TY - JOUR
T1 - Characterization of molecular association of poly(2-oxazoline)s-based micelles with various epoxides and diols via the Flory-Huggins theory
T2 - A molecular dynamics simulation approach
AU - Chun, Byeong Jae
AU - Lu, Jie
AU - Weck, Marcus
AU - Jang, Seung Soon
N1 - Publisher Copyright:
© 2015 the Owner Societies.
PY - 2015
Y1 - 2015
N2 - The hydrolytic kinetic resolution (HKR) of epoxides has been performed in a shell-crosslinked micellar (SCM) nanoreactor consisting of amphiphilic triblock copolymers based on poly(2-oxazline)s polymer derivatives with attached Co(iii)-salens to the micelle core. To investigate the effect of the molecular interaction of reactant/product molecules with the SCM nanoreactor on the rate of HKR, we calculated the Flory-Huggins interaction parameters (χ) using the molecular dynamics simulation method. For this, the blend systems were constructed with various compositions such as 15, 45, and 70 wt% of the reactant/product molecules with respect to the polymers such as poly(2-methyl-2-oxazoline) (PMOX), poly(2-(3-butinyl)2-oxazoline) (PBOX), and poly(methyl-3-oxazol-2-yl)pentanoate with Co(iii)-salen (PSCoX). From the χ parameters, we demonstrate that the miscibility of reactants/products with polymers has a strong correlation with the experimental reaction rate of the HKR: phenyl glycidyl ether (Reac-OPh) > epoxyhexane (Reac-C4) > styrene oxide (Reac-Ph) > epichlorohydrin (Reac-Cl). To validate this finding, we also conducted the potential of mean force analysis using steered molecular dynamics simulation for the molecular displacement of Reac-Cl and Reac-OPh through PMOX and PSCoX, revealing that the free energy reduction was greater when Reac-OPh molecule enters the polymer phase compared to Reac-Cl, which agrees with the findings from the χ parameters calculations.
AB - The hydrolytic kinetic resolution (HKR) of epoxides has been performed in a shell-crosslinked micellar (SCM) nanoreactor consisting of amphiphilic triblock copolymers based on poly(2-oxazline)s polymer derivatives with attached Co(iii)-salens to the micelle core. To investigate the effect of the molecular interaction of reactant/product molecules with the SCM nanoreactor on the rate of HKR, we calculated the Flory-Huggins interaction parameters (χ) using the molecular dynamics simulation method. For this, the blend systems were constructed with various compositions such as 15, 45, and 70 wt% of the reactant/product molecules with respect to the polymers such as poly(2-methyl-2-oxazoline) (PMOX), poly(2-(3-butinyl)2-oxazoline) (PBOX), and poly(methyl-3-oxazol-2-yl)pentanoate with Co(iii)-salen (PSCoX). From the χ parameters, we demonstrate that the miscibility of reactants/products with polymers has a strong correlation with the experimental reaction rate of the HKR: phenyl glycidyl ether (Reac-OPh) > epoxyhexane (Reac-C4) > styrene oxide (Reac-Ph) > epichlorohydrin (Reac-Cl). To validate this finding, we also conducted the potential of mean force analysis using steered molecular dynamics simulation for the molecular displacement of Reac-Cl and Reac-OPh through PMOX and PSCoX, revealing that the free energy reduction was greater when Reac-OPh molecule enters the polymer phase compared to Reac-Cl, which agrees with the findings from the χ parameters calculations.
UR - http://www.scopus.com/inward/record.url?scp=84946050988&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84946050988&partnerID=8YFLogxK
U2 - 10.1039/c5cp03854e
DO - 10.1039/c5cp03854e
M3 - Article
C2 - 26463559
AN - SCOPUS:84946050988
SN - 1463-9076
VL - 17
SP - 29161
EP - 29170
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 43
ER -