title: Synthesis, crystal structure and investigation of mononuclear copper(II) and zinc(II) complexes of a new carboxylate rich tripodal ligand and their interaction with carbohydrates in alkaline aqueous solution.
abstract: A new carboxylate rich asymmetric tripodal ligand, N-[2-carboxybenzomethyl]-N-[carboxymethyl]-β-alanine (H3camb), and its di-copper(II), (NH4)2[1]2, and di-zinc(II), ((CH3)4N)2[2]2, complexes have been synthesized as carbohydrate binding models in aqueous solutions. The ligand and complexes have been fully characterized using several techniques, including single crystal X-ray diffraction. The interactions of (NH4)2[1]2 and ((CH3)4N)2[2]2 with D-glucose, D-mannose, D-xylose and xylitol in aqueous alkaline media were investigated using UV-Vis and (13)C-NMR spectroscopic techniques, respectively. The molar conductance, NMR and ESI-MS studies indicate that the complexes dissociate in solution to produce the respective complex anions, 1(-) and 2(-). Complexes 1(-) and 2(-) showed chelating ability towards the naturally abundant and biologically relevant sugars, D-glucose, D-mannose, D-xylose, and xylitol. The complex ions bind to one molar equivalent of the sugars, even in the presence of stoichiometric excess of the substrates, in solution. Experimentally obtained spectroscopic data and computational results suggest that the substrates bind to the metal center in a bidentate fashion. Apparent binding constant values, pK(app), between the complexes and the substrates were determined and a specific mode of substrate binding is proposed. The pK(app) and relativistic density functional theory (DFT) calculated Gibbs free energy values indicate that D-mannose displayed the strongest interaction with the complexes. Syntheses, characterizations, detailed substrate binding studies using spectroscopic techniques, single crystal X-ray diffraction and geometry optimizations of the complex-substrates with DFT calculations are also reported.
authors.affiliation: Department of Chemistry, The University of Texas at San Antonio, San Antonio, TX 78249, United States.
authors.forename: Christopher D
authors.initials: CD
authors.lastname: Stewart
authors.affiliation: Department of Chemistry, The University of Texas at San Antonio, San Antonio, TX 78249, United States.
authors.forename: Mayra
authors.initials: M
authors.lastname: Pedraza
authors.affiliation: Department of Chemistry, The University of Texas at San Antonio, San Antonio, TX 78249, United States.
authors.forename: Hadi
authors.initials: H
authors.lastname: Arman
authors.affiliation: Department of Chemistry, Prairie View A&M University, Prairie View, TX 77446, United States.
authors.forename: Hua-Jun
authors.initials: HJ
authors.lastname: Fan
authors.affiliation: Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil.
authors.forename: Eduardo Luiz
authors.initials: EL
authors.lastname: Schilling
authors.affiliation: Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil.
authors.forename: Bruno
authors.initials: B
authors.lastname: Szpoganicz
authors.affiliation: Department of Chemistry, The University of Texas at San Antonio, San Antonio, TX 78249, United States. Electronic address: ghezai.musie@utsa.edu.
authors.forename: Ghezai T
authors.initials: GT
authors.lastname: Musie
mesh_terms: D000468:Alkalies / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D008024:Ligands; D009005:Monosaccharides / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D000468:Alkalies; D002264:Carboxylic Acids; D056831:Coordination Complexes; D008024:Ligands; D009005:Monosaccharides; D003300:Copper; D015032:Zinc
keywords: Binding constants; Metal complex; Monosaccharides; Mutarotation; Sugar–metal complex interaction