mSPE前处理-超高效液相色谱串联质谱法测定牛奶中阿维菌素类药物残留

本文建立了采用磁性固相净化材料（mSPE）对牛奶样品进行净化,使用超高效液相色谱-串联质谱（UPLC-MS/MS）对牛奶中阿维菌素类药物残留进行定性和定量的检测方法。牛奶样品使用乙酸锌和亚铁氰化钾沉淀蛋白,8 mL乙腈提取,10 mg磁性HLB净化材料净化,5%乙腈-水、乙腈进行淋洗和洗脱,使用UPLC-MS/MS检测牛奶中阿维菌素、乙酰氨基阿维菌素、伊维菌素和多拉菌素四种药物。在0.2～200.0 μg/L药物浓度范围内线性关系良好(R2 > 0.995)。该方法阿维菌素、伊维菌素和多拉菌素的检测限为0.2 μg/kg,定量限为0.5 μg/kg;乙酰氨基阿维菌素的检测限为0.5 μg/kg,定量限为2.5 μg/kg,回收率为82.3%～ 88.2%,相对标准偏差（RSD）为0.23%～4.19%。本文建立的mSPE前处理技术,同现行国标GB 31659.4-2022相比,极大的提高了样品前处理效率,缩短了样品检测的时间,降低了检测成本,减少了有机溶剂的使用。所建立的方法检出限和定量限均可满足食品安全国家标准GB 31650-2019中规定的牛奶中阿维菌素类药物残留限量的要求,可应用于定量检测牛奶样品中阿维菌素类药物残留,为mSPE前处理方法的广泛应用提供宝贵经验。     

液相色谱-串联质谱法同时检测饲料和牛血清中吡喹酮药物残留

目的建立一种用液相色谱-串联质谱法(liquid chromatography-tandem mass spectrometry,LC-MS/MS)检测饲料和牛血清中吡喹酮药物残留的方法。方法样品经乙腈/水提取液提取,过固相萃取柱净化。采用0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱,采用多离子检测模式对吡喹酮药物的定量离子和定性离子进行监测。结果 8 min内完成目标化合物的分离分析。吡喹酮在0.05、0.1和0.5 ng/m L添加水平的回收率为75.0%~99.0%,相对标准偏差小于5.4%(n=6)。结论该方法快速、准确、灵敏,适合测定食用活动物体内的吡喹酮药物残留。     

玫瑰鲜花饼中四种阿维菌素类药物残留水平分析及慢性膳食风险评估

为了解玫瑰鲜花饼中是否存在药物残留情况,以及是否存在慢性膳食摄入风险情况。本文通过检测玫瑰鲜花饼中四种阿维菌素类药物的残留情况,对其药物残留进行水平分析,评估其慢性膳食摄入风险。四种药物分别是阿维菌素、多拉菌素、乙酰氨基阿维菌素、伊维菌素。共收集了43种玫瑰鲜花饼样品,采用优化的QuEChERS方法对样品进行前处理,并用高效液相色谱-串联质谱仪来测定这4种化合物的残留水平,对它们进行慢性膳食摄入风险评估及风险排序。结果表明,四种阿维菌素类药物标线的判定系数均大于0.99,检出限的范围为0.1～0.7μg/kg,回收率范围为94.97%～102.09%,四种目标化合物只有阿维菌素被检出,检出率是79%,残留量范围为1.89～4.58μg/kg。对四种药物进行食品安全指数分析(IFS),阿维菌素为1.3×10^-3、多拉菌素为1.0×10^-4、乙酰氨基阿维菌素为1.7×10^-6、伊维菌素为1.2×10^-5;对四种目标化合物进行风险评估,并进行风险排序,四种药物总分均低于50,说明目前鲜花饼中阿维菌素类药物...     

