超高效液相色谱-串联质谱法测定茶叶中的百草枯

文章建立了一种利用超高效液相色谱-串联质谱法测定茶叶中百苹枯含量的方法.茶叶样品使用甲醇-0.1 mol/L盐酸溶液(3:7,V/V)提取,经Poly-sery MCX柱净化后用超高效液相液相色谱-串联质谱进行测定.在5～100μg/L浓度范围内,百草枯的线性良好(R2=0.9991),方法定量限为0.01 mg/kg...     

超高效液相色谱-串联质谱法测定茶叶中6种农药残留

目的建立超高效液相色谱-串联质谱法测定茶叶中吡虫啉、多菌灵、啶虫脒、水胺硫磷、三唑磷和甲基异柳磷6种农药残留的方法。方法样品经乙腈提取,NH_2固相萃取小柱富集、净化,以二氯甲烷-甲醇(9:1,V:V)为洗脱溶液;样品经浓缩定容后,采用Thermo C_(18)(2.1 mm×50 mm,1.7μm)色谱柱分离,流速为0.3 mL/min,以水-甲醇-乙腈为流动相进行梯度洗脱,采用超高效液相色谱-串联质谱法多反应监测模式进行测定,采用基质标准溶液外标法定量。结果 6种农药在0.005~0.25μg/mL浓度范围内呈良好的线性关系,相关系数为0.9973~0.9998。当添加水平为0.005、0.025、0.25 mg/kg时,6种农药在茶叶中的加标回收率为72.4%~106.6%,相对标准偏差为1.6%~10.0%。方法定量限为0.5~5μg/kg。结论该方法操作简单、快速,可适用于茶叶中吡虫啉、啶虫脒、多菌灵、水胺硫磷、三唑磷和甲基异柳磷6种农药残留的测定。     

超高效液相色谱-串联质谱法同时测定鸡蛋中7种色素

目的建立同时测定鸡蛋中7种色素含量的超高效液相色谱串联质谱(ultra performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)法。方法鸡蛋样品用乙腈超声提取。经Phenomenex Kinetex F5(100 mm×3.0 mm,2.6μm)色谱柱分离,流动相A:0.1%的甲酸/水溶液;流动相B:0.1%的甲酸/乙腈溶液作为流动相梯度洗脱。电喷雾离子源(electrospray ionization,ESI)正离子多反应监测模式定量分析。结果7种色素在浓度1～20μg/L范围内线性关系良好,相关系数r~2≥0.998。叶黄素、角黄素、苏丹红Ⅰ、苏丹红Ⅱ、苏丹红Ⅲ、苏丹红Ⅳ的检出限均为0.1μg/kg,核黄素的检出限为0.2μg/kg。7种色素在加标量2～10μg/kg范围内,回收率为80.2%～106.7%,相对标准偏差为1.5%～6.0%。结论该方法准确、快速、高效,可用于鸡蛋中色素的定性、定量分析。     

超高效液相色谱串联-质谱法同时测定香辛料中7种真菌毒素

建立了同时测定香辛料中7种真菌毒素的超高效液相色谱-串联质谱分析方法(UPLC-MS/MS)。选用香辛料中的辣椒、花椒和八角为研究对象,粉碎后的样品用70%甲醇水溶液提取,6合1免疫亲和柱净化,ACQUITY UPLC HSS T3色谱柱分离,超高效液相色谱-串联质谱测定,电喷雾正离子(ESI⁺)多反应离子监测方式监测,外标法定量。结果表明,7种真菌毒素在各自的线性响应范围内线性关系良好,相关系数均不低于0.995,7种真菌毒素的定量限为0.5~20 μg/kg。低、中、高3个加标水平平均回收率(n=6)为67.25%~113.47%,相对标准偏差(RSD)为1.07%~10.20%。该方法具有前处理简单、净化效果好、灵敏度高和高通量检测的优点,适用于香辛料中多组分真菌毒素残留的分离和检测。     

