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您的位置:中国色谱网 >> 资讯 >> 技术应用 >> 图书期刊 >> 《色谱》2013年第3期内容摘要
《色谱》2013年第3期内容摘要
2013年3月22日 来源:中国色谱网 责编:李华静

181~184

DOI: 10.3724/SP.J.1123.2012.12029

*通讯联系人.E-mail: lxchen@yic.ac.cn.

基金项目: 国家自然科学基金项目(21105117);中国科学院百人计划项目.

收稿日期: 2012-12-17

 

分子印迹聚合物固相萃取研究进展

李金花1, 温莹莹1,2, 陈令新1*

(1. 中国科学院烟台海岸带研究所, 山东 烟台 264003; 2. 中国科学院大学, 北京 100049)

摘要: 对最新报道的分子印迹聚合物作为固相萃取剂及其在色谱样品前处理方面的应用进行综述和展望,主要包括固相萃取、基质固相分散萃取、固相微萃取、搅拌棒吸附萃取和磁性材料萃取,同时总结了分子印迹聚合物制备技术面临的挑战和问题,提出了可能的解决方案。

关键词: 分子印迹聚合物;固相萃取;固相吸附材料;色谱

文章编号: 1000-8713(2013)03-0181-04

 

Advances of molecularly imprinted polymers for solid phase extraction

LI Jinhua1, WEN Yingying1,2, CHEN Lingxin1*

(1. Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China)

Abstract: Recent advances in molecularly imprinted polymers (MIPs) as solid phase adsorbents for chromatographic sample pretreatments are summarized, including solid phase extraction, matrix solid phase dispersion extraction, solid phase microextraction, stir bar sorptive extraction and magnetic material extraction. A number of challenges and possibly effective strategies are discussed. And some perspectives of MIPs based extraction in chromatography are also proposed.

Key words: molecularly imprinted polymer; solid phase extraction; solid phase adsorbent; chromatography

 

185~190

DOI: 10.3724/SP.J.1123.2012.11029

*通讯联系人.E-mail: guozhimou@dicp.ac.cn.

基金项目: 国家杰出青年科学基金项目(20825518);国家自然科学基金青年基金项目(21005077).

收稿日期: 2012-11-30

 

基于巯基-烯点击化学法的β-环糊精固定相多模式色谱保留行为研究

徐雪峰, 沈爱金, 郭志谋*, 梁鑫淼

(中国科学院大连化学物理研究所, 辽宁 大连 116023)

摘要: 基于巯基硅胶与单取代-6A-烯丙氨基-β-环糊精的巯基-烯点击化学反应,制备了β-环糊精(Click TE-CD)共价键合固定相。元素分析结果表明β-环糊精被成功键合到硅胶表面。以黄酮苷类化合物为模型,考察了Click TE-CD固定相在亲水、反相和超临界流体色谱等分离模式下的色谱保留行为。黄酮苷类化合物保留时间随流动相中乙腈含量的变化呈现典型的U型曲线,表明Click TE-CD固定相具有亲水/反相的双重保留特性。应用几何学方法测得Click TE-CD固定相在反相/亲水、亲水/超临界、反相/超临界混合模式下的正交性分别为69.8%、50.8%、50.8%。对比复杂中药样品降香提取物在反相、亲水、超临界等模式下的分离情况,结果表明Click TE-CD固定相在分离中药复杂样品方面具有极大潜力,可以在一根色谱柱上通过分离模式的改变,实现二维液相色谱的分离。Click TE-CD固定相不同分离模式的分离性能和较好的正交性表明该固定相具有在液相色谱方法发展和二维液相色谱分离方面应用的潜力。

关键词: β-环糊精固定相;巯基-烯点击化学法;黄酮苷类化合物;正交性

文章编号: 1000-8713(2013)03-0185-06

 

Chromatographic evaluation of multi-mode retention behavior of thiol-ene click chemistry based β-cyclodextrin stationary phase

XU Xuefeng, SHEN Aijin, GUO Zhimou*, LIANG Xinmiao

(Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China)

Abstract: A native β-cyclodextrin (β-CD) stationary phase was prepared by covalent bonding of β-CD on silica particles via thiol-ene click chemistry. The resulting β-CD bonded silica (Click TE-CD) was characterized by elemental analysis, which proved the successful immobilization of β-CD on the silica support with thiol-ene click chemistry. Click TE-CD was chromatographically evaluated with a set of flavone glycosides under hydrophilic interaction chromatography (HILIC) mode, reversed-phase chromatography (RPLC) mode and supercritical fluid chromatography (SFC) mode. The acetonitrile content dependent “U” retention curves indicated its HILIC/RPLC mixed-mode retention behavior. The difference of the separation selectivity between HILIC, RPLC and SFC was described as orthogonality by using geometric approach. The orthogonalities between HILIC/RPLC, HILIC/SFC, and RPLC/SFC reached 69.8%, 50.8% and 50.8%, respectively. The separation of Chinese traditional medicine Lignum Dalbergia Odorifera extract under HILIC, RPLC and SFC modes indicated the potential of Click TE-CD stationary phase in the analysis of complex samples. The mixed-mode HPLC properties and excellent orthogonality demonstrated its flexibility in HPLC method development and its great potential in two-dimensional liquid chromatography separation on one HPLC column by different separation modes.

Key words: β-cyclodextrin (β-CD) stationary phase; thiol-ene click chemistry; flavone glycosides; orthogonality

 

191~199

DOI: 10.3724/SP.J.1123.2012.12019

*通讯联系人.Tel: (010)63165239,E-mail: mach@imm.ac.cn.

基金项目: 科技部创新工作专项基金项目(2011 IM 030200).

收稿日期: 2012-12-09

 

超高效液相色谱-串联质谱法测定中药材中三唑类杀菌剂及三嗪类除草剂的残留量

王菲, 李彤, 马辰*

(中国医学科学院&北京协和医学院药物研究所分析室, 北京 100050)

摘要: 建立了超高效液相色谱-串联质谱(UPLC-MS/MS)同时测定甘草、西洋参、三七、人参、丹参5种中药材中10种三唑类杀菌剂、18种三嗪类除草剂(包括有毒代谢物)残留量的分析方法。采用QuEChERS前处理方法,样品经1%(v/v)醋酸乙腈提取,乙二胺-N-丙基硅烷(PSA)净化处理,以Shim-pack XR-ODSII(75 mm×2.0 mm)为色谱柱,0.05%(v/v)甲酸溶液-乙腈为流动相梯度洗脱,在多反应监测(MRM)模式下测定。25种农药及其3种有毒代谢物的定量限(S/N≥10)为0.20~5.52 μg/kg;检出限(S/N≥3)为0.10~2.57 μg/kg;在各自的考察浓度范围内线性关系良好(r≥0.999);在0.20~55.2 μg/kg添加水平内,平均加标回收率为70.6%~125.7%,RSD为0.7%~14.2%。该方法样品前处理简单、快速、灵敏,可用于中药材中三唑类杀菌剂和三嗪类除草剂农药残留量的快速筛查。

关键词: QuEChERS;超高效液相色谱-串联质谱法;三唑类杀菌剂;三嗪类除草剂;中药材

文章编号: 1000-8713(2013)03-0191-09

 

Determination of triazole fungicide and triazine herbicide residues in Chinese herbs by ultra-performance liquid chromatography-tandem mass spectrometry

WANG Fei, LI Tong, MA Chen*

(Department of Analysis, Institute of Materia Medica, Chinese Academy of Medical Sciences, Beijing 100050, China)

