蛋品中苏丹红残留的液相色谱串联质谱测定法研究

采用液相色谱-串联质谱法（LC-MS/MS）测定了蛋品中苏丹红I、II、III、Ⅳ号染料的残留。制样后,装柱,应用基质固相分散技术,用氯仿、乙腈混合溶液（体积比为90：10）淋洗,浓缩定容后经ZORBAX SB-C18柱分离,采用电喷雾正离子,多反应监控（MRM）模式检测。外标曲线定量,苏丹红I、II、III、Ⅳ的线性范围分别为0.5～100ng/g,5.0～100ng/g,1.0～100ng/g和2.0～100ng/g,线性方程的相关系数都大于0.99,添加样品回收率在87.3～113％之间,相对标准偏差均小于9.1％。针对四种苏丹红染料,该方法的检测低限分别可达0.1μg/kg,2.0μg/kg,0.2μg/kg,0.4μg/kg,可以满足国内外蛋品中苏丹红监控要求。     

蛋品中苏丹红残留的液相色谱串联质谱测定法研究

采用液相色谱-串联质谱法（LC-MS/MS）测定了蛋品中苏丹红I、II、III、Ⅳ号染料的残留。制样后,装柱,应用基质固相分散技术,用氯仿、乙腈混合溶液（体积比为90：10）淋洗,浓缩定容后经ZORBAX SB-C18柱分离,采用电喷雾正离子,多反应监控（MRM）模式检测。外标曲线定量,苏丹红I、II、III、Ⅳ的线性范围分别为0.5～100ng/g,5.0～100ng/g,1.0～100ng/g和2.0～100ng/g,线性方程的相关系数都大于0.99,添加样品回收率在87.3～113％之间,相对标准偏差均小于9.1％。针对四种苏丹红染料,该方法的检测低限分别可达0.1μg/kg,2.0μg/kg,0.2μg/kg,0.4μg/kg,可以满足国内外蛋品中苏丹红监控要求。     

凝胶净化/高效液相色谱-串联质谱法检测辣椒制品及肉制品中多种脂溶性着色剂

建立了凝胶渗透色谱净化/高效液相色谱-串联质谱测定辣椒制品和肉制品中苏丹橙G、甲基黄、对位红,柑桔红2号,苏丹红G,苏丹Ⅰ,苏丹Ⅱ,苏丹Ⅲ,苏丹红7B,苏丹红B和苏丹Ⅳ的分析方法。样品经乙酸乙酯或乙腈-乙酸乙酯溶液提取后采用凝胶渗透色谱净化,通过ACQUITY HPLC BEH C18色谱柱以体积分数0.1%甲酸-体积分数0.1%甲酸甲醇溶液作流动相梯度洗脱分离,采用多反应监测模式进行检测。目标分析物使用同位素内标苏丹Ⅰ-D5和苏丹Ⅳ-D6定量,11种待测物质量浓度在10~500 ng/mL范围呈良好线性关系,相关系数大于0.99,方法的定量下限均达到5μg/kg。空白样品在5,10,20μg/kg 3个加标水平下的平均回收率为80.7%~100.9%,相对标准偏差(n=10)均小于10%。     

液相色谱-串联质谱法快速检测番茄制品中苏丹红

采用HPLC/MS-MS鉴定和检测番茄制品中苏丹红染料Ⅰ～Ⅳ。番茄制品中苏丹红Ⅰ、Ⅱ、Ⅲ、Ⅳ,经正己烷加乙酸溶液提取,氧化铝柱净化,再用二氯甲烷洗脱苏丹红,经浓缩至干,流动相定容,液相色谱串联质谱测定,外标法定量。将已用HPLC法测定过的10个可疑样品,用该方法进行检测,结果有4个检了苏丹红Ⅰ。采用本方法检测苏丹红Ⅰ～Ⅳ,检测限均可达到1.0μg/kg,在添加浓度1～100μg/kg之间线性关系良好,相关系数(r)均>0.9990,对于1、5、10μg/kg水平添加回收率在72.3%～103%之间,相对标准偏差在2.5%～9.8%之间。     

