解吸附电晕束电离质谱法快速检测功能保健食品中违禁添加的降糖类药物

目的 建立解吸附电晕束电离质谱快速检测保健食品中违禁添加的6种降糖类化学合成药物(那格列奈, 二甲双胍, 伏格列波糖, 格列吡嗪, 吡格列酮, 瑞格列奈)的分析方法。方法 通过DCBI-MS直接分析, 对比标准物质一级和二级质谱图, 对检测样品中非法添加的那格列奈、二甲双胍、伏格列波糖、格列吡嗪、吡格列酮、瑞格列奈等6种降糖类化学合成药物进行快速定性和半定量检测。结果 各目标物在一定范围内线性关系良好, 线性相关系数R2均大于0.98, 检测限均在1 mg/L以下, 相对标准偏差为8%~40%。结论 此方法可以完成降糖类违禁药物的快速检测, 定性准确, 专属性高, 同时完成半定量分析, 为进一步准确测定样品提供依据。     

解吸附电晕束电离质谱法快速检测微量雌激素

目的 建立解吸附电晕束电离质谱(DCBI-MS)快速检测微量雌激素的分析方法。方法 通过DCBI-MS 直接分析, 对比标准物质一级和二级质谱图, 对检测样品中非法添加的炔诺酮、黄体酮、甲羟孕酮、左炔诺孕酮、醋酸甲地孕酮和枸橼酸氯米芬等 6 种雌激素进行快速定性和半定量检测。结果 各目标化合物均可在 1 min 内被检出。 基于一级分子离子的定量分析, 6 种雌激素的半定量检测结果可信, 线性关系最差的醋 酸甲地孕酮相关系数为 0.9471, 而黄体酮则为 0.9998。最低检出值分别是: 0.0875、0.045、0.1775、0.05、0.15、0.1 mg/L。结论 本方法无需复杂的前处理过程, 简便、快速、灵敏度高, 可用于保健食品和中成药中违禁添加微量雌激素的快速定性及半定量检测。     

高效液相色谱法检测保健食品中的违禁药物

目的建立高效液相色谱法同时测定保健食品中的3大类共10种违禁添加药物的方法。方法样品经色谱分离后采用二极管阵列(PDA)检测器检测,以紫外特征吸收谱图作为定性的依据。结果苯乙双胍、芬氟拉明、格列齐特、格列甲嗪、西力士、格列苯脲、西地那非、格列美脲、伐地那非、盐酸西布曲明的最低检出限分别为8·26、38·34、13·37、22·44、6·90、16·08、25·32、40·43、40·94、11·95ng/ml;线性关系在0·5~50μg/ml浓度范围,相关系数(r)均大于0·9998,样品加标回收率大于85%,RSD小于5·20%。结论该方法样品处理简便,结果准确可靠,重复性好,灵敏度高。     

高效液相色谱法测定减肥类保健食品中酚酞含量的不确定度评定

目的评定高效液相色谱法测定减肥类保健食品中酚酞的不确定度。方法减肥类保健食品中酚酞经甲醇提取,反相色谱柱分离,流动相等度洗脱,外标法定量测定。依据JJF1059.1-2012《测量不确定度评定与表示》,考察了称量、标准溶液配制、仪器重复测量等主要因素引入的不确定度,并对不确定度的各分量进行计算和合成。结果当减肥类保健食品中酚酞含量为(122.5±3.62)mg/g时,在95%的置信区间下,其扩展不确定度为3.62 mg/g(k=2)。评定结果显示,实验过程的不确定度主要来源于对照品称量、对照品溶液制备及样品定容过程。结论本方法适用于高效液相色谱法测定减肥类保健品中酚酞的含量的测定,对检测结果准确度的提高具有指导意义。     

