Seeded Polymerization of an Amide-Functionalized Diketopyrrolopyrrole Dye in Aqueous Media

The self-assembly of an amide-functionalized dithienyldiketopyrrolopyrrole (DPP) dye in aqueous media was achieved through seed-initiated supramolecular polymerization. Temperature- and time-dependent studies showed that the spontaneous polymerization of the DPP derivative was temporally delayed upon cooling the monomer solution in a methanol/water mixture. Theoretical calculations revealed that an amide-functionalized DPP derivative adopts an energetically favorable folded conformation in the presence of water molecules due to hydration. This conformational change is most likely responsible for the trapping of monomers in the initial stage of the cooperative supramolecular polymerization in aqueous media. However, the monomeric species can selectively interact with externally added fragmented aggregates as seeds through concerted π-stacking and hydrogen-bonding interactions. Consequently, the time course of the supramolecular polymerization and the morphology of the aggregated state can be controlled, and one-dimensional fibers that exhibit a J-aggregate-like bathochromically shifted absorption band can be obtained.     

The electronic properties and electron transport of sawtooth penta-graphene nanoribbon under uniaxial strain: ab-initio study

ABSTRACT

The electronic properties and electron transport of a sawtooth penta-graphene nanoribbon (SSPGNR) under uniaxial strains are theoretically studied by density-functional theory (DFT) in combination with the non-equilibrium Green's function formalism. We investigated the electronic structures and the current–voltage (I–V) characteristics of the SSPGNRs under a sequence of uniaxial strains in range from 10% compression to 10% stretch. In this strained range, carbon atoms still keep a pentagon network, but with the changing bond lengths. The C–C bond lengths change almost linearly with the tolerable strain. The value of the band gap of SSPGNRs can be depicted as a parabola under uniaxial strain. Our calculations show that the current is monotonous increase with compressive strain at the same applied bias voltage. In case of tensile strain, the variable rule of the current is different that it increases at first and decrease later. The fundamental physical properties (band structure, I–V characteristic) of SSPGNRs seem to be more sensitive to compressive strain than the stretch strain. The current intensity of the compressive-SSPGNR is by 2 orders of magnitude compared to that of the tensile-SSPGNR at the same strain in range from 6% to 10%. The results obtained from our calculations are beneficial to practical applications of these strained structures in SSPGNRs-based electromechanical devices.     

Density functional theory study on sensing properties of g-C3N4 sheet to atmospheric gasses: Role of zigzag and armchair edges

The ability of the polymer-based graphitic carbon nitride (g-C₃N₄) as a gas sensor toward NO, NO₂, CO, CO₂, SO₂, SO₃, and O₂ gasses is assessed using density functional theory (DFT) calculations in terms of energetic and electronic transport characteristics. In particular, this study is aimed to explore the role of zigzag and armchair edges of the g-C₃N₄ sheet on sensing performances. The electronic properties of adsorption systems, such as Bader charge analysis, band gaps, work function, and density of states (DOS), are used to understand the interaction between the adsorbed gas molecules and the g-C₃N₄ sheet. Our calculated results indicate that SOx (SO₃ and SO₂) gasses have higher adsorption energies on the g-C₃N₄ sheet than other gasses. Furthermore, the transport properties, such as current–voltage (I-V) and resistance-voltage (R-V) curves along the zigzag and armchair directions are calculated using the non-equilibrium Green's function (NEGF) method to understand the performance of the g-C₃N₄ sheet as a prominent conductive/resistive sensor. The I-V/R-V results indicate that the zigzag g-C₃N₄ sheet has excellent sensing ability toward SOx gasses at low applied voltages. However, the presence of H₂O degrades the sensing performance of the armchair g-C₃N₄ sheet. Theoretical recovery time has also been calculated to evaluate the reusability of g-C₃N₄ sheet-based gas sensors. Our results reveal that the zigzag g-C₃N₄ sheet-based sensing device has a remarkably high sensitivity (>300%) and selectivity toward SOx gasses and has the potential to work in a complex environment.     

