| Autor: |
Perez Mellor AF; Department of Physical Chemistry, Sciences II, University of Geneva, 30, Quai Ernest Ansermet, Geneva 1211, Switzerland., Brazard J; Department of Physical Chemistry, Sciences II, University of Geneva, 30, Quai Ernest Ansermet, Geneva 1211, Switzerland., Kozub S; Łukasiewicz Research Network - PORT Polish Center for Technology Development, Stabłowicka 147, Wrocław 54-066, Poland., Bürgi T; Department of Physical Chemistry, Sciences II, University of Geneva, 30, Quai Ernest Ansermet, Geneva 1211, Switzerland., Szweda R; Łukasiewicz Research Network - PORT Polish Center for Technology Development, Stabłowicka 147, Wrocław 54-066, Poland., Adachi TBM; Department of Physical Chemistry, Sciences II, University of Geneva, 30, Quai Ernest Ansermet, Geneva 1211, Switzerland. |
| Abstrakt: |
Carbamate is an emerging class of a polymer backbone for constructing sequence-defined, abiotic polymers. It is expected that new functional materials can be de novo designed by controlling the primary polycarbamate sequence. While amino acids have been actively studied as building blocks for protein folding and peptide self-assembly, carbamates have not been widely investigated from this perspective. Here, we combined infrared (IR), vibrational circular dichroism (VCD), and nuclear magnetic resonance (NMR) spectroscopy with density functional theory (DFT) calculations to understand the conformation of carbamate monomer units in a nonpolar, aprotic environment (chloroform). Compared with amino acid building blocks, carbamates are more rigid, presumably due to the extended delocalization of π-electrons on the backbones. Cis configurations of the amide bond can be energetically stable in carbamates, whereas peptides often assume trans configurations at low energies. This study lays an essential foundation for future developments of carbamate-based sequence-defined polymer material design. |
