Morphologies of a spherical bimodal polyelectrolyte brush induced by polydispersity and solvent selectivity

It is commonly realized that polydispersity may significantly affect the surface modification properties of polymer brush systems. In light of this, we systematically study morphologies of bidisperse polyelectrolyte brush grafted onto a spherical nanocolloid in the presence of trivalent counterions using molecular dynamics simulations. Via varying polydispersity, grafting density, and solvent selectivity, the effects of electrostatic correlation and excluded volume are focused, and rich phase behaviors of binary mixed polyelectrolyte brush are predicted, including a variety of pinned-patch morphologies at low grafting density and micelle-like structures at high grafting density. To pinpoint the mechanism of surface structure formation, the shape factor of two species of polyelectrolyte chains and the pair correlation function between monomers from different polyelectrolyte ligands are analyzed carefully. Also, electrostatic correlations, manifested as the bridging through trivalent counterions, are examined by identifying four states of trivalent counterions. Our simulation results may be useful for designing smart stimuli-responsive materials based on mixed polyelectrolyte coated surfaces.     

Thermal and mechanical properties and micro-mechanism of SiO2/epoxy nanodielectrics

In addition to electrical insulation properties, the thermal properties of nanodielectrics, such as glass transition temperature, thermal expansion coefficients, thermal conductivity, and mechanical properties, including Young's modulus, bulk modulus, and shear modulus, are also very important. This paper describes the molecular dynamics simulations of epoxy resin doped with SiO₂ nanoparticles and with SiO₂ nanoparticles that have been surface grafted with hexamethyldisilazane (HMDS) at 10% and 20% grafting rates. The results show that surface grafting can improve certain thermal and mechanical properties of the system. Our analysis indicates that the improved thermal performance occurs because the formation of thermal chains becomes easier after the surface grafting treatment. The improved mechanical properties originate from two causes. First, doping with SiO₂ nanoparticles inhibits the degree of movement of molecular chains in the system. Second, the surface grafting treatment weakens the molecular repulsion between SiO₂ and epoxy resin, and the van der Waals excluded region becomes thinner. Thus, the compatibility between SiO₂ nanoparticles and polymers is improved by the grafting treatment. The analysis method and conclusions in this paper provide guidance and reference for the future studies of the thermal and mechanical properties of nanodielectrics.     

复杂网络上的意见动力学对谣言传播的影响

通过在SIR(susceptible-infected-recovered)模型中引入抑制者对谣言的辟谣机制研究了在线社交网络上的意见动力学对谣言传播的影响.在这一模型中,节点可以与自身的邻居组成1个群,传播者可以通过该群传播信息,抑制者也可以在此群中对信息发表意见进行辟谣.辟谣机制在降低未知者对于谣言的接受概率的同时也可以促使传播者向抑制者转变.本文采用ER(Erd?s-Rényi)随机网络、无标度网络以及真实的社交网络研究了抑制者的沉默概率对于谣言传播范围的影响.首先发现,谣言传播的过程以传播者的峰值为界可以分为两个阶段,即谣言自由传播的前期以及抑制者和传播者互相制衡的后期;其次,谣言的传播会随着抑制者的沉默概率的增大而突然暴发.在谣言暴发阈值之下,沉默概率的增大不会导致谣言传播范围显著增大,这是由于未知者在感知到谣言并转变为传播者后又迅速转变为抑制者;而当沉默概率达到谣言暴发阈值时,抑制者将不能控制传播者对谣言的传播从而导致抑制者的降低和谣言的暴发;最后,无标度上的谣言自由传播的前期阶段比随机网络持续的时间更短,从而使无标度上的谣言更难以暴发.本文的模型综合考虑了意见动力学和谣言传播的相互作用,更加真实地模拟了真实世界社交网络中的谣言传播过程.为谣言传播的控制和干预提供了一些有用的思路和见解.     