Abstract: A method using QuEChERS clean-up followed by UPLC-MS/MS has been established for the quantitative determination of the residues of 10 triazole fungicides and 18 triazine herbicides in Chinese herbs including Radix Glycyrrhizae, Radix Panacis Quinquefolii, Salvia miltiorrhiza, Radix Notoginseng and Panax ginseng C. The pesticide residues were extracted from the samples by acetonitrile containing 1%(v/v) acetic acid, cleaned-up with primary secondary amine (PSA) and then analyzed using UPLC-MS/MS in multiple reaction monitoring (MRM) mode with positive electrospray ionization. The analytical column was Shim-pack XR-ODSII(75 mm×2.0 mm) and the mobile phases were water containing 0.05% (v/v) formic acid and acetonitrile in gradient elution. The limits of quantification (S/N≥10) of the 28 pesticides were 0.20-5.52 μg/kg and the limits of detection (S/N≥3) were 0.10-2.57 μg/kg. All of the pesticides had good linear responses with r≥0.999 and the average recoveries of the pesticides spiked in the Chinese herbs ranged from 70.6%-125.7% with the RSDs of 0.7%-14.2%. The results demonstrated that the method is simple, fast and sensitive to meet the requirements for the triazole fungicide and triazine herbicide residues and can be used for the analysis of the 28 pesticides in the above five Chinese herbs.

Key words: QuEChERS; ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS); triazole fungicides; triazine herbicides; Chinese herbs

 

200~205

DOI: 10.3724/SP.J.1123.2012.11004

*通讯联系人.E-mail: mr.cai@vip.163.com.

基金项目: 国家质检总局科技项目(2009IK156).

收稿日期: 2012-11-15

 

液相色谱-串联质谱结合谱库检索测定猪组织中的9种β-兴奋剂残留量

蔡勤仁1*, 吴洁珊1, 钱振杰1, 彭玉芬1, 蔡杰1, 杜志峰2

(1. 珠海出入境检验检疫局技术中心, 广东 珠海 519015; 2. 爱博才思亚太应用支持中心, 上海 200233)

摘要: 建立了猪组织中9种β-兴奋剂(克伦特罗、莱克多巴胺、沙丁胺醇、利托君、特布他林、班布特罗、妥布特罗、西马特罗和异舒普林)多残留的液相色谱-四极杆/线性离子阱串联质谱(QTrap LC-MS/MS)检测方法。样品经β-葡萄糖醛苷酶/芳基硫酸酯酶酶解提取,液液萃取净化,以乙腈-甲酸水溶液为流动相,经C18柱分离后用QTrap LC-MS/MS进行多反应监测(MRM)、信息相关采集(IDA)、增强子离子扫描(EPI)和谱库检索分析。9种β-兴奋剂的线性范围为0.1~50.0 μg/L,线性关系良好(r>0.99);样品中9种目标物在0.5、1.0和5.0 μg/kg添加水平下的回收率为72.0%~95.1%,相对标准偏差为3.1%~12.1%;方法检出限为0.1~0.2 μg/kg。实际样品检测结果表明,本方法可实现猪组织样本中β-兴奋剂残留量的灵敏、准确的定性和定量分析。

关键词: 液相色谱-串联质谱;谱库;β-兴奋剂;猪组织

文章编号: 1000-8713(2013)03-0200-06

 

Determination of nine β-agonist residues in pig tissues by liquid chromatography-tandem mass spectrometry combining with library search

CAI Qinren1*, WU Jieshan1, QIAN Zhenjie1, PENG Yufen1, CAI Jie1, DU Zhifeng2

(1. Technical Center of Zhuhai Entry-Exit Inspection and Quarantine Bureau, Zhuhai 519015, China; 2. AB SCIEX Asia Pacific Application Support Center, Shanghai 200233, China)

Abstract: A new method has been developed using a hybrid triple-quadrupole linear ion trap (QTrap) mass spectrometer for the fast detection and identification of nine β-agonists, clenbuterol, salbutamol, ractopamine, ritodrine, terbutaline, isoxsuprine, tulobuterol, cimaterol and bambuterol, in one single liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The homogenized tissue samples were purified with liquid-liquid extraction after enzymatic hydrolysis by β-glucuronidase/aryl sulfatase. After gradient elution separation on C18 LC column using acetonitrile and formic acid aqueous solution as the mobile phases, a multiple reaction monitoring (MRM) scan as survey scan and an enhanced product ion (EPI) scan as dependent scan were performed in an information dependent acquisition (IDA) experiment. Finally, the identification of the drugs was carried out by library search with a newly developed MS/MS library based on EPI spectra at three different collision energies in positive mode. The analytical method in the present study was well validated and good results were obtained with respect to precision, repeatability and spiked recovery. The limits of detection of residues were 0.1-0.2 μg/kg for β-agonists, and with a linear range from 0.1 to 50.0 μg/L. Three concentration levels of 0.5, 1.0 and 5.0 μg/kg were spiked in pig tissues, and the overall recoveries were between 72.0% and 95.1% with the relative standard deviations (RSDs) between 3.1% and 12.1%. The real sample test showed that this method could be used for sensitive and accurate determination of β-agonist residues in pig tissues.

Key words: liquid chromatography-tandem mass spectrometry (LC-MS/MS); spectral library; β-agonists; pig tissue

 

206~210

DOI: 10.3724/SP.J.1123.2012.11010

*通讯联系人.Tel: (021)38620542,E-mail: chuanxian.wang@163.com.

基金项目: 上海市科委重点科技攻关项目(10391901800);上海市科委长三角联合攻关项目(11495810200);上海市科委工程中心建设项目(11DZ2280300).

收稿日期: 2012-11-20

 

液相色谱-串联质谱法检测水产品中残留的硝基呋喃类药物的代谢物

王传现1*, 黄帆2, 王敏1, 盛永刚1, 张缙3, 韩丽1, 宋青1, 李晓虹1, 徐敦明3, 丁卓平2

(1. 上海出入境检验检疫局, 上海 200135; 2. 上海海洋大学, 上海 201306; 3. 厦门出入境检验检疫局, 厦门 361026)

摘要: 建立了液相色谱-串联质谱(LC-MS/MS)法用于同时测定水产品中硝基呋喃类药物的代谢物3-氨基-2-唑烷基酮(AOZ)、5-甲基吗啉-3-氨基-2-唑烷基酮(AMOZ)、氨基脲(SEM)、1-氨基-2-内酰脲(AHD)和3,5-二硝基水杨酸肼(DNSH)。样品经盐酸水解、2-硝基苯甲醛衍生、乙酸乙酯提取净化。氮吹至干后,用1 mL乙腈-0.1%甲酸水(20:80, v/v)定容。经Aquasil C18色谱柱分离,用液相色谱-三重四极杆串联质谱以多反应监测模式(MRM)进行检测分析,内标法定量。结果表明,该方法的线性范围为0.5~10 μg/kg, 5种代谢物的线性相关系数均不小于0.9976,定量限为0.5 μg/kg。在0.5、1.0、2.0和4.0 μg/kg的添加水平下,加标回收率为81.3%~100.5%, RSD为3.4%~10.0%。本法可作为水产品中5种硝基呋喃类药物的代谢物残留量同时分析的有效手段。

关键词: 液相色谱-串联质谱法;硝基呋喃;代谢物;水产品

文章编号: 1000-8713(2013)03-0206-05

 

Determination of metabolite residues of nitrofuran antibiotics in aquatic products by liquid chromatography-tandem mass spectrometry

WANG Chuanxian1*, HUANG Fan2, WANG Min1, SHENG Yonggang1, ZHANG Jin3, HAN Li1, SONG Qing1, LI Xiaohong1, XU Dunming3, DING Zhuoping2

