高效液相色谱-串联质谱法同时测定水产品中氯霉素、甲砜霉素和氟甲砜霉素的残留量

建立了水产品中氯霉素、甲砜霉素和氟甲砜霉素药物残留量同时测定的高效液相色谱-串联质谱方法。以氘代氯霉素做内标,选择乙酸乙酯提取,HLB固相萃取柱净化,洗脱液氮气吹干,采用LC-MS/MS选择反应监测(SRM)负离子模式进行定性、定量分析。结果表明:氯霉素的检出限(LOD)为0.01μg/kg,甲砜霉素和氟甲砜霉素检出限(LOD)为0.03μg/kg,检测结果的相对标准偏差为3.3%～9.7%(n=6),加标回收率达到78.6%～110.5%。该方法在水产品中氯霉素、甲砜霉素和氟甲砜霉素药物的残留测定中具有很好的应用前景。     

气相色谱-质谱联用法测定动物组织中氯霉素、氟甲砜霉素和甲砜霉素的残留量

建立了气相色谱-负离子化学电离源质谱同时测定动物组织中氯霉素(CAP)、甲砜霉素(TAP)和氟甲砜霉素(FF)残留量的方法。样品用乙酸乙酯提取,正己烷分配去脂肪,再用Florisil柱进一步净化,甲苯作为反应介质,用N,O-双(三甲基硅基)三氟乙酰胺(BSTFA)-三甲基氯硅烷(TMCS)(体积比为99∶1)进行硅烷化处理,用间硝基氯霉素(m-CAP)作为内标进行测定。CAP的检测限可达到0.03 μg/kg,TAP和FF的检测限可达到0.2 μg/kg;上述3种药物的标准曲线的线性相关系数均大于0.99。CAP,FF和TAP的批内测定的精密度(以相对标准偏差表示)依次为5.5%,10.4%和8.8%;批间测定的精密度依次为7.4%,20.7%和19.1%。回收率为80.0%~111.5%,相对标准偏差为1.2%~15.4%。该方法前处理步骤简单,处理后杂质干扰少,灵敏度高,适用性强,可用于猪肉及禽类、水产品等多种动物组织中氯霉素类药物残留的检测。     

高效液相色谱-串联质谱法同时测定饲料中氯霉素、甲砜霉素与氟甲砜霉素残留量

建立了饲料中氯霉素(CAP)、甲砜霉素(TAP)、氟甲砜霉素(FF)3种抗生素残留量的高效液相色谱-串联质谱(HPLC-MS/MS)测定方法。样品经碱化乙酸乙酯提取,蒸发浓缩,提取物经正己烷脱脂,液-液分配净化后,采用电喷雾电离源(ESI)负离子多反应监测(MRM)模式检测,内标法定量。氯霉素、氟甲砜霉素和甲砜霉素的线性范围分别为0.2～10.0、0.2～10.0、1.0～50.0μg/L,相关系数(r2)不低于0.990 0;其检出限分别为0.1、0.1、0.5μg/kg,定量下限分别为0.3、0.3、1.5μg/kg。3种抗生素药物的平均回收率为77%～108%,相对标准偏差(RSD)不大于10.9%。     

超高效液相色谱法测定水产品中甲砜霉素和氟甲砜霉素残留

建立了一种同时测定水产品中甲砜霉素和氟甲砜霉素药物残留的超高效液相色谱(UPLC)方法。样品经乙酸乙酯提取,正己烷液-液分配除脂,过HLB固相萃取小柱,用3mL10%甲醇淋洗,5mL100%甲醇洗脱,洗脱液用氮气吹干,残渣用1mL10%乙腈水溶液定容。采用超高效液相色谱分离,二极管阵列检测器检测,外标法定量。甲砜霉素在0.05~2.0mg/L,氟甲砜霉素在0.025~1.0mg/L范围线性关系良好,相关系数分别为0.9996、0.9999;样品加标平均回收率分别为80.0%、95.8%;相对标准偏差分别为5.6%、11.2%,甲砜霉素、氟甲砜霉素检出限分别为10μg/kg、5μg/kg。     