Quantum reaction dynamics of C(1D) + HD → CH(CD) + D(H) on the ground state potential energy surface

We present accurate quantum dynamic calculations of the reaction C(¹D) + HD on the latest version of the potential energy surface [Zhang et al., J. Chem. Phys. 140, 234301 (2014)]. Using a Chebyshev real wave packet method with full Coriolis coupling, we obtain the initial state‐specified ( ) reaction probabilities, integral cross sections, and rate constants. The resulting probabilities display oscillatory structures due to numerous long‐lived resonances supported by the deep potential well. The calculated rate constants and CD/CH product branching ratio at room temperature are in reasonably good agreement with the experimental measurements.     

Temperature‐shuffled parallel cascade selection molecular dynamics accelerates the structural transitions of proteins

Parallel cascade selection molecular dynamics (PaCS‐MD) is an enhanced conformational sampling method for searching structural transition pathways from a given reactant to a product. Recently, a temperature‐aided PaCS‐MD (Vinod et al., Eur. Biophys. J. 2016, 45, 463) has been proposed as its extension, in which the temperatures were introduced as additional parameters in conformational resampling, whereas the temperature is fixed in the original PaCS‐MD. In the present study, temperature‐shuffled PaCS‐MD is proposed as a further extension of temperature‐aided PaCS‐MD in which the temperatures are shuffled among different replicas at the beginning of each cycle of conformational resampling. To evaluate their conformational sampling efficiencies, the original, temperature‐aided, and temperature‐shuffled PaCS‐MD were applied to a protein‐folding process of Trp‐cage, and their minimum computational costs to identify the native state were addressed. Through the evaluation, it was confirmed that temperature‐shuffled PaCS‐MD remarkably accelerated the protein‐folding process of Trp‐cage compared with the other methods. © 2017 Wiley Periodicals, Inc.     

Analysis of droplet behavior in a de-oiling hydrocyclone

A mechanical separation process in a de-oiling hydrocyclone is described in which disperse oil droplets are separated from a continuous water phase. This separation process is influenced by droplet breakage and coalescence. Based on experimental data and simulation results in a stirred tank, a modified breakage model, which can be applied to droplet breakage in the de-oiling hydrocyclone, is developed. Then, a simulation model is developed coupling the numerical solution of the flow field in the hydrocyclone based on computational fluid dynamics (CFD) with population balances. The homogenous discrete method and the inhomogeneous discrete method are applied for solving the population balance model (PBM). The investigations show that the numerical results obtained by the simulation model coupled with the modified PBM using the inhomogeneous discrete method are in good accordance with experimental data under a high flow rate. According to this simulation model, the effect of three different inlet designs on the separation efficiency of the de-oiling hydrocyclone has been discussed. The results indicate that the separation efficiency of the de-oiling hydrocyclone can be improved with an appropriate inlet design.     

Structural dissimilarity sampling with dynamically self‐guiding selection

Structural dissimilarity sampling (SDS) has been proposed as an enhanced conformational sampling method for reproducing the structural transitions of a given protein. SDS consists of cycles of two steps: (1) Selections of initial structures with structural dissimilarities by referring to a measure. (2) Conformational resampling by restarting short‐time molecular dynamics (MD) simulations from the initial structures. In the present study, an efficient measure is proposed as a dynamically self‐guiding selection to accelerate the structural transitions from a reactant state to a product state as an extension to the original SDS. In the extended SDS, the inner product (IP ) between the reactant and the snapshots generated by short‐time MD simulations are evaluated and ranked according to the IP s at every cycle. Then, the snapshots with low IP s are selected as initial structures for the short‐time MD simulations. This scheme enables one to choose dissimilar and distant initial structures from the reactant, and thus the initial structures dynamically head towards the product, promoting structural transitions from the reactant. To confirm the conformational sampling efficiency, the extended SDS was applied to maltodextrin binding protein (MBP), and we successfully reproduced the structural transition from the open to closed states with submicrosecond‐order simulation times. However, a conventional long‐time MD simulation failed to reproduce the same structural transition. We also compared the performance with that obtained by the ordinary SDS and other sampling techniques that have been developed by us to characterize the possible utility of the extended SDS for actual applications. © 2017 Wiley Periodicals, Inc.