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The use of electrospray ionization–mass spectrometry(ESI–MS) for the characterization of noncovalent complexes of biomacromolecules in solution is based upon the gentle nature of the electrospray process that allows a wide range of associations to be transferred intact to the gas phase as fully desolvated complexes. Examples include multimeric proteins, oligonucleotide duplexes, DNA–drug complexes and enzyme-inhibitor complexes. Various studies have indicated that at least some qualities of the three-dimensional solution structures are retained in the gas phase. Recent investigations have also shown the relative stabilities of complexes in the gas phase can be very different than the same complexes in solution. In spite of this, the use of very gentle electrospray interface conditions can provide a direct reflection of relative solution abundances for similar complexes. Competitive binding experiments using …