高效液相色谱/串联质谱法同时测定虾中氯霉素、甲砜霉素和氟甲砜霉素残留量

用高效液相色谱／串联质谱(LC／MS,／MS)同时测定虾中的氯霉素(CAP)、甲砜霉素(TAP)和氟甲砜霉素(FF)。均质后的虾样品,采用碱化乙酸乙酯提取。浓缩提取物经液．液分配(LLP)去除脂肪,C18固相萃取(SPE)柱净化后,采用LC／MS／MS电喷雾电离(ESI),负离子,多反应监测(MRM)模式检测,外标法定量。检出限为：氯霉素和氟甲砜霉素0．01ng/g;甲砜霉素为0．05ng／g。在添加浓度0．1～2．0ng/g范围内,氯霉素回收率为73．9％～96．0％;甲砜霉素回收率为78．6％～99．5％;氟甲砜霉素回收率为74．9％～103．7％;相对标准偏差(RSD)均小于6．4％。     

高效液相色谱-串联质谱法同时测定蜂胶、蜂胶原料保健食品中的氯霉素、甲砜霉素与氟甲砜霉素

建立了同时测定蜂胶、蜂胶原料保健食品(片剂、硬胶囊、软胶囊3种剂型)中氯霉素、甲砜霉素和氟甲砜霉素残留的高效液相色谱-串联质谱(HPLC-MS/MS)方法。样品经0.1 mol/L盐酸溶解,涡旋混匀,超声提取后,通过HLB柱串接NH_2固相萃取柱净化。采用Waters ACQUITY UPLC~?BEH C_(18)(2.1 mm×100 mm,1.7μm)色谱柱进行分离,以0.1%甲酸水-乙腈为流动相梯度洗脱,经HPLC-MS/MS测定,电喷雾离子源负离子模式检测,外标法定量。结果表明3种目标分析物在0.10～20.0μg/L范围内线性关系良好,相关系数(r~2)均大于0.999;蜂胶原胶、片剂和软胶囊剂型中3种目标物的检出限(LOD)为0.037～0.083μg/kg,定量下限(LOQ)为0.12～0.28μg/kg;硬胶囊剂型中的LOD为0.39～0.47μg/kg,LOQ为1.28～1.57μg/kg;在2.5、5.0、10.0μg/kg加标水平下,3种目标物的回收率为66.6%～120%,相对标准偏差(RSD)为0.80%～11%。将该方法应用于45个实际样品检测,其中氯霉素的检出率为22.22%,最大残留量为14.32μg/kg;氟甲砜霉素的检出率为17.78%,最大残留量为21.62μg/kg。该方法操作简单、灵敏度高、适用性强,能够满足蜂胶、蜂胶原料保健食品中此类药物残留的检测要求。     

高效液相色谱串联质谱法同时测定饲料中氯霉素、甲砜霉素与氟甲砜霉素残留

以D5-氯霉素为内标,建立了高效液相色谱-电喷雾串联质谱测定饲料预混料、配合饲料中氯霉素、甲砜霉素与氟甲砜霉素含量的方法.样品磨碎后,采用乙酸乙酯提取,离心后上清液于45℃下氮气吹干,溶解残渣并用正己烷液液萃取净化处理,经C18固相萃取净化后,通过Agilent Eclipse C18(150 mm ×4.6 mm,5μ nn)色谱柱以甲醇-0.1％甲酸作流动相梯度洗脱分离,采用电喷雾电离(ESI)、多反应监测(MRM)负离子扫描方式进行定性与定量分析.方法的检出限(LOD)为0.5μg/L,定量下限(LOQ)为1.0 μg/L,待测物与内标物定量离子的峰面积比值与待测物的质量浓度在0.5～10.0 μg/L范围内呈良好线性关系,相关系数(r2)不低于0.9990.在0.5～2.0 μg/kg范围内,3个水平的加标回收率为78％～107％,相对标准偏差(RSDs,n=6)均小于10％.     

TiO2修饰磁性石墨烯-通过型固相萃取净化人血中氯霉素、甲砜霉素和氟甲砜霉素

采用TiO₂修饰磁性石墨烯作为通过型固相萃取柱填料,并用于净化去除血液样品中磷脂类物质的干扰,建立了一种快速、高效、准确的测定人血中残留氯霉素、甲砜霉素与氟甲砜霉素的超快速液相色谱-串联质谱分析方法。样品经乙腈提取,使用TiO₂修饰磁性石墨烯-通过型固相萃取柱进行净化处理,以Eclipse Plus C18色谱柱（100 mm×2.1 mm,1.8 μm）分离,以0.08%（v/v）氨水溶液与0.08%（v/v）氨水乙腈溶液为流动相梯度洗脱,电喷雾离子源多反应监测负离子模式下检测,采用内标法定量。3种目标化合物在0.1~10.0 μg/L范围内具有良好的线性（决定系数r²>0.999）,定量限（S/N>10）为0.056~0.082 μg/L,目标化合物的加标回收率为90.0%~105%,相对标准偏差为1.2%~6.6%。该方法可用于临床血样中残留氯霉素、甲砜霉素与氟甲砜霉素的快速筛查和确证分析。     