高效液相色谱法检测保健食品中的番茄红素

目的建立高效液相色谱法测定保健食品中番茄红素的分析方法。方法用含有0.1%2,6-二叔丁基-4-甲基苯酚抗氧化剂的甲醇:二氯甲烷(10:90,V:V)作为提取溶液。通过Agilent Eclipse XDB-C_(18)(4.6 mm×250mm,5μm)色谱柱;甲醇:乙酸乙酯(85:15,V:V)作为流动相,二极管阵列检测器,检出波长475 nm,色谱柱温25℃,流速1.0 mL/min,进样体积10μL,作为检测条件。结果番茄红素在0~200μg/mL范围内线性良好,相关系数r=0.9995,最低检出限为0.0815μg/mL,平均回收率在89.7%~109.8%之间,RSD为8.4%。结论本方法可以准确、快速地检测保健食品中的番茄红素。     

高效液相色谱对保健食品中五种违禁的性功能药物成分的同时检测

目的:建立一种同时测定保健食品中5种常见违禁添加的增强性功能药物成分的反相液相色谱方法"用二极管阵列检测器检测,利用色谱峰保留时间和物质的紫外吸收光谱综合定性,外标法定量.方法:采用反相高效液相色谱法实现5种成分完全分离.Agilent C18 4.6×250mm色谱柱,柱温30%,流动相为乙腈/0.02%磷酸,梯度洗脱,流速1.0 mL/min,检测波长为225.0nm.结果:5种违禁性功能药物成分在0.4～20.0 μg/mL浓度范围内工作曲线线性关系良好.相关系数r2≥0.9989,相对标准偏差≤0.47%(n=6),平均回收率＞91.0%,最低检出限≤56ng/mL(信噪比≥3).结论:该方法简便快速,结果准确可靠,可用于保健食品中常见添加的性功能药物成分的测定.     

高效液相色谱法测定减肥类保健食品中番泻苷A、番泻苷B的含量

目的建立一种用于测定减肥类保健食品中番泻苷A、番泻苷B的高效液相色谱(high performance liquid chromatography,HPLC)检测方法。方法采用ZORBAX SB-C_(18)柱(4.6 mm×150 mm,5μm),以乙腈-0.1%磷酸水溶液为流动相进行梯度洗脱,流速为1.0 mL/min,柱温为40℃,二极管阵列检测器进行检测,检测波长为254 nm。结果番泻苷A、番泻苷B分别在2.050~20.50μg/mL(r=0.9999)、1.803~18.03μg/mL(r=0.9993)范围内呈良好线性关系,定量限分别为30、27μg/kg;平均回收率分别为96.8%、95.1%,相对标准偏差分别为1.3%、2.3%。结论该方法简单、可行,结果准确、可靠,适用于减肥类保健食品中番泻苷A、番泻苷B含量的测定。     

高效液相色谱法同时测定辅助改善记忆类保健食品中非法添加的17种化学药物

目的建立辅助改善记忆类保健食品不同剂型中(口服液、丸剂、软胶囊)17种非法添加化学药物的高效液相色谱测定方法。方法 3种不同剂型的保健食品样品以50%甲醇水为提取溶剂进行超声提取,提取后采用C18-SPE柱净化,通过Thermo AccliaimTMMixed-Mode WCX-1色谱柱(150 mm×2.1 mm,3μm)分离,以100 mmol/L磷酸二氢钠水溶液和乙腈为流动相梯度洗脱,采用二极管阵列检测器定性、外标法定量。结果在相应浓度范围内,17种化学药物线性关系良好,r0.99,加标回收率为85%~120%,检出限为10~40μg/ml,相对标准偏差(RSD)为0.8%~4.8%。结论该方法操作简便、准确、快速,能实现3种剂型中17种非法添加化学物的同时分析,可用于辅助改善记忆类保健食品中非法添加化学药品的定性筛查和定量检测。     

高效液相色谱-串联质谱法同时测定减肥类保健食品中27种违法添加化学药品

目的:建立一种高效液相色谱-串联质谱（HPLC-MS/MS）同时测定减肥类保健食品中27种违法添加化学药品的方法。方法:采用Agilent Eclipse Plus C₁₈色谱柱（2.1 mm×100 mm,1.8μm）,以10 mmol/L乙酸铵（用甲酸调节pH至4.0）溶液为流动相A,乙腈为流动相B,梯度洗脱,流速为0.2 m L/min。通过HPLC-MS/MS系统中多反应监测模式（MRM）对减肥类保健食品中27种违法添加化学药品进行定性和定量分析。结果:该方法线性R²均大于0.99,精密度相对标准偏差小于8.0%,不同质量浓度样品平均回收率为74.5%¹06.7%,检出限为0.2²04.2 ng/g。结论:此方法测定快速、准确、灵敏度高、分离度高,可用于减肥类保健食品中27种违法添加化学药品的检测。      

