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Coarse-Grained Models for pH Responsive Polymers

Smart Materials Design, Analysis, & Processing:

Gaurav
Gyawali,
Arjun
Sharma,
Amber
C.
Carpenter,
Steven
W.
Rick
A Louisiana & Mississippi Consortium
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Department of Chemistry, University of New Orleans

Can you not make the body font bold? It might

confuse whats more important and whats less.

Abstract

Methodology!

The pH-responsive polymers have a variety of potential applications, including

controlled drug delivery, industrial coatings, colloid stabilization, and water
remediation. The polymers chain length makes it challenging to study physical
properties to better understand the macroscopic structural and dynamical
properties at longer length scales. In order to overcome the computational
limitations imposed by exclusively using detailed atomistic models, a multi-scale
modeling technique such as coarse-grained (CG) simulations is utilized. In this
study, we aim to develop CG models for the efficient simulations of large
polymer chains. Herein, we present the results from our preliminary work that
involves deriving the interaction potentials for the coarse-grained model of pH
responsive poly(methacrylic acid) (PMAA) using the data from all-atom
simulations and coarse-grained model of Molinero water (mW). The mW model
reproduces the physicochemical properties of water with just the short-range
interactions. The absence of the long-range interactions in the mW model along
with the CG model of PMAA would speedup the computation time to study global
chain structural dynamics processes.

Chemical representation

CH2

CH3

Develop alkane carbon-mW parameters

by MD simulations of simple hydrocarbons
(methane, ethane, propane etc.)

Develop carboxyl carbon-mW parameters

by MD simulations of acetic acid in water

b. Run CG simulation using the

approximate parameters, and
organize [,] to match the
target RDF from a.
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c. Run free energy of solvation

calculations for alkanes
Validate alkane-alkane carbon parameters
by MD simulations of pure hydrocarbons to
reproduce experimental values of heat of
vaporization, density, and surface tension

d. Optimize [,] to match the

experimental solvation free
energy

Develop carboxyl carbon-carboxyl carbon
and carboxyl oxygen-carboxyl oxygen
parameters by MD simulations of pure
acetic acid

HO

Chemical structure of
poly(methacrylic acid)
CG model of trimethylacetic acid. The carboxyl
oxygens are represented by green beads, the
carboxyl carbon by purple bead, the alpha carbon
by cyan bead, and methyl carbons by pink beads.

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a. Run all-atom simulations in

GROMACS (OPLS force field,
TIP3P water) to get radial
distribution function (RDF)
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Preliminary results & Conclusions

mW

Stillinger-weber (SW) potential

CG simulation of pH responsive PMAA using

the aforementioned interaction parameters

a. Run CG simulation using the

approximate parameters
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b. Optimize [,] to match

the experimental heat of
vaporization, density, and
surface tension etc.

Advantages of using SW CG simulations:

Figure 1:
RDF of mW
around the methyl carbon.
The RDF of methyl carbon
for all-atom model and CG
model are represented by
solid and dashed circle red
lines respectively.

Figure 2: RDF of mW around

the carboxyl carbon. The
RDF of carboxyl carbon for
all-atom model and CG model
are represented by solid and
dashed circle black lines
respectively.

Figure 3: RDF of mW
around the alpha carbon.
The RDF of alpha carbon
for all-atom model and CG
model are represented by
solid and dashed circle blue
lines respectively.

Figure 4: RDF of mW around

the carboxyl oxygen. The
RDF of carboxyl oxygen for
all-atom model and CG model
are represented by solid and
dashed circle green lines
respectively.

Carboxyl
oxygen

i. Reduced number of atomic sites (H atoms are eliminated)

o
rik

mW

You missed the first equation which represents

the total potential as the sum of 2body and
3body potentials

Tetrahedral coordination of the mW atom is obtained by

adding two body v2(r) pairwise potential and a three-body
term v3(r,). Those configurations with angles that are not
tetrahedral v=v2(r)+v3(r,) are penalized. The parameter
indicates the tetrahedral strength.

ii. Reduced number of calculations (since the forces are short ranged, interactions
are mostly limited to fewer atomic sites. Charges are only assigned to ions so
no coulombic interactions)
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iii. Increased time step (all-atom MD simulations are mostly limited to 1-2 femto
seconds (fs) time step but SW CG simulations can utilize upto 10 fs. At
present we use 5 fs time step)
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References & Acknowledgements

1. Molinero, V., Moore, E. B., J. Phys. Chem. B. 113, 4008-4016, 2009.
2. Stillinger, F. H., Weber, T. A., Phys. Rev. B, 31, 5262-5270, 1985.
3. Hwang, J.-K., Warshel, A, J. Am. Chem. Soc. 109, 715-720, 1987.
4. Muralidharan U. S., Natarajan U., Ind. Eng. Chem. Res. 21, 11785-11796, 2011.
5. Chockalingam R., Natarajan U., Molecular Simulation. 13, 1110-1121, 2014.
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This research was supported fully or in part by the National Science
Foundations Experimental Program to Stimulate Competitive
Research (EPSCoR) under Cooperative Agreement No. IIA1430280.!