凝胶净化/超高效液相色谱电喷雾质谱法检测调味油中11种禁用偶氮染料及罗丹明B

建立了凝胶渗透色谱(GPC)净化/超高效液相色谱-电喷雾串联四极杆质谱(UPLC-MS/MS)同时检测调味油中11种脂溶性偶氮类工业染料(苏丹红Ⅰ、苏丹红Ⅱ、苏丹红Ⅲ、苏丹红Ⅳ、苏丹红7B、苏丹红G、苏丹黄、苏丹橙G、苏丹蓝Ⅱ、甲苯胺红、对位红)和罗丹明B的分析方法。样品经乙酸乙酯-环己烷(1∶1)提取,采用凝胶渗透色谱(GPC)去除大分子油脂、天然色素等干扰物质;以乙腈-0.1%甲酸为流动相,目标化合物在梯度洗脱条件下经C18柱分离后采用多离子反应监测(MRM)正离子模式进行检测。结果表明:调味油中12种工业染料的线性范围为1～50μg/L,定量下限(LOQ)为0.2～2.5μg/kg,在5、20、40μg/L 3个加标水平下的回收率为54%～125%,相对标准偏差为2.5%～17.2%。随机抽取市售35份样品进行检测,其中两份样品检出罗丹明B。该方法操作简便、灵敏度高,实现了11种禁用偶氮染料和罗丹明B的同时提取和净化,适合于调味油中非法添加脂溶性偶氮工业染料和罗丹明B的筛查与确证。     

柱后紫外光解荧光衍生液相色谱法测定蔬菜中残留的15种苯脲除草剂

建立了蔬菜中15种苯脲除草剂残留的固相萃取-在线柱后紫外光分解和衍生化的高效液相色谱荧光检测分析方法。样品用乙腈提取,弗罗里硅土固相萃取柱净化,目标化合物由反相C18柱分离,经柱后紫外光分解和衍生化后进行荧光检测。对样品的前处理条件、液相色谱分离、柱后紫外光分解和衍生条件等进行了详细的研究。15种苯脲除草剂的高效液相色谱分离在乙腈-水梯度洗脱下完成,目标物的保留时间为9～31 min,线性范围内线性关系良好,相关系数为0.9986~1.0000;在洋葱、菠菜、黄瓜等样品中3个加标水平的平均回收率(n=3)为75.3%～121.6%,相对标准偏差为0.4%-11.6%;15种苯脲除草剂在蔬菜中的检出限为0.005～0.05 mg/kg。该方法操作简便、灵敏度高、选择性好,符合多种农药残留分析的要求。     

在线凝胶渗透色谱-气相色谱/质谱法检测茶叶中的153种农药残留

建立了在线凝胶渗透色谱-气相色谱/质谱(GPC-GC/MS)分析茶叶中153种农药残留的方法。样品用乙腈超声提取,提取液经石墨化炭黑固相萃取柱净化后,经GPC-GC/MS在线净化、分离和检测。方法的加标回收率为73.32%～117.05%,相对标准偏差为0.76%～13.18%。方法的检出限和定量限范围分别为0.0003～0.006 mg/kg和0.001～0.02 mg/kg。该方法样品前处理简单、分析时间短,灵敏度和精密度均符合农药多残留检测技术的要求,适用于茶叶中多种农药残留的检测。     

