Tailoring Pore Structure and Morphologies in Covalent Organic Frameworks for Xe/Kr Capture and Separation

As a rising star among porous solid materials, covalent organic frameworks(COFs) with excellent properties including but not limit to facilely controllable structure, high porosity, and multi-chemical functionality represent significant potential for efficient ¹²⁷Xe/⁸⁵Kr capture and separation. In this study, through tuning the length of the organic ligands, two-dimensional(2D) COF mate-rials with identical connection group but different pore properties, denoted as ATFG-COF and TpPa-COF with AA-stacking model and TpBD-COF with AB-stacking model were synthesized and tested for Kr and Xe adsorption for the first time. Adsorption measurements indicate that the narrower pore apertures and higher porosity are conducive for COF materials to capture Xe and Kr. Furthermore, the Henry's constant, isosteric heat of adsorption(Q_st), and ideal adsorbed solution theory(IAST) selectivity of ATFG-COF, the pore size of which is closest to the kinetic diameter of the Xe atom(0.41 nm) among 2D COF materials, were carried out based on the single component sorption isotherms. The results illustrate that the high isosteric heat values of Xe/Kr adsorption on ATFG-COF are 25 and 16 kJ/mol at room temperature, respectively. Henry's law predicts that the selectivity factor of Xe to Kr is 6.07, consistent with the adsorption selectivity(ca. 6) calculated based on the IAST.     

基于悬滴法的纳米燃油表面张力测量与分析

以柴油为基液、溴化十六烷三甲基铵(Cetyltrimethyl Ammonium Bromide,CTAB)为助溶剂,通过两步法配制CNT(Carbon Nanotubc)、CeO₂及Co₃O₄纳米燃油。采用悬滴法测量柴油与纳米燃油的表面张力,探究纳米物质种类、粒径、质量分数及温度对纳米燃油表面张力的影响。研究发现,在纳米燃油液滴气液界面层内,纳米粒子与柴油分子之间的吸引力使液固分子体系总体的内聚力增强,因而表面张力增大;纳米燃油的表面张力随着粒子质量分数增加而增强,但随着温度升高而线性下降。大粒径的纳米粒子表面电荷密度降低,对表面电子束缚减小,电子游离所产生的与柴油分子之间的极化静电相吸作用更强,使液粒之间的范德华力增强,表面张力增大。在相同质量分数的条件下,非金属CNT的密度较小,纳米燃油中的粒子数目较多,此外其得电子能力更强,极易使周围柴油分子极化形成静电吸引,液粒间范德华力增强,因此CNT纳米燃油的表面张力最大;同为金属氧化物,Co₃O₄的分子量大于CeO_2<...     

Solution property preserving reconstruction for finite volume scheme: a boundary variation diminishing+multidimensional optimal order detection framework

The purpose of this work is to build a general framework to reconstruct the underlying fields within a finite volume (FV) scheme solving a hyperbolic system of PDEs (Partial Differential Equations). In an FV context, the data are piecewise constants per computational cell and the physical fields are reconstructed taking into account neighbor cell values. These reconstructions are further used to evaluate the physical states usually used to feed a Riemann solver which computes the associated numerical fluxes. The physical field reconstructions must obey some properties linked to the system of PDEs such as the positivity, but also some numerically based ones, like an essentially nonoscillatory behavior. Moreover, the reconstructions should be highly accurate for smooth flows and robust/stable for discontinuous solutions. To ensure a solution property preserving reconstruction, we introduce a methodology to blend high-/low-order polynomials and hyperbolic tangent reconstructions. A boundary variation diminishing algorithm is employed to select the best reconstruction in each cell. An a posteriori MOOD detection procedure is employed to ensure the positivity by recomputing the rare problematic cells using a robust first-order FV scheme. We illustrate the performance of the proposed scheme via the numerical simulations for some benchmark tests which involve vacuum or near vacuum states, strong discontinuities, and also smooth flows. The proposed scheme maintains high accuracy on smooth profile, preserves the positivity and can eliminate the oscillations in the vicinity of discontinuities while maintaining sharper discontinuity with superior solution quality compared to classical highly accurate FV schemes.     

A grid-based algorithm in conjunction with a gaussian-based model of atoms for describing molecular geometry

A novel grid-based method is presented, which in conjunction with a smooth Gaussian-based model of atoms, is used to compute molecular volume (MV) and surface area (MSA). The MV and MSA are essential for computing nonpolar component of free energies. The objective of our grid-based approach is to identify solute atom pairs that share overlapping volumes in space. Once completed, this information is used to construct a rooted tree using depth-first method to yield the final volume and SA by using the formulations of the Gaussian model described by Grant and Pickup (J. Phys Chem, 1995, 99 , 3503). The method is designed to function uninterruptedly with the grid-based finite-difference method implemented in Delphi, a popular and open-source package used for solving the Poisson–Boltzmann equation (PBE). We demonstrate the time efficacy of the method while also validating its performance in terms of the effect of grid-resolution, positioning of the solute within the grid-map and accuracy in identification of overlapping atom pairs. We also explore and discuss different aspects of the Gaussian model with key emphasis on its physical meaningfulness. This development and its future release with the Delphi package are intended to provide a physically meaningful, fast, robust and comprehensive tool for MM/PBSA based free energy calculations. © 2019 Wiley Periodicals, Inc.     

增加一种反应物浓度对反应物转化率影响的研究

通过建构模型探讨了多反应物平衡体系中增加反应物浓度对转化率的影响,并用曲线进行表征。模型表明,转化率的变化与反应物和生成物化学计量数相对大小关联紧密。文中结论澄清了某些错误认知,对中学化学教学有一定的指导意义。     

Positron annihilation and electrical studies on the influence of loading magnesia nanoribbons on PVA-PVP blend

This work aims to study the effect of loading magnesia (0.5–2.0 wt%) on the positron annihilation parameters and electrical properties of the PVA-PVP blend. The films were synthesized by solution casting and checked by different techniques. XRD and HR-TEM of sol-gel prepared magnesia revealed that the average crystallite size was 14.29 nm with ribbon-like morphology with varying widths and lengths up to a few micrometers. SEM showed that the blend surface appeared smooth and homogenous and this confirmed the compatibility between PVA and PVP. However, loading magnesia increased surface roughness. TGA confirmed the thermal stability enhancement of blend film with magnesia incorporation. Ortho–positronium lifetime τ₃ and the free volume $V_f$ decrease with loading magnesia while the intensity I₃ is nearly constant. These features were interpreted in view of the hole-filling mechanism, the interaction between magnesia & blend and magnesia morphology. The equilibrium swelling ratio ESR was found for the studied films and a positive correlation between ESR and $V_f$ was reported. The current density-electric field, J-E, characteristics were of non-ohmic type. J increased with increasing magnesia levels and heating. The Richardson-Schottky effect was the dominant dc conduction mechanism at low temperature and low magnesia loading levels while it changed to Poole–Frenkel emission at higher values. Finally, a correlation between Log J and the intensity I₂ was reported.     

Motion,deformation, and coalescence of ferrofluid droplets subjected to a uniform magnetic field

In this article, we present the motion, deformation, and coalescence of ferrofluid droplets suspended in a nonmagnetic fluid, subjected to a uniform magnetic field in both vertical and horizontal directions. A coupling between the simplified multiphase lattice Boltzmann method and the self-correcting scheme is constructed to numerically solve the two-dimensional flow field and the magnetostatics equations, respectively. The Cahn-Hilliard equation is employed to seize the diffuse interface between magnetic and nonmagnetic fluids. In order to validate the model, deformation of a ferrofluid droplet suspended in nonmagnetic fluid is simulated as a test case and the results are compared with numerical and experimental results. Furthermore, a detailed analysis on the behavior of falling ferrofluid droplets and the coalescence between a pair of ferrofluid droplets under the effect of different magnetic fields and different droplets configurations are also presented in this article. The results provide significant insight and a better understanding of these phenomena. It is found that for higher values of magnetic bond number and susceptibility, the droplet deformation is significant and the falling process is faster while a reverse behavior is observed for higher values of Eötvös number. Moreover, the magnetic energy density exhibits an interesting behavior in the vicinity of the droplets. It is concentrated between the droplets with a nonuniform distribution when the droplets are close to each other.     