胶束增敏紫外分光光度法测定甲砜霉素的研究

用紫外分光光度法对pH 6.00Na2 HPO4-NaH2 PO4的缓冲介质中甲砜霉素和溴化十六烷基三甲铵( CTMAB)形成的胶束配合物的性能进行了研究.利用胶束的增敏增稳作用,提出了测定甲砜霉素的紫外分光光度新方法,方法线性范围为0.25～95 μg/mL,检出限为0.12 μg/mL.已应用于片剂中甲砜霉素的测定...     

高效液相色谱-电喷雾电离三级四极杆质谱检测动物源食品中氯霉素、甲砜霉素、氟苯尼考残留量

建立了动物源产品中氯霉素、甲砜霉素、氟苯尼考残留量的高效液相色谱-电喷雾电离三级四极杆质谱(LC-ESI-MS/MS)的方法。前处理方法包括添加同位素内标氯霉素-d5,碱化乙酸乙酯提取,C18小柱净化。该方法采用负离子,多反应监测氯霉素四对离子(321.0/151.9,321.0/256.6,321.0/194.2,321.0/175.4),甲砜霉素两对离子(354.1/185.0,354.1/290.0),氟苯尼考两对离子(356.0/335.9,356.0/185.1)和同位素内标氯霉素-d5(326.0/157.1)。该方法线性范围为0.1~1.6μg/kg;对不同基质样品的加标回收率为80%~112.5%;相对标准偏差小于11%;方法的测定低限为0.1μg/kg。     

Simultaneous determination of betamethasone and dexamethasone residues in bovine liver by liquid chromatography/tandem mass spectrometry

In this study a new method for the simultaneous confirmation of betamethasone and dexamethasone residues in bovine liver is presented. A Quattro LCZ triple quadrupole mass spectrometer, equipped with an atmospheric pressure ionization (API) source, was coupled to a high performance liquid chromatograph (HPLC) system. Spiked liver samples were first extracted with acetonitrile, and the extracts were purified on C-18 columns. LC separations were performed on a Hypercarb column, with acetonitrile/water (90:10, v/v, +0.3% formic acid) as the mobile phase. Retention times for dexa- and betamethasone were 6.60 and 8.50 min, respectively. Fluorometholone had a retention time of 6.70 min and was used as the internal standard. The detection of the analytes was performed in the multiple reaction monitoring (MRM) mode. The assay was linear over the range of 0.5 to 8 microg/kg for both analytes. The estimated determination limits were 0.2 microg/kg for both beta- and dexamethasone and the quantification limits were 0.4 microg/kg for dexamethasone and 0.3 microg/kg for betamethasone. Analysis precision at 1, 2 and 4 microg/kg was lower than 6.1% (relative standard deviation, RSD) and accuracy was at least 97.5%. Recoveries at 1, 2 and 4 microg/kg ranged between 56 and 69%.     

固相萃取-气相色谱串固相萃取-气相色谱-串联质谱法测定水果中11种三唑类杀菌剂

建立了固相萃取-气相色谱-串联质谱同时测定水果中11种三唑类杀菌剂残留的方法。采用乙腈匀浆提取样品中的待测组分,经固相萃取法(SPE)净化,采用气相色谱-串联质谱在多反应监测(MRM)模式下进行测定,外标法定量。分别对水果样品进行4个水平(10、50、100、250 μg/kg)的加标回收试验,回收率为82.6%～117.1%,相对标准偏差小于10%,定量限(LOQ,以信噪比(S/N)为10计)为0.8～3.4 μg/kg。结果显示该方法的背景干扰低,灵敏度高,定量限低于国家标准及有关文献报道值,适合橘子等水果中三唑类杀菌剂的同时测定。     

Multi-class determination of antimicrobials in meat by pressurized liquid extraction and liquid chromatography-tandem mass spectrometry

