Perez Mellor Ariel F, Brazard Johanna, Kozub Sara, Bürgi Thomas, Szweda Roza, Adachi Takuji B M
Department of Physical Chemistry, Sciences II, University of Geneva, 30, Quai Ernest Ansermet, Geneva 1211, Switzerland.
Łukasiewicz Research Network - PORT Polish Center for Technology Development, Stabłowicka 147, Wrocław 54-066, Poland.
J Phys Chem A. 2023 Sep 7;127(35):7309-7322. doi: 10.1021/acs.jpca.3c02442. Epub 2023 Aug 25.
Carbamate is an emerging class of a polymer backbone for constructing sequence-defined, abiotic polymers. It is expected that new functional materials can be 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. configurations of the amide bond can be energetically stable in carbamates, whereas peptides often assume configurations at low energies. This study lays an essential foundation for future developments of carbamate-based sequence-defined polymer material design.
氨基甲酸酯是一类新兴的用于构建序列定义的非生物聚合物的聚合物主链。预计通过控制聚氨基甲酸酯的一级序列可以设计出新的功能材料。虽然氨基酸作为蛋白质折叠和肽自组装的构建单元已得到积极研究，但从这个角度对氨基甲酸酯的研究还不够广泛。在这里，我们将红外（IR）、振动圆二色性（VCD）和核磁共振（NMR）光谱与密度泛函理论（DFT）计算相结合，以了解氨基甲酸酯单体单元在非极性、非质子环境（氯仿）中的构象。与氨基酸构建单元相比，氨基甲酸酯更具刚性，这可能是由于主链上π电子的离域扩展所致。氨基甲酸酯中酰胺键的构型在能量上可以是稳定的，而肽在低能量下通常呈现特定构型。这项研究为未来基于氨基甲酸酯的序列定义聚合物材料设计奠定了重要基础。
