Prof. Dr.-Ing. H. Hasse Molecular Simulation Study of the ...
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
Molecular Simulation Study of the V l T i i f H d lVolume Transition of Hydrogels
Jonathan Walter1, Thorsten Merker1, Viktor Ermatchkov1, Jadran Vrabec2, Hans Hasse1,
1Laboratory of Engineering Thermodynamics,TU Kaiserslautern, Germany
2Thermodynamics and Energy Technology,University of Paderborn GermanyUniversity of Paderborn, Germany
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
H d lHydrogelsWhat is a Hydrogel?• Three dimensional hydrophilic polymer network• Most important property: Swelling in aqueous solutions
Examples for Applications:• Super absorber• Contact lenses
D d li t• Drug delivery systems• Sensors• Actors (e g micro valves)
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Actors (e.g. micro valves)• Biocatalysis
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
P l (N i l l id ) (PNiPAM)Poly(N-isopropylacrylamide) (PNiPAM)Cross Linking of PNiPAM
Single Chaing
• Hydrophilic monomers
Cross Linker
• Chemical• MBA
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
E i t l tExperimental setup
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
D f lli i l tiDegree of swelling in aqueous solutions
Influence of the TemperatureDegree of Swelling Influence of the TemperatureDegree of Swelling depends on:• MonomerMonomer• Co-monomer(s)• Cross linker amount• Solvent• pH-value
Salt concentration• Salt concentration• Temperature• … PNiPAM MBA water
exp. data, this work… PNiPAM, MBA, water
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
M l l M d li d Si l tiModeling:
Molecular Modeling and Simulationg
• Force fields from literature
PNiPAM water: SPC/E water: TIP4P
Gromos87 UA
Gromos96 53a6 UA
Simulation:
OPLS AA
• Molecular dynamics (MD) • NpT-ensemble
Program:• Gromacs 4.0.x
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
MD Si l ti H d l N t kMD-Simulation Hydrogel Network
PNiPAM ith MBA iPNiPAM with MBA in Water, 360 K• 240 PNiPAM monomers• 240 PNiPAM monomers• 15 monomers per chain
(6 mol% cross linker)• 60 000 water molecules• Force field: OPLS-AA +
SPC/ESPC/E• Computational time
1 week on 256 CPUs
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
MD Si l ti Si l Ch iMD-Simulation Single Chain
280 K
360 K
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PNiPAM, water, OPLS-AA + SPC/E, 75 monomers
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
P li i St d Ch i L thPreliminary Study: Chain Length
PNiPAM, water, 360 K
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
T t D d fTemperature Dependence ofSingle Chain Radius of Gyration
PNiPAM tPNiPAM, water, OPLS-AA + SPC/E
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
T t D d fTemperature Dependence ofSingle Chain Radius of Gyration
PNiPAM tPNiPAM, water, OPLS-AA + SPC/E
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
T t D d fTemperature Dependence of Single Chain Radius of Gyration
PNiPAM tPNiPAM, water, OPLS-AA + SPC/E
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
F Fi ld C i R ltForce Field Comparison - Results
PNiPAM water: SPC/E water: TIP4PGromos87 UA - -Gromos87 UA - -Gromos96 53a6 UA - +OPLS AA + +
Legend- Force field does not predict effect+ Force field predicts effecto ce e d p ed c s e ec
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
T t D d f th S lliTemperature Dependence of the Swelling of PNiPAM in Water
Simulation Single Chain Experiment Hydrogel
OPLS-AA + SPC/E PNiPAM, MBAOPLS AA SPC/E PNiPAM, MBA
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J. Walter, V. Ermatchkov, J.Vrabec, H. Hasse, Fluid Phase Equilibria, 296: 164-172 (2010)
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
S lli f PNiPAM i W t M th lSwelling of PNiPAM in Water-Methanol Mixtures
Experiment Hydrogel Simulation Single Chain298 K
Experiment Hydrogel Simulation Single Chain298 K
PNiPAM, MBA OPLS-AA + SPC/E 298 K
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
Summary S lli f h d l PNiPAM Swelling of hydrogels: PNiPAM Molecular modeling and simulation f Temperature dependence of swelling Hydrogel swelling simulations:
N k Networks Single chains
Qualitative predictions with force fields from the literature Qualitative predictions with force fields from the literature
Outlook Development of force fields for quantitative predictions
Outlook
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Laboratory of EngineeringThermodynamicsProf. Dr.-Ing. H. Hasse
Acknowledgements:
German Research Foundation forfinancial Support