(1. Shanghai Exit-Entry Inspection and Quarantine Bureau, Shanghai 200135, China; 2. Shanghai Ocean University, Shanghai 201306, China; 3. Xiamen Exit-Entry Inspection and Quarantine Bureau, Xiamen 361026, China)

Abstract: A method was developed for simultaneous qualitative and quantitative analysis of five metabolites of nitrofuran antibiotics, including 3-amino-2-oxazolidinone (AOZ), 5-morpholino-methyl-3-amino-2-oxazolidinone (AMOZ), semicarbazide (SEM), 1-aminohydantoin (AHD) and 3,5-dinitrosalicylic acid hydrazide (DNSH) in aquatic products by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The samples were hydrolyzed with HCl, and derivatized with 2-nitrobenzaldehyde at 37 ℃ for 16 hours. The derivative solutions were adjusted to pH 7.0-7.5, and the analytes were extracted by ethyl acetate. The separation was based on Thermo Aquasil C18 column (150 mm×4.6 mm, 3.0 μm). The analytes were detected by tandem mass spectrometry with electrospray ionization source with multiple reaction monitoring (MRM) mode. The developed method showed good linear correlation between the peak area ratios of the analyte and the internal standard and the concentration of the analyte with the correlation coefficients all above 0.99 over the dynamic range of 0.5-10 μg/kg. The limits of quantitation (LOQs) of AOZ, AMOZ, SEM, AHD and DNSH were 0.5 μg/kg. The average recoveries of all the compounds at four spiked levels of 0.5, 1.0, 2.0 and 4.0 μg/kg ranged from 81.3% to 100.5% with the RSDs between 3.4% and 10.0% (n=6). The method is proved to be fast and effective for simultaneous qualitative and quantitative analysis of the metabolites of the nitrofuran antibiotics in aquatic products.

Key words: liquid chromatography-tandem mass spectrometry (LC-MS/MS); nitrofuran; metabolites; aquatic products

 

211~217

DOI: 10.3724/SP.J.1123.2012.10018

*通讯联系人.Tel: (0311)86266025,E-mail: jiangye@hebmu.edu.cn.

基金项目:河北省卫生厅科研基金项目(08056).

收稿日期: 2012-10-24

 

超高效液相色谱-串联质谱法同时测定尿样中4种痕量的乌头类生物碱

张盼盼1,5, 张福成2, 王朝虹3, 蒋晔1,5*, 卢永江4

(1. 河北医科大学药学院, 河北 石家庄 050017; 2. 北京空军总医院, 北京 100142; 3. 最高人民检察院司法鉴定中心, 北京 100040; 4. 山东莒县中医院, 山东 莒县 276500; 5. 河北省法医学实验室, 河北 石家庄 050017)

摘要: 建立了超高效液相色谱-串联质谱(UPLC-MS/MS)结合中空纤维微萃取(HF-LPME)同时检测尿样中痕量的乌头碱、次乌头碱、新乌头碱和滇乌头碱等4种生物碱的方法。采用HF-LPME对尿样进行提取、纯化和富集,富集倍数达102~301。同时采用电喷雾电离(ESI)、多反应监测(MRM)进行含量测定,显著提高了尿液中乌头类生物碱的检测灵敏度,4种乌头类生物碱的定量限达到0.01~0.1 ng/L,可大大延长中毒患者尿样中乌头类生物碱的检测时间窗。方法验证结果表明,尿液中乌头碱、新乌头碱和滇乌头碱在0.01~10 ng/L、次乌头碱在0.1~100 ng/L范围内线性关系良好,提取回收率为80.2%~109%,相对标准偏差小于4.6%。该方法适用于乌头类生物碱中毒案件的检测,为痕量乌头类生物碱分析提供了灵敏的分析方法。

关键词: 中空纤维液相微萃取;超高效液相色谱-质谱;乌头碱;次乌头碱;新乌头碱;滇乌头碱;尿样

文章编号: 1000-8713(2013)03-0211-07

 

Simultaneous determination of four trace aconitum alkaloids in urine using ultra performance liquid chromatography-mass spectrometry

ZHANG Panpan1,5, ZHANG Fucheng2, WANG Zhaohong3, JIANG Ye1,5*, LU Yongjiang4

(1. School of Pharmacology, Hebei Medical University, Shijiazhuang 050017, China; 2. Air Force General Hospital, Beijing 100142, China; 3. Institute of Forensic Science of Supreme People’ s Procuratorate, Beijing 100040, China; 4. Ju County Hospital of Traditional Chinese Medicine, Ju County 276500, China; 5. Hebei Key Laboratory of Forensic Medicine, Shijiazhuang 050017, China)

Abstract: A rapid, specific and sensitive ultra performance liquid chromatography-mass spectrometry (UPLC-MS/MS) method was developed for the simultaneous determination of four trace alkaloids, including aconitine (AC), hypaconitine (HA), mesaconitine (MA) and yunaconitine (YA) in human urine samples. UPLC-MS-MS system coupled with an electrospray ionization (ESI) source was performed in multiple reaction monitoring (MRM) mode. The sample preparation was performed with hollow fiber microextraction (HF-LPME) prior to the analysis. The enrichment factors of the four alkaloids were 102-301. The separation was applied on a Waters ACQUITY UPLC BEH C18 column (50 mm×2.1 mm, 1.7 μm) with a gradient elution of acetonitrile and 10 mmol/L NH4HCO3 as mobile phase. The retention times were less than 3 min. This method significantly improved the detection sensitivity, and the limits of quantitation were from 0.01 to 0.1 ng/L. The calibration curves were linear over the ranges of 0.01-10 ng/L for AC, MA and YA, 0.1-100 ng/L for HA in human urine samples, and the correlation coefficients were 0.9981, 0.9984, 0.9995 and 0.9986, respectively. The method was proved to be rapid and sensitive for aconitum alkaloid analysis in urine samples.

Key words: hollow fiber liquid-phase microextraction (HF-LPME); ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS); aconitine; hypaconitine; mesaconitine; yunaconitine; urine samples

 

218~222

DOI: 10.3724/SP.J.1123.2012.10003

*通讯联系人.Tel: (0592)3269506,E-mail: Zhouy@xmciq.gov.cn.

基金项目: 厦门市科技计划项目(3502Z20092009,3502Z20102013);国家质检总局科技计划项目(2010IK192).

收稿日期: 2012-10-10

 

加速溶剂萃取-气相色谱-串联质谱法测定茶叶中10种吡唑和吡咯类农药的残留量

徐敦明1, 卢声宇2, 陈达捷1, 蓝锦昌2, 张志刚1, 杨方2, 周昱1*

(1. 厦门出入境检验检疫局, 福建 厦门 361026; 2. 福建出入境检验检疫局, 福建 福州 350001)

摘要: 建立了加速溶剂萃取(ASE)-气相色谱-串联质谱(GC-MS/MS)法用于测定茶叶中10种吡唑和吡咯类农药残留。ASE萃取压力为1.03×107 Pa,萃取温度为100 ℃,萃取时间为5 min,萃取溶剂为乙酸乙酯-正己烷(1:1, v/v)。萃取循环1次,萃取液浓缩后用Envi-Carb/PSA固相萃取小柱净化,乙酸乙酯-正己烷(1:1, v/v)洗脱。洗脱液浓缩后,用正己烷定容,供GC-MS/MS测定,外标法定量。方法的准确度和精密度均符合残留分析要求。方法的定量限(LOQ)分别为唑螨酯0.003 mg/kg、氟虫腈硫化物0.001 mg/kg、氟虫腈0.002 mg/kg、氟虫腈砜化物0.005 mg/kg、溴虫腈0.002 mg/kg、氟硅唑0.006 mg/kg、野燕枯0.001 mg/kg、吡草醚0.001 mg/kg、吡螨胺0.0003 mg/kg、唑虫酰胺0.005 mg/kg。方法的灵敏度能满足各国有关农药的残留限量要求。