QuEChERS-超高效液相色谱-串联质谱法快速测定饮料中13 种饱和内酯类合成香料

建立超高效液相色谱-串联质谱法快速测定饮料中13 种饱和内酯类合成香料的方法。采用QuEChERS前处理法,以乙腈提取,N-丙基乙二胺填料吸附剂直接净化,电喷雾离子源、多反应监测正离子模式扫描,外标法定量。13 种饱和内酯在0.025～0.50 μg/mL范围内质量浓度与峰面积呈良好的线性关系,仪器检出限为0.025 μg/mL,方法的检出限为0.10 mg/kg,定量限为0.40 mg/kg,添加量为0.10、0.20、0.40 mg/kg时13 种饱和内酯的平均回收率范围分别为88.5%～103%,相对标准偏差为3.8%～11%（n=10）。本方法可用于饮料中饱和内酯类化合物的快速定性、定量检测。     

QuEChERS-超高效液相色谱-串联质谱法同时检测辣椒中5种杀菌剂残留

建立QuEChERS-超高效液相色谱-串联质谱法同时检测鲜食辣椒中多菌灵、甲基硫菌灵、烯酰吗啉、嘧菌酯和苯醚甲环唑5种杀菌剂的分析方法。方法 样品经2.0%乙酸乙腈提取分离, 50 mg C18和20 mg GCB净化, 采用超高效液相色谱-串联质谱法检测, 基质外标法定量。结果 5种杀菌剂在0.01~1.00 mg/L质量浓度范围内, 峰面积与对应的质量浓度间线性关系良好, 相关系数均大于0.989; 5种杀菌剂在0.01、0.1和1.0 mg/kg添加水平下的平均回收率为74%~105%, 相对标准偏差为2.07%~9.61% (n=5), 方法定量限均为 0.01 mg/kg。贵州辣椒中5种杀菌剂的残留量为<0.01-0.092 mg/kg。结论 本方法满足农药残留检测分析要求, 适用于5种农药在鲜食辣椒中的多残留准确定性和定量分析以及市场监督抽查等。实际样品检测显示5种杀菌剂在贵州辣椒上的使用是安全的, 不会产生相关膳食风险与危害, 不影响出口贸易。     

超高效液相色谱串联质谱法同时测定保健食品中的66种非法添加物

目的 建立一种超高效液相色谱串联质谱法同时测定保健食品中66种非法添加物。 方法 样品用甲醇进行超声提取,利用超高效液相色谱质谱联用技术于10分钟min内完成检测,并利用软件对图谱进行分析。对建立的方法进行方法学考察,并对市售液体类、半固体类、粉末类及片剂4类保健品进行测定。通过保留时间及离子丰度比定性,可判断出样品中是否含有非法添加物,并通过标准曲线定量。结果 各组分在 1～200 ng/mL浓度范围内具有良好的线性（r2均大于0.993）,各化合物的检出限为7.8～42.5 μg/kg,该方法加标量为50、100、250 μg/kg时,重复测定8次,精密度为0.5%～26.3%、目标物的回收率在66.3%～120.4%之间,能满足日常检测要求。结论 该方法准确可靠、简便快速,可适用于筛查保健品中非法添加药物的抽检工作,能够减少工作量,提高检测效率,节省资源。     

超高效液相色谱-串联质谱法测定保健食品中78种非法添加化学药物

建立了超高效液相色谱-串联质谱法快速筛查减肥、抗疲劳和增强免疫力类保健食品中非法添加78种化学药物的方法。保健食品样品经甲醇溶剂提取、QuEChERS净化,试样以C18柱分离,多反应监测（MRM）模式进行定量与定性分析,采用外标法定量。采用ACQUITY UPLC HSS T3柱（2.1×100 mm,1.7 μm）进行分离,以乙腈和乙酸铵溶液（含0.1%甲酸）作为流动相,进行梯度洗脱,质谱采用正离子和负离子同时扫描分析。在优化的色谱、质谱条件下,78种化学药物能够得到较好分离,在线性范围内线性关系良好,相关系数均大于0.9991,检出限（LOQ）为0.5 μg/kg~420 μg/kg。各组分在三个不同加标水平下平均回收率为59.9%~120.7%,相对标准偏差（RSD）为1.3%~16.2%。运用本方法对57批次保健食品进行快速筛查,检出41批次样品含有一种或多种非法添加药物,被检出的药物为西布曲明、苄基西布曲明、氯代西布曲明、酚酞、伪麻黄碱、麻黄碱、二甲双胍、咖啡因、茶碱、番泻苷A、番泻苷B、呋塞米、大黄素和西地那非。本方法样品处理过程简单,分析时间短,准确可靠,灵敏度高,适用于保健食品中非法添加化学药物的定性与定量检测及快速筛查。     