Magneto‐Adaptive Surfactants Showing Anti‐Curie Behavior and Tunable Surface Tension as Porogens for Mesoporous Particles with 12‐Fold Symmetry

Gaining external control over self‐organization is of vital importance for future smart materials. Surfactants are extremely valuable for the synthesis of diverse nanomaterials. Their self‐assembly is dictated by microphase separation, the hydrophobic effect, and head‐group repulsion. It is desirable to supplement surfactants with an added mode of long‐range and directional interaction. Magnetic forces are ideal, as they are not shielded in water. We report on surfactants with heads containing tightly bound transition‐metal centers. The magnetic moment of the head was varied systematically while keeping shape and charge constant. Changes in the magnetic moment of the head led to notable differences in surface tension, aggregate size, and contact angle, which could also be altered by an external magnetic field. The most astonishing result was that the use of magnetic surfactants as structure‐directing agents enabled the formation of porous solids with 12‐fold rotational symmetry.     

Towards a new partially integrated transport model for coarse grid and unsteady turbulent flow simulations

A new two-equation model is proposed for large eddy simulations (LESs) using coarse grids. The modeled transport equations are obtained from a direct transposition of well-known statistical models by using multiscale spectrum splitting given by the filtering operation applied to the Navier–Stokes equations. The model formulation is compatible with the two extreme limits that are on one hand a direct numerical simulation and on the other hand a full statistical modeling. The characteristic length scale of subgrid turbulence is no longer given by the spatial discretization step size, but by the use of a dissipation equation. The proposed method is applied to a transposition of the well-known k- statistical model, but the same method can be developed for more advanced closures. This approach is intended to contribute to non-zonal hybrid models that bridge Reynolds-averaged Navier–Stokes (RANS) and LES, by using a continuous change rather than matching zones. The main novelty in the model is the derivation of a new equation for LES that is formally consistent with RANS when the filter width is very large. This approach is dedicated to applications to non-equilibrium turbulence and coarse grid simulations. An illustration is made of large eddy simulations of turbulence submitted to periodic forcing. The model is also an alternative approach to hybrid models. PACS 47.27.Eq     

The contribution of internal degrees of freedom to the non-Newtonian rheology of model polymer fluids

We report non-equilibrium molecular dynamics simulations of rigid and non-rigid dumbbell fluids to determine the contribution of internal degrees of freedom to strain-rate-dependent shear viscosity. The model adopted for non-rigid molecules is a modification of the finitely extensible nonlinear elastic (FENE) dumbbell commonly used in kinetic theories of polymer solutions. We consider model polymer melts — that is, fluids composed of rigid dumbbells and of FENE dumbbells. We report the steady-state stress tensor and the transient stress response to an applied Couerte strain field for several strain rates. We find that the rheological properties of the rigid and FENE dumbbells are qualitatively and quantitatively similar. (The only exception to this is the zero strain rate shear viscosity.) Except at high strain rates, the average conformation of the FENE dumbbells in a Couette strain field is found to be very similar to that of FENE dumbbells in the absence of strain. The theological properties of the two dumbbell fluids are compared to those of a corresponding fluid of spheres which is shown to be the most non-Newtonian of the three fluids considered.Symbol Definition b dimensionless time constant relating vibration to other forms of motion - F force on center of mass of dumbbell - F _i force on bead i of dumbbell - F force between center of masses of dumbbells and - F _ij force between beads i and j - h vector connecting bead to center of mass of dumbbell - H dimensionless spring constant for dumbbells, in units of / ² - I moment of inertia of dumbbell - J general current induced by applied field - k _B Boltzmann's constant - L angular momentum - m mass of bead, (= m/2) - M mass of dumbbell, g - N number of dumbbells in simulation cell - P translational momentum of center of mass of dumbbell - P pressure tensor - P _xy xy component of pressure tensor - Q separation of beads in dumbbell - Q _eq equilibrium extension of FENE dumbbell and fixed extension of rigid dumbbell - Q ₀ maximum extension of dumbbell - r _ij vector connecting beads i and j - r position vector of center of mass dumbbell - R vector connecting centers of mass of two dumbbells - t time - t ^* dimensionless time, in units of m/ - T ^* dimensionless temperature, in units of /k - u potential energy - u velocity vector of flow field - u _x x component of velocity vector - V volume of simulation cell - X general applied field - strain rate, s^–1 - ^* dimensionless shear rate, in units of /m ² - general transport property - Lennard-Jones potential well depth - friction factor for Gaussian thermostat - shear viscosity, g/cms - ^* dimensionless shear viscosity, in units of m/ ² - ^* dimensionless number density, in units of ^–3 - Lennard-Jones separation of minimum energy - relaxation time of a fluid - angular velocity of dumbbell - orientation angle of dumbbell      

