NAM-TMS Mechanism of α-Amino Acid N-Carboxyanhydride Polymerization: A DFT Study

The Journal of Physical Chemistry. a
Tianwen Bai, Jun Ling

Abstract

The normal amine mechanism via the proton-transfer route (NAM-H) is widely accepted for the synthesis of polypeptides with nonionic initiators. Besides proton transfer, the trimethylsilyl (TMS) group transfer process has been found in living/controlled polymerization initiated by N-TMS amine in experiments, but the corresponding mechanism has never been proposed. In this work, we employed density functional theory (DFT) with the solvation model to investigate the details of the TMS-transfer mechanism, defined as NAM-TMS, for the ring-opening polymerization of α-amino acid N-carboxyanhydride. The TMS transfer process of NAM-TMS is thermodynamically more favored than the NAM-H mechanism according to the lower addition energy barrier observed. The rate-determining step (RDS) in NAM-TMS is the decarboxylation step, i.e., the release of CO2, rather than carbonyl addition in NAM-H because of the low dipole stable precursor enlarged energy gap of decarboxylation. It is the first calculation evidence supporting decarboxylation as RDS in the NAM mechanism.

References

Oct 30, 2007·Journal of the American Chemical Society·Hua Lu, Jianjun Cheng
Jul 7, 2015·Chemical Reviews·Timothy J Deming
Dec 25, 2015·Chemical Reviews·Niklas GangloffRobert Luxenhofer

❮ Previous
Next ❯

Citations

Mar 1, 2018·Scientific Reports·Ning ZhuKai Guo
Jun 26, 2020·Physical Chemistry Chemical Physics : PCCP·Tianwen BaiJihong Sun
Mar 29, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Yanzhao NieJing Yang
Oct 24, 2018·ACS Applied Materials & Interfaces·Chao Nan ZhuQiang Zheng
Sep 26, 2021·Macromolecular Rapid Communications·Botuo ZhengJun Ling

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.