超高效液相色谱-串联质谱法同时测定食品中碱性橙、碱性嫩黄O和碱性桃红T

本文建立了同时测定食品中碱性橙、碱性嫩黄O和碱性桃红的超高效液相色谱-串联质谱(UPLC-MS/MS)检测方法.样品经碱化甲醇提取、二氯甲烷萃取、浓缩、酸化甲醇溶解和甲醇饱和正己烷溶液萃取净化后进行测定.本方法检出限分别为碱性橙0.6 μg/kg、碱性嫩黄O 0.3 μg/kg、碱性桃红T 0.7 μg/kg.六种食品样品的回收率为72.1%～91.1%,相对标准偏差(RSD)为2.4%～9.1%(n=6),三种染料在0.01～0.5 μg/mL范围内呈良好的线性关系,线性回归系数r均大于0.9950.     

顶空固相微萃取-气相色谱-质谱法同时测定饮用水源水中24种VOCs

建立了同时测定饮用水源水中24种挥发性有机物(VOCs)的顶空固相微萃取-气相色谱-质谱法.用75 μm CarboxenTM-Polydimethylsiloxane(CAR-PDMS)固相微萃取柱顶空萃取水样中的VOCs,VOCs用气相色谱-质谱联用仪检测,采用内标法定量.对萃取柱涂层、样品盐度、萃取温度和萃取时间等样品前处理条件进行了优化,VOCs的检出限在0.03～0.31 μg/L之间,线性相关系数r＞0.996(二氯甲烷和三氯甲烷除外).对饮用水源水实际水样0.50μg/L和1.00 μg/L两个加标浓度水平的回收率进行了测定,三氯甲烷回收率均值分别为104％和142％,其余VOCs回收率分别为90.0％～120％和88.0％～110％,除二氯甲烷和三氯甲烷外,其余VOCs测定结果的相对标准偏差均小于15.0％(n=6).该方法适用于饮用水源水中挥发性有机物的监测分析.     

高效溶剂萃取－固相萃取/气相色谱－质谱法测定大气颗粒物中多环芳烃和有机磷阻燃剂

建立了高效溶剂萃取（HPSE）－固相萃取（SPE）/气相色谱－质谱（GC－MS）测定大气颗粒物中16种多环芳烃（PAHs）和15种有机磷阻燃剂（OPFRs）的方法。以正己烷－二氯甲烷（1∶1,体积比）溶液为萃取溶剂,萃取液旋转蒸发浓缩后经Florisil固相萃取柱净化,PAHs和OPFRs的洗脱溶剂分别为10 mL正己烷－二氯甲烷（1∶1）和10 mL乙酸乙酯,洗脱液浓缩定容后进行GC－MS测定。16种PAHs和15种OPFRs的线性范围为0.001 ~ 2.0 μg/mL,相关系数（r2）均大于0.99;检出限（LOD,S/N = 3）分别为0.10 ~ 10.00 μg/L和2.59 ~ 75.00 μg/L,定量下限（LOQ,S/N = 10）分别为0.33 ~ 33.33 μg/L和8.63 ~ 250.00 μg/L;平均回收率分别为73.0% ~ 98.0%和69.3% ~ 111%,相对标准偏差（RSD）分别为3.7% ~ 13%和2.5% ~ 17%。该方法适用于大气颗粒物样品中多环芳烃和有机磷阻燃剂的测定。     

气相色谱－串联质谱法测定电子烟烟液中的10种生物碱含量

建立了一种气相色谱－串联质谱法测定电子烟烟液中10种生物碱含量的分析方法,并对仪器分析条件、样品前处理条件等进行了优化。样品加入2.0 mL 2% NaOH水溶液后,以10 mL二氯甲烷-甲醇溶液（体积比4∶1）为萃取溶液,涡旋振荡萃取30 min,萃取液经无水硫酸镁除水后,以气相色谱－串联质谱法多反应监测（MRM）模式检测。结果显示：在优化条件下,烟碱及9种次要生物碱在25～1 000 μg/mL及0.002 5～20 μg/mL范围内呈良好的线性,相关系数（r2）不低于0.997,3个加标水平下的回收率为87.9%～109%,日内及日间精密度（RSD）分别不高于6.8%和7.9%,检出限（LOD）为0.0040～0.10 mg/kg,定量下限（LOQ）为0.013～0.33 mg/kg。用该方法测定23种品牌共计171种型号电子烟烟液中10种生物碱含量,结果发现,电子烟烟液中的烟碱含量为2.16～23.73 mg/g,9种次要生物碱的含量中位值为0.06～7.35 mg/kg,检出率为64.91%～99.42%,其中9种电子烟烟液样品的总次要生物碱含量与烟碱含量比例大于1.0%。该方法灵敏度高、准确性好、重复性好,完全满足电子烟烟液样品中10种生物碱的检测要求。     

