TY - JOUR
T1 - Discovering Monoterpene Catalysis Inside Nanocapsules with Multiscale Modeling and Experiments
AU - Pahima, Efrat
AU - Zhang, Qi
AU - Tiefenbacher, Konrad
AU - Major, Dan T.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/4/17
Y1 - 2019/4/17
N2 - Large-scale production of natural products, such as terpenes, presents a significant scientific and technological challenge. One promising approach to tackle this problem is chemical synthesis inside nanocapsules, although enzyme-like control of such chemistry has not yet been achieved. In order to better understand the complex chemistry inside nanocapsules, we design a multiscale nanoreactor simulation approach. The nanoreactor simulation protocol consists of hybrid quantum mechanics-molecular mechanics-based high temperature Langevin molecular dynamics simulations. Using this approach we model the tail-to-head formation of monoterpenes inside a resorcin[4]arene-based capsule (capsule I). We provide a rationale for the experimentally observed kinetics of monoterpene product formation and product distribution using capsule I, and we explain why additional stable monoterpenes, like camphene, are not observed. On the basis of the in-capsule I simulations, and mechanistic insights, we propose that feeding the capsule with pinene can yield camphene, and this proposal is verified experimentally. This suggests that the capsule may direct the dynamic reaction cascades by virtue of π-cation interactions.
AB - Large-scale production of natural products, such as terpenes, presents a significant scientific and technological challenge. One promising approach to tackle this problem is chemical synthesis inside nanocapsules, although enzyme-like control of such chemistry has not yet been achieved. In order to better understand the complex chemistry inside nanocapsules, we design a multiscale nanoreactor simulation approach. The nanoreactor simulation protocol consists of hybrid quantum mechanics-molecular mechanics-based high temperature Langevin molecular dynamics simulations. Using this approach we model the tail-to-head formation of monoterpenes inside a resorcin[4]arene-based capsule (capsule I). We provide a rationale for the experimentally observed kinetics of monoterpene product formation and product distribution using capsule I, and we explain why additional stable monoterpenes, like camphene, are not observed. On the basis of the in-capsule I simulations, and mechanistic insights, we propose that feeding the capsule with pinene can yield camphene, and this proposal is verified experimentally. This suggests that the capsule may direct the dynamic reaction cascades by virtue of π-cation interactions.
UR - http://www.scopus.com/inward/record.url?scp=85064332338&partnerID=8YFLogxK
U2 - 10.1021/jacs.8b13411
DO - 10.1021/jacs.8b13411
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C2 - 30907083
SN - 0002-7863
VL - 141
SP - 6234
EP - 6246
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 15
ER -