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Review
. 2019 Sep 9;58(37):13127-13132.
doi: 10.1002/anie.201906577. Epub 2019 Aug 19.

Systematic Hydrogen-Bond Manipulations To Establish Polysaccharide Structure-Property Correlations

Yang Yu  1   2 , Theodore Tyrikos-Ergas  1   2 , Yuntao Zhu  1 , Giulio Fittolani  1   2 , Vittorio Bordoni  1 , Ankush Singhal  3 , Richard J Fair  1   4 , Andrea Grafmüller  3 , Peter H Seeberger  1   2 , Martina Delbianco  1
Affiliations
Review

Systematic Hydrogen-Bond Manipulations To Establish Polysaccharide Structure-Property Correlations

Yang Yu et al. Angew Chem Int Ed Engl. .

Abstract

A dense hydrogen-bond network is responsible for the mechanical and structural properties of polysaccharides. Random derivatization alters the properties of the bulk material by disrupting the hydrogen bonds, but obstructs detailed structure-function correlations. We have prepared well-defined unnatural oligosaccharides including methylated, deoxygenated, deoxyfluorinated, as well as carboxymethylated cellulose and chitin analogues with full control over the degree and pattern of substitution. Molecular dynamics simulations and crystallographic analysis show how distinct hydrogen-bond modifications drastically affect the solubility, aggregation behavior, and crystallinity of carbohydrate materials. This systematic approach to establishing detailed structure-property correlations will guide the synthesis of novel, tailor-made carbohydrate materials.

Keywords: automated glycan assembly; carbohydrates; hydrogen bonds; molecular dynamics; structure-property correlations.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Systematic approach to study structure–property correlations in carbohydrate materials.
Figure 2
Figure 2
AGA of tailor‐made cellulose oligosaccharides and representative oligosaccharides conformations as obtained by MD simulations. Yields of isolated products after AGA, deprotection, and purification are reported.
Figure 3
Figure 3
Analysis of the dihedral distributions obtained by MD simulations for A6. Negative degrees of Ψ (green box) are stabilized by the hydrogen bond between OH(3) and O(5), whereas the increased distance between these two residues is reflected by a positive Ψ. The residues are numbered from the nonreducing end (R1) to the reducing end (R6).
Figure 4
Figure 4
Analysis of end‐to‐end distances as a function of MD time and Ψ distribution obtained by MD simulations. The end‐to‐end distance was monitored over 500 ns. Large fluctuations are observed for all modified analogues, indicating that these molecules are more flexible. Changes in the population of Ψ at negative degrees (green box) are correlated to changes in hydrogen bonding between OH(3) and O(5). Changes in intensity are correlated with a decreased (↓) or increased (↑) rigidity, compared to A6; shifts (←) indicate that new geometries become accessible.
Figure 5
Figure 5
a) Representative snapshots of MD simulations of concentrated solutions, b) RDFs, and c) XRD patterns; inset: solubility test.
Figure 6
Figure 6
Powder XRD analysis of natural oligosaccharides (A6, A12, and N6) and all the modified analogues.
See this image and copyright information in PMC

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