关键词: 加速溶剂萃取;气相色谱-串联质谱;吡唑;吡咯;残留分析;农药

文章编号: 1000-8713(2013)03-0218-05

 

Determination of ten pesticides of pyrazoles and pyrroles in tea by accelerated solvent extraction coupled with gas chromatography-tandem mass spectrometry

XU Dunming1, LU Shengyu2, CHEN Dajie1, LAN Jinchang2, ZHANG Zhigang1, YANG Fang2, ZHOU Yu1*

(1. Xiamen Entry-Exit Inspection and Quarantine Bureau, Xiamen 361026, China; 2. Fujian Entry-Exit Inspection and Quarantine Bureau, Fuzhou 350001, China)

Abstract: An effective method was developed and applied to determine the residues of ten pesticides of pyrazoles and pyrroles in tea by accelerated solvent extraction coupled with gas chromatography-tandem mass spectrometry (ASE-GC-MS/MS). The samples were extracted with ethyl acetate-hexane(1:1, v/v) for 5 min at 1.03×107 Pa and 100 ℃ for one cycle. Then, they were purified by Envi-Carb/PSA column, and eluted by ethyl acetate-hexane (1:1, v/v). The analytes were determined by GC-MS/MS and quantified by external standard method. The limits of quantification were 0.003 mg/kg for fenpyroximate, 0.001 mg/kg for fipronil-sulfide, 0.002 mg/kg for fipronil, 0.005 mg/kg for fipronil-sulfone, 0.002 mg/kg for chlorfenapyr, 0.006 mg/kg for flusilazole, 0.001 mg/kg for difenzoquat, 0.001 mg/kg for pyraflufen-ethyl, 0.0003 mg/kg for tebufenpyrad and 0.005 mg/kg for tolfenpyrad. The results show that the proposed method is sensitive and accurate for the determination of the ten pesticide residues.

Key words: accelerated solvent extraction (ASE); gas chromatography-tandem mass spectrometry (GC-MS/MS); pyrazole; pyrrole; residue analysis; pesticide

 

223~227

DOI: 10.3724/SP.J.1123.2012.10020

*通讯联系人.E-mail: xsjn_828@163.com.

基金项目: 科技部公益专项课题(201210060);浙江省质量技术监督系统科研计划项目(20110243).

收稿日期: 2012-10-24

 

气相色谱-质谱联用法测定腌制水产品中的挥发性N-亚硝胺类化合物

赵华1, 王秀元2*, 王萍亚1, 周勇1, 薛超波1, 蒋玲波1

(1. 国家海洋食品质量监督检验中心, 浙江 舟山 316021; 2. 浙江海洋学院食品与医药学院, 浙江 舟山 316000)

摘要: 建立了气相色谱-质谱(GC-MS)快速测定腌制水产品中挥发性N-亚硝胺含量的分析方法。采用GC-MS测定了N-二甲基亚硝胺(NDMA)、N-二乙基亚硝胺(NDEA)、N-二丙基亚硝胺(NDPA)、N-亚硝基吡咯烷(NPYR)、N-亚硝基哌啶(NPIP)、N-二丁基亚硝胺(NDBA)6种化合物,考察了样品不同提取方法、不同固相萃取小柱、不同色谱柱对分离检测的影响。结果显示: 在10~1000 μg/L范围内,线性相关系数可达0.9998以上;重现性良好,相对标准偏差小于8%;回收率可达79%~105%;灵敏度高,检出限低,除NDPA为0.03 μg/kg外,其他5种N-亚硝胺为0.05 μg/kg。该方法前处理快速简捷,易于操作,适用于腌制水产品中N-亚硝胺残留量的检测工作。

关键词: 气相色谱-质谱;N-亚硝胺;腌制水产品

文章编号: 1000-8713(2013)03-0223-05

 

Determination of volatile N-nitrosamine compounds in salted aquatic products by gas chromatography-mass spectrometry

ZHAO Hua1, WANG Xiuyuan2*, WANG Pingya1, ZHOU Yong1, XUE Chaobo1, JIANG Lingbo1

(1. National Marine Food Quality Supervision and Testing Center, Zhoushan 316021, China; 2. School of Food and Pharmacy & Medical School, Zhejiang Ocean University, Zhoushan 316000, China)

Abstract: An analytical method was developed for the determination of the extraction of volatile N-nitrosamine compounds including N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodipropylamine (NDPA), N-nitrosodibutylamine (NDBA), N-nitrosopiperidine (NPIP), and N-nitrosopyrrolidine (NPYR) from salted aquatic products by gas chromatography-mass spectrometry (GC-MS). In this experiment, the separation and detection conditions were optimized for different extraction methods, solid-phase extraction columns, and chromatographic columns. The results showed that the linear correlation coefficients (R2) were higher than 0.9998 within 10-1000 μg/L, and the reproducibilities were good with the relative standard deviations (RSD) less than 8%. The recoveries were 79%-105%. It is noted that this method for the determination of volatile N-nitrosamine compounds in salted aquatic products was much more sensitivity and with a lower detection limits (0.05 μg/kg except NDPA) than the previously reported methods. This proposed method is rapid and convenient for the determination, and easy for the operation. It is appropriate for the determination of volatile N-nitrosamine compounds in various salted aquatic products.

Key words: gas chromatography-mass spectrometry (GC-MS); N-nitrosamines; salted aquatic products

 

228~239

DOI: 10.3724/SP.J.1123.2012.10029

*通讯联系人.Tel: (010)82109532,E-mail: liusu@mail.caas.net.cn.

基金项目: 国家农产品质量安全风险评估专项(农办质[2012]42).

收稿日期: 2012-11-01

 

气相色谱-三重四极杆串联质谱法快速测定蔬菜水果中129种农药的残留量

马智玲, 赵文, 李凌云, 郑姝宁, 林桓, 张延国, 高青珍, 刘肃*

(中国农业科学院蔬菜花卉研究所 农业部蔬菜品质监督检验测试中心, 北京 100081)

摘要: 采用QuEChERS方法结合气相色谱-串联质谱法(GC-MS/MS)建立了蔬菜、水果中129种农药残留同时检测的分析方法。试样用1%乙酸乙腈均质提取,采用混合型固相分散萃取剂净化后,用GC-MS/MS在多反应离子监测(MRM)模式下进行检测,外标法定量。结果表明,129种药物在一定的含量范围内线性关系良好,相关系数(r2)均大于0.98;不同基质在10 μg/kg添加水平下大部分农药的平均回收率为66.2%~124.7%,相对标准偏差(RSD)为0.9%~24.4%;方法的定量限(LOQ)为0.03~16.7 μg/kg。结果表明,该方法简便快速、灵敏可靠、经济有效,适用于蔬菜、水果中农药多残留的同时快速筛查测定。

关键词: 气相色谱-三重四极杆串联质谱;QuEChERS;农药残留;蔬菜;水果

文章编号: 1000-8713(2013)03-0228-12

 

Rapid determination of 129 pesticide residues in vegetables and fruits by gas chromatography-triple quadrupole mass spectrometry

MA Zhiling, ZHAO Wen, LI Lingyun, ZHENG Shuning, LIN Huan, ZHANG Yanguo, GAO Qingzhen, LIU Su*

(Institute of Vegetables and Flowers, Chinese Academy of Agricultural Sciences, Supervision and Testing Center for Vegetable Quality, Ministry of Agriculture, Beijing 100081, China)

Abstract: An analytical method for the simultaneous determination of 129 pesticides in vegetables and fruits was established based on optimized QuEChERS with gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). The samples were extracted with acetonitrile (containing 1% (v/v) acetic acid), then the extracts were determined by GC-MS/MS in multi-reaction monitoring (MRM) mode after being cleaned up with mixed solid-phase dispersion, and the external standard method was applied to quantify the pesticides. The results showed that all the 129 pesticides had good linearity in certain ranges with the correlation coefficients (r2) higher than 0.98. The average recoveries of the most of 129 pesticides in different matrices were in the range of 66.2%-124.7% at the spiked level of 10 μg/kg, with relative standard deviations (RSDs)of 0.9%-24.4%. The limits of quantification (LOQs) of the method were 0.03-16.7 μg/kg. The results demonstrated that the developed method is simple, rapid, sensitive and high efficient for screening multiple pesticide residues in vegetables and fruits.