超高效液相色谱-串联质谱法测定10种食品中的阿维菌素类药物残留

建立以超高效液相色谱-电喷雾串联质谱同时检测10种食品中的阿维菌素类药物(包括阿维菌素、伊维菌素、多拉菌素、依普菌素、莫西丁克和塞拉菌素6种大环内酯类药物)残留的确证方法。样品用乙腈提取,45℃旋蒸蒸干,再用乙腈-水(1:9,V/V)溶液复溶,PEP-C18混合固相萃取柱净化,氮气吹干后用乙腈定容,超高效液相色谱-串联质谱测定,电喷雾正离子(ESI+)、多反应模式下监测;结果表明,6种药物在5～250μg/kg范围内线性良好(R2＞0.99),3个添加水平下,6种药物的回收率在60%～99%之间,相对标准偏差为0.2%～8.9%。6种药物的定量限(RSN≥10)均达5.0μg/kg,符合痕量分析的要求。     

石斑鱼中阿维菌素类药物多残留测定及食用安全风险评估

建立高效液相色谱-串联质谱同时定量检测石斑鱼血浆、肌肉组织、肝脏组织中阿维菌素、伊维菌素、甲氨基阿维菌素苯甲酸盐方法。样品经乙腈提取,碱性氧化铝固相萃取柱和LC-C18固相萃取柱串联净化,Thermo Hypersil Gold C18色谱柱分离,10 mmol/L乙酸铵-0.1%甲酸溶液和乙腈梯度洗脱,电喷雾正离子模式下以多反应监测方式检测,基质匹配法外标定量。分别以环境水体中阿维菌素上下限质量浓度(4、8 ng/mL)、伊维菌素上下限质量浓度(6、12 ng/mL)作为受试质量浓度开展生物富集、消除实验,并对石斑鱼的食用安全进行了风险评估。结果表明,阿维菌素和伊维菌素在2.5~200 ng/mL范围内,甲氨基阿维菌素苯甲酸盐在0.25~20 ng/mL范围内,线性回归系数均大于0.99。方法检出限分别为2.5、2.5、0.25 ng/mL(血浆),1、1、0.1μg/kg(肌肉组织),2.5、2.5、0.25μg/kg(肝脏组织),方法定量限分别为5、5、0.5 ng/mL(血浆),2、2、0.2μg/kg(肌肉组织),5、5、0.5μg/kg(肝脏组织)。3个添加量的平均回收率为74.6%~93.6%,日内相对标准偏差为2.3%~10.9%,日间相对标准偏差为9.2%~12.6%。阿维菌素、伊维菌素均属于非生物累积性物质,在石斑鱼体内代谢规律相同,均按一级动力学过程从体内消除。本研究条件下,环境水体中药物质量浓度是石斑鱼肌肉组织中药物残留质量浓度及消除时间的重要因素。为保证食用安全,环境水体中阿维菌素质量浓度达到4~8 ng/mL时,石斑鱼浸浴72 h后安全食用时间为22 d;环境水体中伊维菌素质量浓度达到6~12 ng/mL时,石斑鱼浸浴72 h后安全食用时间为39 d。     

超高效液相色谱质谱法快速检测动物源性食品中的四种兽药残留

建立了采用超高效液相色谱串联质谱仪快速检测动物组织中甲氧苄胺嘧啶、克林霉素、泰妙菌素和吡喹酮四种药物残留的分析方法。动物组织样品经乙腈提取后,用正己烷去除脂肪等杂质,Waters Acquily UPLC BEH C18色谱柱分离,以乙腈和0.1%甲酸水溶液为流动相进行梯度洗脱,电喷雾正离子(ESI+)模式电离,液相色谱-质谱法(UPLC-MS/MS)测定。结果表明:4种药物在2.5～200μg/L范围内呈现良好的线性关系,相关系数R2均大于0.996,在此范围内添加回收率为65.8%~95.9%,相对标准偏差为3.2%~13.1%,定量下限为0.5μg/kg。     

分散固相萃取结合液相色谱串联质谱法检测牛可食性组织中吡喹酮残留量

目的建立分散固相萃取结合液相色谱串联质谱法检测牛肉、牛脂肪、牛肝和牛肾等可食性组织中的吡喹酮残留量的分析方法。方法取牛组织样品经50%(V:V)乙腈溶液提取,加入无水硫酸镁和氯化钠进行脱水和盐析,正己烷脱脂,高速离心分层后,取适量乙腈层溶液经0.1%(V:V)甲酸稀释后,用酸性氧化铝粉末进行样品净化并以10000r/min离心取上清液,过0.22μm滤膜后上机测定。使用反相色谱柱进行分离,流动相为0.1%甲酸和乙腈溶液,采用梯度程序进行洗脱,三重四极杆质谱进行定性定量分析。结果吡喹酮在2.5～500μg/kg范围内线性关系良好(r0.995),方法的最低检出限为1μg/kg,最低定量限为2.5μg/kg,添加回收率在60%～110%,相对标准偏差(relative standard deviation, RSD)10%。结论该方法具有较好的准确度与精密度,适用于牛可食性组织中吡喹酮残留量的测定。     

