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Theoretical investigations into the intermolecular hydrogen-bonding interactions of N-(hydroxymethyl)acetamide dimers

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Abstract

The structures of the N-(hydroxymethyl)acetamide (model molecule of ceramide) dimers have been fully optimized at B3LYP/6–311++G** level. The intermolecular hydrogen bonding interaction energies have been calculated using the B3LYP/6–311++G**, B3LYP/6–311++G(2df,2p), MP2(full)/6–311++G** and MP2(full)/6–311++G(2df,2p) methods, respectively. The results show that the O–H···O, N–H···O, O–H···N, and C–H···O hydrogen bonding interactions could exist in N-(hydroxymethyl)acetamide dimers, and the O–H···O, N–H···O, and O–H···N hydrogen bonding interactions could be stronger than C–H···O. The three-dimensional network structure formed by ceramide molecules through intermolecular hydrogen bonding interactions may be the main reason why the stratum corneum of skin could prevent foreign substances from entering our body, as is in accordance with the experimental results. The stability of hydrogen-bonding interactions follow the order of (a) > (b) ≈ (c) > (d) > (e) ≈ (f) > (g) > (h). The analyses of the energy decomposition, frequency, atoms in molecules (AIM), natural bond orbital (NBO), and electron density shift are used to further reveal the nature of the complex formation. In the range of 263.0–328.0 K, the complex is formed via an exothermic reaction, and the solvent with lower temperature and dielectric constant is favorable to this process.

The structures and the O–H···O=C, N–H···O=C and C–H···O=C H-bonding interactions in the N-(hydroxymethyl)acetamide (model molecule of ceramide) dimers were investigated using the B3LYP and MP2(full) methods.

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Acknowledgements

The authors thank the reviewer for carefully reading our manuscript and providing many helpful suggestions and comments.

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Authors and Affiliations

  1. Xiangtan Medicine & Health Vocational College, Xiangtan, 411104, People’s Republic of China

    Hai-fei Tang

  2. School of Pharmaceutical Science, Shanxi Medical University, Taiyuan, 030001, People’s Republic of China

    Hua Zhong, Ling-ling Zhang, Ming-xing Gong, Shu-qin Song & Qing-ping Tian

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  1. Hai-fei Tang
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  2. Hua Zhong
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Correspondence to Qing-ping Tian.

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Supplementary data

Supplementary data

Cartesian coordinates of eight N-(hydroxymethyl)acetamide dimers at the B3LYP/6–311++G** level are in Appendix A.

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Tang, Hf., Zhong, H., Zhang, Ll. et al. Theoretical investigations into the intermolecular hydrogen-bonding interactions of N-(hydroxymethyl)acetamide dimers. J Mol Model 24, 139 (2018). https://doi.org/10.1007/s00894-018-3672-1

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