高效液相色谱法测定保健食品中的8种糖皮质激素

目的：建立了保健食品中8种糖皮质激素的高效液相色谱的测定方法。方法：样品采用甲醇超声提取后,HPLC分离测定。LUBEX Kromasil C18色谱柱（250mm×4．6mm,5μm）分离,流动相为乙腈：水（40：60）、检测波长为241nm、流速为1．0mL／min、柱温为40℃。结果：各糖皮质激素成分在定量范围均称良好的线性关系（r≥0．999）,相关系数均大于0．999,平均回收率为96．7％-100．2％,RSD为0．11％--1．71％。结论：本方法准确简便,可应用于保健食品中此8种糖皮质激素的分析。     

Determination of synthetic drugs used to adulterate botanical dietary supplements using QTRAP LC-MS/MS

Adulteration of botanical dietary supplements with prohibited synthetic drugs has become a serious problem. In this paper, a method for testing synthetic drugs used to adulterate botanical dietary supplements was developed using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) coupled with a linearity ion-trap system in the multiple reaction monitoring (MRM) plus enhanced product ion (EPI) mode. Twenty-three drugs exhibiting various pharmacological effects, comprising blood pressure and lipid-lowering agents, sedative drugs, anti-diabetic drugs, weight-reducing agents and aphrodisiac compounds, were studied. For all drugs, a single transition was monitored using protonated molecules as precursor ions. EPI spectra were stored in a library and recognized by library searching. Several undeclared drugs were identified in herbal remedies, e.g., glibenclamide, sibutramine hydrochloride and sildenafil. Overall, 35 positive samples were found out of a total of 105 botanical dietary supplements tested. The method was selective, sensitive, rapid, high-throughput and reliable.     

减肥保健食品中非法添加物检测方法研究进展

本文简介了超重和肥胖的概念和其引起的主要风险,阐述了目前减肥保健食品中违法添加物的种类、提取和测定等方面的状况。减肥保健食品中单独或者联合添加的违法添加物多达百余种,主要有食欲抑制剂、能量消耗增强剂、阻止消化吸收药物、影响脂代谢的药物、利尿剂、抗抑郁剂等6类。重点综述了现有分析方法的适用性和局限性。与气相色谱法、薄层色谱法、酶联免疫吸附法、核磁共振等相比,高效液相色谱仪配质谱检测器是目前最常用的方法。针对片剂、胶囊和冲剂3种剂型,固-液萃取是主要的样品前处理手段。虽然目前的分析方法可基本满足实际检测要求,但面对新增药物种类和高通量筛查,还存在缺陷,如同时提取不同极性的化合物和提高分析速度。实时直接分析离子源-高分辨质谱法具有快速、准确、高效等优点,可以填补此空白,用于减肥保健食品中非法添加物的筛查。     

Detection of adulteration of anti-hypertension dietary supplements and traditional Chinese medicines with synthetic drugs using LC/MS

A sensitive and specific liquid chromatography-electrospray ionization mass spectrometry (LC/ESI-MS) method was developed for the analysis of 18 drugs used for the treatment of anti-hypertension, including diuretics, calcium antagonists, and angiogenesis-converting enzyme inhibitors (ACEI) as adulterants in dietary supplements and traditional Chinese medicines. Separation was accomplished on a Xtimate? C₁₈ reversed-phase column using a mixture of methanol, acetonitrile and 20 mM ammonium formate buffer (pH 3.2) as mobile phase. The method demonstrated linearity from 0.03 to 21.52 mg kg^?1. Limits of detection ranged from 6.5 to 86.0 µg kg^?1. The recoveries of spiked samples ranged from 71% to 109%. The procedure was successfully applied in routine inspection analysis.     

