Unexpectedly Robust N–H···N Hydrogen Bonds in an Individual Polyallylamine Chain

Yu-Chen Wang; Ming-Han Hu; Dong Ding; Wen-Tao Yuan; Yu Bao; Shu-Xun Cui

doi:10.1007/s10118-025-3495-3

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Unexpectedly Robust N–H···N Hydrogen Bonds in an Individual Polyallylamine Chain

RESEARCH ARTICLE | Updated：2026-01-30

- Unexpectedly Robust N–H···N Hydrogen Bonds in an Individual Polyallylamine Chain
- Chinese Journal of Polymer Science Vol. 44, Issue 2, Pages: 398-406(2026)
- Affiliations：
  
  a.School of Chemistry, Southwest Jiaotong University, Chengdu 610031, China
  b.Department of Chemistry, College of Sciences, Northeastern University, Shenyang 110819, China
- Author bio：
  
  baoyu@swjtu.edu.cn (Y.B.)
  cuishuxun@neu.edu.cn (S.X.C.)
- Funds：
- DOI：10.1007/s10118-025-3495-3
  CLC：
- Received：09 October 2025，
  
  Accepted：06 November 2025，
  
  Online First：15 January 2026，
  
  Published：05 February 2026
- Accepted：
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Wang, Y. C.; Hu, M. H.; Ding, D.; Yuan, W. T.; Bao, Y.; Cui, S. X. Unexpectedly robust N–H···N hydrogen bonds in an individual polyallylamine chain. Chinese J. Polym. Sci. 2026, 44, 398–406

Yu-Chen Wang, Ming-Han Hu, Dong Ding, et al. Unexpectedly Robust N–H···N Hydrogen Bonds in an Individual Polyallylamine Chain[J]. Chinese Journal of Polymer Science, 2026, 44(2): 398-406.
Wang, Y. C.; Hu, M. H.; Ding, D.; Yuan, W. T.; Bao, Y.; Cui, S. X. Unexpectedly robust N–H···N hydrogen bonds in an individual polyallylamine chain. Chinese J. Polym. Sci. 2026, 44, 398–406 DOI： 10.1007/s10118-025-3495-3.

Yu-Chen Wang, Ming-Han Hu, Dong Ding, et al. Unexpectedly Robust N–H···N Hydrogen Bonds in an Individual Polyallylamine Chain[J]. Chinese Journal of Polymer Science, 2026, 44(2): 398-406. DOI： 10.1007/s10118-025-3495-3.

摘要

The intrinsic strength of N―H···N H-bonds in polyallylamine

measured as about 5.25 kJ·mol

–1

by vacuum-based single-molecule force spectroscopy

exceeds those of N―H···O and O―H···O H-bonds in other polymers

contrasting with the trend in small-molecule systems and revealing how side-chain spatial configuration governs polymer H-bond strengths.

Abstract

Quantifying the hydrogen bond (H-bond) strength of polymers is essential for rational design of advanced materials. However

direct measurement remains challenging because of the structural complexity of polymers and the weak nature of H-bonds. Vacuum-based single-molecule force spectroscopy (Vac-SMFS) offers a new and precise approach for such measurements. Using polyallylamine (PAAm) as a model polymer

the intrinsic strength (

i.e.

strength without external influences) of representative N―H···N H-bonds was quantified to be about 5.25 kJ·mol

–1

. Comparative Vac-SMFS analysis across different polymer systems revealed that the N―H···N H-bonds in PAAm are unexpectedly stronger than the N―H···O H-bonds in poly(

-isopropylacrylamide) (PNIPAM) and the O―H···O H-bonds in poly(hydroxyethyl methacrylate) (PHEMA). This trend contrasts with that of established small-molecule systems. These results highlight how side-chain length and spatial configuration dictate polymer H-bond strengths

expanding the fundamental knowledge of polymer interactions and enabling the rational design of next-generation functional materials.

关键词

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