Matrix‐assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) mass spectra of small
kappa‐carrageenans are reported and discussed. MALDI spectra can be obtained in both positive and negative ion mode. In the absence of extraneous metal ions, positive ions are formed by the attachment of one Na+ ion to the carrageenan, whereas for negative ions one Na+ ion is detached from the sulfate group. Multiply charged species are not observed in MALDI. Intense ESI spectra can be obtained in negative ion mode and now multiply charged species are seen. Alkali exchange experiments show that in these small carrageenan anions one, but only one, alkali metal ion is bound in a bidentate coordination with two ionic sulfate groups. G2‐type ab initiocalculations on model ions HO− [M+] −OH (M = Li, Na, K, Cs), as well as arguments based on a simple Coulombic interaction model, show that the bidentate stabilization energy drops rapidly as the size of the alkali cation increases. Exchange of Na+ with Li+ leads to expulsion of the Na+ ion generating, in ESI, intense multiply charged anions. An attempt is made to rationalize this behavior in terms of hydration effects. Copyright © 2001 John Wiley & Sons, Ltd.