Amphiphilic gradient copolymers of 2‐methyl‐ and 2‐phenyl‐2‐oxazoline: self‐organization in aqueous media and drug encapsulation

Gradient (or pseudo‐diblock) copolymers were synthesized from 2‐methyl‐2‐oxazoline and 2‐phenyl‐2‐oxazoline monomer mixtures via cationic polymerization. The self‐assembling properties of these biocompatible gradient copolymers in aqueous solutions were investigated, in an effort to use the produced nanostructures as nanocarriers for hydrophobic pharmaceutical molecules. Dynamic and static light scattering as well as AFM measurements showed that the copolymers assemble in different supramolecular nanostructures (spherical micelles, vesicles and aggregates) depending on copolymer composition. Fluorescence spectroscopy studies revealed a microenvironment of unusually high polarity inside the nanostructures. This observation is related partly to the gradient structure of the copolymers. The polymeric nanostructures were stable with time. Their structural properties in different aqueous media—PBS buffer, RPMI solution—simulating conditions used in pharmacological/medicinal studies, have been also investigated and a composition dependent behavior was observed. Finally, the hydrophobic drug indomethacin was successfully encapsulated within the gradient copolymer nanostructures and the properties of the mixed aggregates were studied in respect to the initial copolymer assemblies. The produced aggregates encapsulating indomethacin showed a significant increase of their mass and size compared to original purely polymeric ones. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Two optimal Dai–Liao conjugate gradient methods

Two adaptive choices for the parameter of Dai–Liao conjugate gradient (CG) method are suggested. One of which is obtained by minimizing the distance between search directions of Dai–Liao method and a three-term CG method proposed by Zhang et al. and the other one is obtained by minimizing Frobenius condition number of the search direction matrix. Global convergence analyses are made briefly. Numerical results are reported; they demonstrate effectiveness of the suggested adaptive choices.     

Improvement of moving particle semi‐implicit method for simulation of progressive water waves

Precise simulation of the propagation of surface water waves, especially when involving breaking wave, takes a significant place in computational fluid dynamics. Because of the strong nonlinear properties, the treatment of large surface deformation of free surface flow has always been a challenging work in the development of numerical models. In this paper, the moving particle semi‐implicit (MPS) method, an entirely Lagrangian method, is modified to simulate wave motion in a 2‐D numerical wave flume preferably. In terms of consecutive pressure distribution, a new and simple free surface detection criterion is proposed to enhance the free surface recognition in the MPS method. In addition, a revised gradient model is deduced to diminish the effect of nonuniform particle distribution and then to reduce the numerical wave attenuation occurring in the original MPS model. The applicability and stability of the improved MPS method are firstly demonstrated by the calculation of hydrostatic problem. It is revealed that these modifications are effective to suppress the pressure oscillation, weaken the local particle clustering, and boost the stability of numerical algorithm. It is then applied to investigate the propagation of progressive waves on a flat bed and the wave breaking on a mild slope. Comparisons with the analytical solutions and experimental results indicate that the improved MPS model can give better results about the profiles and heights of surface waves in contrast with the previous MPS models. Copyright © 2017 John Wiley & Sons, Ltd.     

Preparation and characterization of novel organic chelating resin and its application in recovery of Zn(II) from aqueous solutions

An organic polymeric resin was synthesized by anchoring p ‐aminobenzoic acid onto macroporous chloromethylated polystyrene beads, and was used for Zn(II) removal from aqueous solutions. The resin exhibited an initially rapid adsorption property for Zn(II) with equilibrium time of 10 h and the maximum adsorption capability approached 184.5 mg g⁻¹. Optimum pH was 4.5. The mechanism of adsorption was investigated using kinetic, isotherm and thermodynamic models. The adsorption kinetic data were described well by a pseudo second‐order model with R ² of 0.997. There was a negative ΔG (−17.98 kJ mol⁻¹) and positive ΔH (13.58 kJ mol⁻¹). HCl solution (1.0 mol l⁻¹) could achieve an elution rate of 100%. The experimental data were well fitted by the Thomas model with R ² of 0.9826. Copyright © 2016 John Wiley & Sons, Ltd.     

Implicit–explicit schemes for nonlinear nonlocal equations with a gradient flow structure in one space dimension

Nonlinear convection–diffusion equations with nonlocal flux and possibly degenerate diffusion arise in various contexts including interacting gases, porous media flows, and collective behavior in biology. Their numerical solution by an explicit finite difference method is costly due to the necessity of discretizing a local spatial convolution for each evaluation of the convective numerical flux, and due to the disadvantageous Courant–Friedrichs–Lewy (CFL) condition incurred by the diffusion term. Based on explicit schemes for such models devised in the study of Carrillo et al. a second‐order implicit–explicit Runge–Kutta (IMEX‐RK) method can be formulated. This method avoids the restrictive time step limitation of explicit schemes since the diffusion term is handled implicitly, but entails the necessity to solve nonlinear algebraic systems in every time step. It is proven that this method is well defined. Numerical experiments illustrate that for fine discretizations it is more efficient in terms of reduction of error versus central processing unit time than the original explicit method. One of the test cases is given by a strongly degenerate parabolic, nonlocal equation modeling aggregation in study of Betancourt et al. This model can be transformed to a local partial differential equation that can be solved numerically easily to generate a reference solution for the IMEX‐RK method, but is limited to one space dimension.     

