IRMPD Spectroscopic and Theoretical Structural Investigations of Zinc and Cadmium Dications Bound to Histidine Dimers
- 10 December 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 124 (49), 10266-10276
- https://doi.org/10.1021/acs.jpca.0c08861
Abstract
Metallated gas-phase structures consisting of a deprotonated and an intact histidine (His) ligand, yielding M(His-H)(His)(+), where M = Zn and Cd, were examined with infrared multiple photon dissociation (IRMPD) action spectroscopy utilizing light from a free-electron laser (FEL). In parallel, quantum chemical calculations identified several low-energy isomers for each complex. Experimental action spectra were compared to linear spectra calculated at the B3LYP level of theory using the 6-311+G(d,p) and def2-TZVP basis sets for the zinc and cadmium complexes, respectively. For both Zn and Cd species, the definitive assignment is complicated by conflicting relative energetics, which were calculated at B3LYP, B3LYP-GD3BJ, B3P86, and MP2(full) levels. Spectral comparison for both species indicates that the dominant conformation, [N-alpha, N-pi, CO-][CO2-](N pi H+), has the deprotonated His chelating the metal at the amine nitrogen, Jr nitrogen of the imidazole ring, and the deprotonated carbonyl oxygen and that the intact His ligand adopts a salt-bridge bidentate binding motif, coordinating the metal with both carboxylate oxygens. There is also evidence for a conformation where the deprotonated His coordination is maintained, but the intact His ligand adopts a more canonical structure, coordinating with the metal atom at the amine nitrogen and pi nitrogen, [N-alpha, N-pi, CO-][N-alpha, N-pi]gtgg. For both metallated species, B3LYP, B3P86, and B3LYP-GD3BJ levels of theory appear to describe the relative stability of the dominant zwitterionic species more accurately than the MP2(full) level.Funding Information
- Division of Chemistry (CHE-1954142)
- Deutsche Forschungsgemeinschaft (SCHA 871-10/1)
This publication has 41 references indexed in Scilit:
- Infrared multiple photon dissociation spectroscopy of trapped ionsChemical Society Reviews, 2011
- Zn2+ Has a Primary Hydration Sphere of Five: IR Action Spectroscopy and Theoretical Studies of Hydrated Zn2+ Complexes in the Gas PhaseThe Journal of Physical Chemistry A, 2010
- A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-PuThe Journal of Chemical Physics, 2010
- Infrared Multiphoton Dissociation Spectroscopy of Cationized Threonine: Effects of Alkali-Metal Cation Size on Gas-Phase ConformationThe Journal of Physical Chemistry A, 2008
- Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracyPhysical Chemistry Chemical Physics, 2005
- Inhibitory Effect of Copper(II) on Zinc(II)-Induced Aggregation of Amyloid β-PeptideBiochemical and Biophysical Research Communications, 2001
- The role of databases in support of computational chemistry calculationsJournal of Computational Chemistry, 1996
- Rapid induction of Alzheimer A beta amyloid formation by zincScience, 1994
- ZINC PROTEINS: Enzymes, Storage Proteins, Transcription Factors, and Replication ProteinsAnnual Review of Biochemistry, 1992
- Energy-adjustedab initio pseudopotentials for the second and third row transition elementsTheoretical Chemistry Accounts, 1990