Revista Iberoamericana de Polímeros Volumen 16(2), Marzo de 2015

Bautista–Reyes et al. Simulación mesoscópica del PNIPAM-b-PEO

MESOSOPIC SIMULATION OF PNIPAM–b–PEO MICELAR

TRANSPORTATION THROUGH THE WATER PHASES/[BMIM][PF6]

Rubén Bautista–Reyes1, César Soto–Figueroa2, María del Rosario Rodríguez–

Hidalgo3, Luís Vicente1*
1) Departamento de Física y Química Teórica, Facultad de Química, Universidad Nacional Autónoma de
México, 04510, México D.F. Correo electrónico: luis.vicente@unam.mx
2) Facultad de Ciencias Químicas, Universidad Autónoma de Chihuahua, 31125 Chihuahua, México.
3) Departamento de Ciencias Químicas, Facultad de Estudios Superiores Cuautitlán, Universidad Nacional
Autónoma de México Av. 1º de Mayo s/n Campo 1. Cuautitlán Izcallí, 54740. Estado de México, México.

Received: November 2014;Accepted: February 2015

ABSTRACT
We simulate the micellar shuttle of poly(N–isopropylacrylamide–block–ethylene–oxide) (PNIPAM–
b–PEO) diblock copolymer in a water/ionic–liquid [BMIM][PF6] system by means of dissipative particles
dynamics (DPD). At room temperature the PNIPAM–PEO copolymer chains are miscible in aqueous phase,
but with a temperature increase the system turns into micelles. A further temperature increase makes a transfer
to the ionic liquid phase. A demicellization process in hydrophobic ionic liquid was carried out to high
temperatures. The system shows reversibility as the temperature is decreased again. All the simulation
outcomes are qualitatively consistent with the experimental results.
Keywords: copolymers, micellar transfer, mesoscopic simulation.

INTRODUCTION

In recent years has been much interest in the process of synthesis and the study of new
structures that are obtained in a variety of materials at the nanometer scale. The science of polymeric
materials does not escape this interest, in fact, polymeric materials are an important source of new
structures with these dimensions. Within polymeric materials, copolymers are an important option.
The diblock copolymers with amphiphilic character in one hydrophilic end or soluble in water and
another hydrophobic that rejects water; can be self-assembled in the aqueous medium producing
micelles of mesoscopic size [1,2]. Double-amphiphilic diblock copolymers combine two different
amphiphilic blocks and have the ability to self-assemble into a wide variety of complex micellar
structures, such as spherical, lamellar, cylindrical micelles and vesicles in aqueous media. These
micelles are characterized by their core-shell architecture, the hydrophobic segments segregate from
the outside to form an inner core surrounded by hydrophilic segments. The current interest of these
micellar systems is due to the wide scope, such as drugs transporters, dyes, etc., due to the large
charge capacity that lies inside the micelle [3,4].

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Bautista–Reyes et al. Simulación mesoscópica del PNIPAM-b-PEO

In comparison of the micelles formed by surfactants, micelles of diblock copolymers generally have
greater stability and have a lower critical micelle concentration (CMC). They also have a narrow size
distribution with dimensions of the order of tens of nanometers (mesoscopic size). Another quality of
this type of micelles is that they have the capacity to show changes in their properties in response to
the modification of their environment, that is to say when exposed to variations in pH, temperature,
ionic strength, electric field, etc. [5]. According to the response or sensitivity that is observed in the
micellar system when modifying its environment, micelles will be named (thermosensitive,
photosensitive, etc.).

In particular, polymer micelles formed by thermo-responsive block copolymers can carry out
conformational changes, such as reversing their micellar structure, by a simple increase in the
temperature of the system [6]. In this case the existence of a lower critical solubility temperature
(LCST) causes the hydrophilic block to make a transition from soluble to insoluble in water. This
globular transition (coil-globule) means that when the system is at a higher temperature than the
LCST, the hydrophilic polymer block collapses. The process is reversible: the aggregate dissolves by
lowering the temperature below the LCST.

The Poly (N-isopropyl acrylamide) system, PNIPAM, is one of the most studied thermo-
sensitive polymer systems, exhibits a globular transition in water at a temperature of around 305 K
[7], this LCST can be modified by combining with another polymer , for example the copolymer of
PNIPAM and poly (ethylene oxide) (PEO) with different molecular masses, MPNIPAM / MPEO have an
LCST of around 303K [8]. Aqueous solutions of poly (ethylene oxide) show both LSCT and critical
temperature of superior solubility, UCST [9].

An important property of thermo-sensitive copolymers is their ability to be transported through

immiscible phases. This property has been studied recently [10-13] between two immiscible liquids
such as water / ionic liquid, being a reversible property. The term "micelle shuttle" has been proposed
by Zhifeng Bai et al. [10] who have reported the transporter poly (N-isopropyl acrylamide-b-ethylene
oxide) between water and an ionic liquid [BMIM] [PF6]) (1-butyl-3-methylimidazolium
hexafluorophosphate). The interest of studying transport between water and an ionic liquid (LI) lies
in the proposed use of ionic liquids as substitute solvents for volatile organic compounds that are
widely used in industry [14]. Its properties such as low toxicity, good thermal

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Bautista–Reyes et al. Simulación mesoscópica del PNIPAM-b-PEO

stability, low melting points, (they remain in a liquid state over a wide temperature range) make them
good candidates in multiple applications [15].
The reversible micellar transfer between two phases is based on the relative affinity of the two
solvents with the chains that form the crown of the micelles [10]. There is little theoretical work that
helps to understand the delivery process and its interactions with the surrounding environment and
one of the powerful tools is computational simulation [16] that has been widely used in the field of
polymers. A type of simulation that consider the size of the polymer systems, it’s very important,
hence the so-called mesoscopic simulations, the results of the order from 10 to 100 nm and the order
times from 1 ns to 10 ms for fill the gap between atomistic simulations that cannot be considered
large systems and continuous methods. In particular, the method known as Dissipative Particle
Dynamics [17-19] (DPD) has been widely used in problems of block copolymers [20-21], phase
transitions [22], etc. In a recent article we use this methodology to simulate the transfer process of the
poly (1,2-butadiene-b-ethylene oxide) copolymer (PB-b- PEO) from the aqueous phase to the ionic
liquid [BMIM] [PF6]) [23].
In the present work by means of mesoscopic computer simulation and coarse-grained models,
the chain-globule transition of the PNIPAM polymer in water is studied and then the influence of this
transition in the process of formation of the micelle of the diblock copolymer PNIPAM- b-PEO. The
behavior of the system is also studied as the temperature increases, the transport to the ionic liquid
phase, the subsequent demicelization process and the reverse process of transport to the aqueous phase
with the decrease in temperature.

MESOSCALE METHOD

The mesoscopic simulation method known as Dissipative Particle Dynamics (DPD) allows
the study of large molecular systems and uses modeling known as coarse-grained modeling where a
DPD bead or sphere represents a group of atoms or fluid volume that is large compared to the atomic
scale but small macroscopically. These beads are subject to smooth interactions via three forces:
conservative (FijC), dissipative (FijD) and random (FijR).

The conservative force is a mild repulsive force that acts between particles i and j and contains the
underlying chemistry of the species involved. The dissipative force is a frictional force and depends
of the relative speed and position of the particles. The stochastic force represents the freedom degrees
eliminated in the process of coarse grain scaling. The explicit form of the forces is:

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 Revista Iberoamericana de Polímeros Volumen 16(2), Marzo de 2015
Bautista–Reyes et al. Simulación mesoscópica del PNIPAM-b-PEO

aij ωc (rij )r̂ij (rij < rc )

𝐅ijC = { } (1)
0 (rij ≥ rc )

𝐅ijD = −γωD (rij )(𝐯𝐢𝐣 𝐫̂𝐢𝐣 )𝐫̂𝐢𝐣 (2)

1 (3)
𝑭𝑅𝑖𝑗 = 𝜎𝜔𝑅 (𝑟𝑖𝑗 )𝜃𝑖𝑗 𝐫̂𝐢𝐣
√𝛿𝑡

where aij is the repulsion parameter between i and j particles, rij is the relative displacement of the i and
j particles, r̂ij is the unity vector, rc is the radius of cut, ωD (rij) and 𝜔𝑅 (rij) are weight functions of FijD
and 𝐹𝑖𝑗𝑅 , 𝜎 is the stochastic noise amplitude, 𝜃𝑖𝑗 is an aleatory Gaussian number with zero mean and
unity valence and δt is the time pass.

The aij parameter are related with the  Flory–Huggins [18] parameter by:
𝑘𝐵 𝑇𝜒𝑖𝑗 (𝑇)
𝑎𝑖𝑗 = 𝑎𝑖𝑗 + (4)
0.306

The molecular structures of the blocks of the PNIPAM-b-PEO copolymers were constructed
from the repetitive units of each polymer. The molecular chains of each system and solvent were
represented by a set of beads or spherical particles connected by harmonic springs. The diblock
copolymer is then represented by a model consisting of n + m spherical beads denoted by [PNIPAM]n
– [PEO]m. The number of beads for each segment of the copolymer was obtained by the relationship

𝑀𝑃
𝑁𝑐 = (5)
𝑀𝑚 𝐶𝑛

Nc is the number of DPD beads, Mp is polymer bock mass, Mm is the mass of repetitive unity and Cn
is the characteristic ratio of the polymer.
So, if we consider a block with 12·103 g/mol–1 of NIPAM and 19·103 g/mol–1 of PEO,
corresponding to the experiments of Bai et al. [24] we will have a system composed of 6 PNIPAM
beads and 9 PEO beads, Figure 1 (a-b).
The ([BMIM][PF6]) representations of water and ionic liquid, appear in Figure 1 (c-f). The
simulations were carried out in cubic boxes of size (20rc, 20rc, 20rc), rc = 1, with a total of 14,000
particles, with spring constant C = 4 and total density DPD = 3. Each simulation was 10 5 steps with
δt = 0.05 for each temperature value. The values of the parameters 𝜒 were calculated according to the
methodology described in Ref. [23] and the respective values of aij by equation (4).
128 Rev. Iber. Polímeros, 16(2), 125-132 (2015)
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Figure 1. Molecular structures and coarse-grained models: a) and b)

diblock copolymer, c) and d) water, e) and f) ionic liquid.

RESULTS AND DISCUSSIONS

Table 1 shows the values of  used in the simulations of the interacting species (PNIPAM,
PEO, H2O, [BMIM][PF6]) at different temperatures. In fact, a sweep was made at intervals of T=10
K but only the values 298, 303, 308, 334 and 346 K are shown because they are the most
representative. As can be observed, the interaction parameter  between H2O and PNIPAM is very
small at room temperature, which implies a high affinity and the value increases as the temperature
increases, which implies the separation of the phases. There is no great variation between the H2O
and the ionic liquid [BMIM][PF6] with the temperature change (immiscible liquids), but if between
PEO–[BMIM][PF6].

Table 1. Interaction parameter  of the species (PNIPAM, PEO, H2O, [BMIM][PF6]) at

different temperatures.
T H2O– H2O– H2O– PNIPAM– PNIPAM– PEO–
K PNIPAM PEO [BMIM][PF6] PEO [BMIM][PF6] [BMIM][PF6]
298 0,15 1,53 6,14 0,45 3,82 4,85
303 2,94 1,30 5,91 0,45 3,79 4,75
308 3,92 1,23 5,84 0,45 3,76 4,18
334 4,03 1,21 5,71 0,33 3,33 1,01
346 4,06 1,19 5,67 0,17 3,09 0,49

First, we did a simulation considering only a polymeric chain composed exclusively of 15 DPIP
accounts of PNIPAM in water to verify the globular transition. We use as a statistical criterion for
compaction the modification of the mean square distance between the ends of the chain, (RMS end–
to–end–distance). At the 298 K temperature the chains are extended and have an RMS distance of
3,65±1,33, at the temperature T = 303 K the distance is 1,96 ± 0,77, at T = 304,5 K d = 1,74 ± 0,63
and for T = 308 K d = 1,68 ± 0,69. For higher temperatures there is no appreciable variation and the
chains remain in the compact state. We see that at low temperature the system is very open or extended

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and there is a variation of the order of 30% when changing from T = 298 to 303 K.

The simulation for the PNIPAM-b-PEO system begins with a set of diblock copolymer chains
(31 copolymer chains) randomly arranged in the simulation box. The temperature is set at 298 K, which
is obtained after 105 steps is that the chains remain solubilized in the aqueous phase, Figure (2a). As
the temperature increases, the chains begin to group together to form a micelle, Figure (2b) corresponds
to a T = 303 K. The micelles are spherical, with the PNIPAM core and the crown constituted by the
PEO part. It must be remembered that around this temperature occurs the globular transition of
PNIPAM, so that the nucleus is formed by the insoluble part and the crown by the segments of PEO
that remain soluble in water. The micelles remain in the aqueous phase up to a temperature of 332 K,
but as the solubility of the components is modified, the migration of the copolymer towards the ionic
liquid is promoted. Upon reaching the temperature of 333 K, the transfer to the ionic liquid phase
occurs, Figure (2c). This occurs because there is a decrease in the value of the interaction parameter
between the PNIPAM nuclei and between the PEO crowns and the ionic liquid, as can be seen in Table
1. As the parameter PEO–[BMIM][PF6] decreases, it implies that the solubility of the PEO chains with the
ionic liquid decreases, and the process of demicelization or breakage of the micelle occurs at a
temperature of the order of 346 K, Fig. 2d), being a consequence of the solubility between the
polymeric segments and the ionic liquid.

Figure 2. Images of the process of transferring the aqueous phase to the ionic liquid
phase. a) at T = 298 K the chains are dissolved in water. b) at T ~ 303 K the micelles are formed.
c) at T ~ 334 K the micelle is transferred to the ionic liquid. d) at T ~ 346 K demicelization occurs.

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Finally, the process is reversible: as the temperature decreases, the micelle is formed again
and returns to the aqueous phase. The results of the simulation are consistent and qualitatively
comparable with the experimental results reported by Bai et al. [24], who found the water
micellization temperature Tm ~ 307 K (we obtained 303 K), transfer temperature Td ~ 341 K (we
obtained 334 K) and demicelization temperature Td ~ 354 K (we obtained 346 K). To obtain better
quantitative results, a better knowledge of the interaction parameters is required, and in any case better
modeling of the interaction potentials, which in the DPD approach only considers repulsions between
the particles.

CONCLUSIONS
By means of mesoscopic computational simulations it is possible to study the complex process
of micelle formation and transport of the aqueous phase to the other immiscible phase. Our calculations
agree qualitatively with experimental results. The interesting result is that with the application of this
methodology it is possible to consider other copolymers and different non-aqueous phases and
determine the conditions for micellar transport.

Acknowledgments. The authors thank the financing of Universidad Nacional Autónoma de México
(UNAM), PAIP 500090109. R. Bautista–Reyes Thanks CONACYT for the postgraduate scholarship. No.
326053.
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Translation by: Isaac Hernández.

131 Rev. Iber. Polímeros, 16(2), 125-132 (2015)