Abstract

AbstractCarnitine inner salt, (CH3)3N+ CH2CH(OH)CH2COO−, and carnitine hydrochloride, (CH3)3N+CH2CH (OH)CH2COOH Cl−, in the solid state undergo ion‐beam‐induced intermolecular methyl transfer reactions as shown by (CH3)3N+ CH2CH(OH)CH2COOCH3 ions at m/z 176 in their positive ion spectra. In the case of carnitine HCl, the product ion is three times as abundant as the intact cation. For the inner salt however, the product is less than one‐tenth as abundant as [M + H] +. In both cases, the reaction can be precluded by dissolution of the sample, supporting an intermolecular mechanism. The negative ion spectra for these compounds contain no [M − CH3]− ions, suggesting that simple transmethylation does not occur. Rather it is proposed that the inner salt abstracts a methyl group from the intact carnitine cation to yield [M + CH3]+ and a neutral species, the driving force being a minimization of the total number of charges desorbed into the gas phase. Thermodynamic data favor this mechanism as do data for other carnitine salts. The reaction appears to be inhibited when one reactant is present in excess. This is the case for carnitine HNO3 and CH3SO3H, which tend to liberate the intact cation since the anions are large and polarizable. It is also the case for small, hard anions like fluoride, which appear to favor release of the inner salt, hence the cation at m/z 162 is of low abundance and the transmethylation product (m/z 176) is absent. The extent of the reaction is also dependent on the methods of preparation of the sample, and deposition of the salts from solution greatly reduces the extent of methyl transfer. [M − CH3]− is observed when glycerol is used as a matrix, possibly due to a matrix‐analyte methyl transfer reaction.

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