超高效液相色谱-四级杆-飞行时间串联质谱法检测中药及保健食品中21种非法添加的降脂类药物

目的建立超高效液相色谱-四级杆-飞行时间串联质谱仪(ultra performance liquid chromatography/quadrupole-time-of-flight mass spectrometry,UPLC/Q-TOF-MS)快速检测中药及保健食品中的21种降脂类药物。方法样品经甲醇超声提取后,采用Agilent Poroshell 120 SB-C_(18)色谱柱分离,以0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱,流速为0.4 mL/min;质谱采用Q-TOF-MS作检测器,采用电喷雾离子源(electronic spray ion,ESI)正负离子模式,以保留时间、精确分子量和二级碎片比对进行定性分析。结果 21种降脂类药物的检出限为0.05~25 ng。对96批市售中成药及保健食品进行定性检测,结果 1批片剂中检出洛伐他丁,其余均未检出。结论本方法灵敏、准确、高效,可适用常见降脂类药物的快速检测。     

用高效液相色谱(HPLC)法测定饮料中维生素C的含量

建立了一种饮料中Vc的反相高效液相色谱 (HPLC)测定法。高效液相色谱系统采用Shim packVP ODSC 18柱 ,甲醇 /磷酸二氢钾缓冲液 =75 /2 5 (V/V)作流动相 ,流速为 1 0ml/min ,检测波长为 2 6 6nm。Vc在浓度 0 0 5 0～ 0 30 0mg/ml内有良好的线性关系 ,线性回归方程为y =4845 5 716 96 3x 772 6 0 10 (R =0 9999)。分析方法中回收率平均为 99 2 3%,标准偏差s =0 0 0 18,变异系数CV =1 90 %。Vc的最低检测限为 2 5 0× 10 7mg。     

Analysis of six synthetic adulterants in herbal weight-reducing dietary supplements by LC electrospray ionization-MS

A liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) method was developed for the simultaneous determination of six synthetic adulterants, namely fenfluramine, phenolphthalein, N-di-desmethyl sibutramine, N-mono-desmethyl sibutramine, sibutramine, and orlistat. The method was applied to the analysis of herbal weight-reducing dietary supplements. Chromatographic separation of the analytes on a C₈ reversed-phase column was achieved using a gradient elution of solvent A: acetonitrile and solvent B: aqueous 20 mM ammonium formate solution. Sildenafil was utilized as an internal standard for quantification. The MS detector was operated in positive electrospray ionization mode. Selected-ion monitoring (SIM) was carried out for m/z 232, 319, 252, 266, 280, 496, and 475 for fenfluramine, phenolphthalein, N-di-desmethyl sibutramine, N-mono-desmethyl sibutramine, sibutramine, orlistat, and sildenafil, respectively. The method was validated for accuracy, precision, linearity, and selectivity. The limits of detection for the six synthetic adulterants ranged from 0.0018 to 0.73 µg g^?1. The proposed method was used for a small survey of 22 dietary supplements of which eleven samples were adulterated with phenolphthalein, N-mono-desmethyl sibutramine, and sibutramine at levels from 0.212 to 96.2 mg g^?1.     

Determination of illegal adulteration of dietary supplements with synthetic hair-growth compounds by UPLC and LC-Q-TOF/MS

In this study, we developed a UPLC-PDA and LC-Q-TOF/MS method to identify and measure the following prohibited substances that may be found in dietary supplements:triaminodil, minoxidil, bimatoprost, alimemazine, diphenylcyclopropenone, α-tradiol, finasteride, methyltestosterone, spironolatone, flutamide, cyproterone, dutasteride, and testosterone 17-propionate.The method was validated according to International Conference on Harmonization guidelines in terms of specificity, linearity, accuracy, precision, LOD, LOQ, recovery, and stability. The method was completely validated showing satisfactory data for all method validation parameters. The linearity was good (R² > 0.999) with intra- and inter-day precision values of 0.2–3.4% and 0.3–2.9%, respectively. Moreover, the intra- and inter-day accuracies were 87–102% and 86–103%, respectively, and the precision was better than 9.4% (relative standard deviation).Hence, the proposed method is precise and has high quality,and can be utilised to comprehensively and continually monitor illegal drug adulteration in various forms of dietary supplements. Furthermore, to evaluate the applicability of the proposed method, we analysed 13 hair-growth compounds in 78 samples including food and dietary supplements. Minoxidil and triaminodil were detected in capsules at concentrations of 4.69 mg/g and 6.54 mg/g. In addition, finasteride was detected in a tablet at 13.45 mg/g. In addition, the major characteristic fragment ions were confirmed once again using LC-Q-TOF/MS for higher accuracy.     

