磁性微球表面光引发聚合制备金属配位印迹层及选择性富集奶样中氟喹诺酮类药物残留

目的发展一种金属配位印迹磁性微球的制备方法,并用于奶样中氟喹诺酮类药物残留的选择性富集。方法采用简便的溶剂热法合成磁性纳米粒子,再采用溶胶-凝胶法制备磁性硅胶微球,然后在磁性硅胶微球表面接枝光引发剂,在125 W紫外灯辐射下合成恩诺沙星-Co(Ⅱ)配位印迹层,并用于磁分散萃取奶样中恩诺沙星、环丙沙星和洛美沙星。结果该方法的加标回收率为89.6%~100.8%,相对标准偏差为1.4%~5.5%,其中环丙沙星的检出限和定量限分别为1.72μg/kg和5.74μg/kg,洛美沙星的检出限和定量限分别为2.05μg/kg和6.82μg/kg,恩诺沙星的检出限和定量限分别为1.18μg/kg和3.94μg/kg。结论该样品处理方法是一种选择性好、简单快速的分离检测奶样中氟喹诺酮类药物残留的方法。     

QuEChERS结合高效液相色谱-串联质谱法测定大白菜中10种喹诺酮类药物残留

摘 要: 目的 建立QuEChERS结合高效液相色谱-串联质谱法测定大白菜中10种喹诺酮类药物残留的检测方法。方法 大白菜样品经提取,采用QuEChERS净化方法,以诺氟沙星-D5为内标,用高效液相色谱-串联质谱法测定,采用正离子电喷雾,多反应监测模式（multiple reactions monitoring, MRM),内标法定量分析10种喹诺酮类药物残留的含量。结果 10种喹诺酮类在5~100 ng/mL的浓度范围内线性良好,检出限为0.1~0.3 μg/kg,定量限为0.3~1.0 μg/kg,平均回收率为76.0%~107%,相对标准偏差为1.5%~8.1%。 结论 本研究建立的QuEChERS结合高效液相色谱-串联质谱法测定大白菜中10种喹诺酮类药物残留的检测方法准确、可靠, 适用于大白菜中喹诺酮类药物残留的检测。     

高效液相色谱- 串联质谱法快速测定鱼肉中4 种氟喹诺酮类药物残留

建立快速测定鱼肉中4 种氟喹诺酮类药物残留的高效液相色谱- 串联质谱方法。采用酸性乙腈提取样品中的氟喹诺酮药物残留,然后用正己烷脱脂,氮吹浓缩定容后,用反相液相色谱分离,以液相色谱- 串联质谱仪测定,外标法定量。该法对4 种氟喹诺酮类药物的线性范围为2～40μg/kg,相关系数(r2)大于0.997,在4、10、20μg/kg 3 个添加水平范围内的回收率为79.9%～98.1%,相对标准偏差为2.7%～8.7%,检出限为0.1～0.4μg/kg,定量限为0.3～1.0μg/kg。结果表明,该方法简便快速、灵敏度高、重现性好、选择性强,适用于鱼肉中氟喹诺酮类药物残留的定量测定。     

同位素稀释法-超高效液相色谱-串联质谱法测定豆芽中6种喹诺酮类药物残留

目的建立通过式固相萃取(solid phase extraction,SPE)柱净化、氘代同位素内标、超高效液相色谱-串联质谱法同时测定豆芽中6种喹诺酮类药物残留的方法。方法用0.1%甲酸-乙腈作为提取溶剂,经通过式固相萃取柱净化提取液,超高效液相色谱-串联质谱测定豆芽中6种喹诺酮药物残留。结果 6种喹诺酮在5.0～200μg/L范围内线性关系良好,r~2≥0.999;方法检出限(S/N=3)为0.7μg/kg,定量限(S/N=10)为2.0μg/kg;加标水平为2.0～80μg/kg时,平均回收率在85.5%～119.4%,相对标准偏差(relative standard deviation,RSD)(n=6)为0.13%～9 93%。结论本方法前处理简单,定量结果准确,回收率高,可以应用于大批次豆芽中喹诺酮药物残留的监测。     