超高效液相色谱-串联质谱法同时测定蜂蜜中8种生物胺

建立了同时测定蜂蜜中色胺(TR)、2-苯乙胺(PHE)、腐胺(PUT)、尸胺(CAD)、组胺(HIS)、酪胺(TYR)、亚精胺(SPD)和精胺(SP)8种生物胺的超高效液相色谱串联质谱柱前衍生的分析方法。样品经5%三氯乙酸溶液提取后用丹磺酰氯柱前衍生,采用Agilent Poroshell 120 SB-C₁₈(50 mm×2.1 mm,2.7 μm)柱,以0.1%甲酸水溶液-0.1%甲酸乙腈溶液为流动相进行定性和定量分析。采用本方法对22种市售蜂蜜进行检测,结果显示8种生物胺在不同的蜂蜜中检出,所有蜂蜜样品中均检测到2-苯乙胺和腐胺,其中2-苯乙胺也是蜂蜜样品中平均含量最多的生物胺。本方法中8种生物胺的线性相关系数均大于0.99,检出限为0.01~0.51 μg/L。在添加水平为100、500、1000 μg/kg时,样品的平均回收率在76%~112%之间,日内精密度小于等于9.8%,日间精密度小于等于13.1%。该方法快速简单,灵敏准确,且回收率稳定,适用于蜂蜜中生物胺的检测。     

QuEChERS-超高效液相色谱串联质谱法检测粮谷中10种农药残留

建立了液质联用法同时测定粮谷中异稻瘟净、腈苯唑、嘧菌酯、稻瘟酰胺、环酯草醚、苯噻酰草胺、甲胺磷、肟菌脂、戊唑醇、啶虫脒10种农药残留。样品经乙腈溶液提取,QuEChERS前处理,Waters Acquity UPLC~? BEHC18色谱柱分离,用超高效液相色谱串联质谱系统测定,外标法定量。结果表明10种农药残留在线性范围内线性相关性R2≥0.999 1,检出限在0.08～5.00μg/kg之间,加标回收率在88.0%～100.0%之间,相对标准偏差在1.6%～4.4%之间。该方法操作简单、灵敏度高、回收率好,适用于粮谷中多种农药残留的同时检测。     

气相色谱-串联质谱法测定大米中非法添加的石蜡

建立测定大米中石蜡的气相色谱-串联质谱（GC-MS/MS）法。 样品经石油醚提取,浓缩后用正己烷溶解,加浓硫酸净化,通过 对C24、C26、C28、C30、C335种烷烃的测定,进行石蜡的定性分析,用上述5种烷烃的峰面积之和进行定量分析。 该方法的检出限为0.25mg/kg, 定量限为0.75mg/kg,加标回收率及精密度实验的平均回收率为93.38%～110.22%,相对标准偏差（RSD）为5.42%～12.11%,相关系数为 0.9980。结果表明,该方法精密度良好,检测结果可靠,可作为大米中石蜡的测定方法。     

伪制红薯粉条中非法添加3种合成色素的检测方法

建立了二极管阵列高效液相色谱法(HPLC-DAD)及高效液相色谱-串联质谱法(HPLC-MS/MS)测定伪制红薯粉条中非法添加人工合成色素柠檬黄、日落黄、亮蓝的检测方法。样品经粉碎后加0.25 mL氨水(氨水和水体积比为1∶1)、50 mL水涡旋2 min,超声20 min,加水定容后进行检测。结果表明:3种合成色素在添加浓度范围均有良好的线性关系,HPLC-DAD的相关系数(R2)为0.999 2~0.999 3,HPLC-MS/MS的相关系数(R2)为0.996 1~0.997 9,HPLC-DAD和HPLC-MS/MS的检出低限分别为0.08~0.3 mg/kg和0.02~0.05 mg/kg,在低、中、高3个水平进行加标回收实验,HPLC-DAD和HPLC-MS/MS回收率分别为83.5%~89.9%和84.2%~92.5%,相对标准偏差分别为0.62%~4.10%和0.96%~4.92%。方法准确、灵敏度高、回收率高,适用于伪制红薯粉条中非法添加合成色素的检测。     