Statistics of reaction progress variable and mixture fraction gradients of a pulverised coal jet flame using Direct Numerical Simulation data

The statistical behaviour of the variances, covariance and gradients of the reaction progress variable (c), and the mixture fraction (ξ) have been analysed in a pulverised coal jet flame using a three-dimensional carrier phase direct numerical simulation (DNS) dataset. It has been observed that the Favre-probability density functions (PDFs) of c and ξ can be parametrised by the standard β function. Furthermore, the log-normal distribution has been found to accurately represent |?c| and |?ξ|. It is also found that ?c and ?ξ remain aligned throughout the flame brush. Finally the joint PDF of |?c| and |?ξ| has been compared with the product of the PDF of |?c| and PDF of |?ξ| extracted from carrier phase DNS, and it has been found that |?c| and |?ξ| are not statistically independent in the case investigated.The bivariate log-normal distributions with and without correlation have also been considered, and the former is found to be in better agreement with the carrier phase DNS data.     

“Grafting through” polymerization involving surface-bound monomers

“Grafting through” polymerization represents copolymerization of free monomers in solution and polymerizable units bound to a substrate. Free polymer chains are formed initially in solution and can incorporate the surface-bound monomers, and thereby, get covalently bonded to the surface during the polymerization process. As more growing chains attach to the surface-bound monomers, an immobilized polymer layer is formed on the surface. We use a combination of computer simulation and experiments to comprehend this process for monomers bound to a flat impenetrable substrate. We concentrate specifically on addressing the effect of spatial density of the surface-bound monomers on the formation of the surface-attached polymers. We employ a lattice-based Monte Carlo model utilizing the bond fluctuation model scheme to provide molecular-level insight into the grafting process. For experimental validation, we create gradients of density of bound methacrylate units on flat silicon wafers using organosilane chemistry and carry out “grafting through” free radical polymerization initiated in bulk. We report that the proximity of the surface-bound polymerizable units promotes the “grafting through” process but prevents more free growing chains to “graft through'' the polymerizable units. The “grafting through” process is self-limiting in nature and does not affect the overall density of the surface-bound polymer layer, except in case of the highest theoretical packing density of surface-bound monomers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 263–274     

A computational method for geometric optimization of enhanced heat transfer devices based upon entropy generation minimization

A computational fluid dynamics‐based optimization methodology is developed, appropriate for the geometric optimization of enhanced heat transfer devices based upon the principle of entropy generation minimization, in which the objective function is evaluated from a flow field obtained by computational simulation. A quasi‐Newton optimization procedure is employed, with computation of the objective function gradients based upon a finite difference approach. The optimization procedure is developed to be general with regard to the choice of objective function, the details of the problem under consideration, and the computational methodology employed in solving the fluid flow and heat transfer problems. A novel implementation of a Taylor series‐based procedure for the fast solution of nearby problems is presented, which is found to greatly benefit the efficiency of the present methodology. Finally, a numerical experiment is presented, illustrating the use of the present method in the geometric optimization of a practical enhanced heat transfer device on the basis of the criterion of entropy generation minimization. The optimization of the fin spacing of a simple plate fin heat sink is considered, and a comparison of the computational results with results obtained by analytical optimization based upon empirical friction factor and Nusselt number correlations is given. Copyright © 2012 John Wiley & Sons, Ltd.     

Strain gradient plasticity analysis of elasto-plastic contact between rough surfaces

From a microscopic point of view, the real contact area between two rough surfaces is the sum of the areas of contact between facing asperities. Since the real contact area is a fraction of the nominal contact area, the real contact pressure is much higher than the nominal contact pressure, which results in plastic deformation of asperities. As plasticity is size dependent at size scales below tens of micrometers, with the general trend of smaller being harder, macroscopic plasticity is not suitable to describe plastic deformation of small asperities and thus fails to capture the real contact area and pressure accurately. Here we adopt conventional mechanism-based strain gradient plasticity (CMSGP) to analyze the contact between a rigid platen and an elasto-plastic solid with a rough surface. Flattening of a single sinusoidal asperity is analyzed first to highlight the difference between CMSGP and J₂ isotropic plasticity. For the rough surface contact, besides CMSGP, pure elastic and J₂ isotropic plasticity analysis is also carried out for comparison. In all cases, the contact area A rises linearly with the applied load, but with a different slope which implies that the mean contact pressures are different. CMSGP produces qualitative changes in the distributions of local contact pressures compared with pure elastic and J₂ isotropic plasticity analysis, furthermore, bounded by the two.     

Experiment on relationship between the magnetic gradient of low-carbon steel and its stress

In geomagnetic field, a series of tensile experiments on the low-carbon steel sticks were carried out. A special homemade detector was used to measure the magnetic gradient on the material surface. The results showed that the relationship between the magnetic gradient and the stress varied with different conditions of measurement. There was no obvious correlation between the magnetic gradient and the tensile stress if the sample remained on the material test machine. If the sample was taken off from the machine, the measured magnetic gradient was linear with the prior maximum stress. In Nanjing, PR China, a place of 32°N latitude, the slope of the linear relationship was about 67 (uT/m)/MPa. This offered a new method of non-destructive stress testing by measuring the magnetic gradient on the ferromagnetic component surface. The prior maximum applied stress of the sample could be tested by measuring the present surface magnetic gradient. Actually this phenomenon was the metal magnetic memory (MMM). The magnetic gradient near the stress concentration zone of the sample, the necking point, was much larger than other area. Thus, the hidden damage in the ferromagnetic component could be detected early by measuring the magnetic gradient distribution on its surface. In addition, the magnetic memory signal gradually weakened as the sample was taken off and laid aside. Therefore, it was effective for a given period of time to detect the stress or stress concentration based on the MMM testing.