Issue 18, 2012

Discrimination between coupling networks of glucopyranosides varying at a single stereocenter using two-dimensional vibrational correlation spectroscopy

Abstract

A combination of two-dimensional infrared (2DIR) correlation spectroscopy, linear absorption spectroscopy, and density functional theory quantum calculations was used to identify characteristic spectral features of two anomers of acetylated 2-azido-2-deoxy-D-glucopyranose. While the linear absorption spectra for the α and β anomers were distinctive, a substantial difference between them was observed only in the spectral region below 1200 cm−1. The infrared correlation spectra of the two anomers differed significantly, even in regions where their linear absorption spectra were similar. Very substantial differences were found for the N[triple bond, length as m-dash]N/C[double bond, length as m-dash]O stretch mode region of the 2DIR correlation spectrum, indicating differences in the anharmonic coupling of the N[triple bond, length as m-dash]N stretching mode of the equatorially oriented N3 group with the CO modes when the C1 ester was either in the axial (α anomer) or equatorial (β anomer) orientation. In addition, the energy transport patterns originating from the excited N[triple bond, length as m-dash]N stretching mode were found to be different for the two anomers; up to a 1.8-fold difference in the energy transport times was observed for the probed modes of the same type in the two anomers. The results demonstrate the capability of 2DIR and relaxation-assisted 2DIR (RA 2DIR) spectroscopies to provide unique spectroscopic data specific to sugar anomers that vary at a single stereochemical center. These methods identify unique coupling networks within individual sugar stereochemical units and demonstrate the potential to identify a number of stereochemical differences among them.

Graphical abstract: Discrimination between coupling networks of glucopyranosides varying at a single stereocenter using two-dimensional vibrational correlation spectroscopy

Supplementary files

Article information

Article type
Paper
Submitted
15 Oct 2011
Accepted
13 Dec 2011
First published
14 Dec 2011

Phys. Chem. Chem. Phys., 2012,14, 6179-6191

Discrimination between coupling networks of glucopyranosides varying at a single stereocenter using two-dimensional vibrational correlation spectroscopy

Z. Lin, B. Bendiak and I. V. Rubtsov, Phys. Chem. Chem. Phys., 2012, 14, 6179 DOI: 10.1039/C2CP23245F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements