偶電子離子裂解規(guī)律專家講座

偶電子離子裂解規(guī)律偶電子離子裂解規(guī)律第1頁ESI源內(nèi)CID(瘦肉精)ESIIn-sourceCID(clenbuterol)

偶電子離子裂解規(guī)律第2頁ESI源內(nèi)CIDESIIn-sourceCID偶電子離子裂解規(guī)律第3頁m/z609m/z577m/z397m/z365-CH3OHre-CH3OHreESI源內(nèi)CIDESIIn-sourceCID偶電子離子裂解規(guī)律第4頁三聚氰胺(MS/MS)DAPCI分析乳制品中三聚氰胺(MS/MS)定量離子偶電子離子裂解規(guī)律第5頁尼古丁(MS/MS)尼古丁C10H14N2162.1尼古丁偶電子離子裂解規(guī)律第6頁咖啡因咖啡因咖啡因(MS/MS)偶電子離子裂解規(guī)律第7頁水楊酸甲酯(MS/MS)偶電子離子裂解規(guī)律第8頁Atrazine(MS/MS)MS/MS偶電子離子裂解規(guī)律第9頁尼古丁代謝產(chǎn)物FullMS(FT-ICR)[M+H]+C10H12N2O2measured:m/z193.09740calculated:m/z193.09714Delta0.26mmu/1.3ppm+NNHOCH3-Nicotine-1'-N-oxide

[M+H]+C10H14N2O1measured:m/z179.11801calculated:m/z179.11788Delta0.13mmu/0.7ppm3possibleisomersdifferentCIDspectraNNHCH3O1'2'3'4'5'Cotinine[M+H]+C10H12N2O1measured:m/z177.10248calculated:m/z177.10223Delta0.25mmu/1.4ppmNornicotineNNHH[M+H]+C9H12N2measured:m/z149.10753calculated:m/z149.10732Delta0.2mmu/1.4ppm130135140145150155160165170175180185190195200205m/z179.11801193.09740177.10248180.12151149.1075305101520253035404550556065707580859095100RelativeAbundance偶電子離子裂解規(guī)律第10頁ESIMS/MSofm/z193.1C10H12N2O25'-Hydroxycotinine162.05499175.08653Calculated:175.0871尼古丁代謝產(chǎn)物高能碎裂，由偶電子離子產(chǎn)生奇電子離子(改變羥基位置，即不出現(xiàn)m/z162離子)(見下列圖)-CH3O?偶電子離子裂解規(guī)律第11頁134.05917149.07008175.08553C10H12N2O23'-HydroxycotinineESIMS/MSofm/z193.1尼古丁代謝產(chǎn)物偶電子離子裂解規(guī)律第12頁產(chǎn)生m/z134反應歷程質(zhì)子轉(zhuǎn)移到羰基?偶電子離子裂解規(guī)律第13頁來自某國際機構考評樣品主成份為：少許雜質(zhì)：MH+223.08232級MS3級MS4級MS4級MS139.0503166.0611206.0571139.0510149.0354122.023085.0388121.040993.0454[C9H11N4O3]+223.0826(1.3ppm)偶電子離子裂解規(guī)律第14頁雜質(zhì)C9H10N4O3222.07529(1.3ppm)主成份CaffeineC8H10N4O2

194.08038(1)(2)(3)(4)(5)偶電子離子裂解規(guī)律第15頁2級MS[C9H8N3O3]+206.0561i[M+H]+-17[C9H11N4O3]+223.0826223.08231.3ppm206.05714.8ppm測量值2級MS[C9H11N4O3]+223.0826re[C7H8N3O2]+166.0611[M+H]+-57ii166.0611偶電子離子裂解規(guī)律第16頁[C7H8N3O2]+166.0611irH,irH,i,[-HCN][C6H7N2O2]+139.0502139.0510,5.8ppm3級MS[C6H7N2O2]+139.0502i,[-NH3]

[C6H4NO2]+122.0237[C3H5N2O]+85.0396質(zhì)子轉(zhuǎn)移i122.0230,5.7ppm85.0388,9.4ppm4級MS偶電子離子裂解規(guī)律第17頁[C7H8N3O2]+166.0611質(zhì)子轉(zhuǎn)移i,[-NH3][C7H5N2O2]+149.0346149.0354,5.4ppm3級MS[C6H5N2O]+121.0396[-CO][C5H5N2]+93.044793.0454,7.5ppm[C6H5N2O]+121.0396i[C7H5N2O2]+149.0346121.0409,10,7ppm4級MS偶電子離子裂解規(guī)律第18頁質(zhì)子化多肽裂解偶電子離子裂解規(guī)律第19頁質(zhì)子化多肽裂解偶電子離子裂解規(guī)律第20頁146ElectronCaptureDissociation(ECD)電子捕捉解離ElectronTransferDissociation(ETD)電子轉(zhuǎn)移解離Fluoranthen