Qu ECHERS-LC-MS/MS法测定牛奶中喹诺酮类药物

建立分散固相萃取-超高效液相色谱串联质谱同时测定牛奶中12种喹诺酮类药物残留的方法。牛奶样品中喹诺酮类药物经酸化乙腈提取,分散固相萃取净化,电喷雾离子源-三重四级杆串联质谱对喹诺酮类药物进行测定。12种喹诺酮类药物在5～200 ng/mL质量浓度范围内,其回归标准曲线方程的相关系数r为0.996 4～0.999 9。对空白牛奶添加5, 20和50μg/kg 3种浓度的喹诺酮类标准品,回收率为78.7%～96.3%,相对标准偏差(n=6)为1.99%～10.09%,方法检出限在1μg/kg以下。使用该方法对唐山本地牛奶样品进行检测,未发现有喹诺酮类药物检出。     

高效液相色谱-串联质谱法检测鸡蛋中的氟喹诺酮类药物残留

对GB/T 21312-2007 《动物源性食品中14种喹诺酮药物残留检测方法液相色谱-质谱/质谱法》检测方法进行了优化,并试验了鸡蛋中常用的8种氟喹诺酮类药物(氧氟沙星、洛美沙星、培氟沙星、诺氟沙星、恩诺沙星、环丙沙星、达氟沙星、沙拉沙星)的检测效果。结果显示,8种氟喹诺酮类药物在5.0 ng/mL～100.0 ng/mL范围内线性关系良好,相关系数R均在0.999以上,回收率在81.60%～103.88%之间,相对标准偏差在0.78%～9.91%之间,各指标均可达到国家标准相应要求。该方法适用于鸡蛋中8种氟喹诺酮类药物残留的定性定量检测。     

固相萃取结合超高效液相色谱-质谱法测定畜禽肉及肉制品中肾上腺素和多巴胺的残留量

建立畜禽肉及肉制品中2 种儿茶酚胺类化合物（肾上腺素和多巴胺）的超高效液相色谱-质谱联用检测方法。样品采用10 mmol/L磷酸二氢钾溶液提取,WCX固相萃取柱净化,Waters Acquity BEH C18柱分离,采用电喷雾离子源,正离子多反应模式监测,基质匹配内标法定量。结果表明：肾上腺素和多巴胺在0.5～50 ng/mL范围内,相关系数（R2）均大于0.996;在畜肉中的检出限和定量限分别为0.39～0.40 μg/kg和1.00 μg/kg,在禽肉中的检出限和定量限分别为0.36～0.37 μg/kg和0.98 μg/kg,在肉制品中的检出限和定量限分别为0.38 μg/kg和0.96～0.97 μg/kg;加标量为1～10 μg/kg时,方法回收率为83.7%～111.2%,相对标准偏差为1.28%～5.76%。该方法具有灵敏度高、定量准确等优点,适用于畜禽肉及肉制品中残留儿茶酚胺类化合物含量的测定。     

UPLC-MS/MS法测定蜂蜜中4种喹诺酮类药物残留

本研究旨在建立UPLC-MS/MS法测定蜂蜜中4种喹诺酮类药物残留。方法:蜂蜜样品用80%甲醇水溶解,经Prime HLP固相萃取柱净化,超高效液相电喷雾串联四级杆质谱检测,外标法定量。结果:本方法在10、25、50 ng/mL添加水平的回收率为为72.48%～103.22%,RSD均不大于10.00%。结论:在最佳色谱条件下,本研究建立的UPLCMS/MS法具有较好的线性、回收率和精密度,可用于测定蜂蜜中4种喹诺酮类药物残留。     

