Resonance Raman Optical Activity Shows Unusual Structural Sensitivity for Systems in Resonance with Multiple Excited States: Vitamin B 12 Case.

Autor:	Machalska E; Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, Krakow 30-387, Poland.; Jagiellonian Centre for Experimental Therapeutics (JCET), Jagiellonian University, Bobrzynskiego 14, Krakow 30-348, Poland., Zajac G; Jagiellonian Centre for Experimental Therapeutics (JCET), Jagiellonian University, Bobrzynskiego 14, Krakow 30-348, Poland., Gruca A; Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, Krakow 30-387, Poland.; Jagiellonian Centre for Experimental Therapeutics (JCET), Jagiellonian University, Bobrzynskiego 14, Krakow 30-348, Poland., Zobi F; Department of Chemistry, University of Fribourg, Chemin du Musée 9, 1700 Fribourg, Switzerland., Baranska M; Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, Krakow 30-387, Poland.; Jagiellonian Centre for Experimental Therapeutics (JCET), Jagiellonian University, Bobrzynskiego 14, Krakow 30-348, Poland., Kaczor A; Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, Krakow 30-387, Poland.; Jagiellonian Centre for Experimental Therapeutics (JCET), Jagiellonian University, Bobrzynskiego 14, Krakow 30-348, Poland.
Jazyk:	angličtina
Zdroj:	The journal of physical chemistry letters [J Phys Chem Lett] 2020 Jul 02; Vol. 11 (13), pp. 5037-5043. Date of Electronic Publication: 2020 Jun 16.
DOI:	10.1021/acs.jpclett.0c01218
Abstrakt:	In this work, cobalamins with different upper axial substituents and a cobalamin derivative with a ring modification were studied using chiroptical spectroscopies, in particular resonance Raman optical activity (RROA), to shed light on the influence of structural modifications on RROA spectra in these strongly chiral systems in resonance with multiple excited states at 532 nm excitation. We have demonstrated that for these unique systems RROA possesses augmented structural specificity, surpassing resonance Raman spectroscopy and enabling at the same time measurement of cobalamins at fairy low concentrations of ∼10 -5 mol dm -3 . The enhanced structural specificity of RROA is a result of bisignate spectra due to resonance via more than one electronic state. The observation of increased structural capability of RROA for cobalamins opens a new perspective for studying chiral properties of other biological systems incorporating d-metal ions.
Databáze:	MEDLINE
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