An Ion/Molecule Reaction for the Identification of Analytes with Two Basic Functional Groups

A mass spectrometric method is presented for the identification of analytes with two basic functionalities and PA between 222 and 245 kcal/mol, including diamines. This method utilizes gas-phase ion–molecule reactions of protonated analytes with neutral 1,1-diethoxyethene (DEE) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR). A variety of protonated mono-, bi-, and trifunctional analytes containing different functional groups, namely, amido, amino, N-oxide, hydroxy, carboxylic acid, keto, thio, thioether, alkene, phosphite, and phosphonate, were tested in the FT-ICR. The results demonstrate that basic protonated bifunctional compounds (PA between 222 and 245 kcal/mol) react selectively with DEE by forming a specific addition/elimination product ion (adduct − EtOH) (this product was also observed for lysine with three functionalities). The diagnostic reaction sequence involves proton transfer from the protonated analyte to the basic vinyl group in DEE, followed by addition of one of the functional groups of the analyte to the electrophilic α-carbon in protonated DEE. The next step involves proton transfer from this functionality to the other analyte functionality, followed by proton transfer to DEE and elimination of ethanol. Since the mechanism involves proton transfer between two functional groups of the analyte, the reaction does not occur for analytes where the two functionalities cannot be in close proximity (i.e., meta-phenylenediamine), and where no proton is available (i.e., dimethylaminoketone).

Graphical AbstractA mass spectrometric method is presented for the identification of analytes with two basic functionalities and PA between 222 and 245 kcal/mol.Figure optionsDownload full-size imageDownload high-quality image (76 K)Download as PowerPoint slide