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1.
A novel infrared‐assisted extraction coupled to headspace solid‐phase microextraction followed by gas chromatography with mass spectrometry method has been developed for the rapid determination of the volatile components in tobacco. The optimal extraction conditions for maximizing the extraction efficiency were as follows: 65 μm polydimethylsiloxane‐divinylbenzene fiber, extraction time of 20 min, infrared power of 175 W, and distance between the infrared lamp and the headspace vial of 2 cm. Under the optimum conditions, 50 components were found to exist in all ten tobacco samples from different geographical origins. Compared with conventional water‐bath heating and nonheating extraction methods, the extraction efficiency of infrared‐assisted extraction was greatly improved. Furthermore, multivariate analysis including principal component analysis, hierarchical cluster analysis, and similarity analysis were performed to evaluate the chemical information of these samples and divided them into three classifications, including rich, moderate, and fresh flavors. The above‐mentioned classification results were consistent with the sensory evaluation, which was pivotal and meaningful for tobacco discrimination. As a simple, fast, cost‐effective, and highly efficient method, the infrared‐assisted extraction coupled to headspace solid‐phase microextraction technique is powerful and promising for distinguishing the geographical origins of the tobacco samples coupled to suitable chemometrics.  相似文献   

2.
An ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction was first employed to determine the volatile components in tobacco samples. The method combined the advantages of ultrasound, microwave, and headspace solid‐phase microextraction. The extraction, separation, and enrichment were performed in a single step, which could greatly simplify the operation and reduce the whole pretreatment time. In the developed method, several experimental parameters, such as fiber type, ultrasound power, and irradiation time, were optimized to improve sampling efficiency. Under the optimal conditions, there were 37, 36, 34, and 36 components identified in tobacco from Guizhou, Hunan, Yunnan, and Zimbabwe, respectively, including esters, heterocycles, alkanes, ketones, terpenoids, acids, phenols, and alcohols. The compound types were roughly the same while the contents were varied from different origins due to the disparity of their growing conditions, such as soil, water, and climate. In addition, the ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction method was compared with the microwave‐assisted extraction coupled to headspace solid‐phase microextraction and headspace solid‐phase microextraction methods. More types of volatile components were obtained by using the ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction method, moreover, the contents were high. The results indicated that the ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction technique was a simple, time‐saving and highly efficient approach, which was especially suitable for analysis of the volatile components in tobacco.  相似文献   

3.
An ultrasound‐assisted magnetic solid‐phase extraction procedure with chloromethylated polystyrene‐coated Fe3O4 nanospheres as magnetic adsorbents has been developed to determine eight phthalate esters (bis(4‐methyl‐2‐pentyl) phthalate, dipentyl phthalate, dihexyl phthalate, benzyl butyl phthalate, bis(2‐butoxyethyl) phthalate, dicyclohexyl phthalate, di‐n‐octyl phthalate, and dinonyl phthalate) simultaneously in beverage samples, in combination with gas chromatography coupled to tandem mass spectrometry for the first time. Several factors related to magnetic solid‐phase extraction efficiencies, such as amount of adsorbent, extracting time, ionic strength, and desorption conditions were investigated. The enrichment factors of the method for the eight analytes were over 2482. A good linearity was observed in the range of 10–500 ng/L for bis(2‐butoxyethyl) phthalate and 2–500 ng/L for the other phthalate esters with correlation coefficients ranging from 0.9980 to 0.9998. The limits of detection and quantification for the eight phthalate esters were in the range of 0.20–2.90 and 0.67–9.67 ng/L, respectively. The mean recoveries at three spiked levels were 75.8–117.7%, the coefficients of variations were <11.6%. The proposed method was demonstrated to be a simple and efficient technique for the trace analysis of the phthalate esters in beverage samples.  相似文献   

4.
An LC‐MS/MS method developed for simultaneous analysis of 54 veterinary drug residues of six families in pork meat samples, including sulfanilamide, nitroimidazoles, quinolones, macrolide antibiotics, lincosamides, and praziquantel. The pork meat sample was prepared by extraction with ACN, and clean‐up on a C18 SPE cartridge. The sample was separated on a C8 column and eluted with ACN, methanol, and formic acid. The MS/MS detector is operated in the multiple reaction monitoring mode, acquiring two specific precursor‐product ion transitions per target compound. The method showed excellent linearity (R2 ≥ 0.99) and high precision (relative SD, RSD ≤ 19.8%) for all compounds. The method quantification limits of 54 veterinary drug residues were in the range of 0.3–3.0 μg/kg. Recoveries for most analytes based on matrix‐matched calibration in matrices were 20.9–121.0%. This method has been successfully applied for analysis of more than 100 pork meat samples from the local market; five of the 54 drugs were detected.  相似文献   