A multi-residue method using pressurized liquid extraction (PLE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed for determining trace levels of 31 antimicrobials, including beta-lactams, lincosamides, macrolides, quinolones, sulfonamides, tetracyclines, nitroimidazoles and trimethoprim. The extraction method required pre-homogeneization of the meat with EDTA-washed sand and subsequent one-static-cycle extraction for 10 min with 40 ml of water at 1500 psi and 70 degrees C. The effect of operation temperature, pressure, flush volume, and static cycles on PLE performance was studied. Average recoveries ranged from 75 to 99% with relative standard deviations <18%. The method was validated according to the European Union requirements (2002/657/EC). In addition to the quality parameters included in that decision, the limits of detection (LODs) and quantification (LOQs) were determined. The use of LC-MS/MS provided LODs (between 3 and 15 microg kg(-1)) and LOQs (between 10 and 50 microg kg(-1)), by far lower than half of their maximum residue limits (MRLs) (between 50 and 1200 microg kg(-1)). Confirmation of the presence of any of the studied compounds was accomplished in 1h after sample receipt. This methodology has been successfully applied to the analysis of cattle and pig tissue samples from local markets and slaughterhouses of the Valencian Community (Spain). The results showed the presence of some antimicrobials at different concentrations. Quinolones and tetracyclines were the antimicrobials most detected in cattle and pig samples, respectively. Sulfonamides were also frequently detected in both types of samples.     

高效液相色谱串联质谱法检测腰果中黄曲霉毒素

建立了腰果中4种黄曲霉毒素的高效液相色谱-串联质谱检测方法(HPLC-MS/MS)。样品用甲醇-水(8:2, v/v)溶液提取后用弗罗里硅土柱净化,5 mL丙酮-水-甲酸溶液(96:3.5:0.5, v/v/v)洗脱,氮吹至干,1 mL甲醇定容;在资生堂MG C18色谱柱(100 mm×3.0 mm, 3 μm)上梯度洗脱分离,然后采用电喷雾离子化三重四极杆串联质谱测定。实验结果表明,4种黄曲霉毒素在各自的线性范围内峰面积与其质量浓度线性关系良好,相关系数(r2)大于0.997;检出限(信噪比为3)为0.009～0.04 μg/kg,定量限(信噪比为10)为0.03～0.12 μg/kg;平均回收率为63.0%～78.5%,相对标准偏差为2.8%～9.1%,均符合痕量分析的要求。评价了基质效应,信号抑制/增强值为88.8%～99.4%,说明净化后的基质效应较小。该方法简单快速、准确可靠,可用于腰果中黄曲霉毒素的检测。     

超高效液相色谱-串联四极杆质谱联用分析鸭蛋黄中的苏丹红Ⅰ～Ⅳ

建立了鸭蛋黄中苏丹红Ⅰ～Ⅳ号的超高效液相色谱-串联四极杆质谱联用（UPLC-MS/MS）的分析方法。采用乙腈提取样品中的苏丹红,加水反沉淀除去蛋白质和脂肪等杂质,冷冻后高速离心,取上层清液供UPLC-MS/MS分析。经Waters Acquity BHE C18超高效液相色谱柱分离,串联四极杆质谱多反应监测模式检测,4种物质的检出限均为0.05 μg/L,实际样品中4种物质的检出限为10 μg/kg。采用标准添加法测定苏丹红的回收率,100.0,200.0,300.0 μg/kg 3个不同添加水平的回收率为50.2%～101.3%。实验结果表明该方法灵敏度高,检出限低,确证能力强,分析时间短,可满足高通量食品样品中苏丹红的日常检测。     

高效液相色谱-电喷雾串联质谱法同时测定鸡肉中残留的磺胺类和氟喹诺酮类兽药

建立了一种同时测定鸡肉中两类共10种兽药(3种磺胺和7种氟喹诺酮类药物)残留量的高效液相色谱-电喷雾串联质谱方法(HPLC -ESI-MS2)。样品经2%醋酸-乙腈提取,正己烷脱脂,过ENVI-18固相萃取柱净化,经氮气吹干后,残余物用流动相定容到1 mL。以乙腈和 0.05%甲酸溶液作为流动相,采用梯度洗脱程序进行液相色谱分离,用质谱检测器进行定性和定量分析,并对10种药物的二级质谱碎裂方 式进行分析。10种药物在0.02～2.0 mg/L范围内线性良好,相关系数均大于0.9988。检出限(LOD)为1.10～6.85 μg/kg,定量限(LOQ) 为3.68～22.85 μg/kg,样品的平均加标回收率为68.9%～102.6%,相对标准偏差均小于8.6%(n=3)。实验结果表明,该方法灵敏度高,重 现性好,确证能力强,分析时间短,可满足动物源性食品中磺胺和氟喹诺酮类药物的残留分析。     

