Co-non-solvency: Mean-field polymer theory does not describe polymer collapse transition in a mixture of two competing good solvents

Smart polymers are a modern class of polymeric materials that often exhibit unpredictable behavior in mixtures of solvents. One such phenomenon is co-non-solvency. Co-non-solvency occurs when two (perfectly) miscible and competing good solvents, for a given polymer, are mixed together. As a result, the same polymer collapses into a compact globule within intermediate mixing ratios. More interestingly, polymer collapses when the solvent quality remains good and even gets increasingly better by the addition of the better cosolvent. This is a puzzling phenomenon that is driven by strong local concentration fluctuations. Because of the discrete particle based nature of the interactions, Flory-Huggins type mean field arguments become unsuitable. In this work, we extend the analysis of the co-non-solvency effect presented earlier [Nature Communications 5, 4882 (2014)]. We explain why co-non-solvency is a generic phenomenon that can be understood by the thermodynamic treatment of the competitive displacement of (co)solvent components. This competition can result in a polymer collapse upon improvement of the solvent quality. Specific chemical details are not required to understand these complex conformational transitions. Therefore, a broad range of polymers are expected to exhibit similar reentrant coil-globule-coil transitions in competing good solvents

C−\mathcal {C}-IBI: Targeting cumulative coordination within an iterative protocol to derive coarse-grained models of (multi-component) complex fluids

We present a coarse-graining strategy that we test for aqueous mixtures. The method uses pair-wise cumulative coordination as a target function within an iterative Boltzmann inversion (IBI) like protocol. We name this method coordination iterative Boltzmann inversion ($\mathcal {C}-$IBI). While the underlying coarse-grained model is still structure based and, thus, preserves pair-wise solution structure, our method also reproduces solvation thermodynamics of binary and/or ternary mixtures. Additionally, we observe much faster convergence within $\mathcal {C}-$IBI compared to IBI. To validate the robustness, we apply $\mathcal {C}-$IBI to study test cases of solvation thermodynamics of aqueous urea and a triglycine solvation in aqueous urea

Thermal conductivity of bottle-brush polymers

Using molecular dynamics (MD) simulations of a generic model, we investigate heat propagation in bottle--brush polymers (BBP). An architecture is referred to as a BBP when a linear (backbone) polymer is grafted with the side chains of different length $N_{\rm s}$ and grafting density $\rho_{\rm g}$, which control the bending stiffness of a backbone. A BBP is of particular interest due to two competing mechanics: increased backbone stiffness, via $N_{\rm s}$ and $\rho_{\rm g}$, increases the thermal transport coefficient $\kappa$, while the presence of side chains provides additional pathways for heat leakage. We show how a delicate competition between these two effects controls $\kappa$. These results reveal that going from a weakly grafting ($\rho_{\rm g} < 1$) to a highly grafting ($\rho_{\rm g} \ge 1$) regime, $\kappa$ changes non--monotonically that is independent of $N_{\rm s}$. The effect of side chain mass on $\kappa$ and heat flow in the BBP melts are also discussed

Dynamic instability of microtubules: effect of catastrophe-suppressing drugs

Microtubules are stiff filamentary proteins that constitute an important component of the cytoskeleton of cells. These are known to exhibit a dynamic instability. A steadily growing microtubule can suddenly start depolymerizing very rapidly; this phenomenon is known as ``catastrophe''. However, often a shrinking microtubule is ``rescued'' and starts polymerizing again. Here we develope a model for the polymerization-depolymerization dynamics of microtubules in the presence of {\it catastrophe-suppressing drugs}. Solving the dynamical equations in the steady-state, we derive exact analytical expressions for the length distributions of the microtubules tipped with drug-bound tubulin subunits as well as those of the microtubules, in the growing and shrinking phases, tipped with drug-free pure tubulin subunits. We also examine the stability of the steady-state solutions.Comment: Minor corrections; final published versio

Why Do Elastin-Like Polypeptides Possibly Have Different Solvation Behaviors in Water-Ethanol and Water-Urea Mixtures?

The solvent quality determines the collapsed or the expanded state of a polymer. For example, a polymer dissolved in a poor solvent collapses, whereas in a good solvent it opens up. While this standard understanding is generally valid, there are examples when a polymer collapses even in a mixture of two good solvents. This phenomenon, commonly known as co-non-solvency, is usually associated with smart polymers. Moreover, recent experiments have shown that the elastin-like polypeptides (ELPs) show co-non-solvency behavior in aqueous-ethanol mixtures. In this study, we investigate the phase behavior of ELPs in aqueous binary mixtures using molecular dynamics simulations of all-atom and complementary explicit solvent generic models. The model is parameterized by mapping the solvation free energy obtained from the all-atom simulations onto the generic interaction parameters. For this purpose, we derive segment based generic parameters for four different peptides, namely proline (P), valine (V), glycine (G) and alanine (A). Here we compare the conformational behavior of two ELP sequences, namely VPGGG and VPGVG, in aqueous-ethanol and -urea mixtures. Consistent with recent experiments, we find that ELPs show co-non-solvency in aqueous-ethanol mixtures. Ethanol molecules have preferential binding with all ELP residues and thus driving the coil-to-globule transition. On the contrary, ELP conformations show weak variation in aqueous-urea mixtures. Our simulations suggest that the glycine residues dictate the overall behavior of ELPs in aqueous-urea, where urea molecules have a rather weak preferential binding with glycine, i.e., less than kT. While the validation of the latter findings will require more detailed experimental investigation, the results presented here may provide a new twist to the present understanding of cosolvent interactions with peptides and proteins.Comment: Accepted for publication in Macromolecule

Tuning the thermal conductivity of silicon nanowires by surface passivation

Using large scale molecular dynamics simulations, we study the thermal conductivity of bare and surface passivated silicon nanowires (SiNWs). For the smaller cross-sectional widths $w$, SiNWs become unstable because of the surface amorphousization and even evaporation of a certain fraction of Si atoms when $w \leq 2$ nm. Our results suggest that the surface (in--)stability is related to a large excess energy $\Delta$ of the surface Si atoms with respect to the bulk Si. This is because the surface Si atoms being less coordinated and having dangling bonds. As a first step of our study, we propose a practically relevant method that uses $\Delta$ as a guiding tool to passivate these dangling bonds and thus stabilizes SiNWs. The surface stabilization is achieved by passivation of Si atoms by hydrogen or oxygen. These passivated SiNWs are then used for the calculation of the thermal conductivity coefficient $\kappa$. While the expected trend of $\kappa \propto w$ is observed for all SiNWs, surface passivation provides an added flexibility of tuning $\kappa$ with the surface coverage concentration $c$ of passivated atoms. Analyzing the phonon band structures via spectral energy density, we discuss separate contributions from the surface and the core to $\kappa$. The effect of passivation on SiNW stiffness is also discussed