Monitoring of 29 weight loss compounds in foods and dietary supplements by LC-MS/MS

Because of the rapid growth in dietary supplement availability and public concern for weight control, the investigation of foods and various dietary supplements illegally adulterated with weight loss compounds has become increasingly important. A total of 29 weight loss compounds, including sennoside, sibutramine, ephedrine and their analogues, found to be adulterated in foods and dietary supplements were simultaneously examined by LC-MS/MS. The 188 samples were collected between 2009 and 2012 in South Korea, and method validation was performed to determine the adulterants to the weight loss compounds. LODs, LOQs and linearity ranged from 0.03 to 7.5 ng ml^?1, from 0.08 to 30.00 ng ml^?1, and from 0.990 to 0.999, respectively. The results showed that nine weight loss compounds, namely bisacodyl, desmethylsibutramine, didesmethylsibutramine, ephedrine, fluoxetine, pseudoephedrine, sennoside A, sennoside B and sibutramine, were detected in 62 of all collected samples and were found in order of frequency as follows: sibutramine, 25.7%; sennoside A, 22.9%; sennoside B, 20.0%; fluoxetine, 8.6%; desmethylsibutramine, 7.1%; bisacodyl, ephedrine, and pseudoephedrine, 4.3%; and didesmethylsibutramine, 2.9%. Sibutramine, which was the most frequently found adulterant, ranged in levels from 0.03 to 132.40 mg g^?1 (2010), from 0.88 to 76.2 mg g^?1 (2011), and from 0.07 to 0.24 mg g^?1 (2012). Although the concentrations of most compounds ranged widely, some compounds such as bisacodyl and fluoxetine were found at high concentrations in several samples.     

高效液相色谱-串联质谱法检测保健食品中25种非甾体类抗炎药

目的 建立高效液相色谱-串联质谱法(high performance liquid chromatography-tandem mass spectrometry, HPLC-MS/MS)分析保健食品中25种非法添加非甾体类抗炎药的分析方法。方法 保健食品固体试样经甲醇超声提取, 液体试样经水-甲醇萃取来提取, 经液相色谱柱分离后, 在多反应监测(multiple reaction monitoring, MRM)模式下测进行25种非甾体类抗炎药含量的测定, 外标法定量。结果 25种非甾体抗炎药在1~500 ng/mL范围内呈现良好线性关系, 相关系数均大于0.99, 方法检出限为1.5~2.0 μg/kg, 定量限为5.0~6.0 μg/kg, 6.0、12.0和60.0 μg/kg 3个水平平均加标回收率为80.0%~108.2%, 相对标准偏差为6.4%~9.9% (n=6)。结论 该方法针对保健食品基质, 对固体和液体样品分别采取超声萃取和液液直接萃取的提取方式, 操作简便、节约成本、专属性强且灵敏度、回收率高, 满足保健食品中非甾体类抗炎药的检测。     

HPLC法同时测定红曲色素中的红曲素和安卡红曲黄素

目的：建立同时测定红曲混合色素中的红曲素和安卡红曲黄素的高效液相色谱方法。方法：采用Shim-Pack HRC-ODS色谱柱,甲醇-水溶液(80:20)为流动相,流速1.0ml/min,检测波长394nm,以自制的两种色素标准品定性定量。结果：该方法在10～500mg/L范围内呈良好的线性关系,回归方程和相关系数分别为：红曲素：Y=0.00015X+0.82365,R2=0.99988;安卡红曲黄素：Y=0.00031X－0.45,R2=0.99987。多次测定的相对标准偏差均小于4%,采用该方法对收集到的国内部分企业的红曲色素产品进行了检测。结论：该方法具有较好的重复性和稳定性,可用于红曲色素中红曲素和安卡红曲黄素的检测,进而可用于红曲色素产品组成和质量分析。