分散固相萃取结合液相色谱-串联质谱法测定淡水鱼中9种磺胺类和3种喹诺酮类药物残留量

目的 采用分散固相萃取结合液相色谱-串联质谱仪,建立淡水鱼中9种磺胺和3种喹诺酮类药物的分析方法。方法 淡水鱼肉样品用1%甲酸乙腈提取,提取液经盐析后取乙腈层,用分散固相萃取净化包净化,目标物用C18色谱柱（2.1×50 mm,1.7 μm）分离,采用0.1%甲酸乙腈作为流动相进行梯度洗脱,利用电喷雾离子源正离子多反应监测模式进行测定,内标法定量。结果 9种磺胺和3种喹诺酮类药物在 1.0~50.0 ng/mL 浓度范围内线性关系良好, 相关系数均大于 0.999。检出限和定量限分别为 0.1~1.0 μg/kg、1.0~5.0 μg/kg,在3个不同浓度添加水平下的平均回收率为84.4%~114.0%,相对标准偏差（relative standard deviation, RSD）为 1.2%~7.8%(n=6)。结论 该方法操作简单、快速,灵敏度高,适用于淡水鱼中磺胺和喹诺酮类兽药残留测定。     

高效液相色谱-电喷雾质谱法测定牛肉中3种氟喹诺酮药物残留

采用高效液相色谱-电喷雾质谱(HPLC-ESI-MS)建立牛肉中3种氟喹诺酮类药物(环丙沙星、恩诺沙星和沙拉沙星)残留的分析测定方法。试样经酸化甲醇萃取后直接用于分析,内标法定量。在1～20pg/μl范围内,3种氟喹诺酮药物的线性相关系数均大于0.992。在16.7～50.0μg/kg添加水平内,3种化合物的加标回收率为75.2%～96.3%,相对标准偏差为2.5%～8.3%,检出限为8～19μg/kg。这一检测限远低于我国农业部、JECFA以及欧盟等规定的牛肉组织中氟喹诺酮类药物的最大残留限量(MRL)。该方法简便、快速,可用作动物可食性产品中氟喹诺酮类药物残留分析确证的参考。     

Analysis of chloramphenicol in honey and royal jelly by LC/MS/MS

A sensitive and selective method using liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was developed for the determination of chloramphenicol (CAP) in honey and royal jelly. Mass spectral acquisition was performed in the negative mode by applying multiple reaction monitoring. In LC separation, Mightyl RP-18GP and 10 mmol/L ammonium acetate-acetonitrile were used as the column and mobile phase, respectively. CAP in honey samples was diluted with water, while CAP in royal jelly was extracted with 1% metaphosphoric acid-methanol (4 : 6). The solutions were cleaned up with an Oasis HLB cartridge. The quantification limits of CAP in honey and royal jelly were 0.3 ng/g and 1.5 ng/g, respectively. The recoveries of CAP from both honey and royal jelly at the quantification limits were over 92%. Twenty honey products and seven royal jelly products were analyzed by the developed method. CAP was detected in one honey product at 0.6 ng/g and in six royal jelly products at the level of 1.5-17.8 ng/g. These results show that the developed method has satisfactory sensitivity selectivity and is useful for the determination of CAP residues in honey and royal jelly.     

Analysis of tetracyclines in honey and royal jelly by LC/MS/MS

A simple and accurate method using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS) was developed for the determination of tetracyclines (TCs), i.e., oxytetracycline (OTC), chlortetracycline (CTC) and tetracycline (TC), in honey and royal jelly. Mass spectral acquisition was performed in the positive mode. In LC separation, L-column ODS and 0.01% formic acid-acetonitrile were used as the column and mobile phase, respectively. TCs in a honey sample were diluted with water, while TCs in royal jelly were extracted with 2% metaphosphoric acid-methanol (6:4). They were cleaned up with Oasis HLB and Sep Pak C18 cartridges, respectively. The quantification limits of TC, OTC, and CTC were 5, 5, and 10 ng/g, respectively, while those in royal jelly were 25, 25, and 50 ng/g, respectively. The recoveries of TCs from both honey and royal jelly were 75-120%.     