UPLC-MS/MS法同时测定减肥食品中55种非法添加物

目的 建立超高效液相色谱-串联质谱同时测定减肥类食品中55种非法添加物的分析方法。方法 样品经甲醇超声提取后,采用Agilent Eclipse Plus C₁₈ RRHD色谱柱(2.1 mm×100 mm,1.8μm)分离,以乙腈-0.1%甲酸为流动相进行梯度洗脱。在正负离子扫描条件下,采用动态多反应监测模式监测。结果 55种非法添加药物在相应的线性范围内均呈现良好线性关系,相关系数大于0.995,平均回收率75.2%～121.6%,相对标准偏差<12%,各化学药物的检测限在0.02～1.25μg/g。应用该方法对50批样品进行了检测,其中有38批次样品检出托拉塞米、大黄素、西布曲明、N-单去甲基西布曲明、N,N-双去甲基西布曲明、比沙可啶、麻黄碱、甲基麻黄碱、氢氯噻嗪、氟西汀等非法添加物。结论 该方法简单、快速、灵敏、准确、高效,兼具定性定量检测的优点,可用于食品中减肥类化学药物的高通量检测。     

超高效液相色谱-串联质谱法检测茶制品中非法添加13种抗风湿类药物

目的建立超高效液相色谱-串联质谱法检测茶制品中非法添加13种抗风湿类药物(氨基比林、对乙酰氨基酚、甲氧苄啶、氢化可的松、吡罗昔康、醋酸泼尼松、地塞米松、双氯芬酸钠、吲哚美辛、保泰松、罗通定、安替比林、非那西丁)的分析方法。方法样品甲醇超声提取后,以0.1%的甲酸溶液-乙腈为流动相梯度洗脱,经Inertsil ODS-3(2.1 mm×75 mm, 2μm)色谱柱分离,目标化合物在ESI源正离子模式下电离,采用多反应监测模式进行定性、定量分析。结果 13种抗风湿的方法检出限(S/N=3)为0.3～1.6μg/kg,定量限(S/N=10)为1.4～6.5μg/kg。在低、中、高3个加标水平下的平均回收率为80.20%～110.31%。对25批次市售抗风湿类茶制品进行检测,均未发现上述13种抗风湿类药物。结论该方法灵敏高、专属性强,适用于茶制品中抗风湿类非法添加的定量及确证分析。     

A novel method for the simultaneous determination of 14 sweeteners of regulatory interest using UHPLC-MS/MS

An improved, efficient, sensitive method for the determination of 14 non-nutritive sweeteners in food products was developed using electrospray ionisation (ESI) ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) in the negative-ion mode. Fourteen sweeteners and three internal standards were separated on a reversed-phase UHPLC column using a simple gradient programme. Analyte quantitation and confirmation were performed with data collection in multiple reaction monitoring (MRM) mode. Limits of detection (LODs) were determined in a representative drink, candy and yogurt sample and ranged from 0.1 to 1.8 ng ml^–1 (drinks) and from 0.1 to 2.5 ng g^–1 (candy and yogurt). Repeatability at the limit of quantitation (LOQ) ranged from 1% to 13% relative standard deviation (RSD). Twenty-seven commercially available food products were tested using the optimised method showing that the majority of products contained sweetener concentrations below their assigned maximum usable dose. Recovery studies were performed and accuracy data are presented.     

Development and validation of an UHPLC-MS/MS method for the determination of mycotoxins in grass silages

An ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) multi-mycotoxin analytical method was developed to simultaneously identify and quantify 20 mycotoxins in grass silages, inclusive of mycotoxins that are currently regulated in European Union feeds. Extraction of mycotoxins from dried grass silages was performed using of a modified QuEChERS extraction employing an acidified aqueous extraction (0.1 N HCl) with no further clean-up. Following chromatographic separation, analytes were detected using a fast polarity-switching MS/MS method that allowed both positive and negative ions to be analysed from a single injection, thus the reducing time and cost of analysis. The limits of detection and quantification ranged between 3 µg kg^–1 DM (aflatoxin B₁, beauvericin and enniatin A and A₁) and 200 µg kg^–1 DM (deoxynivalenol), and between 10 µg kg^–1 DM (aflatoxin B₁, beauvericin and enniatin A₁) and 500 µg kg^–1 DM (deoxynivalenol), respectively. Inter-assay accuracy and precision ranged between 90% and 107% and between 3.9% and 15.0% CV, respectively. The accuracy of the method was assessed through the application to a range of incurred samples in an inter-laboratory study.     

