飞行时间质谱解析课件.ppt

1、 谭建华2012.12.14一、仪器原理、特点简介一、仪器原理、特点简介二、仪器主要应用范围（质检行业）二、仪器主要应用范围（质检行业）三、仪器应用典型案例三、仪器应用典型案例四、结语、展望四、结语、展望仪器特点(Synapt G1)：精确质量数 8000,W模式16000全扫模式下高扫描速率 DRE模式下12.5 张/秒 非DRE模式下20 张/秒其他未知物定性（Identification）结构阐明（Elucidation）目标物高通量筛查（Screen）目标物确证（Comfirmation）定量（Quantitation）未知物定性（Identification）范围（不限于）：食品添加

2、剂、化工原料、部分食品和化妆品中禁限用物质（农残、兽残、激素等）。未知物定性（Identification）思路：1、采用直接提取方式，对样品进行完全提取；建立液相方法,利用紫外检测器进行初筛。（可分别采用C18和Hillic色谱柱，全梯度洗脱）2、结合工作经验，排除常见添加剂，确定拟定性目标物。3、优化提取方法和液相方法，上UPLC-PDA-Q-TOF进行质谱全扫描。4、解析质谱图，确定分量离子峰，进行分子式匹配，并通过离子碎片确定最合理的分子式组成。（N规则，同位素分布）5、借鉴常用化合物谱库，搜索分子式可能的商品化合物。（ChemspiderGoogleMerck Index Data

3、Base）6、购买对照品或其他方式确证（紫外、红外、核磁等）注：对于无法进行液相分离的样品可采用流动注射方式。结构阐明（Elucidation）范围：目标化合物的存在形式、转化、质谱断裂机理研究。（精确质量数，N规则，同位素分布）MCO2 =43.9898 MC2H4O =44.0262目标物高通量筛查（Screen）范围（不限于）：食品和化妆品中禁限用物质（非法食品添加剂、农残、兽残、激素等）目标物高通量筛查（Screen）思路：1、收集尽可能多的标准物质或对照品（STD）；2、将STD按性质进行分类，建立几种典型的提取、净化和UPLC-Q-TOF仪器分析方法，能将各种STD进行覆盖，并得到

4、最大化的分离度及灵敏度。3、采用Chromalynx分析软件，建立筛查数据库。4、样品分析、数据处理、阳性样品的确证。目标物确证（Comfirmation）范围（不限于）：食品和化妆品中禁限用物质（非法食品添加剂、农残、兽残、激素等）目标物确证（Comfirmation）European Commission Decision 2002/657/EC:regulated compounds:3 IPs nonregulated compounds:4 IPsa precursor iona product ionHigh resolution(10%峰谷FWHM10000)2.0 IPs2.5

5、 IPs low resolution1.0 IPs1.5 IPs From Susana Grimalt et al.,Anal.Chem.2007 In our opinion,the use of massaccuracy provided by TOF MS seems a more appropriate criterion for a reliable confirmation rather the instrumental resolution specifications,this being surely the reason for several authors to a

6、ssign the same number of IPs to TOF and to HR instruments.It is desirable that mass accuracy is also considered in futureguidelines for identification/confirmation criteria due to the outstanding importance of this parameter.美白面膜中氟轻松的定性 祛痘化妆品中酮康唑的定性食品中农药残留的快速筛查掺假橄榄油的鉴定 美白面膜中氟轻松的定性 步骤：1、取0.5 g样品，甲醇超声

7、提取并定容至25 mL，过滤。2、液相色谱条件：BEH C18柱，流动相为乙腈+水，梯度洗脱，5%乙腈于8 min内升至100%，保持2min。3、排除常见防腐剂的色谱峰后，发现一峰可疑（=240 nm）。4、优化前处理条件，乙腈超声提取，加饱和氯化钠溶液混匀2min，离心，取上层清液过滤。同时，优化液相梯度条件。5、经UPLC-PDA-Q-TOF正负离子模式分析，M+Na+为475.1936，M-H-为451.1900，结合MSE离子碎片信息，确定分子式组合可能为C24H30F2O6。6、查Chemspider可能为氟轻松，购标准品确证。Time0.000.501.001.502.002.5

8、03.003.504.004.505.005.50%01000.000.501.001.502.002.503.003.504.004.505.005.50%360.000.501.001.502.002.503.003.504.004.505.005.50AU0.01.0e-32.0e-33.0e-30.000.501.001.502.002.503.003.504.004.505.005.50AU0.02.0e-24.0e-20921 mianmo43:Diode Array Range:5.329e-20.620.330.544.654.591.210921 mianmo43:Diode

9、 Array Range:5.329e-20.620.331.210.994.980921 mianmo41:TOF MS ES+TIC6.26e44.691.055.140921 mianmo71:TOF MS ES-TIC1.45e50.730.413.651.301.052.913.334.694.01m/z140160180200220240260280300320340360380400420440460480500520%0100m/z140160180200220240260280300320340360380400420440460480500520%01000921 mian

10、mo7 30(1.084)1:TOF MS ES-3.19e3431.1851373.1436355.1337157.1225151.0400220.1470162.8919!188.9387233.1560315.0423283.2664250.1425335.1303374.1472393.1497411.1826432.1903497.1968487.1692451.1900473.1744514.1902515.18380921 mianmo4 29(1.050)1:TOF MS ES+1.47e3367.1379301.1418179.0652164.9235149.0237128.

11、9552195.0035229.1428197.0029213.0133282.2245237.0134281.0547249.1542261.1306337.1449302.1444!;355.0718411.1643368.1432!369.0883475.1936!413.1967!413.2742425.1275453.3408476.1967!503.1085!536.1725祛痘化妆品中酮康唑的定性步骤：1、取0.5 g样品，甲醇超声提取并定容至25 mL，过滤。2、液相色谱条件：BEH C18柱，流动相为乙腈+水，梯度洗脱，5%乙腈于5 min内升至90%，保持1min。3、排除

12、常见防腐剂的色谱峰后，发现一峰可疑（t=4.38）。4、采用原液相方法，经UPLC-PDA-Q-TOF负离子模式分析，M-H-为531.1566，结合MSE离子碎片信息，确定分子式组合可能为C26H28Cl2N4O4 。5、查Chemspider可能为酮康唑，采用标准品确证。Time0.501.001.502.002.503.003.504.004.505.005.50%01000.501.001.502.002.503.003.504.004.505.005.50AU0.02.0e-24.0e-26.0e-28.0e-20.501.001.502.002.503.003.504.004.50

13、5.005.50AU0.05.0e-11.01.520120406-XIAOLIN-25:Diode Array Range:1.8053.903.4620120406-XIAOLIN-25:Diode Array Range:1.8053.901.440.944.804.3820120406-XIAOLIN-21:TOF MS ES+BPI2.12e53.544.014.48m/z120140160180200220240260280300320340360380400420440460480500520540560580%010020120406-XIAOLIN-2 58(4.480)1:

14、TOF MS ES+3.61e4531.1566495.1803245.0679227.0822156.0107144.9832171.1486246.0686291.1428246.5744266.0764489.1461295.0846401.0880329.0464386.0996446.1027435.0533497.1865498.1729513.1887533.1540534.1567535.1525536.1640!;537.1599!563.1379食品中农药残留的快速筛查 步骤：1、收集尽可能多的标准物质或对照品（STD）；2、将STD按性质进行分类，建立几种典型的提取、净化

15、和UPLC-Q-TOF仪器分析方法，能将各种STD进行覆盖，并得到最大化的分离度及灵敏度。3、采用Chromalynx分析软件，建立筛查数据库。4、样品分析、数据处理、阳性样品的确证。FormulaExact massFragment massRetention timePeak areaScan No.Measured RTiFitmDa ErrorNegativePositiveTentativePositive+FragmentExtracted ion mass chromatogram Mass spectrumCandidate listNegativePositiveTentat

16、ivePeak areaScan No.Expected RTiFitmDa ErrorPositiveTentativeNegativeExact mass flaggingConcentration and i-Fit掺假橄榄油的鉴定（Marklynx 分析软件的应用）Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.381.200.801.641.892.131.96Time0.200.400.600.801.001.201.401.601.802.

17、002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.2

18、00.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601

19、.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.

20、391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.40

21、1.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831

22、.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.94Time0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.403.603.80%01001.831.581.391.200.801.641.892.121.945 different groups20 sample

23、s per groupTriplicate injectionsTotal:300 injectionsHazelnut adulteratedolive oil(%)Non adulteratedolive oilRape adulteratedolive oil(%)Same olive oil non adulterated一、一、未知物分析筛查技术的必要性未知物分析筛查技术的必要性 客观：客观：传统的锁定目标化合物的检测已难以满足要求。传统的锁定目标化合物的检测已难以满足要求。新型农兽药、激素、抗生素及防腐剂等化学制品的不断研发和使用；新型农兽药、激素、抗生素及防腐剂等化学制品的不断研发和使用；农兽药残留的检测由单一目标化合物到按化合物种类的多残留到目前农兽药残留的检测由单一目标化合物到按化合物种类的多残留到目前的未知残留物的筛查；的未知残留物的筛查；食品中非法使用非食用添加剂的事件如食品中非法使用非食用添加剂的事件如“三聚氰胺奶粉三聚氰胺奶粉”事件。事件。谢 谢！