牦牛肉中阿维菌素残留的时间分辨荧光免疫层析检测方法的建立

为建立定量检测牦牛肉中阿维菌素残留的时间分辨荧光免疫层析方法,以羧基化铕微球作为荧光标记物,与阿维菌素鼠单克隆抗体G10703进行共价偶联后喷涂于释放垫上,将阿维菌素抗原和羊抗鼠免疫球蛋白G分别包被于硝酸纤维素膜上作为检测线（T）和质控线（C）,制备免疫层析试纸条;利用牦牛肉样本阿维菌素添加量和对应的T线与C线荧光信号峰值比值（T/C）拟合得到四参数标准曲线,建立牦牛肉中阿维菌素残留的时间分辨荧光免疫层析检测方法,并对所建立方法的灵敏度、准确度、特异性、精密度和稳定性等进行评价,用液相色谱-串联质谱方法对所建立方法的性能进行确证。结果表明：本方法对牦牛肉中阿维菌素的定量限为1.0 μg/kg,加标回收率为86.9%～105.2%,与阿维菌素、伊维菌素、多拉菌素及依普菌素的交叉反应率分别为100.0%、73.1%、42.6%和97.5%,批内变异系数为5.4%～9.5%,批间变异系数为7.5%～11.2%,该方法准确度、精密度、灵敏度均较高,且性能稳定。     

液相色谱-质谱联用技术测定豆制品中碱性嫩黄残留

本文建立了豆制品中碱性嫩黄残留的高效液相色谱-串联四极杆质谱联用测定方法。该方法用50%乙腈水溶液（含0.1%甲酸）提取样品,以MGⅢ-C18柱（2.1×150mm,5μm）分离,流动相为乙腈和0.1%甲酸水溶液（35∶65,V/V）,电喷雾正离子MRM模式检测。该方法的检出限0.5μg/kg,线性范围0.04～20.0 ng/mL,加标回收率86.2%～102.7%,相对标准偏差为5.52%。     

超高效液相色谱法测定水体和沉积物中4 种硝基呋喃类抗生素

建立超高效液相色谱法同时测定水体和沉积物中的呋喃妥因、呋喃西林、呋喃它酮和呋喃唑酮4 种硝基呋喃类抗生素。水体样品过滤后直接用混合型阳离子交换（mixed-mode cation exchange,MCX）固相萃取柱富集净化;沉积物样品经乙腈-0.1%甲酸溶液（8∶2,V/V）提取,MCX固相萃取柱净化。采用BEH C18（100 mm×2.1 mm,1.7 μm）色谱柱分离,以0.1%甲酸溶液-乙腈为流动相梯度洗脱。4 种硝基呋喃类药物在10.0～200 μg/L质量浓度内范围线性关系良好,相关系数R2均大于0.999。水体和沉积物中的加标回收率分别为81.5%～103.2%和73.3%～91.9%,相对标准偏差分别为2.0%～5.8%和3.4%～9.6%（n=5）,检出限分别为0.03 μg/L和0.6 μg/kg,定量限分别为0.1 μg/L和2.0 μg/kg。该方法可应用于水体和沉积物中硝基呋喃类抗生素的残留检测。     

Multi-residue method for the confirmation of four avermectin residues in food products of animal origin by ultra-performance liquid chromatography-tandem mass spectrometry

