Mass spectrometric study of interactions of amino acids with cryoprotectors. Proline and oxyethylated glycerol derivatives
Keywords:
amino acids, proline, cryoprotectors, oxyethylated glycerol derivatives, alkali metal ions, solvatation, mass spectrometryAbstract
In the framework of a problem of investigation of the interaction of biopolymers components - amino acids - with cryoprotection compounds on the level of intermolecular complexes a model system comprised of proline (Pro) solution in oxyethylated glycerol oligomers, OEG-5 (Mn) was investigated. Application of a set of mass spectrometric methods with fast atom bombardment, laser desorption/ionization, electrospray ionization (from solutions) allowed us to obtain complementary data on the composition of the ion-solvate shell of amino acid proline in liquid cryoprotection compound OEG-5. A set of protonated associates of proline molecule with the oligomers - Pro·Mn·H+ - observed in the positive ion mass spectra indicated the salvation of the amino acid in OEG-5 solvent. Complexes of the amino acid with oligomers cationized by alkali metal ions were not detected even when the intensity of associates Mn·Na+, Mn·K+ was high, which pointed to a competition between protonated proline and Na+, K+ ions for binding with oligomers of OEG-5. In electrospray mass spectra in the negative ion mode intensity of deprotonated proline peak [Pro-Н]- significantly exceeded that of the protonated form of proline [Pro+Н]+ in the positive ion mode, which indicated domination of the dissociated form of amino acid in solution. A model was proposed, which explained the stabilization of Pro·Mn·H+ complexes by wrapping of the oligomers around a protonated molecule of proline with the formation of a quasi-cyclic structure similar to crown-ethers, in which ether oxygens were turned to the organic cation. A comparison with literature data about poly-ethers - alkali metal ions interaction allowed us to explain a molecular mechanism of the observed competition between organic and inorganic cations for binding with oligomers of OEG-5. A possibility of the existence of triple associates of deprotonated proline with cation complexes Mn·Na+, Mn·K+, which neutral net charge does not permit their mass spectrometric detection, is discussed. Further investigation perspectives consist of theoretical modeling of complexes which include proline, alkali metal ions, and OEG-5 in different charge states.
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