Forced convection of gaseous slip-flow in porous micro-channels under Local Thermal Non-Equilibrium conditions

Steady laminar forced convection gaseous slip-flow through parallel-plates micro-channel filled with porous medium under Local Thermal Non-Equilibrium (LTNE) condition is studied numerically. We consider incompressible Newtonian gas flow, which is hydrodynamically fully developed while thermally is developing. The Darcy–Brinkman–Forchheimer model embedded in the Navier–Stokes equations is used to model the flow within the porous domain. The present study reports the effect of several operating parameters on velocity slip and temperature jump at the wall. Mainly, the current study demonstrates the effects of: Knudsen number (Kn), Darcy number (Da), Forchheimer number (Γ), Peclet number (Pe), Biot number (Bi), and effective thermal conductivity ratio (K _R) on velocity slip and temperature jump at the wall. Results are given in terms of skin friction (C _f Re ^*) and Nusselt number (Nu). It is found that the skin friction: (1) increases as Darcy number increases; (2) decreases as Forchheimer number or Knudsen number increases. Heat transfer is found to (1) decreases as the Knudsen number, Forchheimer number, or K _R increases; (2) increases as the Peclet number, Darcy number, or Biot number increases.     

飞秒激光辐射纳米薄膜脱附的能量输运机理研究

从微观能量传输角度,对飞秒脉冲激光的辐射传热及其产生的金属薄膜吸附层分子脱附过程的能量输运机理进行了研究。以非平衡态传热和随机过程理论为基础,建立了描述吸附分子脱附过程的数学模型;并分别对单脉冲与双脉冲飞秒激光辐射下,金属Ru基体表面层的电子和声子的温度分布、吸附层分子CO的脱附概率分布进行了数值模拟。其结果与实验规律相符,为飞秒脉冲激光应用于微机电系统中杂质脱附提供了重要信息。     

Dynamic behaviour of a bubble near an elastic infinite interface

This paper presents a study to describe the behaviour of a non-equilibrium bubble in a fluid (Fluid 1) that is in contact with another fluid (Fluid 2). Fluid 2 is assumed to incorporate some elastic properties, which are modelled through a pressure term at the fluid–fluid interface. The Laplace equation is assumed to be valid in both fluids and the boundary integral method is employed to simulate the dynamics of the bubble and the fluid–fluid interface. Interesting characteristic phenomena concerning bubble oscillations and the deformation of the fluid–fluid interface are studied for a range of parameters (distance from the fluid–fluid interface, density ratios of the two fluids and elastic properties of Fluid 2). Some of the phenomena observed are jet formation in the bubble, bubble splitting, a ring bubble separating from the main bubble, mushroom-shaped bubbles and the dynamic elevation of the elastic interface. Most of these phenomena are only observed when Fluid 2 possesses some elastic properties (besides the usual formation of a high speed liquid jet). Comparisons with experimental observations confirm the validity of our simulations.     

大气压非平衡等离子体甲烷干法重整零维数值模拟

大气压非平衡等离子体由于其独特的非平衡特性,可为甲烷和二氧化碳稳定温室气体分子活化和重整提供非热平衡和活化环境.本文采用了零维等离子体化学反应动力学模型,考虑了详细的CH₄/CO₂等离子体化学反应集,重点研究了反应气体CH₄/CO₂摩尔分数(5%—95%)对大气压非平衡等离子体甲烷干法重整制合成气和重要含氧化合物的影响.首先,给出了进料气体不同体积比时电子密度和温度随时间的演化规律,结果表明初始甲烷摩尔分数的提高有利于获得较高的电子密度和电子温度.随后,讨论了主要自由基和离子数密度在不同的甲烷摩尔分数下随着时间的变化规律,并给出了反应气体的转化率、合成气体和重要含氧化合物的选择性.此外,还明确了合成气和含氧化合物主要生成和损耗的化学反应路径,发现甲基和羟基是合成含氧化合物的关键中间体.最后,归纳总结给出了主要等离子体粒子之间的总体等离子体化学反应流程图.