The present article is a survey of ESI and MALDI mass spectrometric an
alysis of nucleic acid oligomers and polymers. In order to limit the e
xtent of the review, mass spectrometry of mononucleotides is generally
not considered, except where such data are important for an understan
ding of the analysis of larger nucleic acids. The first part of the re
view is a condensed description of the structure and the acid-base pro
perties of nucleic acids. The remaining part is divided into three mai
n sections, dealing with the practical aspects of the two ionization t
echniques, fragmentation, and applications, respectively. The first se
ction includes an extensive discussion of experimental parameters and
problems, which are important for the analysis of differ ent types of
nucleic acid samples, including non-covalent complexes and mixtures. A
t the end of this section, as well as the following one, a comparison
between MALDI and ESI as ionization techniques for nucleic acids is gi
ven. In addition to a detailed discussion of ion fragmentation, the fr
agmentation section includes an overview of the direct mass spectromet
ric sequencing of nucleic acids performed with either technique. The f
ragmentation reactions occurring upon MALDI and ESI are compared. The
last section describes the life science applications of ESI-MS and MAL
DI-MS of nucleic acids; an account of experiments demonstrating the po
tential of a method, and of the bona fide solving of problems by ESI a
nd MALDI is given. (C) 1997 John Wiley & Sons, Inc.