Recognition and resolution of isomeric alkyl anilines by mass spectrometry

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• 作者：Mario Benassi (1)
  Yuri E. Corilo (1)
  Diana Uria (2)
  Rodinei Augusti (3)
  Marcos N. Eberlin (1)
  
• 刊名：Journal of The American Society for Mass Spectrometry
• 出版年：2009
• 出版时间：February 2009
• 年：2009
• 卷：20
• 期：2
• 页码：269-277
• 全文大小：805KB
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• 作者单位：Mario Benassi (1)
  Yuri E. Corilo (1)
  Diana Uria (2)
  Rodinei Augusti (3)
  Marcos N. Eberlin (1)
  
  1. Institute of Chemistry, Thomson Mass Spectrometry Laboratory, State University of Campinas-UNICAMP, 13083-970, Campinas, Brazil
  2. Federal University of Minas Gerais, Belo Horizonte, Brazil
  3. Waters Corporation, Simonsway, United Kingdom
  

文摘

Two MS techniques have been used to recognize and resolve a representative isomeric pair of N-alkyl and ring-alkyl substituted anilines. The first technique (1) uses MS/MS to perform ion/molecule reactions of structurally-diagnostic fragment ions (SDFI) whereas the second (2) uses traveling wave ion mobility spectrometry (TWIMS) of the pair of protonated molecules followed by on-line collision-induced dissociation (CID), that is, MS/TWIMS-CID/MS. Isomeric C7H7N+ ions of m/z 106 (1-from 4-butylaniline and 2 from N-butylaniline) are formed as abundant fragments by 70 eV EI of the anilines, and found to function as suitable SDFI. Ions 1-and 2 display nearly identical unimolecular dissociation chemistry, but contrasting bimolecular reactivity with ethyl vinyl ether, isoprene, acrolein, and 2-methyl-1,3-dioxolane. Ion 2 forms adducts to a large extent whereas 1-is nearly inert towards all reactants tested. The intact protonated anilines are readily resolved and recognized by MS/TWIMS-CID/MS in a SYNAPT mass spectrometer (Waters Corporation, Manchester, UK). The protonated N-butyl aniline (the more compact isomer) displays shorter drift time and higher lability towards CID than its 4-butyl isomer. The general application of SDFI 1-and 2 and other homologous and analogous ions and MS/TWIMS-CID/MS for absolute recognition and resolution of isomeric families of N-alkyl and ring-alkyl mono-substituted anilines and analogues is discussed.