Influence of Solvent Size on Structural Properties of Bottle-brush Polymers

We proposed a modified dissipative particle dynamics simulation model by which one can effectively avoid the bond-crossing problem, and investigated the effect of solvent size on the structural properties of bottle-brush polymers in dilute solution on the basis of this model. It was found that with the increase of solvent size, the radius of the gyration of the bottle-brush polymer decreases considerably in the athermal solvent but increases in the selective solvent favoring the backbone, respectively.     

Fatty Acid Carboxylate‐ and Anionic Surfactant‐Controlled Delivery Systems That Use Mesoporous Silica Supports

We report the preparation of a MCM‐41 mesoporous material that contains the dye [Ru(bipy)₃]Cl₂ (bipy=bipyridine) inside the mesopores and functionalised with suitable binding groups at the entrance of the pores. Solids S1 – S3 were obtained by the reaction of the mesoporous material with N‐methyl‐N′‐propyltrimethoxysilylimidazolium chloride, N‐phenyl‐N′‐[3‐(trimethoxysilyl)propyl]thiourea, or N‐phenyl‐N′‐[3‐(trimethoxysilyl)propyl]urea, respectively. A study of the dye delivery of these systems in buffered water (pH 7.0, 2‐[4‐(2‐hydroxyethyl)piperazin‐1‐yl]ethanesulfonic acid (HEPES), 10^?3 mol dm^?3) in the presence of a family of carboxylate ions was carried out. In the interaction of the anions with the surface of the solids, the response depends on the characteristics of the binding groups (i.e., imidazolium, urea and thiourea) at the pore outlets and their specific interaction with the corresponding anion. The interaction of long‐chain carboxylate ions with the binding sites at the surface of the solids resulted in a remarkable inhibition of the delivery of the dye. This inhibition was observed clearly for the dodecanoate anion, whereas the octanoate, decanoate, cholate, deoxycholate, glycodeoxycholate and taurocholate anions induced a certain pore blockage that varied according to the solid studied. The interaction of smaller anions, such as acetate, butanoate, hexanoate and octanoate, with the solids had no effect on the dye release process. The possible use of the gating system for the chromo‐fluorogenic detection of anionic surfactants through selective dye delivery inhibition was also explored. Molecular dynamic simulations that use force‐field methods have been made to theoretically study the capping carboxylate mechanism. The calculations are in agreement with the experimental results, thus allowing a representation of the dye delivery inhibition in the presence of long‐chain carboxylate ions.     

A Surface Femtosecond Two-Photon Photoemission Spectrometer for Excited Electron Dynamics and Time-Dependent Photochemical Kinetics

A surface femtosecond two-photon photoemission (2PPE) spectrometer devoted to the study of ultrafast excited electron dynamics and photochemical kinetics on metal and metal oxide surfaces has been constructed. Low energy photoelectrons are measured using a hemispheri-cal electron energy analyzer with an imaging detector that allows us to detect the energy and the angular distributions of the photoelectrons simultaneously. A Mach-Zehnder interferom-eter was built for the time-resolved 2PPE (TR-2PPE) measurement to study ultrafast surface excited electron dynamics, which was demonstrated on the Cu(111) surface. A scheme for measuring time-dependent 2PPE (TD-2PPE) spectra has also been developed for studies of surface photochemistry. This technique has been applied to a preliminary study on the photochemical kinetics on ethanol/TiO₂(110). We have also shown that the ultrafast dy-namics of photoinduced surface excited resonances can be investigated in a reliable way by combining the TR-2PPE and TD-2PPE techniques.     