5.
Pesticides, widely applied in agriculture, can produce a variety of transformation products and their continuous use causes deleterious effects to ecosystem. Efficient and sensitive analytical techniques for enrichment and analysis of pesticides samples are highly required. Compared with other extraction methods, solid‐phase micro extraction is a solvent free, cost effective, robust, versatile, and high throughput sample preparation technique, especially for the analysis of pesticides from complicated matrices. Coupling of solid‐phase micro extraction with gas chromatography and mass spectrometry and liquid chromatography–mass spectrometry has been extensively applied in pesticide analysis. On the other hand, in recent years, combination of fast separation using solid‐phase micro extraction and rapid detection using ambient mass spectrometry is providing highly efficient pesticide screening. This article summarizes the applications of solid‐phase micro extraction coupled to mass spectrometry for pesticides analysis.  相似文献   

6.
A method for the simultaneous extraction of four tricyclic antidepressants from human plasma samples using pipette tip SPE with MonoTip C(18) tips is presented. Human plasma (0.1 mL) containing four tricyclic antidepressants (amitriptyline, amoxapine, imipramine, and trimipramine) and an internal standard (IS), protriptyline, was mixed with 0.4 mL of distilled water and 100 microL 1 M NaOH solution. After centrifugation of the mixture, the supernatant was extracted to the C(18) phase of the tip by 20 repeated aspirating/dispensing cycles using a manual micropipettor. The analytes retained in the tip were eluted with methanol by five repeated aspirating/dispensing cycles. Without evaporation and reconstitution, the eluate was directly injected into a gas chromatograph injector and detected by a mass spectrometer with SIM in the positive-ion electron impact mode. Recovery of the four antidepressants and IS spiked into human plasma was 80.2-92.1%. The regression equations for the four antidepressants showed excellent linearity in the range of 0.2-40 ng/0.1 mL. LODs and LOQs for the four drugs were 0.05-0.2 ng/0.1 mL and 0.2-0.5 ng/0.1 mL, respectively. Intra- and interday CVs for the four drugs in plasma were no greater than 9.5%.  相似文献   

7.
A solid‐phase extraction combined with a liquid chromatography‐tandem mass spectrometry analysis has been developed and validated for the simultaneous determination of 44 pharmaceuticals belonging to different therapeutic classes (i.e., antibiotics, anti‐inflammatories, cardiovascular agents, hormones, neuroleptics, and anxiolytics) in water samples. The sample preparation was optimized by studying target compounds retrieval after the following processes: i) water filtration, ii) solid phase extraction using Waters Oasis HLB cartridges at various pH, and iii) several evaporation techniques. The method was then validated by the analysis of spiked estuarine waters and wastewaters before and after treatment. Analytical performances were evaluated in terms of linearity, accuracy, precision, detection, and quantification limits. Recoveries of the pharmaceuticals were acceptable, instrumental detection limits varied between 0.001 and 25 pg injected and method quantification limits ranged from 0.01 to 30.3 ng/L. The precision of the method, calculated as relative standard deviation, ranged from 0.3 to 49.4%. This procedure has been successfully applied to the determination of the target analytes in estuarine waters and wastewaters. Eight of these 44 pharmaceuticals were detected in estuarine water, while 26 of them were detected in wastewater effluent. As expected, the highest values of occurrence and concentration were found in wastewater influent.  相似文献   

8.
Tetracyclines abuse has frequently occurred in aquaculture against bacteria, rickettsiae, spirochetes, and mycoplasmas. In this study, a high‐throughput sample preparation method was developed using 96‐well plate solid‐phase extraction (p‐SPE) and the extract was analyzed by ultra‐performance liquid chromatography tandem mass spectrometry (UPLC‐MS/MS). The experimental conditions were optimized such that the pH is 4, the eluting solvent is methanol (2 mL), and the sorbent is hydrophilic‐lipophilic balance (HLB) microsphere. The whole protocol was validated, and it showed that the tetracyclines were linear with correlation coefficients ≥ 0.9990, precision and accuracy (RSD%) in 3.9–6.1%, and mean recoveries of 88.6–103.6%. To exhibit the potential of 96‐well p‐SPE as a routine tool for inspection and quarantine, fresh aquatic samples were tested, and among which positive samples were observed. This method was demonstrated to be promising for the purification and enrichment of tetracyclines with reduced time and labor, and indeed practically and particularly suitable for widespread tetracyclines analysis.  相似文献   