分散固相萃取结合液相色谱-串联质谱法测定饲料中8种脂溶性着色剂

建立了饲料中8种脂溶性着色剂(对位红、苏丹红Ⅰ、苏丹红Ⅱ、苏丹红Ⅲ、苏丹红Ⅳ、苏丹红7B、苏丹红G、苏丹黄)含量的液相色谱-串联质谱测定方法。饲料样品中脂溶性着色剂经乙腈提取,离心后上清液采用分散固相萃取净化,净化液稀释后进行LC-MS/MS分析。样品测定时采用Acquity BEH C18色谱柱进行色谱分离,以0.2%甲酸溶液-乙腈作为流动相进行梯度洗脱,电喷雾正离子(ESI+)模式电离,多反应监测(MRM)模式检测,同位素稀释内标法定量。8种脂溶性着色剂在1.0~200μg/L范围内线性关系良好,相关系数(r~2)均大于0.998;在饲料中的方法检出限为5.0μg/kg,定量下限为10μg/kg。在10,50,500μg/kg加标浓度下8种脂溶性着色剂的回收率为102%~111%,批内相对标准偏差(RSD)为2.8%~8.0%,批间RSD为2.8%~7.8%。该方法能满足饲料样品中脂溶性着色剂监控的需要。     

在线衍生–高效液相色谱法测定食品中的甲醛次硫酸氢钠

建立在线衍生–高效液相色谱法测定食品中的甲醛次硫酸氢钠。食品中的甲醛次硫酸氢钠用碘酸钾溶液氧化后释放出甲醛并被水提取,以2,4-二硝基苯肼(DNPH)的乙腈–乙酸溶液为衍生液,在线衍生2 min,衍生物在Agilent C_(18)色谱柱上分离,以乙腈–水(65∶35)溶液为流动相进行洗脱,用二极管阵列检测器测定,检测波长为350 nm。试验结果表明,在0.1～5.0 mg/L范围内,甲醛的质量浓度与色谱峰面积呈良好的线性关系(r~2=0.999),方法检出限为0.4 mg/kg,样品的加标回收率为89.84%～97.46%,测定结果的相对标准偏差为0.25%～0.43%(n=6)。该方法操作简单快捷,分离效果好,适用于食品中甲醛次硫酸氢钠的日常分析测试。     

在线凝胶渗透色谱-气相色谱-质谱法测定茶叶中多种有机锡化合物残留

建立了茶叶中6种有机锡化合物残留的在线凝胶渗透色谱-气相色谱/质谱(GPC-GC/MS)分析方法.样品用盐酸酸化,以丙酮-正己烷为提取剂振荡提取,浓缩、干燥后加入正戊基溴化镁进行衍生,衍生产物用正己烷提取,经Envi-Carb活性碳和Florisil串联固相萃取柱净化,再经在线GPC进入GC/MS检测.当加标水平为0.01、0.05和0.10mg/kg时,回收率为66.2%～105.6%,相对标准偏差为2.7%～10.4%.方法的检出限为0.01mg/kg.实验证明,该方法快速、简便、准确、灵敏度高,可用于茶叶中有机锡化合物残留的同时检测.     

凝胶柱净化-高效液相色谱检测食品中的苏丹红

建立了凝胶柱净化-高效液相色谱同时检测食品中苏丹红Ⅰ,Ⅱ,Ⅲ和Ⅳ的方法。样品用乙醇提取,提取液经Bio-Beads SX3凝胶柱(200 mm×10 mm i.d.)净化,用环己烷-乙酸乙酯(体积比为1∶1)洗脱。采用Symmetry Shield RP18柱(250 mm×4.6 mm i.d.,　5　μm)分离,以100%甲醇为流动相,流速1.5 mL/min;用二极管阵列检测器检测,检测波长478 nm。上述4种苏丹红组分在其质量浓度为0.1~10.0 mg/L时有良好的线性关系(r>0.999),方法的检测限为7~14 μg/kg;平均加标回收率为80.7%~96.3%(添加水平为0.25,2.5 mg/kg),相对标准偏差为2.4%~5.9%。方法灵敏可靠,能满足食品中苏丹红检测的需要。     