A confirmatory method was developed for the rapid determination of abamectin, ivermectin, doramectin and eprinomectin residues in various food products of animal origin, such as pork muscle, pork liver, fish and milk. Samples were homogenized, extracted and de-proteinized by acetonitrile, cleaned via two-step cleaning procedure using Bond Elut C(18) SPE columns and then alumina-N cartridges. All the four avermectin residues in different animal-food products were simultaneously separated and determined by ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) within 3.5 min. Data acquisition under positive ESI-MS/MS was performed by applying multiple reaction monitoring (MRM) for both identification and quantification, and mass spectrometric conditions were optimized to increase selectivity and sensitivity. The matrix-matched calibration curves for different matrices, such as pork muscle, pork liver, fish and milk, were constructed and the interference effect of different sample matrices on the ionization was effectively eliminated. The UPLC-MS/MS method was validated with satisfactory linearity, recovery, precision and stability. Matrix-matched calibration curves of abamectin, ivermectin, doramectin and eprinomectin in four different matrices were linear (r(2)( )≥ 0.990, goodness-of-fit coefficients ≤12.8%) in the range 2.5-200 μg kg(-1). The limits of detection and quantification for the four avermectins were in the range 0.05-0.68 and 0.17-2.27 μg kg(-1), respectively. Recoveries were 62.4-104.5% with good intra- and inter-day precision. The method was rapid, sensitive and reliable, and can be applied to the quantitative analysis of avermectin residues in different animal-food products.     

超高效液相色谱-串联质谱法同时测定牛乳中3 类15 种抗生素残留

建立牛乳中青霉素类、磺胺类、四环素类3 类 15 种抗生素残留量同时测定的超高效液相色谱-串联质谱检测方法。样品经乙腈-水溶液（3∶1,V/V）提取、HLB固相萃取小柱净化、氮气吹干后用1.0 mL流动相溶解残余物。采用ZORBAX Ecliplus C18色谱柱,乙腈和5 mmol/L甲酸铵溶液（含体积分数0.2%甲酸）作流动相梯度,质谱选择多反应监测正离子模式测定,外标法定量。结果表明,15 种抗生素在相应的浓度范围内线性良好,相关系数均大于0.999;在3 个不同添加水平下,平均回收率为75.1%～103.7%,相对标准偏差为1.4%～7.3%,检出限（RSN≥3）和定量限（RSN≥10）分别为0.2～4.0 μg/kg和1.0～4.0 μg/kg。方法简便快速、灵敏度高,适合15 种抗生素同时检测,为牛乳中抗生素多残留测定提供了新的方法。     

Multi-residue method for the confirmation of four avermectin residues in food products of animal origin by ultra-performance liquid chromatography–tandem mass spectrometry

A confirmatory method was developed for the rapid determination of abamectin, ivermectin, doramectin and eprinomectin residues in various food products of animal origin, such as pork muscle, pork liver, fish and milk. Samples were homogenized, extracted and de-proteinized by acetonitrile, cleaned via two-step cleaning procedure using Bond Elut C₁₈ SPE columns and then alumina-N cartridges. All the four avermectin residues in different animal-food products were simultaneously separated and determined by ultra-performance liquid chromatography–electrospray ionization tandem mass spectrometry (UPLC–ESI–MS/MS) within 3.5?min. Data acquisition under positive ESI–MS/MS was performed by applying multiple reaction monitoring (MRM) for both identification and quantification, and mass spectrometric conditions were optimized to increase selectivity and sensitivity. The matrix-matched calibration curves for different matrices, such as pork muscle, pork liver, fish and milk, were constructed and the interference effect of different sample matrices on the ionization was effectively eliminated. The UPLC–MS/MS method was validated with satisfactory linearity, recovery, precision and stability. Matrix-matched calibration curves of abamectin, ivermectin, doramectin and eprinomectin in four different matrices were linear (r^{2 ?}≥?0.990, goodness-of-fit coefficients ≤12.8%) in the range 2.5–200?µg?kg^?1. The limits of detection and quantification for the four avermectins were in the range 0.05–0.68 and 0.17–2.27?µg?kg^?1, respectively. Recoveries were 62.4–104.5% with good intra- and inter-day precision. The method was rapid, sensitive and reliable, and can be applied to the quantitative analysis of avermectin residues in different animal-food products.     