薄层色谱法分析葵花仁粕中的绿原酸

 以聚酰胺薄膜为固定相、体积分数为 36 %的乙酸溶液为流动相 ,研究建立了薄层色谱分离测定葵花仁粕中绿原酸的方法。绿原酸样品溶液上行展开 8 5cm ,其Rf 值为 0 6 1。绿原酸的检测量在 0 0 5 μg～ 0 6 μg范围内 ,其斑点的面积与绿原酸的检测量具有良好的线性关系。绿原酸的回收率为 97 5 3 % ,不同薄层板之间的RSD为2 5 7% ,最低检出限为 0 0 2 5 μg。在以体积分数为 70 %的乙醇溶液为萃取剂、搅拌振荡萃取时间为 30min的条件下 ,以该方法测定萃取液中绿原酸的含量和葵花仁粕中绿原酸的残留量 ,确定了最佳萃取次数。     

气相色谱法测定聚碳酸酯中的二氯甲烷

建立蒸馏提取–气相色谱法快速测定聚碳酸酯中二氯甲烷含量的方法。以三氯甲烷作溶剂溶解聚碳酸酯,配制成含8%～10%聚碳酸酯的三氯甲烷溶液,在蒸馏温度为90℃,冷凝介质的温度为–15℃的条件下,通过蒸馏法将溶液中的三氯甲烷蒸出,用气相色谱法测定二氯甲烷的含量。二氯甲烷的含量在1～80 mg/kg范围内与色谱峰面积呈良好的线性关系,线性相关系数为0.999 3,检出限为1.7 mg/kg。二氯甲烷测定结果的相对标准偏差为1.64%(n=6),加标回收率为95.7%～100.3%。该方法准确、可靠,可用于聚碳酸酯中二氯甲烷含量的快速检测。     

一滴溶剂微萃取-毛细管气相色谱法分析水中的七种硝基苯类化合物

用一滴溶剂微萃取(SDME)-毛细管气相色谱联用技术测定水中的硝基苯、硝基甲苯类和硝基氯苯类化合物,对影响萃取的因素如萃取溶剂种类、液滴体积、搅拌速度、针尖入水深度、水样体积、萃取时间、萃取温度等进行了优化,结果表明:硝基苯和硝基甲苯类化合物在0.8～32 μg/L 范围内,硝基氯苯类化合物在0.04～3.2 μg/L 范围内均呈现良好的线性(r2>0.999),检出限可达0.01～0.3 μg/L。自来水加标样品测定的相对标准偏差和平均回收率(n=5)范围分别为3.1%～7.9%和101%～105%,废水加标样品测定的相对标准偏差和平均回收率(n=5)范围分别为3.3%～7.9%和92.5%～97.0%。优化后的SDME具有环保、灵敏、快速、简便等特点,适用于萃取水中的痕量硝基苯、硝基甲苯类和硝基氯苯类化合物。     

血浆辅酶Q10的高效液相色谱快速测定

建立了一种简单快速测定血浆辅酶Q10(CoQ10)的反相高效液相色谱方法.血浆经正丙醇萃取,上层清液直接进样分析.色谱柱为Hypersil ODS2 5μm,150 mm ×4.6 mm i.d,以异丙醇-甲醇(体积比19)作流动相,275 nm作检测波长,外标法定量.在0.05～20 mg/L范围内,峰高与质量浓度呈良好的线性关系(r=0.999 8),血浆中辅酶Q10的检出限为0.03 mg/L(S/N=3).该方法简单、快速、精密度高(RSD＜5%),适宜于血浆辅酶Q10含量的检测.     

