偶电子离子裂解规律专家讲座

偶电子离子裂解规律偶电子离子裂解规律第1页ESI源内CID(瘦肉精)ESIIn-sourceCID(clenbuterol)

偶电子离子裂解规律第2页ESI源内CIDESIIn-sourceCID偶电子离子裂解规律第3页m/z609m/z577m/z397m/z365-CH3OHre-CH3OHreESI源内CIDESIIn-sourceCID偶电子离子裂解规律第4页三聚氰胺(MS/MS)DAPCI分析乳制品中三聚氰胺(MS/MS)定量离子偶电子离子裂解规律第5页尼古丁(MS/MS)尼古丁C10H14N2162.1尼古丁偶电子离子裂解规律第6页咖啡因咖啡因咖啡因(MS/MS)偶电子离子裂解规律第7页水杨酸甲酯(MS/MS)偶电子离子裂解规律第8页Atrazine(MS/MS)MS/MS偶电子离子裂解规律第9页尼古丁代谢产物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偶电子离子裂解规律第10页ESIMS/MSofm/z193.1C10H12N2O25'-Hydroxycotinine162.05499175.08653Calculated:175.0871尼古丁代谢产物高能碎裂，由偶电子离子产生奇电子离子(改变羟基位置，即不出现m/z162离子)(见下列图)-CH3O•偶电子离子裂解规律第11页134.05917149.07008175.08553C10H12N2O23'-HydroxycotinineESIMS/MSofm/z193.1尼古丁代谢产物偶电子离子裂解规律第12页产生m/z134反应历程质子转移到羰基?偶电子离子裂解规律第13页来自某国际机构考评样品主成份为：少许杂质：MH+223.08232级MS3级MS4级MS4级MS139.0503166.0611206.0571139.0510149.0354122.023085.0388121.040993.0454[C9H11N4O3]+223.0826(1.3ppm)偶电子离子裂解规律第14页杂质C9H10N4O3222.07529(1.3ppm)主成份CaffeineC8H10N4O2

194.08038(1)(2)(3)(4)(5)偶电子离子裂解规律第15页2级MS[C9H8N3O3]+206.0561i[M+H]+-17[C9H11N4O3]+223.0826223.08231.3ppm206.05714.8ppm测量值2级MS[C9H11N4O3]+223.0826re[C7H8N3O2]+166.0611[M+H]+-57ii166.0611偶电子离子裂解规律第16页[C7H8N3O2]+166.0611irH,irH,i,[-HCN][C6H7N2O2]+139.0502139.0510,5.8ppm3级MS[C6H7N2O2]+139.0502i,[-NH3]

[C6H4NO2]+122.0237[C3H5N2O]+85.0396质子转移i122.0230,5.7ppm85.0388,9.4ppm4级MS偶电子离子裂解规律第17页[C7H8N3O2]+166.0611质子转移i,[-NH3][C7H5N2O2]+149.0346149.0354,5.4ppm3级MS[C6H5N2O]+121.0396[-CO][C5H5N2]+93.044793.0454,7.5ppm[C6H5N2O]+121.0396i[C7H5N2O2]+149.0346121.0409,10,7ppm4级MS偶电子离子裂解规律第18页质子化多肽裂解偶电子离子裂解规律第19页质子化多肽裂解偶电子离子裂解规律第20页146ElectronCaptureDissociation(ECD)电子捕捉解离ElectronTransferDissociation(ETD)电子转移解离Fluoranthen