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Chemical Modification of the Tryptophan Residue in a Recombinant Ca2+-ATPase N-domain for Studying Tryptophan-ANS FRET
Published on: October 9, 2021
Dimeric complexes of tryptophan with M2+ metal ions.
Robert C Dunbar1, Jeffrey D Steill, Nick C Polfer
1Department of Chemistry, Case Western Reserve University, Cleveland, Ohio 44106, USA. rcd@po.cwru.edu
Metal ions influence tryptophan dimer structures. Most complexes feature charge-solvated (CS) and zwitterionic (ZW) ligands, except for Nickel, which shows a unique double CS configuration due to its small size and strong binding.
Area of Science:
- Physical Chemistry
- Spectroscopy
- Computational Chemistry
Background:
- Understanding metal-ligand interactions is crucial in chemistry.
- Tryptophan, an amino acid, can form complexes with metal ions.
- The structural configurations of these complexes influence their properties.
Purpose of the Study:
- To characterize the structures of metal-tryptophan dimer complexes.
- To investigate the influence of different metal ions on complex formation.
- To elucidate the binding configurations of tryptophan ligands.
Main Methods:
- Infrared Photodissociation (IRMPD) spectroscopy using FELIX free electron laser.
- Fourier transform ion cyclotron resonance mass spectrometry.
- Density Functional Theory (DFT) calculations for thermochemical analysis.
Main Results:
- Identified at least three distinct structural motifs for M(2+)Trp(2) complexes.
- All complexes contained at least one charge-solvated (CS) tryptophan ligand.
- Most complexes exhibited a mixed charge-solvated/zwitterionic (CS/ZW) configuration.
- Nickel complex (Ni(2+)Trp(2)) uniquely showed a CS/CS configuration.
- Structural differences correlated with metal ion size and binding strength.
Conclusions:
- The structure of metal-tryptophan dimer complexes is highly dependent on the metal ion.
- A charge-solvated ligand is consistently present in these dimeric complexes.
- The Ni(2+) cation's properties lead to an exceptional CS/CS ligand configuration.
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