腐殖酸键合硅胶固相萃取-液相色谱法测定辣椒粉及辣椒油中的苏丹红

以腐殖酸键合硅胶作为固相萃取介质,建立了固相萃取柱净化、高效液相色谱同时     

复合免疫亲和柱-高效液相色谱法同时测定谷物及其制品中9种真菌毒素

建立了复合免疫亲和柱-在线光化学衍生-高效液相色谱同时测定谷物及其制品中9种真菌毒素的检测方法。以乙腈-水（80：20,v/v）混合溶液提取样品中9种真菌毒素,提取液经自制真菌毒素复合免疫亲和柱净化,采用高效液相色谱进行分离,在线光化学衍生后进入荧光检测器测定,外标法定量。结果表明,9种真菌毒素在相应浓度范围内线性关系良好,相关系数均大于0.999;在低、中、高3个不同加标浓度下,9种真菌毒素的回收率均大于80%,相对标准偏差（RSD）为1.0%~5.6%;方法的检出限（LOD）为0.02~5.00 μg/kg,定量限（LOQ）为0.07~16.70 μg/kg。该方法具有重现性好、灵敏度高、结果准确的特点,适用于谷物及其制品中9种真菌毒素残留的分析检测。     

Effective extraction and simultaneous determination of Sudan dyes from tomato sauce and chili‐containing foods using magnetite/reduced graphene oxide nanoparticles coupled with high‐performance liquid chromatography

A simple, effective, and robust magnetic solid‐phase extraction method was developed using magnetite/reduced graphene oxide nanoparticles as the adsorbent for the simultaneous determination of Sudan dyes (I, II, III, and IV) in foodstuffs. The magnetite/reduced graphene oxide nanoparticles were characterized by X‐ray diffraction, scanning electron microscopy, and vibrating sample magnetometry. The extraction parameters including extraction time, elution solution, and elution time and volume were investigated in detail. Such magnetite/reduced graphene oxide nanoparticles based magnetic solid‐phase extraction in combination with high‐performance liquid chromatography and variable wavelength detection gave the detection limits of 3–6 μg/kg for Sudan I–IV in chili sauce, tomato sauce, chili powder, and chili flake samples. The recoveries were 79.6–108% at three spiked levels with the intra‐ and inter‐day relative standard deviations of 1.2–8.6 and 4.5–9.6%, respectively. The feasibility was further performed by a comparison with commercial alumina‐N. This method is suitable for the routine analysis of Sudan dyes due to its sensitivity, simplicity, and low cost.     

Development and optimization of an analytical method for the determination of Sudan dyes in hot chilli pepper by high-performance liquid chromatography with on-line electrogenerated BrO- -luminol chemiluminescence detection

The determination of four Sudan dyes by means of high-performance liquid chromatography (HPLC) with chemiluminescence (CL) detection was proposed. The method was based on the enhancement effect of Sudan dyes on the chemiluminescence reaction between luminol and BrO-, which was on-line electrogenerated by constant current electrolysis. The separation was carried out on Nucleosil RP-C18 column (250 mm x 4.6 mm i.d., 5 microm, pore size, 100 A) at 35 degrees C. The mobile phase consisted of a V (methanol): V (0.2% aqueous formic acid) = 90:10 solution. At a flow-rate of 1.0 ml min(-1), the total run time was 25 min. The effects of several parameters on the HPLC resolution and CL emission were studied systematically. For the four Sudan dyes, the limits of detection (LOD) at a signal-to-noise of 3 ranged from 4 to 8 microg kg(-1) and the limits of quantification (LOQ) at a signal-to-noise of 10 ranged from 13 to 27 microg kg(-1). The relative standard deviations (RSD) of intra-and inter-day precision were below 4.4%. The average recoveries for all four Sudan dyes (spiked at the levels of 1.0 and 1.5 mg kg(-1)) in chilli tomato sauce and hot chilli pepper ranged from 94% to 105%, and the relative standard deviations of the quantitative results were from 2.5 to 4.2%. The proposed method had been successfully applied to the determination of four Sudan dyes in hot chilli products.     