DVC analysis of a polymer material subjected to tensile loading with synchrotron radiation tomography

Subsurface deformation behavior of a polymeric material is studied through the digital volume correlation (DVC) technique. Fundamental principles of the DVC technique are presented and the supplemental state-of-the-art algorithmic schemes to improve the efficiency and accuracy of the DVC analysis are also introduced. Tensile tests on an epoxy material are performed in conjunction with synchrotron radiation tomography. In order to create randomly distributed grayscale values in the tomograms for the following image analysis, microscale high-density particles are embedded when the epoxy specimens are fabricated. 3D tomographic images taken at multiple loading steps are utilized for the DVC analysis. The performance of the present DVC analysis is evaluated with the experimental data.     

Amphiphilic nature of polyethylene glycols and their role in medical research

BackgroundPolyethylene glycol (PEG) is a polyether compound which is an excellent candidate to study possible specific interactions of protein-polymer systems at the atomic level. Such studies would be beneficial in obtaining a more thorough understanding of PEG-protein interactions and might help to explain PEG's effects on protein behavior when used as a crowder.Scope of reviewPEGs has been called double edged sword showing assorted effects on the protein due its hydrophilic, hydrophobic and amphiphatic nature. It has been observed that the stabilization of the protein due to PEGs is because of exclusion volume effect (hard core interactions) shown by the higher molecular sizes of the crowder, however there are soft (chemical) interactions also which leads to destabilization of proteins. Most of low molecular size PEGs are noticed to destabilize proteins due to soft interactions.General significanceHere, the core characteristics of the polyethylene glycols that are responsible for the various interactions with proteins and trying to delineate the behaviour of PEGs being ambiguous, are discussed. To conclude its paradox nature being a factual inert molecule or not, many different reports of PEG interactions with various proteins are clubbed together. In addition, owing to low toxicity, high polarity, high water solubility, typically unhydrolysing or undeteriorating characteristics, it has a practical significance in pharmaceutical and cosmetic industries, and in the research field on which this review shall enlighten from earlier to now.     

不同环境氧浓度下聚甲氧基二甲醚（PODE）喷雾燃烧的羟基光谱分布及其反演重构研究

聚甲氧基二甲醚（PODE）是一种有潜力的柴油替代燃料，目前针对PODE的研究更多集中在发动机台架试验，相应的基础喷雾燃烧研究较少，制约了其在动力装置中高效清洁燃烧性能的提升。羟基（OH）性质活泼，大量存在的区域通常认为是高温反应区域。利用羟基光谱可以获得火焰结构、燃烧反应位置以及热释放速率等重要参数。环境氧浓度对火焰结构有很大影响，也是控制燃烧反应速率和污染物排放的重要参数。因此，在一台光学定容燃烧弹上，首先利用羟基的自发光光谱测量，研究了宽环境氧浓度变化（15%～80%）对PODE喷雾火焰浮起长度的影响，进一步利用阿贝尔逆变换方法将羟基自发光光谱强度由积分值反演为点位值，研究了富氧条件下（40%～80%）氧浓度变化对PODE喷雾羟基分布的影响。研究结果表明：环境氧浓度由15%增至40%，PODE火焰浮起长度迅速缩短；氧浓度进一步增加至80%，火焰浮起长度下降趋势逐渐变缓，直至基本不变；相同氧气浓度下PODE火焰浮起长度明显小于柴油。反演后的羟基光谱分布特征表面，富氧条件下PODE羟基光谱的高光强区域主要集中于喷雾边缘扩散火焰薄层中，同时，局部温度的显著提升使得羟基光谱强度在预混反应区下游附近达到最大；羟基光谱高光强区域随氧气浓度增加逐渐向火焰中上游区域迁移，并且其分布表现为轴向上更短，径向上更窄；在火焰达到准稳态时，相较40%氧气浓度条件，60%和80%氧气浓度下的羟基光谱强度在火焰中下游明显减弱，表明高的环境氧浓度下喷雾上游的燃油高浓度区域更快的参与到剧烈的燃烧反应中。