Modification of PAE-degrading Esterase(CarEW) for Higher Degradation Efficiency Through Integrated Homology Modeling,Molecular Docking,and Molecular Dynamics Simulation

Six phthalate acid esters(PAEs) priority pollutants[dimethyl phthalate(DMP), diethyl phthalate(DEP), dibutyl phthalate (DBP or DNBP), di-n-octyl phthalate(DNOP), di 2-ethyl hexyl phthalate(DEHP), and butyl benzyl phthalate(BBP)] were opted as the research object. PAE-degrading esterase CarEW(PDB ID:1C7I) isolated from Bacillus subtilis acting as a template and an iterative saturation mutation strategy was adopted to modify key amino acids to attain efficient PAE-degrading esterase substitutes with a reasonable structure constructed by homology modeling method. Present study designed a total of 285 unit-site and multi-site substitutions of PAE-degrading esterase using the homology modeling method. Among them, 207 PAE-degrading esterase substitutions, which contained the 6-site PAE-degrading esterase substitute 1C7I-6-9 with 84.21% enhancement intensity of degradation ability revealed better degradability to all the 6 PAEs after modification. Moreover, molecular dynamics simulation based on the Taguchi method reported the optimal external application environment for PAE-degrading esterase substitutes as follows:pH=6, T=35℃, the rhamnolipid concentration was 50 mg/L, the molar ratio of nitrogen to phosphorus(N:P) was 10:1, the concentration of H₂O₂ was 50 mg/L, and the voltage gradient was 1.5 V/cm. The degradation ability of PAE-degrading esterase substitutes was found to be elevated by 13.04% as compared to that of the blank control under the optimal condition. Moreover, 11 highly efficient PAE-degrading esterase substitutes with thermal stability were designed.     

Predicting ion selectivity in water purification by capacitive deionization: Electric double layer models

Ion-selective water treatment is needed to address emerging problems in an energy- and cost-efficient manner. Capacitive deionization (CDI) is a membraneless water treatment technology, which relies on storing ions in charged electric double layers (EDLs) of micropores. CDI has shown remarkable selectivity, with local density approximations (LDAs) showing some success in guiding selective separations. However, many underlying processes are represented by lumped fitting parameters in LDA models, hindering further progress. Atomistic models help unravel selectivity mechanisms, but are difficult to integrate with cell-level CDI theory. Here, we review and extend LDA models for CDI, highlight a knowledge gap in connecting between LDA and atomistic models for CDI, and emphasize and build upon analogies between micropore EDLs and nanofiltration membranes.     

Ferrozine colorimetry and reverse flow injection analysis (rFIA) based method for the determination of total iron in aqueous solutions at nanomolar concentrations

Iron is one of the most microbiologically and chemically important metals in natural waters. The biogeochemical cycling of iron is significantly influenced by the redox cycling of Fe(II) and Fe(III). Because of the unique chemistry of iron, it is often needed to analyze iron at nano-molar concentrations. This article describes a reverse flow injection analysis (rFIA) based method with ferrozine spectrophotometric detection to quantify total iron concentration in stream water at nanomolar concentrations. The rFIA system has a 0.65 nM detection limit and a linear dynamic range up to 1.40 μM for the total iron analysis. The detection limit was achieved using a 1.0 m long liquid waveguide capillary flow cell, 1.50 m long knotted reaction coil, 87.50 μL injection loop and a miniature fiber optics spectrophotometer. The optimized colorimetric reagent has 1.0 mM ferrozine, 0.1 M ascorbic acid, 1.0 mM citric acid and 0.10 M acetate buffer adjusted to pH 4.0. The best sample flow rate is 2.1 mL min^?1 providing a sample throughput of more than 15 samples h^?1. The linear dynamic range of the method can be adjusted by changing the volume of the injection loop. The rFIA manifold was assembled exclusively from commercially available components.     

纳米孔缺陷导致单层黑磷电荷局域极大抑制非辐射电子-空穴复合的时域模拟

通常认为缺陷加速黑磷的非辐射电子-空穴复合,阻碍器件性能的持续提高。实验打破了这一认识。采用含时密度泛函理论结合非绝热分子动力学,我们发现P-P伸缩振动驱动非辐射电子-空穴复合,使纳米孔修饰的单层黑磷的激发态寿命比完美体系延长了约5.5倍。这主要归因于三个因素。一,纳米孔结构不但没有在禁带中引入深能级缺陷,而且由于价带顶下移使带隙增加了0.22 eV。二,除了带隙增加,纳米孔减小了电子和空穴波函数重叠,并抑制了原子核热运动,从而使非绝热耦合降低至完美体系的约1/2。三,退相干时间比完美体系延长了1.5倍。前两个因素战胜了第三个因素,使纳米孔结构激发态寿命延长至2.74 ns,而其在完美体系中约为480 ps。我们的研究表明可以制造合理数量和形貌的缺陷,如纳米孔,降低黑磷非辐射电子-空穴复合,提高光电器件效率。这一研究对于理解和调控黑磷和其它二维材料的激发态性质有重要意义。     

气驱油油气混相过程的界面传质特性及其分子机制

油气混相过程的界面传质特性对气驱提高原油采收率技术非常重要。本文针对吉林某油田的实际油组分,采用分子动力学模拟研究了气驱油过程,分析了不同气体和驱替压力下油气两相的状态变化以及界面特性,获得不同驱替气体的最小混相压力(MMP)。结果表明,随着驱替气体压力的升高,气相的密度逐渐增大,油相膨胀密度降低,气相与油相的混合程度增强,油气两相界面厚度增加,界面张力随之减小。同时发现,驱替相中二氧化碳浓度越高,在同等气体压力下,油气界面更厚,油气混合程度更高。纯CO₂驱油得到的MMP远远小于纯N₂驱油,当这两种气体摩尔比为1 : 1混合时MMP介于两种纯气体之间,说明要达到同样的驱油效果二氧化碳需要的压力更小。最后,本文从分子微观作用力角度解释了驱替气体不同时影响油气混相程度的机制,通过分子平均作用势曲线发现油相分子对CO₂的吸引力要大于N₂分子,因此CO₂分子更容易与油相混合,驱替效果更明显。     

Performance evaluation of functionalized ordered mesoporous silica for VOCs adsorption by molecular dynamics simulation

Volatile organic compounds (VOCs) are growing pollutants now that cause the serious environmental pollution and threaten human health. The functionalized ordered mesoporous silica (FOMS) has attracted considerable attention in adsorbing VOCs. In this paper, the molecular dynamics simulation was used to simulate the adsorption performance of FOMS on VOCs (acetone, ethyl acetate and toluene). After simulating different pore sizes (2 nm, 3 nm and 4 nm) adsorption performances of ordered mesoporous silica (OMS) on VOCs, OMS with a pore size of 4 nm was selected to further study the influence of functional groups (vinyl, methyl, and phenyl). The following law was obtained: the saturated adsorption capacities of vinyl-functionalized OMS (V-FOMS) to acetone, ethyl acetate and toluene were 3.045 mmol.g^?1, 2.568 mmol.g^?1 and 1.976 mmol.g^?1 respectively; the saturated adsorption capacities of methyl-functionalized OMS (M-FOMS) to acetone, ethyl acetate and toluene were 2.798 mmol.g^?1, 2.312 mmol.g^?1 and 1.698 mmol.g^?1 respectively; the saturated adsorption capacities of phenyl-functionalized OMS (P-FOMS) to acetone, ethyl acetate and toluene were 2.124 mmol.g^?1, 1.941 mmol.g^?1 and 1.539 mmol.g^?1 respectively. These results show that the adsorption ability of FOMS for different adsorbates follows the sequence of acetone > ethyl acetate > toluene. Furthermore, the interaction between functional groups (vinyl, methyl and phenyl) in FOMS and VOCs was explored. It is found that the interaction between different functional groups and adsorbates is different (interaction energy effect). This interaction energy effect promotes FOMS to better adsorb VOCs. This work would provide fundamental understanding and guidance for the development of novel adsorption materials for the adsorption of VOCs.