] and di-（1-propoxy） in ortho-cone conformation was synthesized and used. The related parameters including ligand concentration, the volume of water disperser, salt effect, and extraction time were optimized. The linear range, detection limit（S/N=3） and precision（RSD, n=6） were determined to be 0.2―50, 0.07 μg/L and 5.3%, respectively. The results reveal that the new approach is competitive analytical tool and an alternative of the traditional methods in the crude oil and related systems.

Liquid-liquid Microextraction Based on Solidification of Floating Organic Drops Coupled with Gas Chromatography for Analyzing Trace Benzene, Toluene and Xylene in Water Samples

A new liquid-liquid microextraction method based on the solidification of floating organic drops coupled with gas chromatography was developed for the determination of trace benzene, toluene and xylene（BTX） in water samples. In the microextraction procedure, a microdrop of n-decanol was delivered to the surface of the analytes’ solution, and stirred for a desired time. Following the absolute extraction, the sample vial was cooled in an ice bath for 10 min. The solidified n-decanol was then transferred into a plastic tube and melted naturally; and 1 μL of it was injected into gas chromatography for analysis. Factors relevant to the extraction efficiency were studied and optimized. The optimal experimental conditions were： 15 μL of n-decanol as extractive solvent, 30 mL of solution containing analytes, no salt, the stirring rate 400 r/min, the extraction temperature 30 °C, and the extraction time 30 min. Under those optimized conditions, the detection limit（LOD） of analytes was in a range of 0.05―0.10 ng/mL by the developed method. A good linearity（r0.99） in a calibration range of 0.01―100 μg/mL was obtained. The recoveries of the real samples at different spiked levels of BTX were in the range from 92.2% to 103.4%.

分散液液微萃取-高效液相测定食用植物油中对羟基肉桂酸和橙皮素含量

通过分散液液微萃取-高效液相(DLLME-HPLC)建立一种同时测定食用植物油中对羟基肉桂酸和橙皮素的分析方法。以正己烷为分散剂,以含体积分数5%氨水(500μL)和体积分数10%乙腈的水溶液为萃取剂萃取样品,以体积分数0.3%三氟乙酸溶液-乙腈为流动相,在柱温25℃条件下进行梯度洗脱,萃取液放置过夜后再进行测定。结果表明:样品峰面积的相对标准偏差均小于3%,对羟基肉桂酸和橙皮素在各自质量浓度范围内的线性相关系数均大于0.99,检测限分别为8.7、6.2 ng/g,定量限分别为26.1、18.5 ng/g,回收率分别为93.1%~103.7%、100.5%~111.1%。

分散液液微萃取结合气相色谱-四极杆-飞行时间质谱法测定橄榄油中180种农药残留

建立了分散液液微萃取(DLLME)结合气相色谱-四极杆-飞行时间质谱(GC-QTOF MS)快速测定橄榄油中180种农药残留的分析方法,并考察了乙腈酸化浓度、水相体积、萃取剂种类的影响。通过分散液液微萃取进行样品前处理,经含2%甲酸的乙腈溶液提取后,上清液与萃取剂快速注入水相,取待测物供仪器分析,采用基质标准溶液进行定量。结果表明:87.8%农药的线性范围为0.02~2µg/mL,12.2%农药的线性范围为0.1~2µg/mL,相关系数(r^(2))均大于0.99;所有待测农药的检出限为0.002~0.020 mg/kg,定量下限为0.007~0.067 mg/kg,其中有135种农药的定量下限达0.007 mg/kg,23种农药的定量下限达0.017 mg/kg,占总数量的88%;在0.02、0.1、0.2 mg/kg 3个加标水平下,回收率为70%~120%的农药占全部待测农药的76.3%,相对标准偏差(RSD)小于10%的农药占总数的94.4%以上。应用该方法对10份市售橄榄油样品进行检测,共检出5种农药,检出量为0.0057~0.0427 mg/kg。该方法操作简单、快速,精密度及准确度良好,试剂消耗少且绿色环保,能够满足橄榄油中多种农药残留检测的需求。