9.
In this study, an effective speed‐regulated directly suspended droplet microextraction method was developed to condense pesticide residues from teas through dispersive solid‐phase extraction prior to analysis by gas chromatography with tandem mass spectrometry. The extractant was intentionally dispersed into the sample solution in the form of globules through high‐speed agitation. This procedure increases the contact area between the binary phases and shortens the distribution equilibrium time. The fine globules reassembled by decelerating stirring speed, the extractant could be taken out for gas chromatography with tandem mass spectrometry. Recovery studies were performed under optimized extraction conditions by using matrix blanks fortified with pesticides at three concentrations (10, 50, and 100 µg/kg). Over 87% of the recoveries for the analytes in four tea matrices were acceptable given their recovery ranges of 70–120% and relative standard deviations of ≤20%. The limits of quantification of most pesticides were lower than 10 µg/kg and thus satisfied the requirements for maximum residue levels prescribed by the European Community. A total of 38 tea samples from local markets were analyzed by using the proposed method. Results showed that chlorpyrifos was the most frequently detected pesticide in teas. The method is a potential choice for the routine monitoring of pesticide residues in complex matrices.  相似文献   

10.
A rapid environmental pollution screening and monitoring workflow based on fabric phase sorptive extraction‐gas chromatography‐tandem mass spectrometry (FPSE‐GC‐MS/MS) is proposed for the first time for the analysis of 17 widespread used fungicides (metalaxyl, cyprodinil, tolylfluanid, procymidone, folpet, fludioxonil, myclobutanil, kresoxim methyl, iprovalicarb, benalaxyl, trifloxystrobin, fenhexamid, tebuconazole, iprodione, pyraclostrobin, azoxystrobin and dimethomorph) in environmental waters. The most critical parameters affecting FPSE, such as sample volume, matrix pH, desorption solvent and time, and ionic strength were optimized by statistical design of experiment to obtain the highest extraction efficiency. Under the optimized conditions, the proposed FPSE‐GC‐MS/MS method was validated in terms of linearity, repeatability, reproducibility, accuracy and precision. To assess matrix effects, recovery studies were performed employing different water matrices including ultrapure, fountain, river, spring, and tap water at 4 different concentration levels (0.1, 0.5, 1 and 5 µg/L). Recoveries were quantitative with values ranging between 70–115%, and relative standard deviation values lower than 14%. Limits of quantification were at the low ng/L for all the target fungicides. Finally, the validated FPSE‐GC‐MS/MS method was applied to real water samples, revealing the presence of 11 out of the 17 target fungicides.  相似文献   

11.
In this work, an easy, effective, and sensitive method based on graphene oxide@silica@magnetite composites as adsorbent of magnetic solid‐phase extraction combined with liquid chromatography and tandem mass spectrometry, was established and validated for the trace analysis of cytokinins in different plants. The prepared magnetic composite was characterized by infrared spectroscopy, transmission electron microscopy, Brunauer–Emmett–Teller analysis, and magnetic hysteresis. Under the optimized conditions, good linearities in the range of 0.5–100 ng/mL were obtained with the corresponding linear correlation coefficient >0.9989 for the investigated four cytokinins, and good sensitivity levels were achieved with low detection limits ranging from 93 to 120 pg/mL. The established magnetic solid‐phase extraction with liquid chromatography and tandem mass spectrometry method has been validated in the separation and analysis of four cytokinins in plant samples with good recoveries between 78.9 and 97.3% for four cytokinins with the relative standard deviations lower than 13.5%.  相似文献   

12.
A new multiresidue method has been developed and validated for the simultaneous extraction of more than two hundred pesticides, including non-polar and polar pesticides (carbamates, organochlorine, organophosphorous, pyrethroids, herbicides and insecticides) in urine at trace levels by gas and ultra high pressure liquid chromatography coupled to ion trap and triple quadrupole mass spectrometry, respectively (GC-IT-MS/MS, UHPLC-QqQ-MS/MS). Non-polar and polar pesticides were simultaneously extracted from urine samples by a simple and fast solid phase extraction (SPE) procedure using C18 cartridges as sorbent, and dichloromethane as elution solvent. Recovery was in the range of 60-120%. Precision values expressed as relative standard deviation (RSD) were lower than 25%. Identification and confirmation of the compounds were performed by the use of retention time windows, comparison of spectra (GC-amenable compounds) or the estimation of the ion ratio (LC-amenable compounds). For GC-amenable pesticides, limits of detection (LODs) ranged from 0.001 to 0.436 μg L−1 and limits of quantification (LOQs) from 0.003 to 1.452 μg L−1. For LC-amenable pesticides, LODs ranged from 0.003 to 1.048 μg L−1 and LOQs ranged from 0.011 to 3.494 μg L−1. Finally, the optimized method was applied to the analysis of fourteen real samples of infants from agricultural population. Some pesticides such as methoxyfenozide, tebufenozide, piperonyl butoxide and propoxur were found at concentrations ranged from 1.61 to 24.4 μg L−1, whereas methiocarb sulfoxide was detected at trace levels in two samples.  相似文献   