高效液相色谱荧光检测法测定蔬菜中残留的甲氨基阿维菌素苯甲酸盐

建立了甘蓝和蘑菇中甲氨基阿维菌素苯甲酸盐的固相萃取-高效液相色谱荧光分析方法。蔬菜样品用乙酸乙酯提取,提取液旋转浓缩近干后用少量乙酸乙酯溶解,再经PRS固相萃取(SPE)柱净化,洗脱液经氮气吹干后用氮甲基咪唑和三氟乙酸酐衍生,衍生物用高效液相色谱分析,采用外标法定量。在添加浓度1.0～20.0 μg/kg范围内,平均添加回收率为78.6%～84.9%,日内相对标准偏差(RSD)为2.7%～6.0%,日间RSD为3.1%～8.9%,检出限为0.10 μg/kg。甲氨基阿维菌素苯甲酸盐衍生物在0.002～0.10 mg/L范围内呈良好的线性关系,相关系数为0.9999。     

Determination of banned 10 azo-dyes in hot chili products by gel permeation chromatography-liquid chromatography-electrospray ionization-tandem mass spectrometry

An accurate method based on the use of gel permeation chromatography (GPC)-liquid chromatography-tandem mass spectrometry interfaced with electrospray ionization (GPC-LC-ESI-MS/MS) was devised for the simultaneous determination of Sudan (I-IV), Sudan Orange G, Sudan Red B, Sudan Red G, Sudan Red 7B, Butter Yellow and Para Red in hot chili products. A GPC clean-up procedure was developed for simultaneous quantification of 10 dyes in hot chili and hot chili products avoiding some interference and permitting multiple injections without damaging the column. A HPLC was performed on an Inertsil C18 column using a multistep gradient elution with 0.1% formic acid and methanol as the mobile phase. Mass spectral acquisition was done in positive ion mode. Linearity of around three orders in the magnitude of concentration was generally obtained with the correlation coefficients (r2) of 0.9984-0.9997. Limit of detection (LOD) and limit of quantification (LOQ) for the investigated dyes were in the ranges of 0.1-1.8 and 0.4-5.0 microg/kg depending on matrices, respectively. The recoveries of the 10 synthetic dyes in five matrices ranged from 81.7 to 92.9%. The intra- and inter-day precision (RSDs) was between 2.9-7.8 and 3.9-8.1%, respectively. This method has been applied successfully for the determination of the studied 10 banned dyes in hot chili products.     

高效液相色谱-柱后衍生法检测养殖水体及沉积物中11种磺胺药物残留

建立了养殖水体及沉积物中11种磺胺化合物的高效液相色谱-柱后衍生分析方法。养殖水体过滤后采用HLB固相萃取柱进行净化、富集;沉积物采用甲醇/EDTA-Mcllvaine缓冲液(1:1, v/v)提取,HLB固相萃取柱净化富集。经高效液相色谱分离,用荧光胺衍生试剂进行柱后衍生,荧光检测器检测。对柱后衍生系统参数进行了优化,确定了荧光胺溶液的浓度、流速和反应温度分别为0.2 g/L、0.15 mL/min和50 ℃,磺胺化合物在0.01~1.0 mg/L范围内线性显著,其相关系数r²值大于0.99995。11种磺胺类药物在养殖水体和沉积物中的加标回收率分别为79.3%~100.7%和74.6%~95.3%,相对标准偏差为2.2%~11.0%和2.6%~10.3%,检出限(LOD, S/N=3)为0.9~5.5 ng/L和0.3~1.3 μg/kg,定量限(LOQ, S/N=10)为3.0~18.1 ng/L和1.0~4.4 μg/kg。该法可应用于养殖环境中磺胺类药物的定性定量检测,具有较好的实用性。