液液微萃取-气相色谱法测定地表水中五氯酚

建立液液微萃取–气相色谱法测定地表水中五氯酚的方法。利用液液微萃取技术对水样进行富集预处理,萃取剂:氯苯,体积为80μL;分散剂:甲醇,体积为0.8 mL;氯化钠加入量为0.4 g。样品萃取液用气相色谱测定,内标法定量。五氯酚的质量浓度在0.00～60.0μg/L范围内与色谱峰面积呈良好的线性关系,线性相关系数为0.999 4,检出限为0.8μg/L。7次测定结果的相对标准偏差小于3%,加标回收率为94.1%～102.4%。该方法操作方便、快捷,富集效率高,有机溶剂用量少,检出限低,测定结果准确可靠,适用于地表水中痕量五氯酚的测定。     

气泡微萃取-气相色谱-质谱法测定尿中咖啡因

建立了气泡微萃取结合气相色谱/质谱技术(GC-MS)测定尿中咖啡因的方法.对影响萃取效率的实验条件进行了优化,确定了最佳萃取条件:三氯甲烷作为萃取溶剂,萃取溶剂暴露体积1 μL,气泡体积1.6 μL,搅拌速度300 r/min,萃取时间5 min,盐度15%(m/V),气泡与磁子间距离1 cm.在优化条件下,所建立方法在咖啡因浓度0.005~10 mg/L范围内有较好的线性关系,相关系数可达0.986,检出限为0.003 mg/L.在人尿液中添加不同浓度的咖啡因(0.050、0.500和5.000 mg/L),回收率为89.2%~107.5%,相对标准偏差小于8%(n=6).     

顶空-气相色谱法测定水中三氯甲烷和四氯化碳方法的改进

改进了顶空-气相色谱法测定水中三氯甲烷和四氯化碳的方法,对平衡温度和平衡时间进行了优化,对不同溶剂配制的标准使用液和不同方法制作的工作曲线对测定结果的影响进行了比较.试验结果表明,样品最佳平衡温度和时间分别为50℃和35 min.采用甲醇代替标准中规定的纯水配制标准使用液,采用微量进样针取样到预先密封的顶空瓶中,三氯甲...     

室温离子液体作溶剂顶空气-质联用测定药物中溶剂残留

基于室温离子液体无蒸汽压、良好溶解性和分散性的特点,用室温离子液体[bm im][PF6]作溶剂顶空气-质联用测定非那雄胺中二氯甲烷、三氯甲烷及二氧六环的残留量,优化了顶空气-质联用分析条件。二氯甲烷、三氯甲烷及二氧六环的检出限分别为0.2、0.02和0.50 ng,线性相关系数大于0.99;相对标准偏差(RSD)0.39%~4.60%;回收率为90.5%~111.9%。室温离子液体作为顶空溶剂的灵敏度有所提高。     

苄基功能化离子液体对有机磷和苯环化合物的分散液-液微萃取性能研究

以苄基功能化的离子液体1-苄基-3-甲基咪唑双三氟甲烷磺酰亚胺(1-Benzyl-3-methylimidazolium bis [(trifluoromethyl)sulfonyl]imide,[BeMIM][Tf2 N])作为分散液-液微萃取的萃取剂,与高效液相色谱联用,用于环境水样中5种有机磷农药(辛硫磷、杀螟松、毒死蜱、甲拌磷和对硫磷)以及2种苯环化合物(氯化萘和蒽)的萃取与富集。并与其它离子液体([OMIM][Tf2 N])以及普通有机溶剂(CCl4和 C2 Cl4)的萃取效能进行了对比。萃取优化条件为：40μL [BeMIM][Tf2 N]作为萃取剂,1 mL 甲醇作为分散剂,离心时间5 min,样品溶液中不添加盐。在优化的条件下,本方法的线性关系良好(R2=0.9994~0.9998);对10,40和100μg/ L 不同添加浓度重复测定5次的日内和日间 RSD 分别为1.1%~4.3%和0.8%~4.8%,LOD 为0.01~1.0μg/ L (S/ N=3)。将本方法用于3种实际水样中目标分析物的测定,加标回收率和 RSD 分别为82.7%~118.3%和0.7%~5.6%。由于在咪唑环上引入了苄基基团,[BeMIM][Tf2 N]与目标分析物之间除存在疏水作用外,还存在π-π作用,故对目标物的萃取效率明显提高,富集倍数和回收率分别高达339和81.4%。测定了分析物在[BeMIM][Tf2 N]-DLLME 体系中的分配系数,对萃取机制进行初步探讨。     

