Derivatization to increase the detectability of small peptides in blood serum in the analysis by ESI and MALDI high resolution mass spectrometric methods.

This work highlights the efficient approach to highly sensitive determination of dipeptides that can present in biological liquids at very low and trace quantities. The approach involves preliminary derivatization of peptides with tris(2,4,6-trimethoxyphenyl)-methyl carbenium hexafluoroborate followed by ESI and MALDI high-resolution mass spectrometry. Using model dipeptides with various amino acid compositions and sequences, it was shown that the derivatization reaction proceeded smoothly in mild conditions and gave rise to pink-red colored salt derivatives.

A triphenylcyclopropenylium mass tag: synthesis and application to ultrasensitive LC/MS analysis of amines.

Thiol adducts of triphenylcyclopropenylium undergo efficient heterolytic dissociation under conditions of both electrospray (ESI) and laser desorption ionization (LDI) mass spectrometry giving rise to a prominent signal of an aromatic C3Ph3(+) cation. A functionalized mass tagging reagent, an activated ester carrying an S-linked C3Ph3 unit, has been developed and used for the derivatization of amines and their subsequent HPLC/ESI-MS detection in low attomolar amounts.