An electrospray ionization study of some novel alkylamine thiohydantoin amino acid derivatives

An electrospray ionization-mass spectrometric (ES-MS) study of some novel alkylamine thiohydantoin amino acid derivatives is presented. The alkylamine derivatives are being developed as part of an on-going effort to couple an Edmanlike protein sequencer to a bench-top electrospray ionization (ES) mass spectrometer. The ES-MS and capillary-skimmer collision-induced dissociation (CID) mass spectra of eight dimethylaminopropylthiohydantoin (DMAP-TH) amino acid derivatives as well as the trimethylaminopropylthiohydantoin (TMAP-TH), diethylaminopropylthiohydantoin, and dibutylaminopropylthiohydantoin (DBAP-TH) derivatives of Phe are presented. The spectra contain prominent [M + H](+) ions as well as fragment ions due to the loss of the respective neutral alkylamines. The CID spectrum of DMAP-TH-Phe also contains the dibutylaminoethyl cation. The relative responses of the alkylamine thiohydantoin derivatives obtained under identical solvent conditions are found to increase as the solvophobicity of the amino acid R group increases; the most solvophobic DBAP-TH-Phe gives rise to the highest overall response. DMAP-TH-Phe and the quaternary amine derivative TMAP-TH-Phe have comparable sensitivities when a sufficiently acidic solvent (pH = 3) is employed. Implications of these studies in the coupling of a protein sequencer to an ES mass spectrometer are discussed as are the requisite modifications of a single quadrupole mass spectrometer for ES analyses.