高效液相色谱/荧光检测法同时测定高分子材料中6种异氰酸酯

建立了高分子材料中6种异氰酸酯含量的高效液相色谱/荧光检测法。样品中的异氰酸酯经萃取衍生,C18色谱柱梯度洗脱分离后,以荧光检测器检测,外标法定量。考察了萃取剂、萃取方式、衍生化时间及流动相组成对异氰酸酯萃取量、衍生化效果及分离效果的影响。结果表明,选用极性萃取剂二氯甲烷超声萃取的回收率高于非极性萃取剂环己烷振荡萃取的回收率,最佳衍生化时间为30 min。流动相采用乙腈-三乙胺缓冲液梯度洗脱时,目标组分的分离度高于1.5,在10~100 μg/L范围内异氰酸酯衍生物的线性相关系数不低于0.999 1。高分子样品中异氰酸酯的加标量在0.1~1.0 mg/kg范围内,平均回收率为90%~95%,相对标准偏差(RSD,n=5)为2.2%~4.2%。检出限(信噪比为3)为30.3 ~42.3 μg/kg。实际样品检测结果表明,除苯基异氰酸酯(PI)外的5种异氰酸酯在样品中均有不同程度检出,总含量为79.7~326.3 μg/kg。该方法准确、灵敏、重现性好,适用于高分子材料中异氰酸酯残留量的检测。     

分散液液微萃取-气相色谱法快速测定水中15种硝基苯类物质

建立了分散液液微萃取-气相色谱电子捕获检测器测定水中15种硝基苯类物质的方法.筛选出了具有高密度且能够适用于电子捕获检测器的萃取剂.优化了色谱条件,对萃取剂种类及用量、分散剂种类及用量、萃取时间、萃取温度等条件进行了优化.DB-35毛细管柱对15种硝基苯类物质具有最好的分离效果.使用程序升温,初始80℃ 保持2 min,以5℃/min速率升温至180℃,可以在22 min内完成分离.以100μL氯苯作为萃取剂、400μL甲醇作为分散剂,对5.00 mL水样在室温下进行萃取,仅需30 s即可达到萃取平衡,15种目标物的萃取率均可达到90%以上,富集倍数达到45.0~48.8.离心分离,取下层沉积相进行气相色谱测定,使用电子捕获检测器检测,方法的定量限为0.03~0.15μg/L,线性范围为0.20~50.0μg/L,相关系数不低于0.998.方法的相对标准偏差在3.3%~8.9%之间,加标回收率在86.0%~103.5%之间.     

Determination of volatile chlorinated hydrocarbons in water samples by static headspace gas chromatography with electron capture detection

A simple, efficient, solvent‐free, and commercial readily available approach for determination of five volatile chlorinated hydrocarbons in water samples using the static headspace sampling and gas chromatography with electron capture detection has been described. The proposed static headspace sampling method was initially optimized and the optimum experimental conditions found were 10 mL water sample containing 20% w/v sodium chloride placed in a 20 mL vial and stirred at 50ºC for 20 min. The linearity of the method was in the range of 1.2–240 μg/L for dichloromethane, 0.2–40 μg/L for trichloromethane, 0.005–1 μg/L for perchloromethane, 0.025–5 μg/L for trichloroethylene, and 0.01–2 μg/L for perchloroethylene, with coefficients of determination ranging between 0.9979 and 0.9990. The limits of detection were in the low μg/L level, ranging between 0.001 and 0.3 μg/L. The relative recoveries of spiked five volatile chlorinated hydrocarbons with external calibration method at different concentration levels in pure, tap, sea water of Jiaojiang Estuary, and sea water of waters of Xiaomendao were in the range of 91–116, 96–105, 86–112, and 80–111%, respectively, and with relative standard deviations of 1.9–3.6, 2.3–3.5, 1.5–2.7, and 2.3–3.7% (n = 5), respectively. The performance of the proposed method was compared with traditional liquid–liquid extraction on the real water samples (i.e., pure, tap, and sea water, etc.) and comparable efficiencies were obtained. It is concluded that this method can be successfully applied for the determination of volatile chlorinated hydrocarbons in different water samples.     

Comparison of C18 silica and multi‐walled carbon nanotubes as the adsorbents for the solid‐phase extraction of Chlorpyrifos and Phosalone in water samples using HPLC

A comparison between C₁₈ silica and multi‐walled carbon nanotubes (MWCNTs) in the extraction of Chlorpyrifos and Phosalone in environmental water samples was carried out using HPLC. Parameters affecting the extraction were type and volume of elution solvent, pH and flow rate of sample through the adsorbent. The optimum conditions obtained by C₁₈ cartridge for adsorption of these pesticides were 4 mL dichloromethane as elution solvent, sample pH of 5, flow rate of 1 mL/min, and those for MWCNT cartridge were 3 mL dichloromethane, pH of 5 and flow rate of 10 mL/min, respectively. Optimized mobile phase for separation and determination of these compounds by HPLC was methanol/water (80:20 v/v) with pH=5 (adjusted with phosphate buffer). Under optimal chromatographic and SPE conditions, LOD, linear range and precision (RSD n=8) were 3.03×10^?3, 0.01–5.00 μg/mL and 2.7% for Chlorpyrifos and 4.03×10^?4, 0.01–5.00 μg/mL and 2.3% for Phosalone, in C₁₈ cartridge, respectively. These values for MWCNT were 4.02×10^?6, 0.001–0.500 μg/mL and 1.8% for Chlorpyrifos and 1.02×10^?6, 0.001–0.500 μg/mL and 1.5% for Phosalone, respectively.     