基于低共熔溶剂的分散液液微萃取法测定茶饮料中68种农药残留

为同时定量检测茶饮料中68种农药的多残留情况,本研究利用低共熔溶剂(DES)作为萃取剂,结合分散液液微萃取(DLLME)技术对目标农药进行萃取富集,再通过高效液相色谱-串联质谱法(HPLCMS/MS)检测目标农药残留量。结果表明,通过DES提取和涡旋离心处理可有效去除茶饮料中的杂质,并将目标农药富集。茶饮料中68种目标农药在1~500 ng·mL^(-1)范围内线性关系良好,线性关系系数均高于0.996,定量限为0.2~10μg·kg-1,3个添加水平(10、50、100μg·kg^(-1))的平均回收率为59.1%~113.7%,相对标准偏差均<10%。综上,本方法具有快速简便、绿色环保、性能良好等优势,可满足茶饮料中农药多残留的检测要求。本研究结果为茶饮料中农药残留检测提供了技术支持。

六方氮化硼应用于样品前处理的研究进展

近几年,六方氮化硼由于孔隙率高、比表面积大、机械强度高、化学稳定性好、亲水性好、生物相容性好等优点,作为前处理材料获得了广泛关注,已被用于生物化学、食品安全、环境污染等领域的样品前处理,是一种理想的吸附剂。目前已开发了多种基于六方氮化硼材料作为吸附剂的样品前处理技术,包括固相萃取、分散固相萃取、固相微萃取、磁性固相萃取、管内固相微萃取、分散固相微萃取等,可实现多氯联苯、罗丹明B、黄酮类化合物、多环芳烃等分析物的萃取富集。综述了六方氮化硼材料在样品前处理领域的应用进展,并对今后的发展方向进行了展望。

Determination of multiple drugs of abuse in human urine using dispersive liquid–liquid microextraction and capillary electrophoresis with PDA detection

A new method was developed for pre-concentration and determination of multiple drugs of abuse in human urine using dispersive liquid–liquid microextraction(DLLME)and capillary electrophoresis(CE)with photodiode array detection.The method was based on the formation of tiny droplets of an organic extractant in the prepared sample solution using water-immiscible organic solvent(chloroform)dissolved in water-miscible organic dispersive solvent(isopropyl alcohol).The organic phase,which extracted eight drugs of abuse from the prepared urine solution,was separated by centrifugation.The sedimented phase was transferred into a small volume CE auto-sampler vial with 10μL of 1%HCl methanol solution and evaporated to dryness.The residue was reconstituted in lidocaine hydrochloride(internal standard)aqueous solution and introduced by electrokinetic injection into CE.Under the optimum conditions,acceptable linear relationship was observed in the range of 3.0–500 ng/mL with the correlation coefficient(r)of 0.9982–0.9994 for spiked urine samples.The limit of detection(LOD)(S/N=3)was estimated to be 1.0 ng/mL.A recovery of 75.7%–90.6%was obtained for spiked samples.The mean relative error(MRE)was within±7.0%and the relative standard deviation(RSD)was less than 6.9%.The proposed DLLME-CE procedure offers an alternative analytical approach for the sensitive detection of drugs of abuse in real urine samples.

扩大分散液液微萃取法测定水中20种有机氯和菊酯农药残留

本研究建立了扩大液液分散微萃取测定饮用水中20种有机氯和菊酯农药残留的方法。通过扩大分散液液萃取(dispersive liquid-liquid microextraction,DLLME)提取水中农药残留,对DLLME萃取相关的影响因素进行了优化:40 mL水样用0.4 mL三氯甲烷与4 mL乙腈作为萃取剂和分散剂,萃取离心后取出用氮吹吹干,100μL正己烷溶剂置换后进气相色谱电子捕获检测器(GC-ECD)检测。结果显示,水中20种有机氯及拟除虫菊酯农药的线性分别在0.002~0.10μg·mL-1和0.01~0.20μg·mL-1的浓度范围内良好,相关系数r>0.998,方法检出限为0.001~0.002μg·L-1,方法富集倍数为168~206,高、中、低3水平浓度加标回收率在83.30%~116.70%,相对标准偏差(RSD)为0.84%~9.87%。采用所建立的方法对135个农村饮用水样品进行检测,结果均远低于限量值。该方法灵敏度、准确性高,稳定性好,批量分析时更具有可操作性,适用于饮用水中有机氯及拟除虫菊酯的定性定量分析。