Simultaneous determination of 30 hormones illegally added to anti-ageing functional foods using UPLC-MS/MS coupled with SPE clean-up

A novel analytical method employing solid-phase extraction (SPE) coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of 30 hormones in anti-ageing functional foods (capsules, powders and tablets). The analytes were extracted with acetic acid–acetonitrile (1–99 v/v), methanol and acetone, respectively. The extract was purified using a combined column, followed by analyte detection with electrospray ionisation in positive- or negative-ion modes. The results indicated that the 30 compounds had good linear correlations in the range of 1–1000 μg kg^–1, and the correlation coefficients were above 0.99. The limits of detection (LOD) and limits of quantification (LOQ) were 0.03–2 and 0.1–5 μg kg^–1, respectively. The average recovery of 30 compounds at the three spiked levels varied from 74.7% to 124.1%, and the relative standard deviation (RSD) was 2.4–15.0%. This method was applied to the analysis of hormones in 14 real samples of which seven hormones (such as estrone, dienestrol) were detected in four samples, but the remainder of the hormones were not detected. The developed method is sensitive, efficient, reliable and applicable to real samples.     

Development and validation of a quantitative UHPLC-MS/MS method for selected brominated flame retardants in food

An ultra-high performance liquid chromatography – tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated (in-house) for the quantification of selected brominated flame retardants (BFRs), including tetrabromobisphenol A (TBBPA), hexabromocyclododecanes (HBCDs), tetrabromobisphenol S (TBBPS) and bromophenols (BPs), in various food matrices. The sample preparation consisted of extraction of TBBPS with acidified acetonitrile followed by a fast dispersive solid-phase extraction (dSPE) clean-up and extraction of the other BFRs with a mixture of hexane and dichloromethane (1:1, v/v) with subsequent clean-up using acidified silica (44%, w/w). The limits of quantification of the method varied widely for the types of food matrices and the different classes of BFRs from 4 pg g^?1 wet weight (ww) to 8 ng g^?1 ww. For most of the analytes the apparent recovery was in the range 70–120%, and the method precision (under repeatability conditions) was below 20%. The method was successfully applied in proficiency testing exercises as well as for analysis of various food items. Only 25% of the collected food samples contained BFRs, with 4-bromophenol and α-HBCD as the only detected compounds. The contaminated foodstuffs were fish and eggs with concentrations in the range from 48 to 305 pg g^?1 ww.     

高效液相色谱-串联质谱法同时测定调味品中8种人工合成甜味剂

目的 建立一种高效液相色谱-串联质谱法(HPLC-MS/MS)同时测定调味品中8种人工合成甜味剂(安赛蜜、甜蜜素、糖精、阿斯巴甜、阿力甜、纽甜、三氯蔗糖、新橘皮苷二氢查耳酮).方法 样品用水提取,提取液用甲醇沉淀水溶性大分子化合物,离心后取上清液经过中性氧化铝固相萃取柱分离色素,采用C18色谱分离柱,以10 mmol/L甲酸铵溶液-乙腈进行梯度洗脱,电喷雾负离子模式下多反应监测(MRM)模式检测.结果 线性范围分别为糖精于0.05～5μg/ml,三氯蔗糖于0.1～ 10 μg/ml,其它甜味剂于0.01～1μg/ml,线性关系良好,r2＞0.990.在3个添加水平下,样品平均回收率为82.7％～117.9％,RSD为0.6％～10.6％.甜味剂于液体及半固体基质中的检出限均为0.01 ～0.1 mg/kg,于固体基质中的检出限为0.1～1 mg/kg.结论 本方法选择性强、灵敏度高、处理方法简单,可用于调味品中8种人工合成甜味剂的测定.     

A rapid quantitative method for polysaccharides in green tea and oolong tea

Tea polysaccharides (TPS) from five different kinds of tea contain similar composition of sugars and amino acids. Polysaccharide part of TPS is mainly composed of arabinose, galactose and glucose with the approximate molar ratio of 1:1:0.5. Protein part of TPS is composed of 16 normal amino acids among which Val, Ala, Gly, Glu are the major proportion. Based on the results, the purified TPS was used as the calibration standard in phenol sulfuric acid reaction for the calibration curve that was constructed by plotting absorbance versus mass of TPS with a correlation coefficient of 0.9961. In the developed method, TPS mass recovery ranges from 84.88 to 95.7% with a relative standard deviation of 5.53%. It is found that the developed method is simple, rapid, reliable and is ideally suitable for quantifying TPS from green tea or oolong tea.