Decomposition of charge-state distributions for a better understanding of electrospray mass spectra of bioorganic compounds. Part 1: basic formalism.

Further development in our approach for the interpretation of a mass spectral peak series resulting from unique modifications at a number of molecular sites is described and its application for the analysis of electrospray mass spectra of multiply-charged ions of biopolymers is specified. This method was based initially on the assumption that the modifications are mutually independent. The output is a set of modification probabilities for the considered molecular sites, which explains the observed peak intensity distribution with the best accuracy. It is shown here that the method is also applicable, in some cases, to the strong interaction between modified sites. This is important for the formation of multiply-charged ions, at least in the gas phase, since it should be significantly influenced by the internal electric fields. The capabilities and limitations of this approach are discussed. One limitation is that only unimodal distributions (those having only one maximum) are possible in the considered model. Another is that relatively large biomolecules may not be suitable for this type of analysis. Some experimental results of the application of this method are described in Part 2 of this work.