13.
A method was developed for the determination of nine volatile N‐nitrosamines in tobacco and smokeless tobacco products. The targets are N‐nitrosodimethylamine, N‐nitrosopyrrolidine, N‐nitrosopiperidine, N‐nitrosomorpholine, N‐nitrosoethylmethylamine, N‐nitrosodiethylamine, N‐nitrosodipropylamine, N‐nitrosobuylmethylmine, and N‐nitrosodibutylamine. The samples were treated by dispersive solid‐phase extraction using 1 g of primary secondary amine and 0.5 g of carbon and then analyzed by gas chromatography with tandem mass spectrometry with an electron impact ion source. The recoveries for the targets ranged from 84 to 118%, with <16% relative standard deviations at three spiking levels of 0.5, 1.25, and 2.5 ng/g. The limits of detection ranged from 0.03 to 0.15 ng/g. With the use of the proposed method, we detected the presence of six nitrosamines in the range of 0.4–30.7 ng/g. The study demonstrated that the method could be used as a rapid, convenient, and high‐throughput method for N‐nitrosamines analysis in tobacco matrix.  相似文献   

14.
A sensitive and robust multiresidue method for the simultaneous analysis of 114 pesticides in tobacco was developed based on solid‐phase extraction coupled with gas chromatography and tandem mass spectrometry. In this strategy, tobacco samples were extracted with acetonitrile and cleaned up with a multilayer solid‐phase extraction cartridge Cleanert TPT using acetonitrile/toluene (3:1) as the elution solvent. Two internal standards of different polarity were used to meet simultaneous pesticides quantification demands in the tobacco matrix. Satisfactory linearity in the range of 10–500 ng/mL was obtained for all 114 pesticides with linear regression coefficients higher than 0.994. The limit of detection and limit of quantification values were 0.02–5.27 and 0.06–17.6 ng/g, respectively. For most of the pesticides, acceptable recoveries in the range of 70–120% and repeatabilities (relative standard deviation) of <11% were achieved at spiking levels of 20, 100, and 400 ng/g. Compared with the reported multiresidue analytical method, the proposed method provided a cleaner test solution with smaller amounts of pigments, fatty acids as well as other undesirable interferences. The development and validation of the high sensitivity, high selectivity, easy automation, and high‐throughput analytical method meant that it could be successfully used for the determination of pesticides in tobacco samples.  相似文献   

15.
In the present study, highly efficient and simple dispersive solid‐phase extraction procedure for the determination of haloacetic acids in water samples has been established. Three different types of layered double hydroxides were synthesized and used as a sorbent in dispersive solid‐phase extraction. Due to the interesting behavior of layered double hydroxides in an acidic medium (pH?4), the analyte elution step was not needed; the layered double hydroxides are simply dissolved in acid immediately after extraction to release the analytes which are then directly introduced into a liquid chromatography with tandem mass spectrometry system for analysis. Several dispersive solid‐phase extraction parameters were optimized to increase the extraction efficiency of haloacetic acids such as temperature, extraction time and pH. Under optimum conditions, good linearity was achieved over the concentration range of 0.05–100 μg/L with detection limits in the range of 0.006–0.05 μg/L. The relative standard deviations were 0.33–3.64% (n = 6). The proposed method was applied to different water samples collected from a drinking water plant to determine the concentrations of haloacetic acids.  相似文献   

16.
Here, we present a method for measuring barbiturates (butalbital, secobarbital, pentobarbital, and phenobarbital) in whole blood samples. To accomplish these measurements, analytes were extracted by means of hollow‐fiber liquid‐phase microextraction in the three‐phase mode. Hollow‐fiber pores were filled with decanol, and a solution of sodium hydroxide (pH 13) was introduced into the lumen of the fiber (acceptor phase). The fiber was submersed in the acidified blood sample, and the system was subjected to an ultrasonic bath. After a 5 min extraction, the acceptor phase was withdrawn from the fiber and dried under a nitrogen stream. The residue was reconstituted with ethyl acetate and trimethylanilinium hydroxide. An aliquot of 1.0 μL of this solution was injected into the gas chromatograph/mass spectrometer, with the derivatization reaction occurring in the hot injector port (flash methylation). The method proved to be simple and rapid, and only a small amount of organic solvent (decanol) was needed for extraction. The detection limit was 0.5 μg/mL for all the analyzed barbiturates. The calibration curves were linear over the specified range (1.0 to 10.0 μg/mL). This method was successfully applied to postmortem samples (heart blood and femoral blood) collected from three deceased persons previously exposed to barbiturates.  相似文献   