超高效液相色谱-同位素稀释质谱法测定配方奶粉中的泛酸

建立测定配方奶粉中泛酸的超高效液相色谱-同位素稀释质谱方法。样品经乙酸铵溶液提取、三氯甲烷除 蛋白后,进行超高效液相色谱-串联质谱分析,采用HSS T3液相色谱柱分离,以10 mmol/L乙酸铵溶液（含0.1%甲 酸）和乙腈为流动相进行梯度洗脱,多反应监测模式,内标法定量。结果表明：方法定量限为0.040 mg/100 g,线 性范围内低、中、高3 个标准添加水平的回收率为96.9%～104.3%,相对标准偏差为3.78%～5.04%。该方法操作过 程简单、分析周期短、灵敏度高、重复性好,适用于奶粉中泛酸的测定。     

液相色谱-串联质谱法快速测定果蔬中16 种新型酰胺类杀菌剂残留量

建立果蔬（白菜、芹菜、草莓和葡萄）中16 种新型酰胺类杀菌剂的液相色谱-串联质谱快速分析方法。样品用乙腈提取和氯化钠盐析分层后,上清液直接用0.1%甲酸溶液稀释10 倍后进行液相色谱-串联质谱分析。采用Acquity BEH C18色谱柱分离,用0.1%甲酸溶液-乙腈作为流动相进行梯度洗脱,电喷雾正离子模式电离,多反应监测模式检测,基质校准外标法定量。各物质峰面积与样品质量浓度在2.5×10－4～0.25 mg/L范围内呈良好的线性关系,线性回归系数不低于0.994 9。在添加量0.01～5.0 mg/kg范围内,4 种果蔬加标16 种杀菌剂的平均添加回收率在85.7%～103.9%范围内,批内相对标准偏差在2.6%～5.2%之间。16 种新型酰胺类杀菌剂的检出限为1.0×10－4～3.0×10－3 mg/kg,定量限为3.0×10－4～0.01 mg/kg。该方法能满足果蔬中16 种新型酰胺类杀菌剂残留量分析的要求。     

UPLC-IDMS法测定配方奶粉中的生物素含量

建立一种超高效液相色谱-同位素稀释质谱法测定配方奶粉中生物素含量的方法。样品中加入生物素-D2作为同位素内标,经水超声提取后,以含体积分数0.1%甲酸的10 mmol/L乙酸铵溶液和乙腈作为流动相进行梯度洗脱,采用电喷雾正离子模式、多反应监测方式进行定性定量分析。结果表明：生物素在1～50 ng/mL范围内线性关系良好,线性范围内对已知生物素含量样品3 个标准添加水平的平均回收率为89.6%～93.1%,相对标准偏差为1.71%～4.33%。方法检出限为0.6 μg/100 g,定量限为1.5 μg/100 g,该方法具有灵敏度高、重复性好、分析时间短等优点,可以满足配方奶粉中生物素含量的测定要求。     

The effects of heat applications on macrocyclic lactone-structured antiparasitic drug residues in cows’ milk

ABSTRACT

The study aimed to evaluate the effects of heat on macrocyclic lactone residues in cows’ milk. Ivermectin, abamectin, doramectin, eprinomectin and moxidectin were added to raw milk in three concentrations. The milk was then pasteurised (40 seconds at 74°C or 1 minute at 80°C) and boiled (10 minutes at 100°C). The analyses were performed with a validated method: LC-MS/MS. Thermal treatment resulted in a statistically significant decrease in the abamectin, eprinomectin, and moxidectin concentrations in the milk; however, the residues did not completely degrade. Boiling resulted in a greater decrease in the moxidectin concentrations than was observed with pasteurisation. The high pasteurisation and boiling processes had a greater effect on the eprinomectin residues than did the low pasteurisation process. The pasteurisation and boiling processes did not have an effect on the doramectin and ivermectin. The study concluded that the macrocyclic lactones are generally resistant to such processes.     

功能性饮料中9 种水溶性维生素的HPLC-MS-MS同步检测技术

建立高效液相色谱-质谱法测定功能性饮料中9 种水溶性维生素的定性定量同步检测方法。样品利用Supelco C18（500 mg）固相萃取柱萃取后,采用Agilent plus C18（100 mm ×2.1 mm,3.5 μm）色谱柱进行分离;流动相为0.1%甲酸溶液和乙腈,梯度洗脱,采用电喷雾离子源多反应监测模式进行检测。结果表明,9 种水溶性维生素在10～1 000 ng/mL范围内线性关系良好（R2≥0.997）,检出限在0.157～0.836 μg/L之间。在加标量为0.05、0.1 mg/L和1 mg/L水平下,待测物的平均回收率在80.11%～115.56%之间,测定结果的相对标准偏差小于10%。