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Review
. 2021 May 14;26(10):2928.
doi: 10.3390/molecules26102928.

Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Milind M Deshmukh  1 , Shridhar R Gadre  2
Affiliations
Review

Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Milind M Deshmukh et al. Molecules. .

Abstract

Hydrogen bonds (HBs) play a crucial role in many physicochemical and biological processes. Theoretical methods can reliably estimate the intermolecular HB energies. However, the methods for the quantification of intramolecular HB (IHB) energy available in the literature are mostly empirical or indirect and limited only to evaluating the energy of a single HB. During the past decade, the authors have developed a direct procedure for the IHB energy estimation based on the molecular tailoring approach (MTA), a fragmentation method. This MTA-based method can yield a reliable estimate of individual IHB energy in a system containing multiple H-bonds. After explaining and illustrating the methodology of MTA, we present its use for the IHB energy estimation in molecules and clusters. We also discuss the use of this method by other researchers as a standard, state-of-the-art method for estimating IHB energy as well as those of other noncovalent interactions.

Keywords: bond energy estimation; fragmentation methods; hydrogen bond (HB); intramolecular hydrogen bond (IHB); molecular tailoring approach (MTA); noncovalent interactions.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Illustration of the molecular tailoring approach (MTA)-based fragmentation procedure for α-tocopherol, shown as the parent molecule, M. See text for details.
Scheme 2
Scheme 2
Fragmentation procedure for estimating the energies of the H-bonds, HB1, and HB2 in 1,2,4-butanetriol (Parent M) molecule. See text for details.
Scheme 3
Scheme 3
Some possible isodesmic reactions for the estimation of H-bond energy, EHB2 in 1,2,5-Pentanetriol. See text and Ref. [52] for details.
Figure 1
Figure 1
The H-bond energy, EHB2, in 1,2,5-pentanetriol calculated at different levels of theory using isodesmic reactions (see Scheme 3) and also by molecular tailoring approach (MTA). See text for details.
Figure 2
Figure 2
General structure of the aldopyranose sugar. In Table, ax represents axial, and eq represents equatorial orientations of the hydroxyl group at carbons C2-C4. Figure partially reproduced from Ref. [67] with the permission from American Chemical Society (ACS). Copyright (2008) The American Chemical Society.
Figure 3
Figure 3
(a) A schematic structure of β-cyclodextrin molecule (containing seven glucose units) indicating different types of hydroxyl groups and (b) a CD bowl, secondary hydroxyl groups at smaller and primary ones at the larger rim, respectively. See text for details.
Figure 4
Figure 4
The MP2-optimized geometries of various water clusters (Wn). Figure reproduced from Ref. [88] with the permission from American Chemical Society (ACS). Copyright (2020) The American Chemical Society.
Figure 5
Figure 5
Hydrogen-bonded chains in the helical peptide structures. “X” represents the substituent at the second position. A, B, C and D are four hydrogen bonds. See text for details. Reprinted from Ref. [89] with permission from American Chemical Society. Copyright (2009) The American Chemical Society.
Figure 6
Figure 6
Structures of meta-benziporphodimethene 1 and N-confused meta-benziporphodimethene containing γ-lactam ring isomer (O-up, 2). See text for details.
See this image and copyright information in PMC

References

    1. Pauling L. The Nature of the Chemical Bond. Oxford University Press; London, UK: 1939.
    1. Jeffery G.A. An Introduction to Hydrogen Bonding. Oxford University Press; New York, NY, USA: 1997.
    1. Desiraju G.R., Steiner T. Structural Chemistry and Biology. Oxford University Press; New York, NY, USA: 1999. The Weak Hydrogen Bond.
    1. Scheiner S. Hydrogen Bond: A Theoretical Perspective. Oxford University Press; New York, NY, USA: 1997.
    1. Huggins M.L. Hydrogen Bridges in Ice and Liquid Water. J. Phys. Chem. 1936;40:723–731. doi: 10.1021/j150375a004. - DOI

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