Key words: gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS); QuEChERS; pesticide residues; vegetables; fruits

 

240~248

DOI: 10.3724/SP.J.1123.2012.10031

*通讯联系人.E-mail: zqzhang@snnu.edu.cn.

基金项目: 国家自然科学基金项目(21275098).

收稿日期: 2012-11-05

 

微波-超声波协同一步提取衍生化-气相色谱-质谱联用快速分析中药材猫爪草中的脂肪酸

詹汉英, 刘瑞林, 王德金, 袁静, 胥生杰, 张志琪*

(药用资源与天然药物化学教育部重点实验室, 陕西师范大学化学化工学院, 陕西 西安 710100)

摘要: 建立了一种微波-超声波协同一步提取衍生化、气相色谱-质谱联用快速测定中药材猫爪草中低含量脂肪酸的方法。以总脂肪酸的色谱峰面积为响应指标,采用响应曲面法优化了主要工艺参数,其结果为: 猫爪草粉末5.0 g,正己烷50.0 mL,微波功率500 W,反应温度50 ℃,催化剂用量0.30 g,甲醇用量4.0 mL,提取衍生化时间8 min。以内标法定量各个脂肪酸的含量,一步提取衍生化法获得的总脂肪酸峰面积((3.327±0.023)×107, n=3)和总不饱和脂肪酸含量((13.59±0.30) mg/g, n=3)明显高于传统方法((2.410±0.036)×107(n=3)和(12.05±0.34) mg/g(n=3))。该方法简化了复杂的样品处理过程,缩短了反应时间,降低了分析成本,改善了提取和衍生化效率,尤其是减少了不饱和脂肪酸的氧化和分解。该方法具有简单、快速和实用性的特点,是一种极具应用潜力的中药材中低含量脂肪酸的快速分析方法。

关键词: 一步提取衍生化;微波-超声波协同作用;气相色谱-质谱联用;响应曲面优化法;脂肪酸;猫爪草

文章编号: 1000-8713(2013)03-0240-09

 

Rapid determination of fatty acids in Ranunculus ternatus Thunb. by microwave-ultrasonic synergistic one-step extraction-derivatization and gas chromatography-mass spectrometry

ZHAN Hanying, LIU Ruilin, WANG Dejin, YUAN Jing, XU Shengjie, ZHANG Zhiqi*

(Key Laboratory of Medicinal Resource and Natural Pharmaceutical Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710100, China)

Abstract: A rapid and simple microwave-ultrasonic synergistic one-step extraction-derivatization (MUED) method and gas chromatography-mass spectrometry was established for the determination of low content fatty acids (FAs) profile in Ranunculus ternatus Thunb. The critical experimental parameters for MUED method were optimized with response surface methodology by taking the chromatographic peak areas of total FAs as a major response index. The best technological parameters were determined as 5.0 g of Ranunculus ternatus Thunb. powder, 50.0 mL of n-hexane, 500 W of microwave power, 50 ℃ of reaction temperature, 0.30 g of catalyst (KOH), 4.0 mL of derivatization reagent (methanol) and the time of extraction-derivatization of 8 min. The contents of individual FAs were quantified by internal standard method. The results showed that the chromatographic peak areas of the total FAs and the total unsaturated FAs contents obtained with MUED were (3.327±0.023)×107 (n=3) and (13.59±0.30) mg/g (n=3) respectively. They were markedly higher than those obtained by the conventional method which were (2.410±0.036)×107 (n=3) and (12.05±0.34) mg/g (n=3) respectively. The MUED method simplified the complicated sample handling steps, shortened the sample preparation time, reduced the cost of analysis, and improved the extraction and derivatization efficiency of the lipids, especially weakened the oxidization and decomposition of the unsaturated FAs. The simplicity, speed and practicability suggest the proposed method has significant potential for the determination of low content FAs in herbal medicines.

Key words: one-step extraction-derivatization; microwave-ultrasonic synergistic action; gas chromatography-mass spectrometry (GC-MS); response surface methodology; fatty acids; Ranunculus ternatus Thunb.

 

249~253

DOI: 10.3724/SP.J.1123.2012.10039

*通讯联系人.E-mail: zqzhang@snnu.edu.cn.

基金项目: 国家自然科学基金项目(21275098).

收稿日期: 2012-11-12

 

以离子液体作流动相添加剂的高效液相色谱法测定复方苦参注射液中4种生物碱

亓亮, 张婧, 张志琪*

(药用资源与天然药物化学教育部重点实验室, 陕西师范大学, 陕西 西安 710062)

摘要: 将离子液体1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF4)作为流动相添加剂建立了同时测定复方苦参注射液中4种主要生物碱的HPLC分析方法。以Agilent TC-C18柱(250 mm×4.6 mm, 5 μm)为分离柱,甲醇-0.1%磷酸水溶液(含2.2×10-4mol/L [BMIM]BF4)(5:95, v/v)为流动相,流速1.0 mL/min,柱温30 ℃,进样量20 μL,在205 nm下检测。结果表明,苦参碱、槐定碱、氧化槐果碱以及氧化苦参碱的质量浓度分别在25.8~155.0 mg/L, 40.0~240.0 mg/L, 21.7~130.0 mg/L和37.5~225.0 mg/L范围内线性关系良好,相关系数均大于0.9990,平均回收率(n=9)在96.2%和98.9%之间。离子液体的加入能明显改善C18柱分离生物碱的色谱峰形并提高分离度。本法简便、快速、重复性好,可用于复方苦参注射液中生物碱的分离与测定。

关键词: 离子液体;流动相添加剂;高效液相色谱法;生物碱;苦参;复方苦参注射液

文章编号: 1000-8713(2013)03-0249-05

 

Determination of four alkaloids in Compound Kushen Injection by high performance liquid chromatography with ionic liquid as mobile phase additive

QI Liang, ZHANG Jing, ZHANG Zhiqi*

(Key Laboratory of the Ministry of Education for Medicinal Resources and Natural Pharmaceutical Chemistry, Shaanxi Normal University, Xi’an 710062, China)

Abstract: In order to improve the resolution and peak shape, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4) was used as mobile phase additive to develop an HPLC method for the determination of four main alkaloids in Compound Kushen Injection. An Agilent TC-C18 column was used with the mobile phase of methanol-0.1% phosphoric acid solution (containing 2.2×10-4mol/L [BMIM]BF4) (5:95, v/v), flow rate of 1.0 mL/min, column temperature of 30 ℃, and injection volume of 20 μL, detected at 205 nm. The calibration curves of matrine, sophoridine, oxymatrine and oxysophocarpine were in good linearity over the ranges of 25.8-155.0 mg/L, 40.0-240.0 mg/L, 21.7-130.0 mg/L and 37.5-225.0 mg/L, respectively, with correlation coefficients above 0.9990. The mean recoveries (n=9) were between 96.2% and 98.9%. Ionic liquid, [BMIM]BF4, can obviously improve the resolution and peak shape. The method is simple, rapid, and reliable, and can be used for the determination of alkaloids in Sophora flavescens Ait in Compound Kushen Injection.

Key words: ionic liquid; additive in mobile phase; high performance liquid chromatography (HPLC); alkaloids; Sophora flavescens Ait; Compound Kushen Injection

 

254~259

DOI: 10.3724/SP.J.1123.2012.10033

*通讯联系人.E-mail: shliu815@126.com.

基金项目: 西北农林科技大学人才专项项目(Z111021005).

收稿日期: 2012-10-26

 

亚临界水萃取-高效液相色谱法测定聚碳酸酯水杯中双酚A和苯酚的迁移量

白玮玮, 刘书慧*, 曹江平, 范盈盈, 解启龙

(西北农林科技大学理学院, 陕西 杨凌 712100)

摘要: 建立了亚临界水萃取-高效液相色谱同时测定聚碳酸酯(PC)水杯中双酚A和苯酚迁移量的方法。选择萃取温度120 ℃、萃取压力6.89 MPa(1000 psi)、静态萃取时间1 h、萃取1次对11种样品进行测定。双酚A的迁移量为6.81~11.16 μg/g。5种样品中未检出苯酚,其余样品中苯酚迁移量为3.25~6.08 μg/g。在优化的测定条件下,双酚A和苯酚在8 min内达到基线分离。双酚A和苯酚分别在0.05~20 mg/L和0.02~20 mg/L范围内线性关系良好,相关系数(r)均大于0.9997,检出限分别为7.6 μg/L和2.0 μg/L。日内及日间的重复性(以RSD计)分别小于5.21%及11.63%。传统的浸提法结果表明长时间浸提会使PC材料发生微弱水解。相比传统的浸提法,该方法的萃取效率提高了49~106倍。该方法简便、快速、环保,可用来测定PC水杯中双酚A和苯酚的迁移量。

关键词: 亚临界水萃取;高效液相色谱;双酚A;苯酚;聚碳酸酯水杯

文章编号: 1000-8713(2013)03-0254-06

 

Simultaneous determination of the migrations of bisphenol A and phenol in polycarbonate bottles based on subcritical water extraction and high performance liquid chromatography

BAI Weiwei, LIU Shuhui*, CAO Jiangping, FAN Yingying, XIE Qilong

(College of Science, Northwest A & F University, Yangling 712100, China)

Abstract: A new method was established for the simultaneous determination of the migration amounts of bisphenol A (BPA) and phenol from polycarbonate (PC) bottles based on subcritical water extraction (SWE) and high performance liquid chromatography. The optimum extraction conditions included an extraction temperature of 120 ℃, a pressure of 6.89 MPa (1000 psi), a static extraction time of 1 h and one cycle. Under the conditions, the migration amounts of the BPA ranged from 6.81 to 11.16 μg/g in 11 samples. Phenol was not detectable in 5 samples, and in other ones the migration amounts of phenol varied in the range of 3.25-6.08 μg/g. The traditional soaking extraction experiments showed that PC was subjected to weak hydrolysis after long-time leaching. The BPA and phenol were separated in 8 min. Good linearities were obtained in the range of 0.05-20 mg/L for BPA and 0.02-20 mg/L for phenol (r>0.9997). The limits of detection were 7.6 μg/L for BPA and 2.0 μg/L for phenol. Intra-day and inter-day repeatabilities (expressed as RSD) were less than 5.21% and 11.63%, respectively. Compared with traditional water soaking extraction, the extraction efficiencies increased 49-106 times using this developed SWE method. The procedure is simple, rapid and environment friendly, and can be utilized to determine the migration amounts of BPA and phenol in PC bottles.

Key words: subcritical water extraction (SWE); high performance liquid chromatography (HPLC); bisphenol A; phenol; polycarbonate (PC) bottles

 

260~263

DOI: 10.3724/SP.J.1123.2012.11005

*通讯联系人.E-mail: hygkd@mails.tjmu.edu.cn.

基金项目: 国家自然科学基金项目(20977038).

收稿日期: 2012-11-19

 

微囊藻毒素-RR的纯化及鉴定

张永路, 黄夏宁, 肖雯晴, 钟晴, 谷康定*

(华中科技大学同济医学院公共卫生学院环境医学研究所 教育部环境与健康重点实验室, 湖北 武汉 430030)

摘要: 将固相萃取和凝胶色谱技术相结合,建立了以野外采集的水华蓝藻为原料提取和纯化微囊藻毒素-RR(MC-RR)的有效方法。用70%的甲醇溶液溶解35 g藻浆,经离心等系列处理,得粗提液,旋转蒸发去除甲醇;粗提液经HLB柱固相萃取后,得到7.5 mL洗脱液,然后将其浓缩至2 mL,再用Sephadex LH-20凝胶色谱柱分离纯化,洗脱液分管收集,用紫外分光光度计测定每管洗脱液在238 nm的吸收值,并绘制洗脱曲线。使用高效液相色谱对峰值组分进行鉴定,同时利用紫外分光光度计对毒素的光谱特征进行鉴定。最终获得3.65 mg纯度超过90%的MC-RR样品,产品得率为74.1%。其紫外吸收光谱在238 nm处有特征吸收,证明所纯化的样品为MC-RR。

关键词: 固相萃取;凝胶色谱;微囊藻毒素-RR(MC-RR);纯化

文章编号: 1000-8713(2013)03-0260-04

 

Purification and identification of microcystin-RR

ZHANG Yonglu, HUANG Xianing, XIAO Wenqing, ZHONG Qing, GU Kangding*

(Key Laboratory of Environment and Health of Ministry of Education, Institute of Environmental Medicine, School of Public Health, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, China)

Abstract: An effective method based on the combination of solid phase extraction and gel chromatography to extract and purify microcystin-RR (MC-RR) from natural cyanobacteria bloom was developed. Thirty five gram natural cyanobacterial bloom scum was extracted with 70% aqueous methanol. After the methanol in the crude extract was removed by a rotary evaporator, the solid phase extraction was used for preliminary purification and concentration. And then 7.5 mL eluent was concentrated to 2 mL and loaded onto a Sephadex LH-20 gel chromatographic column for further purification. The eluate was collected by tubes and detected at 238 nm. The elution curve was plotted by tube numbers as X-axis and the absorbance at 238 nm as Y-axis. The purity and the spectral characteristics of the final extract were identified with high performance liquid chromatograph (HPLC) and spectrophotometer, respectively. A total of 3.65 mg of MC-RR with a final yield of 74.1% was obtained, and the purity was more than 90% with characteristic UV absorption spectra at 238 nm.

Key words: solid phase extraction; gel chromatography; microcystin-RR (MC-RR); purification

 

264~269

DOI: 10.3724/SP.J.1123.2012.10021

*通讯联系人.Tel: (0571)81100628,E-mail: zxy@ziq.gov.cn.

基金项目: 质量检验公益性行业科研专项(201310149-01).

收稿日期: 2012-10-25

 

固相萃取-液相色谱-串联质谱法测定中药材中7种甲氧基丙烯酸酯类杀菌剂的残留量

张育乐1, 黄超群2, 朱晓雨2*, 陈笑梅1,2, 莫卫民1

(1. 浙江工业大学化学工程与材料学院, 浙江 杭州 310014; 2. 浙江出入境检验检疫局, 浙江 杭州 310016)

摘要: 建立了采用固相萃取-液相色谱-串联质谱同时测定麦冬、玄参、延胡索中7种甲氧基丙烯酸酯类杀菌剂残留量的方法。样品经乙酸乙酯提取,氨基固相萃取柱净化后,经C18色谱柱分离,以甲醇和1.0‰甲酸溶液为流动相梯度洗脱,电喷雾正离子模式离子化,选择反应监测方式监测,串联质谱测定,外标法定量。结果显示,各目标物在1或2个数量级浓度范围内的线性关系良好,相关系数均大于0.996。醚菌胺、啶氧菌酯和肟菌酯的定量限为2 μg/kg,嘧菌酯和吡唑醚菌酯的定量限为4 μg/kg, Z-苯氧菌胺和醚菌酯的定量限为10 μg/kg。各杀菌剂的回收率为60.4%~110%,相对标准偏差为1.2%~17%。该方法能满足麦冬、玄参、延胡索中7种目标杀菌剂残留量的检测。

关键词: 固相萃取;液相色谱-串联质谱法;甲氧基丙烯酸酯类杀虫剂;中药材

文章编号: 1000-8713(2013)03-0264-06

 

Determination of seven strobilurin fungicide residues in Chinese herbs by liquid chromatography-tandem mass spectrometry coupled with solid phase extraction

ZHANG Yule1, HUANG Chaoqun2, ZHU Xiaoyu2*, CHEN Xiaomei1,2, MO Weimin1

(1. College of Chemical Engineering and Material, Zhejiang University of Technology, Hangzhou 310014, China; 2. Zhejiang Entry-Exit Inspection and Quarantine Bureau, Hangzhou 310016, China)

Abstract: An LC-MS/MS method was developed for the simultaneously determination of seven strobilurin fungicide residues in Chinese herbs. The strobilurin fungicides include Z-metominostrobin, kresoxim-methyl, dimoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin and trifloxystrobin. The sample was extracted with ethyl acetate and cleaned-up by an amino SPE column. The seven strobilurin fungicide residues were separated on a C18 column with gradient elution of 1.0‰ formic acid and methanol as mobile phases, and detected by ESI-MS in positive ion and selective reaction monitoring (SRM) mode. External standard method was used to the quantification with good linear relationships (r≥0.996). The LOQs were 2 μg/kg for dimoxystrobin, picoxystrobin and trifloxystrobin, 4 μg/kg for pyraclostrobin and azoxystrobin, 10 μg/kg for Z-metominostrobin and kresoxim-methyl. The recoveries were from 60.4% to 110% with the RSDs between 1.2% and 17%. The developed method is suitable for the determination and confirmation of the seven strobilurin fungicide residues in the three of Eight Zhes (Ophiopogon japonicus (Thunb.), Scrophularia ningpoensis Hemsl. and Corydalis yanhusuo W T Wang).

Key words: solid phase extraction(SPE); liquid chromatography-tandem mass spectrometry (LC-MS/MS); strobilurin fungicides; Chinese herbs

 

270~274

DOI: 10.3724/SP.J.1123.2012.10038

*通讯联系人.Tel: (010)80799170,E-mail: jcxbac@sohu.com.

基金项目: 北京农学院基础科学基金重点资助项目(2067516001).

收稿日期: 2012-11-12

 

高效液相色谱-串联质谱检测牛奶中的甲状腺素

王宗义1, 杨定忠2, 冀梦瑶1, 贾昌喜1*, 黄漫青1

(1. 北京农学院食品科学与工程学院 农产品安全检测与控制北京市重点实验室, 北京 102206; 2. 天津博纳艾杰尔科技有限公司, 天津 300462)

摘要: 建立了高效液相色谱-串联质谱(HPLC-MS/MS)检测牛奶中甲状腺素3,3′,5,5′-四碘-L-甲腺原氨酸(T4), 3,3′,5-三碘-L-甲腺原氨酸(T3)和3,3′,5′-三碘-L-甲腺原氨酸(rT3)的方法。样品用乙腈提取,离心,上清液经氨水碱化和Cleanert PAX固相萃取小柱净化,在Zorbax Eclipse XDB-C18 (150 mm×2.1 mm, 3.5 μm)色谱柱上以0.1%(v/v)乙酸水溶液和甲醇为流动相等度洗脱分离,以电喷雾正离子(ESI+)模式电离,多反应监测(MRM)模式质谱检测,内标法定量。结果表明,甲状腺素的检出限(LOD)不大于0.03 ng/g,定量限(LOQ)不大于0.1 ng/g;在考察的浓度范围内线性关系良好(r2> 0.998);回收率为80.61%~101.7%,相对标准偏差(RSD)为1.48%~9.70%。室温下样品溶液中的甲状腺素保持稳定。对5个牛奶样品的测定结果显示,T3含量为0.59~1.30 ng/g, RSD为2.06%~7.70%; T4和rT3未检出。该方法具有样品处理简单,灵敏度高,重现性好,定性和定量结果可靠等特点,为牛奶中甲状腺素的测定和相关质量安全评价提供了可靠手段。

关键词: 高效液相色谱-串联质谱;甲状腺素;牛奶

文章编号: 1000-8713(2013)03-0270-05

 

Determination of thyroid hormones in milk by high performance liquid chromatography-tandem mass spectrometry

WANG Zongyi1, YANG Dingzhong2, JI Mengyao1, JIA Changxi1*, HUANG Manqing1

(1. Beijing Key Laboratory of Agricultural Products Safety Detection and Control, College of Food Science and Engineering, Beijing University of Agriculture, Beijing 102206, China; 2. Bonna-Agela Technologies, Tianjin 300462, China)

Abstract: A method of high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed for the determination of thyroid hormones in milk including 3,3′,5,5′-tetraiodothyronine (T4), 3,3′,5-triiodothyronine (T3) and 3,3′,5′-triiodothyronine (rT3). The sample was extracted with acetonitrile and centrifuged, then the up layer was alkalized with concentrated ammonia water and cleaned up with a Cleanert PAX cartridge. The chromatographic separation was carried out on a Zorbax Eclipse XDB-C18 column (150 mm×2.1 mm, 3.5 μm) with the mobile phase of 37% water containing 0.1% (v/v) acetic acid and 63% of methanol with an isocratic elution mode at a flow rate of 0.3 mL/min. The mass spectrometry detection was performed in positive electrospray ionization and monitored using multiple reaction monitoring (MRM) mode (m/z 652.0/605.5 and 652.0/478.6 for T3 and rT3; m/z 777.7/731.7 and 777.7/604.9 for T4; m/z 784.0/737.9 and 784.0/639.4 for T4-13C6). The analytes were identified by their retention times and relative abundance ratios of the characteristic product ions, and quantified by internal standard method. The method was linear with the correlation coefficients (r2) greater than 0.998 in the concentration ranges investigated. The limits of detection (LODs) were not more than 0.03 ng/g, and the limits of quantification (LOQ) were not more than 0.1 ng/g for the analytes. The recoveries were 80.61%-101.7% with the relative standard deviations (RSDs) of 1.48%-9.70%. The results of five real milk samples showed that the contents of T3 were 0.59-1.30 ng/g with the RSDs of 2.06%-7.70%, and T4 and rT3 weren’t found. The method presents many merits including simple sample pretreatment, high sensitivity, good reproducibility and unequivocal confirmation and quantification for the analytes. It could be used to monitor the levels of thyroid hormones in the milk for safety quality evaluation.

Key words: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS); thyroid hormone; milk

 

275~280

DOI: 10.3724/SP.J.1123.2012.11011

*通讯联系人.E-mail: xuxianzhu@hit.edu.cn.

基金项目: 中央级非营利科研机构财政专项基金项目(2012A1004,201106,2007 HSYZX-ZH-26).