17.
UV filters, contained in sunscreens and other cosmetic products, as well as in some plastics and industrial products, are nowadays considered contaminants of emerging concern because their widespread and increasing use has lead to their presence in the environment. Furthermore, some UV filters are suspected to have endocrine disruption activity. In the present work, we developed an analytical method based on liquid chromatography with tandem mass spectrometry for the determination of UV filters in tap and lake waters. Sixteen UV filters were extracted from water samples by solid‐phase extraction employing graphitized carbon black as adsorbent material. Handling 200 mL of water sample, satisfactory recoveries were obtained for almost all the analytes. The limits of detection and quantification of the method were comparable to those reported in other works, and ranged between 0.7–3.5 and 1.9–11.8 ng/L, respectively; however in our case the number of investigated compounds was larger. The major encountered problem in method development was to identify the background contamination sources and reduce their contribution. UV filters were not detected in tap water samples, whereas the analyses conducted on samples collected from three different lakes showed that the swimming areas are most subject to UV filter contamination.  相似文献   

18.
A method was developed for the determination of clenbuterol in meat using stable‐isotope‐dilution gas chromatography with mass spectrometry coupled with solid‐phase microextraction and on‐fiber derivatization. The samples were first homogenized with hydrochloric acid followed by protein deposition. After headspace solid‐phase microextraction and on‐fiber derivatization, the content of clenbuterol was measured with the aid of stable‐isotope dilution. The condition of solid‐phase microextraction was optimized by central composite design. The relative standard deviations, limit of detection, and recoveries for clenbuterol were 4.2–9.2%, 0.48 μg/kg, and 96–104%, respectively. The proposed method was satisfactory for analysis of real samples as compared with the Chinese standard method.  相似文献   

19.
A new facile, rapid, inexpensive, and sensitive method for the analysis of six trace trichlorophenols in seawater samples was developed by magnetic micro‐solid‐phase extraction coupled to liquid chromatography with tandem mass spectrometry. Core–shell covalently functionalized ferroferric oxide coated with aminated silicon dioxide and decorated with multiwalled carbon nanotubes was applied as an adsorbent to perform the extraction process. The effect of factors including solution pH, contact time, adsorbent amount, and ionic strength were investigated in detail. The obtained results revealed that the proposed adsorbent was a highly effective and low‐cost magnetic micro‐solid‐phase extraction material for the enrichment of 2,3,4‐trichlorophenol, 2,3,5‐trichlorophenol, 2,3,6‐trichlorophenol, 2,4,5‐trichlorophenol, 2,4,6‐trichlorophenol, and 3,4,5‐trichlorophenol from seawater. Under the optimized conditions, the recoveries ranged from 88.0 to 99.5% at the three spiking levels, the limits of detection and the limits of quantification were 0.002 and 0.007 μg/L for the six trichlorophenols, respectively. The intra‐ and interday relative standard deviations were 2.0–6.7 and 4.5–8.9%, respectively. The calibration curves showed a good linearity in the range of 0.02–5.0 μg/L. The routine run analyses showed that the developed method was fast, simple, accurate, solvent‐saving and high resolution, and it was suitable for the determination of trace trichlorophenols in seawater.  相似文献   

20.
Through the use of a homemade sol–gel‐derived fiber, a headspace solid‐phase microextraction technique coupled to gas chromatography with mass spectrometry was developed for the determination of fatty acids with long, even‐numbered carbon chains (C12–C24) in soil samples. The experimental parameters such as reaction time, temperature, and ionic strength that might affect derivatization, extraction, and desorption were investigated. Under the optimized conditions, the linearity of the method ranged from 0.1 to 100 mg/L with a correlation coefficient >0.997. The limit of detection values based on a signal‐to‐noise ratio of 3:1 were determined with the concentration from 0.39 to 39.4 μg/L. The recoveries of the method for the soil samples were from 91.15 to 108.1%. This developed method using a homemade fiber showed a higher sensitivity than that using a commercial polydimethylsiloxane fiber and was also for the analysis of real soil samples from the Paomaling geological park of China.  相似文献   

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