超高效液相色谱-串联质谱法同时测定蜂蜜中雷公藤红素和雷公藤次碱

建立了一种超高效液相色谱-串联质谱同时检测蜂蜜中雷公藤红素和雷公藤次碱的快速分析方法。样品用水溶解后,乙腈盐析提取,采用Hypersil GOLD C18柱（50 mm×2.1 mm,1.9 μm）分离,电喷雾离子源正离子多反应监测模式串联质谱进行检测。结果表明：雷公藤红素和雷公藤次碱在0.01～20 ng/mL范围内具有较好的线性关系,相关系数均大于0.997。该方法定量限均为0.05 μg/kg。在0.05 μg/kg和1.0 μg/kg添加量条件下,雷公藤红素和雷公藤次碱的回收率为69.9%～101.5%,相对标准偏差均不大于10%（n=6）。本方法快速、灵敏、准确,适用于蜂蜜中雷公藤相关物质残留的定性、定量检测。     

凝胶渗透色谱-超高效液相色谱-串联质谱测定茶叶中吡虫啉和啶虫脒

建立用凝胶渗透色谱-超高效液相色谱-串联质谱仪测定茶叶中吡虫啉和啶虫脒残留的方法。样品经乙酸乙酯-环己烷（1∶1,V/V）溶液涡旋混匀后超声提取,经凝胶渗透色谱净化后,采用超高效液相色谱-串联质谱仪测定。结果显示,2 种农药在0.5～100 μg/L范围内线性良好,相关系数R2均大于0.99。吡虫啉和啶虫脒的检出限分别为2.0 μg/kg和1.0 μg/kg,定量限分别为5.0 μg/kg和3.0 μg/kg。吡虫啉和啶虫脒在3 个水平的加标平均回收率为76.94%～91.68%,相对标准偏差为2.67%～7.90%。     

Magnetic graphene oxide nanocomposites as the adsorbent for extraction and pre-concentration of azo dyes in different food samples followed by high-performance liquid chromatography analysis

ABSTRACT

This work presents a method of magnetic solid-phase extraction (MSPE) combined with high-performance liquid chromatography (HPLC) to analyse five synthetic azo dyes (tartrazine, amaranth, carmine, sunset yellow, allura red) in different food samples. The magnetic graphene oxide nanocomposite (GO@Fe₃O₄) was prepared by a one-step solvothermal method and used as the sorbent for extraction and pre-concentration of azo dyes in food samples. The as-prepared GO@Fe₃O₄ nanocomposite was characterised by transmission electron microscope, Fourier transform-infrared spectroscopy, X-ray diffraction, vibrating sample magnetometer, and Brunuer-Emmett-Teller analysis. The extraction and desorption parameters were investigated, including the material amount, extraction time, pH of the solution, desorption temperature, and desorption solvents. Under the optimised conditions, the limits of detection (LODs) were 1.14–2.23, 0.36–0.77 and 0.68–1.26 ng/g for candy, jelly, and plum candy, respectively. The limits of quantification (LOQs) were 4.02–7.73, 1.21–2.50 and 2.31–4.20 ng/g for candy, jelly, and plum candy, respectively. For the analysis of spiked jelly, recoveries were between 73.2% and 107.7%, with RSDs lower than 1.34 %. The developed method was successfully applied to the analysis of real samples including jelly, candy and plum candy.     

高效液相色谱-荧光检测器测定蜂王浆中氟喹诺酮类药物残留的研究

本研究采用液液萃取进行样品前处理,用带荧光检测器的液相色谱仪检测蜂王浆中的5 种QNs,具有方法简单、快速、准确、试剂用量少、检测成本低的特点。方法检测限为氧氟沙星5μg/kg,恩诺沙星、环丙沙星、诺氟沙星2.5μg/kg,丹诺沙星1μg/kg,能够满足目前对蜂王浆中QNs 允许限量的检测要求。     

