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Polymerization of expanded l-amino acids containing terminal pyridyl groups by silver(I) ions in nonpolar solvent

Polymer Journal volume 54, pages 883–891 (2022)Cite this article

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Abstract

Combinations of chiral ligands with metal ions are very promising for constructing artificial architectures that lead to functional spaces, such as those widely found in biological systems. Previously, expanded poly(l-amino acid) derivatives have been reported to form unique helical structures, depending on the side chain in the crystal. Herein, silver(I) ions in nonpolar solvents were used to polymerize expanded l-lysine and l-ornithine derivatives. Introducing a bulky hydrophobic acyl group into the terminal amino group of the side chain increased the solubility of the amino acid in chloroform. Polymerization proceeded via the formation of head-to-head and tail-to-tail linkages. 1H diffusion-ordered NMR spectroscopy (DOSY) was used to determine the structures of the oligomeric products. Circular dichroism measurements and density functional theory calculations were then used to estimate the overall secondary structures, which were significantly different from each other despite the small difference, namely, with or without the fourth CH2 moiety.

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Acknowledgements

This work was supported by the Analytical Instrument Facility, Graduate School of Science, Osaka University.

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  1. Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan

    Taka-aki Okamura, Kyoko Tsubouchi, Ayumi Okada & Kiyotaka Onitsuka

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  1. Taka-aki Okamura
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  2. Kyoko Tsubouchi
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  3. Ayumi Okada
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Correspondence to Taka-aki Okamura.

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Okamura, Ta., Tsubouchi, K., Okada, A. et al. Polymerization of expanded l-amino acids containing terminal pyridyl groups by silver(I) ions in nonpolar solvent. Polym J 54, 883–891 (2022). https://doi.org/10.1038/s41428-022-00645-9

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