skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: O -Acetyl Side-Chains in Monosaccharides: Redundant NMR Spin-Couplings and Statistical Models for Acetate Ester Conformational Analysis

Abstract

α- and β-D-glucopyranose monoacetates 1–3 were prepared with selective 13C enrichment in the O-acetyl side-chain, and ensembles of 13C– 1H and 13C– 13C NMR spin-couplings (J-couplings) were measured involving the labeled carbons. Density functional theory (DFT) was applied to a set of model structures to determine which J-couplings are sensitive to rotation of the ester bond θ. Eight J-couplings ( 1J CC, 2J CH, 2J CC, 3J CH, and 3J CC) were found to be sensitive to θ, and four equations were parametrized to allow quantitative interpretations of experimental J-values. Inspection of J-coupling ensembles in 1–3 showed that O-acetyl side-chain conformation depends on molecular context, with flanking groups playing a dominant role in determining the properties of θ in solution. To quantify these effects, ensembles of J-couplings containing four values were used to determine the precision and accuracy of several 2-parameter statistical models of rotamer distributions across θ in 1–3. The statistical method used to generate these models has been encoded in a newly developed program, MA'AT, which is available for public use. These models were compared to O-acetyl side-chain behavior observed in a representative sample of crystal structures, and in molecular dynamics (MD) simulations of O-acetylated model structures. Whilemore » the functional form of the model had little effect on the precision of the calculated mean of θ in 1–3, platykurtic models were found to give more precise estimates of the width of the distribution about the mean (expressed as circular standard deviations). Validation of these 2-parameter models to interpret ensembles of redundant J-couplings using the O-acetyl system as a test case enables future extension of the approach to other flexible elements in saccharides, such as glycosidic linkage conformation.« less

Authors:
 [1];  [2];  [3];  [1];  [1];  [4];  [4]; ORCiD logo [1]
  1. Univ. of Notre Dame, IN (United States)
  2. Omicron Biochemicals Inc., South Bend, Indiana 46617-2701, United States
  3. Facebook Inc., Seattle, WA (United States)
  4. Univ. of Georgia, Athens, GA (United States)
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1463135
Grant/Contract Number:  
FC02-04ER15533
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 1; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Turney, Toby, Pan, Qingfeng, Sernau, Luke, Carmichael, Ian, Zhang, Wenhui, Wang, Xiaocong, Woods, Robert J., and Serianni, Anthony S. O -Acetyl Side-Chains in Monosaccharides: Redundant NMR Spin-Couplings and Statistical Models for Acetate Ester Conformational Analysis. United States: N. p., 2016. Web. doi:10.1021/acs.jpcb.6b10028.
Turney, Toby, Pan, Qingfeng, Sernau, Luke, Carmichael, Ian, Zhang, Wenhui, Wang, Xiaocong, Woods, Robert J., & Serianni, Anthony S. O -Acetyl Side-Chains in Monosaccharides: Redundant NMR Spin-Couplings and Statistical Models for Acetate Ester Conformational Analysis. United States. doi:10.1021/acs.jpcb.6b10028.
Turney, Toby, Pan, Qingfeng, Sernau, Luke, Carmichael, Ian, Zhang, Wenhui, Wang, Xiaocong, Woods, Robert J., and Serianni, Anthony S. Mon . "O -Acetyl Side-Chains in Monosaccharides: Redundant NMR Spin-Couplings and Statistical Models for Acetate Ester Conformational Analysis". United States. doi:10.1021/acs.jpcb.6b10028. https://www.osti.gov/servlets/purl/1463135.
@article{osti_1463135,
title = {O -Acetyl Side-Chains in Monosaccharides: Redundant NMR Spin-Couplings and Statistical Models for Acetate Ester Conformational Analysis},
author = {Turney, Toby and Pan, Qingfeng and Sernau, Luke and Carmichael, Ian and Zhang, Wenhui and Wang, Xiaocong and Woods, Robert J. and Serianni, Anthony S.},
abstractNote = {α- and β-D-glucopyranose monoacetates 1–3 were prepared with selective 13C enrichment in the O-acetyl side-chain, and ensembles of 13C–1H and 13C–13C NMR spin-couplings (J-couplings) were measured involving the labeled carbons. Density functional theory (DFT) was applied to a set of model structures to determine which J-couplings are sensitive to rotation of the ester bond θ. Eight J-couplings (1JCC, 2JCH, 2JCC, 3JCH, and 3JCC) were found to be sensitive to θ, and four equations were parametrized to allow quantitative interpretations of experimental J-values. Inspection of J-coupling ensembles in 1–3 showed that O-acetyl side-chain conformation depends on molecular context, with flanking groups playing a dominant role in determining the properties of θ in solution. To quantify these effects, ensembles of J-couplings containing four values were used to determine the precision and accuracy of several 2-parameter statistical models of rotamer distributions across θ in 1–3. The statistical method used to generate these models has been encoded in a newly developed program, MA'AT, which is available for public use. These models were compared to O-acetyl side-chain behavior observed in a representative sample of crystal structures, and in molecular dynamics (MD) simulations of O-acetylated model structures. While the functional form of the model had little effect on the precision of the calculated mean of θ in 1–3, platykurtic models were found to give more precise estimates of the width of the distribution about the mean (expressed as circular standard deviations). Validation of these 2-parameter models to interpret ensembles of redundant J-couplings using the O-acetyl system as a test case enables future extension of the approach to other flexible elements in saccharides, such as glycosidic linkage conformation.},
doi = {10.1021/acs.jpcb.6b10028},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 1,
volume = 121,
place = {United States},
year = {2016},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record: