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2005
Simulation Studies Of Self-assembly And Phase Diagram Of Amphiphilic Molecules
Geuorgui Kostadinov Bourov University of Central Florida
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STARS Citation Bourov, Geuorgui Kostadinov, "Simulation Studies Of Self-assembly And Phase Diagram Of Amphiphilic Molecules" (2005). Electronic Theses and Dissertations, 2004-2019. 435. https://stars.library.ucf.edu/etd/435
SIMULATION STUDIES OF SELF-ASSEMBLY AND PHASE DIAGRAM OF AMPHIPHILIC MOLECULES
by GEUORGUI BOUROV M.S. Sofia University, 1993 M.S. University of Central Florida, 2003
A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Physics in the College of Art and Science at the University of Central Florida Orlando, Florida
Summer Term 2005 ABSTRACT
The aim of this dissertation is to investigate self-assembled structures and the phase
diagram of amphiphilic molecules of diverse geometric shapes using a number of different
computer simulation methods. The semi-realistic coarse-grained model, used extensively for
simulation of polymers and surfactant molecules, is adopted in an off-lattice approach to study
how the geometric structure of amphiphiles affects the aggregation properties. The results of
simulations show that the model system behavior is consistent with theoretical predictions,
experiments and lattice simulation models. We demonstrate that by modifying the geometry of
the molecules, self-assembled aggregates are altered in a way close to theoretical predictions. In
several two and three dimensional off-lattice Brownian Dynamics simulations, the influence of
the shape of the amphiphilic molecules on the size and form of the aggregates is studied systematically. Model phospholipid molecules, with two hydrophobic chains connected to one hydrophilic head group, are simulated and the formation of stable bilayers is observed. In addition, (practically very important) mixtures of amphiphiles with diverse structures are studied under different mixing ratios and molecular structures. We find that in several systems, with
Poisson distributed chain lengths, the effect on the aggregation distribution is negligible compared to that of the pure amphiphilic system with the mean length of the Poisson distribution.
The phase diagrams of different amphiphilic molecular structures are investigated in separate simulations by employing the Gibbs Ensemble Monte Carlo method with an implemented configurational-bias technique. The computer simulations of the above mentioned amphiphilic systems are done in an area where physics, biology and chemistry are closely
ii connected and advances in applications require the use of new theoretical, experimental and simulation methods for a better understanding of their self-assembling properties. Obtained simulation results demonstrate the connection between the structure of amphiphilic molecules and the properties of their thermodynamically stable aggregates and thus build a foundation for many applications of the remarkable phenomena of amphiphilic self-assembly in the area of nanotechnology.
iii Dedicated to my parents, Vasilka and Kostadin Bourov.
iv ACKNOWLEDGEMENTS
I would like to thank my advisor Prof. Aniket Bhattacharya for all time and efforts he
spent guiding me through my research. In addition, I would like to thank the Committee
members: Prof. Kevin Belfield, Prof. Viatcheslav Kokoouline and Prof. Hari Saha. I greatly appreciate the efforts of all my teachers from the Physics Department at UCF and especially I would like to thank Prof. Subir Bose, Prof. Michael Johnson, Prof. Brian Tonner and Prof.
Alfons Schulte.
I have learned a lot about the nanotechnology from the members of the Nano
Interdisciplinary Research Team (NIRT): Prof. Weili Luo, Prof. David Tomanek (MSU) and
Prof. Rosensweig (University of New Orleans).
I greatly appreciate the editing help from my colleagues Karlo Kitanovski and Robert
Macey. I also would like to thank my wife, Stanimira, for her encouragement and support during
the entire candidacy, and my daughter Katerina
This research was supported by a NIRT grant No. 0103587 from the National Science
Foundation.
v PUBLICATIONS BASED ON THIS WORK
1. G. K. Bourov and A. Bhattacharya, The role of geometric constrains in amphiphilic
self-assembly: A Brownian dynamics study, J. Chem. Phys. 119, 9219 (2003).
2. A. Bhattacharya and G. K. Bourov, Effect of packing parameter on amphiphilic self-
assembly: A Brownian dynamics study, in Computer Simulation Studies in Condensed Matter
Physics XVI, Springer Verlag (2003).
3. G. K. Bourov and A. Bhattacharya, Brownian dynamics simulation study of self-
assembly of amphiphiles with large hydrophobic heads, J. Chem. Phys. 122, 044702 (2005).
4. G. K. Bourov and A. Bhattacharya, Brownian dynamics of mixed surfactant micelles
(submitted to J. Chem. Phys.).
Under preparation:
5. G. K. Bourov and A. Bhattacharya, Effect of head group geometry in phase diagram of amphiphilic molecules - a Gibbs ensemble Monte Carlo study.
vi TABLE OF CONTENTS
LIST OF FIGURES ...... ix
LIST OF TABLES...... xiv
LIST OF ACRONYMS AND ABBREVIATIONS ...... xv
CHAPTER ONE: INTRODUCTION...... 1
1. Self-assembly phenomena ...... 1
2. Amphiphiles...... 3
3. Thermodynamics of aggregation ...... 5
CHAPTER TWO: COMPUTER SIMULATIONS ...... 13
1. Bead-spring model...... 14
2. Verlet Algorithm...... 16
3. Brownian Dynamics...... 17
4. Gibbs Ensemble Monte Carlo method...... 19
4.1. Statistical Mechanics of the Gibbs Ensemble...... 22
4.2. Acceptance rules ...... 23
5. Configurational-Bias Method ...... 26
6. Correlation Functions...... 28
7. Verlet and cell-list methods ...... 29
CHAPTER THREE: STUDIES OF AMPHIPHILIC SELF-ASSEMBLY...... 32
1. The model of amphiphiles ...... 32
1.1. Random number generator...... 36
2. Critical Micelle Concentration...... 38
vii 3. Shapes and distribution of Aggregates ...... 43
4. Autocorrelation Function...... 48
CHAPTER FOUR: STUDIES ON MIXED AMPHIPHILIC SYSTEMS AND
PHOSPHOLIPIDS...... 52
1. Mixtures of amphiphiles ...... 52
2. Critical Micelle Concentration...... 56
3. Cluster distributions in binary amphiphilic systems...... 59
4. Mixtures with the Poisson distribution of lengths ...... 64
5. Self-assembly of phospholipid molecules ...... 66
CHAPTER FIVE: PHASE DIAGRAMS OF MODEL AMPHIPHILES ...... 71
1. Phase behavior of chain molecules...... 73
2. Computational methods for study of chain molecules Phase Diagram ...... 76
3. Some details of GEMC simulation ...... 78
4. Results and Discussion ...... 80
4.1. Obtaining the phase diagram of LJ dimers ...... 80
4.2. Phase diagrams of model polymers ...... 87
4.3. Phase diagrams of amphiphiles...... 88
4.4. Aggregation versus phase separation of amphiphiles...... 93
CHAPTER SIX: CONCLUSION AND FUTURE WORK...... 102
LIST OF REFERENCES...... 105
viii LIST OF FIGURES
Figure 1. Structure of an amphiphilic molecule...... 3
Figure 2. A scheme of an aggregate of N=8 amphiphiles...... 6
Figure 3. A scheme of concentration of monomers and aggregates as a function of total
concentration...... 9
Figure 4. The concept of an optimal head group area a0 and volume V of an amphiphilic
...... 11 molecule
Figure 5. Bead-spring model of an amphiphile...... 15
Figure 6. A schematic diagram of the Gibbs ensemble technique...... 20
Figure 7. Three types of “moves” performed in a Gibbs ensemble simulations. The transfer of a
molecule to the dense phase often results in an overlap and therefore the configurational-
bias method is needed...... 21
Figure 8. Cell-list method ...... 30
Figure 9. LJ and FENE potentials...... 34
Figure 10. A test of the random number generator ran3 ...... 37
Figure 11. A test of producing a Gaussian distribution using ran3...... 37
Figure 12. Variation of free chain concentration X1 as a function of the total concentration of
amphiphiles X at reduced temperature of T=0.45 for three different head sizes. The open
and the closed symbols correspond to h1t4 and h1t6 types amphiphiles, respectively.
Simulations are done in 2 dimensions...... 39
ix Figure 13. Free amphiphile concentration X1 versus the total concentration X of the amphiphiles
obtained from 2D simulations of the amphiphiles with varying head size and at two
different temperatures T=0.5 and T=0.45. Simulation are done in 2 dimensions...... 40
Figure 14. CMC of the amphiphiles with different head sizes and geometry obtained from
simulations in 3D ...... 42
Figure 15. Cluster distribution for h1t6 amphiphiles with different hydrophilic sizes.
Simulations are done in 2D...... 44
Figure 16. Cluster distribution and variation of the shape parameter η (right) for two different
chain lengths ...... 45
Figure 17. Snapshots of 2D amphiphile aggregates at T=0.45, X=0.03 for h1t6 with head sizes
two and three times, respectively, bigger than the tail beads...... 46
Figure 18. Cluster distribution as a function of the cluster size for two different head group sizes
σhh =2σtt and σhh =1.5σtt (inset) for different concentrations...... 47
Figure 19. A snapshot of the system ht14 with σ hh =1.5σ tt at X = 0.02...... 48
Figure 20. Time dependence of A(t)for different concentrations X for ht14 type amphiphiles. 49
Figure 21. The autocorrelation function A(t) for three different geometries of amphiphile
molecules...... 49
Figure 22. a) Specific heat and b) the characteristic time τ c as a function of amphiphilic
concentration for ht14type molecules. The lines serve as a guide...... 50
Figure 23. CMC graph for an amphiphile mixture of type-1 and type-2 amphiphiles at different
composition x1 ...... 57
x Figure 24. Simulation results and theory prediction for the CMC of the mixed system of
amphiphilic molecules of type-1 and type-2...... 58
Figure 25. Cluster Distribution for different mixture composition x1 for the mix of the type-1
and type-2 amphiphiles...... 60
Figure 26. Cluster Distribution graph for two amphiphile mixtures at the same composition
x = 0.5 of the (a) type-1 with type-4 and type-5; (b) type-1 with type-6 and type-7...... 61 1
Figure 27. Cluster Distribution for (a) pure ht16 (a) pure ht18 and (c) a 50:50 mixture of them.
The insert shows the ratio of the number of chains involved as a function of the cluster size.
...... 62
Figure 28. Spherical micelles obtained in MD simulation...... 63
Figure 29. Cluster Distribution for pure and mixed amphiphilic system with Poisson distribution
of the lengths for two different head sizes...... 66
Figure 30. Coarse-grained model of phospholipid molecule...... 68
Figure 31. A snapshot of a phospholipid bilayer obtained from the MD simulations at T=0.9 and
X=34%...... 69
Figure 32. (a) A snapshot of a phospholipid bilayer obtained from the MD simulations at T=0.9
and X=24%. (b) the same bilayer seen in perpendicular direction. A channel through the
membrane is clearly seen on the upper right corner of the picture...... 69
Figure 33. A polymer Phase Diagram as predicted by Flory-Huggins theory...... 75
Figure 34. Number of dimers t2 per box...... 82
Figure 35. The evolution of box sizes in a GEMC at low reduced temperature...... 83
Figure 36. Calculated densities of two phases for t2...... 84
xi Figure 37. Histogram of densities corresponding to Fig.36...... 84
Figure 38. Histogram of densities close to the critical temperature...... 86
Figure 39. Phase diagram for dimers from the simulations and Ref. [Veg03] ...... 86
Figure 40. Phase diagram for t4 from simulations ...... 87
Figure 41. Phase diagram for t8 from simulations and Ref. [Esc96]...... 88
Figure 42. Density “evolution” in the two subsystems of ht17amphiphile GEMC simulation at
reduced temperature of T=1.9 ε/kB ...... 91
Figure 43. Density “evolution” in the two subsystems of ht17amphiphile GEMC simulation at