高效液相色谱-串联质谱法测定食品中多杀菌素A和D的残留量

建立了食品中多杀菌素(spinosyn) A和D残留的液相色谱-串联质谱(HPLC-MS/MS)检测方法。甘蓝等食品样品经乙腈-水(50:50, v/v)提取、HLB固相萃取柱净化后,采用HPLC-MS/MS进行检测分析,利用外标法定量。质谱分析采用电喷雾电离,正离子扫描,多反应监测模式。结果表明,柱净化后无明显的基质效应,多杀菌素在1～20 μg/L内具有较好的线性关系,其相关系数可达0.9999;样品中添加1～10 μg/kg的多杀菌素,其回收率为76.2%～114.0%,相对标准偏差(n=10)小于10%;检出限(信噪比（S/N）=3): 多杀菌素A为0.2 μg/kg,多杀菌素D为0.5 μg/kg;定量限(S/N=10): 多杀菌素A为0.5 μg/kg,多杀菌素D为1.0 μg/kg。在最佳实验条件下,对来自福建厦门的969份食品样品进行了检测,其中15份样品检测结果呈阳性。实验结果表明,该方法提取效果好,具有良好的灵敏度、回收率和重复性。     

Evaluation of different sample treatments for determining pesticide residues in fat vegetable matrices like avocado by low-pressure gas chromatography-tandem mass spectrometry

A multi-residue method has been developed for determining 65 pesticide residues in greasy vegetable matrices such as avocado. Conventional organic solvent extraction assisted by a high-speed homogenizer was compared to pressurized liquid extraction (PLE) as extraction techniques. Following this, the lipophilic extract was purified using gel permeation chromatography (GPC). Alternative clean-up methods were also evaluated, as solid-phase extraction cartridges individually used and downstream coupled, but less effective lipophilic separation was archived. The pesticide residue determination was carried out using low-pressure gas chromatography coupled to tandem mass spectrometry (LP-GC-MS-MS), showing the applicability of this type of GC columns for the analysis of fat vegetable matrices. The proposed methodology was validated in avocado matrix. The recoveries were in the range 70-110%, with RSD values lower than 19%, at 12 and 50 microg/kg spiking levels. The limits of quantitation (LOQs) were in the range 0.04-8.33 microg/kg and the limits of detection (LODs) were between 0.01 and 2.50 microg/kg. All of them were lower than the maximum residue levels (MRLs) set by the European Union (EU) in avocado. The proposed method was evaluated analyzing pesticide residues in real avocado samples.     

Simultaneous determination of 16 sulfonamides in honey by liquid chromatography/tandem mass spectrometry

A method is described for the determination of 16 sulfonamides in honey. Samples are dissolved in phosphoric acid solution (pH2), cleaned up with 2 solid-phase extraction (SPE) cartridges, an aromatic sulfonic cation-exchange cartridge and an Oasis HLB SPE cartridge, and analyzed both qualitatively and quantitatively by liquid chromatography/tandem mass spectrometry (LC/MS/MS) under the selected conditions. Without exception, calibration curves were linear (r = > 0.995), when sulfamethizole was between 1.0 and 25.0 microg/kg; sulfacetamide, sulfapyridine, sulfadiazine, sulfachloropyridazine, sulfamethoxazole, sulfamerazine, sulfisoxazole, sulfamonomethoxine, and sulfadoxine were between 2.0 and 50.0 microg/kg; sulfamethoxypyridazine, sulfadimethoxine, and sulfathiazole were between 4.0 and 100.0 microg/kg; sulfamethazine and sulfameter were between 8.0 and 200.0 microg/kg; and sulfaphenazole was between 12.0 and 300.0 microg/kg. Average recoveries at 4 fortification levels in the range of 1.0-300 microg/kg in honey were 70.9-102.5%, and relative standard deviations were 2.02-11.52%. The limits of quantitation for the 16 sulfonamides were between 1.0 and 12.0 microg/kg, with the LC/MS/MS method.     

液相色谱-串联质谱法测定鸡肌肉组织中的四环素类药物残留

建立了一种专属、灵敏的方法,用于同时检测鸡肌肉组织中土霉素、四环素和金霉素的残留。首先对鸡肌肉组织中的四环素类药物进行提取,再经C18固相萃取柱净化,采用电喷雾离子源,以正离子检测方式进行质谱分析。实验结果表明,在25～500 μg/L这一质量浓度范围内上述3种四环素类药物均呈线性,其相关系数r＞0.99。在低、中、高3个质量浓度添加水平,3种四环素类药物的平均回收率为72.4%～94.9%,相对标准偏差小于11%。3种四环素类药物的检测限均可达到10 μg/kg。其方法学考察符合农牧发［2003］1号文件的有关规定。