title: Experimental and theoretical studies of potassium cation interactions with the acidic amino acids and their amide derivatives.
abstract: The binding of K(+) to aspartic acid (Asp), glutamic acid (Glu), asparagine (Asn), and glutamine (Gln) is examined in detail by studying the collision-induced dissociation (CID) of the four potassium cation-bound amino acid complexes with Xe using a guided ion beam tandem mass spectrometer (GIBMS). Formed by electrospray ionization, these complexes have energy-dependent CID cross sections that are analyzed to provide 0 K bond energies after accounting for unimolecular decay rates, internal energy of reactant ions, and multiple ion-molecule collisions. Quantum chemical calculations for a number of geometric conformations of each K(+)(L) complex are determined at the B3LYP/6-311+G(d,p) level with single-point energies calculated at B3LYP, B3P86, and MP2(full) levels using a 6-311+G(2d,2p) basis set. Theoretical bond dissociation energies are in good agreement with the experimental values. This coordinated examination of both experimental work and quantum chemical calculations allows for a comprehensive understanding of the molecular interactions of K(+) with the Asx and Glx amino acids. K(+) binding affinities for the amide complexes are systematically stronger than those for the acid complexes by 9+/-1 kJ/mol, which is attributed to an inductive effect of the OH group in the carboxylic acid side chain. Additionally, the K(+) binding affinity for the longer-chain amino acids (Glx) is enhanced by 5+/-1 kJ/mol compared to the shorter-chain Asx because steric effects are reduced. Further, a detailed comparison between experimental and theoretical results reveals interesting differences in the binding of K(+) and Na(+) to these amino acids.
authors: Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
authors: A L
authors: AL
authors: Heaton
authors: P B
authors: PB
authors: Armentrout
mesh_terms: D000577:Amides / Q000737:chemistry*; D024342:Amino Acids, Acidic / Q000737:chemistry*; D002412:Cations / Q000737:chemistry; D008958:Models, Molecular; D011188:Potassium / Q000737:chemistry*; D053719:Tandem Mass Spectrometry; D013816:Thermodynamics
chemical_list: D000577:Amides; D024342:Amino Acids, Acidic; D002412:Cations; D011188:Potassium