reduced temperature of T=1.65 ε/kB ...... 91
Figure 44. Density “evolution” in the two subsystems of ht26amphiphile GEMC simulation at
reduced temperature of T=1.6 ε/kB ...... 92
Figure 45. A histogram of the densities corresponding to Fig.44...... 93
Figure 46. Calculated phase diagram for modeled amphiphilic system ht17...... 94
Figure 47. Comparison of the phase diagrams for two modeled amphiphilic system with
different structure: h1t7 and h2t6 ...... 95
Figure 48. A comparison of two phase diagrams for modeled amphiphilic system ht26 and
1.26ht16...... 96
Figure 49. Cluster distribution in an ht amphiphilic system...... 97 35
Figure 50. Single-phase presence in an h1t7 amphiphilic system...... 98
Figure 51. Single-phase presence in an ht26amphiphilic system...... 98
xii Figure 52. Evolution of the density of the liquid and gas phases at T=1.75 for 1.2h1t7 type of
amphiphiles. First 50 000 GEMC cycles are for equilibrating...... 99
Figure 53. Evolution of the density in the two boxes at T=1.8 for 1.2h1t7 type of amphiphiles.
First 50 000 GEMC cycles are for equilibrating...... 100
Figure 54. Phase diagrams of amphiphiles with different hydrophilic head size...... 101
xiii
LIST OF TABLES
Table 1. Examples of common amphiphiles (adapted from Ref.[Jon02])...... 4
Table 2. LJ parameters corresponding to the real CmEn surfactant...... 33
Table 3. LJ parameters for different bead interactions ...... 35
Table 4. Types of amphiphile molecules studied...... 56
Table 5. Characteristic of amphiphile molecules with Poisson distribution of the length ...... 64
Table 6. Bead-bead interactions...... 89
Table 7. Micellization versus phase separation. Amphiphile structures in the orange boxes form
aggregates while the other structures exhibit a phase separation. The green column shows
the amphiphilic systems simulated in this work. The asterisk indicates the systems studied
with lattice Grand canonical simulations [Pan02]...... 101
xiv LIST OF ACRONYMS AND ABBREVIATIONS
A dynamic variable
A thermodynamical average of the dynamic variable A
A(t) autocorrelation function
a0 optimal head group of an amphiphile
CV specific heat at constant volume
CM critical micelle concentration of a mixed amphiphilic system
Ci critical micelle concentration of pure i type amphiphilic molecules
Cm alkyl chain of m carbon atoms
En n oxyethylene units f activity coefficient
Ftin() force acting on the bead i at time tn
G Gibbs free energy
H Helmholtz free energy h Plank’s constant
htnm model of an amphiphile with n hydrophilic and m hydrophobic beads
H(,r N pN ) Hamiltonian of the system
K kinetic energy
kB Boltzmann’s constant
L length of the simulation box
xv Li characteristic length of a cluster
lc critical chain length lmax fully extended length of the hydrophobic chain
N number of particles; number of amphiphiles in an aggregate
Nt() the size of the aggregate where the tracer chain resides at time t
P pressure
QN(,V,T) canonical partition function
Ri ()t random force acting on the i-th bead at time t
rc cut-off distance for LJ potential
T temperature
−1 T reduced temperature kTB ε
Tc critical temperature
T (t) instantaneous temperature at time t of the MD simulations
∆t time step in MD simulations
U potential energy; internal energy
U LJ Lennard-Jones potential
U FENE FENE potential
V volume of the system; volume of the hydrophobic part of an amphiphile
WR(i ) distribution of the random force Ri acting on the i-th bead
W Rosenbluth factor
X1 concentration of the monomers in the system
xvi X N concentration of the amphiphiles residing in aggregates of size N
X N concentration of aggregates of size N N
X concentration of amphiphiles in the system
xi(tn) coordinate of the bead I at time tn