Interactions between densely grafted molten polymer brushes:\\ Scaling theories versus molecular simulations

AbstractWe investigated the interplay between different mechanisms of the lateral and vertical segregation in the synthesized via “grafting from” approach symmetric A/B (where A and B are poly(styrene-co-2,3,4,5,6-pentafluorostyrene) and poly(methylmethacrylate), respectively) polymer brushes upon exposure to different solvents. We used X-ray photoemission electron spectroscopy and microscopy (X-PEEM), AFM, water contact angle measurements, and oxygen plasma etching to study morphology of the brushes. The ripple morphology after toluene (nonselective solvent) revealed elongated lamellar-like domains of A and B polymers alternating across the surface. The dimple-A morphology consisting of round clusters of the polymer A was observed after acetone (selective solvent for B). The top layer was enriched with the polymer B showing that the brush underwent both the lateral and vertical phase segregation. A qualitative agreement with predictions of SCF theory was found.

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CALIBRATION AND RANKING OF COARSE-GRAINED MODELS IN MOLECULAR SIMULATIONS USING BAYESIAN FORMALISM

International Journal for Uncertainty Quantification ◽

10.1615/int.j.uncertaintyquantification.2017013407 ◽

2017 ◽

Vol 7 (2) ◽

pp. 99-115 ◽

Cited By ~ 2

Author(s):

Hadi Meidani ◽

Justin B. Hooper ◽

Dmitry Bedrov ◽

Robert M. Kirby

Keyword(s):

Molecular Simulations ◽

Coarse Grained

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ESTIMATION OF MICROMECHANICAL NiAl SINTERING MODEL PARAMETERS FROM THE MOLECULAR SIMULATIONS

International Journal for Multiscale Computational Engineering ◽

10.1615/intjmultcompeng.2017020289 ◽

2017 ◽

Vol 15 (4) ◽

pp. 343-358 ◽

Cited By ~ 3

Author(s):

Marcin Maździarz ◽

Jerzy Rojek ◽

Szymon Nosewicz

Keyword(s):

Molecular Simulations ◽

Model Parameters

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Multi-Stimuli-Responsive Mesoporous Membranes and Effect of Molecular Architecture on Thermo- and pH-Responsive Behavior of the grafted Block Copolymer brushes

10.26434/chemrxiv.7037699 ◽

2019 ◽

Author(s):

Yanchun Tang ◽

Kohzo Ito ◽

Hideaki Yokoyama

Keyword(s):

Polymer Brushes ◽

Diblock Copolymers ◽

Neutron Reflectivity ◽

Molecular Architecture ◽

Stimuli Responsive ◽

Responsive Polymer ◽

The Matrix ◽

Stable Part ◽

Copolymer Brushes ◽

Mesoporous Membranes

In this study, we prepared ultrafiltration membranes with a decoupled responses of filtration property to temperature and pH. The membrane preparation method was developed based on our previous work. We utilized methanol-supercritical carbon dioxide (methanol-scCO<sub>2</sub>) selective swelling method to introduce nanopores to block copolymers containing poly(diethylene glycol) methyl ether methacrylate (PMEO<sub>2</sub>MA), poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and polystyrene (PS) blocks. Formation of the mesoporous barrier layer with PS being the mechanically stable part of the matrix was driven by selective swelling of the PMEO<sub>2</sub>MA-b-PDMAEMA domains. Due to the selective swelling of PMEO<sub>2</sub>MA or PDMAEMA domains to introduce pores, the interior of the pores are covered with PMEO<sub>2</sub>MA or PDMAEMA blocks after pore formation. The PMEO<sub>2</sub>MA-b-PDMAEMA polymer brushes are naturally attached on the pore walls and worked as functional gates. PMEO<sub>2</sub>MA is a non-toxic, neutral thermo-responsive polymer with LCST at 26 ᴼC. PDMAEMA is a typical weak polyelectrolyte with pK<sub>a</sub> value at 7.0-7.5 and also a thermo-responsive polymer revealed a LCST of 20-80 °C in aqueous solution. Therefore, these membranes were expected to have multi dimensions as function of the combination of temperature and pH. Moreover, to understand the detail of the temperature and pH depended conformation transitions of PMEO<sub>2</sub>MA-b-PDMAEMA brushes, those diblock copolymers were end-tethered on flat substrates and analyzed via neutron reflectivity (NR).

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Split the Charge Difference in Two! a Rule of Thumb for Adding Proper Amounts of Ions in MD Simulations

10.26434/chemrxiv.9783155.v2 ◽

2020 ◽

Author(s):

Matías R. Machado ◽

Sergio Pantano

Keyword(s):

Molecular Dynamics ◽

Ionic Strength ◽

Molecular Simulations ◽

Md Simulations ◽

Good Practices ◽

Rule Of Thumb ◽

Ionic Concentrations

<p> Despite the relevance of properly setting ionic concentrations in Molecular Dynamics (MD) simulations, methods or practical rules to set ionic strength are scarce and rarely documented. Based on a recently proposed thermodynamics method we provide an accurate rule of thumb to define the electrolytic content in simulation boxes. Extending the use of good practices in setting up MD systems is promptly needed to ensure reproducibility and consistency in molecular simulations.</p>

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On the Use of Quantum Thermal Bath in Unimolecular Fragmentation Simulations

10.26434/chemrxiv.8870594.v2 ◽

2019 ◽

Author(s):

Riccardo Spezia ◽

Hichem Dammak

Keyword(s):

Degrees Of Freedom ◽

Molecular Simulations ◽

Zero Point ◽

Thermal Bath ◽

Unimolecular Dissociation ◽

Point Energy ◽

Rotational Degrees Of Freedom ◽

The Difference ◽

Nuclear Effects

<div> <div> <div> <p>In the present work we have investigated the possibility of using the Quantum Thermal Bath (QTB) method in molecular simulations of unimolecular dissociation processes. Notably, QTB is aimed in introducing quantum nuclear effects with a com- putational time which is basically the same as in newtonian simulations. At this end we have considered the model fragmentation of CH4 for which an analytical function is present in the literature. Moreover, based on the same model a microcanonical algorithm which monitor zero-point energy of products, and eventually modifies tra- jectories, was recently proposed. We have thus compared classical and quantum rate constant with these different models. QTB seems to correctly reproduce some quantum features, in particular the difference between classical and quantum activation energies, making it a promising method to study unimolecular fragmentation of much complex systems with molecular simulations. The role of QTB thermostat on rotational degrees of freedom is also analyzed and discussed. </p> </div> </div> </div>

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