通过式固相萃取-气相色谱-串联质谱法测定动物源性食品中11种N-亚硝胺类化合物

选取通过式固相萃取技术,结合气相色谱-串联质谱法（gas chromatography-tandem mass spectrometry,GC-MS/MS）,建立动物源性食品中11种N-亚硝胺类化合物的分析方法。样品加水浸泡后采用乙腈提取,经Prime HLB通过式固相萃取柱（200 mg/6 mL）快速净化,采用多反应监测模式监测,以空白基质匹配标准溶液外标法定量。结果表明：11种N-亚硝胺类化合物在0.5～500.0 ng/m L范围内线性关系良好,相关系数为0.999 4～0.999 8,检出限为0.2～0.3μg/kg,定量限为0.5～1.0μg/kg;在1、4、10μg/kg 3个加标水平下,11种N-亚硝胺类化合物平均加标回收率为80.1%～97.4%,相对标准偏差为2.3%～8.8%;该方法提取及净化时间仅需15 min/样品,与GB 5009.26—2016《食品安全国家标准食品中N-亚硝胺类化合物的测定》方法相比,提取与净化时间大幅缩短,检测效率提升10倍,可实现动物源性食品中N-亚硝胺类化合物的快速测定。     

离子色谱法测定蜂花粉与蜂王浆中的葡萄糖、果糖、蔗糖和麦芽糖

研究了蜂花粉与蜂王浆中葡萄糖、果糖、蔗糖和麦芽糖的离子色谱分析方法。样品用热水溶解,乙腈沉降蛋白,使用2个固相萃取小柱去除色素与脂肪等干扰成分后,以CarboPac PA10分析柱为色谱柱,氢氧化钠和乙酸钠溶液为流动相进行离子色谱分离。葡萄糖、果糖、蔗糖和麦芽糖的检出限分别为0.12,0.14,0.21,0.33mg/L。蜂花粉的回收率93.5%～102.2%,精密度为4.4%～6.3%,蜂王浆的回收率为95.0%～103.5%,精密度为6.7%～10.2%。利用该方法对20个蜂花粉和20个蜂王浆样品进行了分析,花粉中葡萄糖含量为9.9%～20.6%,果糖14.2%～26.9%,蔗糖1.8%～8.3%,麦芽糖0.33%～1.4%;王浆中葡萄糖含量为6.2%～8.3%,果糖7.0%～8.7%,蔗糖0.38%～3.6%,麦芽糖0.27%～0.83%。该方法简单、灵敏度高,可作为标准方法对蜂花粉与蜂王浆中葡萄糖、果糖、蔗糖和麦芽糖进行分析。     

蜂王浆在贮藏过程中5-羟甲基糠醛、10-羟基-2-癸烯酸及精氨酸双糖苷含量的变化

将10 个蜂王浆样品贮藏在不同温度（室温、4、－20、－80 ℃）和时间（15、45、65、80 d）条件下,采用高效液相色谱法检测其5-羟甲基糠醛（5-hydroxymethylfurfural,5-HMF）、10-羟基-2-癸烯酸（10-hydroxy-2-decanoicacid,10-HDA）和精氨酸双糖苷（arginyl fructosyl glucose,AFG）含量的变化。结果表明,蜂王浆样品中10-HDA的含量稳定,不随贮藏温度和时间的变化而变化;5-HMF和AFG的含量随贮藏温度升高及时间的延长而增加。因此5-HMF和AFG可作为衡量蜂王浆新鲜程度的指标性成分,而10-HDA不可以作为此标准。但10-HDA是蜂王浆中特有成分,其含量高低会直接影响蜂王浆的功效,故5-HMF、AFG与10-HDA三者结合对蜂王浆的品质进行评价会更加准确。     

Application of enzyme-linked immunosorbent assay for quantification of the insecticides imidacloprid and thiamethoxam in honey samples

An enzyme-linked immunosorbent assay (ELISA) was used for the determination of residues of imidacloprid and thiamethoxam insecticides in honey after simple dilution of the samples without either extraction or cleanup. The ELISA enabled accurate determination of imidacloprid and thiamethoxam down to limits of 20 and 5 ng g^?1 in honey, respectively. Average recoveries of imidacloprid and thiamethoxam from the fortified honey samples were 90–120 and 96–122%, and coefficients of variation ranged 5–12 and 3–15%, respectively. The results from the ELISA agreed well with those by liquid chromatography–mass spectrometry (LC–MS) for the insecticide-spiked samples, with a correlation coefficient (r ²) of 0.96 and a regression coefficient (slope) of 1.03. The results indicate that ELISA is a suitable tool for the quantification of imidacloprid and thiamethoxam in honey.