收稿日期: 2012-11-07

 

柱前衍生-超高效液相色谱法测定鱼卵中的17种氨基酸

孙言春1,2, 许宪祝1*, 徐衍岭1, 谭志军3, 牟振波2, 杜宁宁2

(1. 哈尔滨工业大学基础与交叉科学研究院, 黑龙江 哈尔滨 150001; 2. 中国水产科学研究院黑龙江水产研究所, 黑龙江 哈尔滨 150070; 3. 中国水产科学研究院黄海水产研究所, 山东 青岛 266071)

摘要: 建立了一种快速、灵敏的柱前衍生-超高效液相色谱-光电二极管阵列检测器(UPLC-PDA)测定史氏鲟(Acipenser schrenckii)、达氏鳇(Huso dauricus)和小体鲟(Acipenser ruthenus)鱼卵中17种氨基酸含量的方法。采用6.0 mol/L的盐酸水解鱼卵,提取液经低压浓缩、碱性中和,然后以6-氨基喹啉-N-羟基琥珀酰亚胺基氨基甲酸酯(AQC)为衍生试剂在pH 8.8硼酸盐缓冲溶液中衍生化。采用的色谱分离柱为Waters BEH C18柱(100 mm×2.1 mm, 1.7 μm),流动相为30 mmol/L乙酸铵水溶液(pH 3.5)和乙腈(含0.15%(v/v)甲酸及30 mmol/L乙酸铵),梯度洗脱,流速为0.7 mL/min,在260 nm波长下检测。17种氨基酸在5.0~1000 μmol/L浓度范围内,峰面积与浓度之间的线性关系良好(r2≥0.9950)。以标准加入法测定回收率和相对标准偏差(RSD),在100、500、750 μmol/L的添加水平下,17种氨基酸的平均回收率为75.4%~107.3%, RSD为2.19%~12.3%。以3倍信噪比(S/N>3)计方法的检出限,17种氨基酸的检出限为0.94~4.04 μmol/L。应用该方法检测了3种鲟鳇鱼鱼卵中的17种氨基酸含量。结果表明,该方法简便、准确、快速、可靠。

关键词: 柱前衍生;超高效液相色谱;氨基酸;鱼卵

文章编号: 1000-8713(2013)03-0275-06

 

Determination of 17 amino acids in fish eggs by ultra performance liquid chromatography coupled with precolumn derivatization

SUN Yanchun1,2, XU Xianzhu1*, XU Yanling1, TAN Zhijun3, MOU Zhenbo2, DU Ningning2

(1. Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150001, China; 2. Heilongjiang River Research Institute, Chinese Academy of Fishery Sciences, Harbin 150070, China; 3. Yellow Sea Fisheries Research Institute, Chinese Academy of Fishery Sciences, Qingdao 266071, China)

Abstract: A rapid quantitative method of ultra performance liquid chromatography (UPLC) has been developed for the analysis of 17 amino acids in fish eggs from Acipenser schrenckii, Huso dauricus and Acipenser ruthenus. The analytes were hydrolyzed with 6.0 mol/L HCl. The extraction solution was concentrated under low pressure and neutralized with NaOH solution before derivatization with 6-aminoquinolyl-N-hydroxy-succinimidyl carbamate (AQC) as derivatization agent in borate buffer solution (pH 8.8). Gradient UPLC separation was performed on a C18 column (BEH C18, 100 mm×2.1 mm, 1.7 μm) with 30 mmol/L ammonium acetate (pH 3.5 adjusted with formic acid) and acetonitrile (containing 0.15%(v/v) formic acid and 30 mmol/L ammonium acetate) as the mobile phases at a flow rate of 0.7 mL/min. The detection was carried out with a photo-diode array (PDA) detector and the wavelength was set at 260 nm. The linear ranges were from 5.0 to 1000 μmol/L with the correlation coefficients (r2) ≥ 0.9950. The method was validated by the analysis of seven replicates. The 17 amino acid standards were spiked in fish eggs at three levels of 100, 500 and 750 μmol/L, and the average recoveries were 75.4%-107.3% with the relative standard deviations of 2.19%-12.3%. The limits of detection (LOD) for the analytes were from 0.94 μmol/L to 4.04 μmol/L. The method was successfully applied to the analysis of the 17 amino acids in fish eggs from Acipenser schrenckii, Huso dauricus and Acipenser ruthenus. The method is simple, rapid, precise and reliable.

Key words: precolumn derivatization; ultra performance liquid chromatography (UPLC); amino acids; fish eggs

 

281~285

DOI: 10.3724/SP.J.1123.2012.10034

*通讯联系人.E-mail: linli77422@yahoo.com.cn.

基金项目: 质检公益性行业科研专项(201110042);国家重大科学仪器设备开发专项(2012YQ090229).

收稿日期: 2012-11-06

 

二维离子色谱法同时测定环境水样中的碘离子、硫氰酸根和高氯酸根

林立1,3*, 王海波2, 史亚利2

(1. 国家食品质量安全监督检验中心, 北京 100094; 2. 中国科学院生态环境研究中心 环境化学与生态毒理学国家重点实验室, 北京 100085; 3. 北京工业大学,北京100022)

摘要: 建立了二维离子色谱法同时测定环境水样中的碘离子、硫氰酸根离子和高氯酸根离子的方法。先采用常规阴离子色谱柱(IonPac AS16, 250 mm×4 mm)将水样中的碘离子、硫氰酸根离子和高氯酸根离子与干扰离子进行分离。样品溶液通过抑制器后,将含有碘离子、硫氰酸根离子和高氯酸根离子的淋洗液导入富集柱(MAC-200, 80 mm×0.75 mm),再通过毛细管阴离子色谱柱(IonPac AS20 Capillary, 250 mm×0.4 mm)进行分离和定量分析。方法的线性范围为0.05~100 μg/L,相关系数达到0.9999,检出限为0.02~0.05 μg/L。样品中碘离子、硫氰酸根离子和高氯酸根离子的加标回收率在85.1%~100.1%之间,回收率的相对标准偏差(RSD)(n=6)在1.7%~4.9%之间。该法试剂用量小,灵敏度比常规离子色谱提高30~40倍,同时去除了样液中的高浓度基体杂质,适用于水样中低含量碘离子、硫氰酸根离子和高氯酸根离子的检测。

关键词: 二维离子色谱;毛细管离子色谱;碘离子;硫氰酸根离子;高氯酸根离子;地表水

文章编号: 1000-8713(2013)03-0281-05

 

Determination of iodide, thiocyanate and perchlorate ions in environmental water by two-dimensional ion chromatography

LIN Li1,3*, WANG Haibo2, SHI Yali2

(1. China National Food and Safety Supervision and Inspection Center, Beijing 100094, China; 2. State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; 3. Beijing University of Technology, Beijing 100022, China)

Abstract: A procedure for the determination of iodide, thiocyanate and perchlorate ions in environmental water by two-dimensional ion chromatography has been developed. At first the iodide, thiocyanate and perchlorate ions were separated from interfering ions by a column (IonPac AS16, 250 mm×4 mm). The iodide ion, thiocyanate and perchlorate ions were then enriched with an enrichment column (MAC-200, 80 mm×0.75 mm). In the 2nd-dimensional chromatography, iodide thiocyanate and perchlorate ions were separated and quantified by a capillary column (IonPac AS20 Capillary, 250 mm×0.4 mm). The linear ranges were 0.05-100 μg/L with correlation coefficients of 0.9999, and the detection limits were 0.02-0.05 μg/L. The spiked recoveries of iodide, thiocyanate and perchlorate ions were in the range of 85.1% to 100.1%. The relative standard deviations of the recoveries were 1.7% to 4.9%.

Key words: two-dimensional ion chromatography; capillary ion chromatography (CIC); iodide ion; thiocyanate ion; perchlorate ion; surface water

 

 


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