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In this study, dimensional, conformational and dynamic behaviors of a short-chain branched styrene/1-octene copolymer chain with different 1-octene percentages, i.e., 0, 2, 4 and 6%, in toluene are investigated at the temperature of 298.15 K via molecular dynamics simulation. The chain dimensions and flexibility in the solvent are evaluated by calculating the radius of gyration (R g ), end-to-end distance (0 >), surface area (A ch ), and volume (V ch ) of the copolymer chain. The mean square displacement (MSD) and diffusivity coefficient for each copolymer chain are measured to determine its dynamic behavior and mobility in aromatic media. To consider the effect of increasing the 1-octene co-monomer percentage on the copolymer chain affinity to the solvent molecules, the interaction energy (E int ) and Flory-Huggins (FH) interaction parameter are calculated for each equilibrated solution model. The simulation results indicate that the co-monomer level increment in the copolymer structure reduces the chain R g amount and its interaction with the solvent. The 0 > of the chain increases up to 4% co-monomer content, while further co-monomer content decreases the 0 > value. Additionally, the viscosity of the equilibrated dilute solutions is calculated via non-equilibrium molecular dynamics simulation (NEMD). Moreover, the steric hindrance of the copolymers and the solvent molecules capturing in the dilute solution is determined via radial distribution function (RDF) analysis. Helmholtz free energy and the system entropy changes are calculated to evaluate the tendency of the copolymer to the solvent molecules and its dilute solution irregularity, respectively. Graphical abstract The figure shows the variations trend of the poly(styrene-co-1-octene) chain dimensions in toluene aromatic solvent by increasing the 1-octene content (x), after the equilibration state. Red and blue colors represent the carbon atoms of the copolymer chain backbone and 1-octene side chains, respectively. The styrene rings and the hydrogen atoms of the chains were removed for better view.

The self-assembly behaviour of dual-responsive block copolymers and their ability to solubilize the anticancer drug doxorubicin (DOX) has been investigated using all-atom molecular dynamics (MD) simulations, MARTINI coarse-grained (CG) force field simulation and Scheutjens-Fleer self-consistent field (SCF) computations. These diblock copolymers, composed of poly{γ-2-[2-(2-methoxyethoxy)ethoxy]ethoxy-ε-caprolactone} (PMEEECL) and poly(β-amino ester) (PAE) are dual-responsive: the PMEEECL block is thermoresponsive (becomes insoluble above a certain temperature), while the PAE block is pH-responsive (becomes soluble below a certain pH). Three MEEECL 20 -AE M compositions with M = 5, 10, and 15, have been studied. All-atom MD simulations have been performed to calculate the coil-to-globule transition temperature ( T cg ) of these copolymers and finding appropriate CG mapping for both PMEEECL-PAE and DOX. The output of the MARTINI CG simulations is in agreement with SCF predictions. The results show that DOX is solubilized with high efficiency (75-80%) at different concentrations inside the PMEEECL-PAE micelles, although, interestingly, the loading efficiency is reduced by increasing the drug concentration. The non-bonded interaction energy and the RDF between DOX and water beads confirm this result. Finally, MD simulations and SCF computations reveal that the responsive behaviour of PMEEECL-PAE self-assembled structures take place at temperature and pH ranges appropriate for drug delivery., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Molecular characteristics of an atactic polystyrene (aPS) chain with different lengths in a theta solvent, cyclohexane at 307.65 K, were studied via molecular dynamics (MD) simulation. The interaction energy of the aPS dilute solution models and Flory-Huggins (FH) interaction parameter were calculated to investigate the effect of the chain molecular weight on its compatibility with the solvent molecules. The simulation results illustrated that increasing the chain length increased the interactions between the chain and the solvent molecules. The chain dimensions via calculating the radius of gyration (R g ) and end-to-end distance, 0 >, were measured. Mean square displacement (MSD) and diffusivity coefficient of the chains were calculated to determine their dynamic behavior. The results exhibited that two factors of the chain movability and size were important for the diffusion in oligomeric state. Additionally, viscosity of the resultant dilute solutions was calculated via nonequilibrium molecular dynamics simulation (NEMD). Moreover, the steric hindrance of the chains was determined by radial distribution function (RDF) analysis. The calculated characteristics of the chain and solution viscosity results showed a good agreement with experimental published works. Measurement of the potential field of cyclohexane-cyclohexane and aPS-cyclohexane pairs was also based on their potential field via quantum chemical calculations to determine the special orientation of the solvent molecules to each other and to the polymer segments, respectively. Graphical abstract (a) The equilibrated dilute solution model of polystyrene in cyclohexane at theta temperature (the red and yellow balls represent carbon and hydrogen atoms, respectively. The cyclohexane molecules are illustrated in line style in the box), (b) the electrostatic potential field around an optimized structure containing two cyclohexane molecules, and (c) around the sole cyclohexane molecule and polystyrene with two repeating units (carbon and hydrogen atoms are represented in green and yellow, respectively).

In this study, interfacial adhesion between functionalized polyethylene (PE) surfaces and graphene were examined using molecular simulation. Various functional groups including amino, carboxy, hydroxy, cyano, isocyanato, oxo, and ethylamino were used to cover the PE surface with surface densities of 0.48, 1.30, and 4.84 groups per nm(2). The interfacial adhesion between the modified PE surfaces and the graphene was quantified via calculation of work of separation (Wsep), the amount of the required work to separate two surfaces without occurring any relaxation and diffusion phenomena. Insertion of the functional groups on the PE surface decreased the amount of Wsep, except for the oxo, amino, and higher densities of the carboxy groups. Increasing the surface group density enhanced the adhesion due to decreasing the surface atomic roughness and increasing the atomic density at the interface. In addition, the effect of surface group rearrangement was investigated via calculation of the work of adhesion (Wadh) while sufficient time had been devoted to relax the interface. The surface reorganization during the relaxation process significantly enhanced adhesion due to eliminating the surface roughness and increasing the surface atomic density.