A rapid and environmental friendly determination of the dithiocarbamate metabolites ethylenethiourea and propylenethiourea in fruit and vegetables by ultra high performance liquid chromatography tandem mass spectrometry

Previous published methods for the analysis of ETU and PTU are time-consuming and furthermore use dichloromethane (DCM) for extraction or clean-up. This study details the development and validation of a rapid method that combines a simple extraction step with UHPLC-ESI(+)-MS/MS. This is the first application of UHPLC-MS/MS to analyse these compounds. Besides that, we replaced DCM with a more environmental-friendly solvent. The analytical performance was evaluated with the analysis of spiked celery samples at 50 μg kg(-1) (LOQ) and 300 μg kg(-1). The recoveries were between 65% and 90% for ETU and between 71% and 127% for PTU with RSDs in repeatability and reproducibility conditions below 10% for ETU. This method is rapid (a chromatographic run time of 2 min) and can easily be performed (no laborious clean-up). The presented method is environmental friendly with significant reduction in solvent consumption.     

气相色谱质谱法测定6种加香目标物质的含量及对烟丝加香均匀性的评价

建立了一种运用气相色谱-质谱联用技术(GC-MS)同时测定卷烟烟丝中呋喃酮、异戊酸异戊酯、麦芽酚、薄荷醇、乙基麦芽酚和茴香脑6种烟用加香目标物的检测方法。试样用二氯甲烷溶液振荡提取,旋转蒸发仪浓缩,气相色谱-质谱联用仪检测分析。分别对样品量、萃取溶剂和萃取时间等前处理条件进行了优化。该方法的线性相关系数r均在0.998以上,采用SIM法定量分析,其平均加标回收率为86%～92%,相对标准偏差(RSD,n=6)为4.7%～7.1%,检出限(S/N=3)和定量下限(S/N=10)分别为0.014 7～0.0746μg/g和0.048 9～0.248 8μg/g。结果表明,该方法简便、灵敏度高、线性关系好,能满足同时测定烟丝中此6种加香目标物质的要求。方法还通过测定烟丝样品中加香目标物的含量及其含量的RSD值对卷烟制丝工艺加香的均匀性进行了评价。     

Analysis of Cembranoids in Flue‐cured Tobacco by Accelerated Solvent Extraction and Gas Chromatography‐Mass Spectrometry‐Selected Ion Monitoring

An efficient and sensitive analytical method based on accelerated solvent extraction (ASE) and gas chromatography‐mass spectrometry‐selected ion monitoring (GC‐MS‐SIM) was developed and validated for analysis of cembranoids in flue‐cured tobacco leaves. Extraction efficiency of different pretreatment methods including liquid‐solid extraction (LSE), ultrasound‐assisted extraction (UAE), Soxlet extraction and accelerated solvent extraction (ASE) was compared and ASE was chosen as the optimal extraction method. During ASE procedure, effect of four parameters on extraction efficiency was considered and the experimental conditions were selected as follows: extraction solvent: dichloromethane; oven temperature: 50 °C; static time: 5 min and number of cycles: 2. Working standards of cembranoids were isolated by silica gel column chromatography and the identification was performed by mass spectrometry. Performance characteristics such as linearity, limit of detection (LOD), limit of quantitation (LOQ), precision and recovery were studied. The LOD and LOQ values were ranging from 5.0 × 10^?3 to 6.9 × 10^?3 μg/mL and 1.7 × 10^?2 to 2.3 × 10^?2 μg/mL for all analytes. At three different spiked levels, recoveries for CBT‐ol, α‐CBT‐diol and β‐CBT‐diol were 94.6%‐105.1%, 93.0%‐97.2% and 88.7%‐107.5% while the relative standard deviations (RSDs) were in the ranges of 3.9%‐6.2%, 1.8%‐8.7% and 1.7%‐6.0%, respectively. The proposed analytical methodology was successfully applied in the analysis of cembranoids in tobacco samples.