Facile construction of aggregation-induced emission molecular liquids via Piers-Rubinsztajn reaction for green fluorescent ink

Solvent-free luminescent molecular liquids(LMLs), which exhibit nonvolatile fluidic nature and active optoelectronic properties, were widely used. For further development, we introduced siloxane units into AIE molecules, designed and synthesized TPE derivatives with siloxane side chains via facile Piers-Rubinsztajn reaction. The obtained AIE molecular liquids exhibit unique photophysical properties. Compared with the obtained alkyl TPE-solids, siloxane TPE show liquid state, which proves that the siloxane units have stronger liquefaction effect than alkyl. Viscosity test shows that siloxane TPE-liquids has far more lower viscosity and better fluidity than the long-chain alkyl molecular liquids in previous research. All those properties are attributed to the weak interaction between flexible molecular chains of siloxane. Besides,fluorescence test shows temperature responsiveness of siloxane TPE-liquids. We developed this lowviscosity nonvolatile AIE molecular liquid as green fluorescent ink.

Effect of an external electric field on liquid water using molecular dynamics simulation with a flexible potential

Molecular dynamics simulations of liquid water were performed at 258 K and density of 1.0 g/cm^3 under different strengths of an external electric field, ranging from 0 to 8.0×10^9V/m, to investigate the influence of an external field on structural and dynamic properties of water. The flexible simple point charge model is used for water molecules. An enhancement of the water hydrogen bond structure with increasing strength of the electric field has been deduced from the radial distribution functions and the analysis of hydrogen bond structure. With increasing field strength, water system has a more perfect structure, which is shnilar to ice structure. However, the electrofreezing phenomenon of liquid water has not been detected because of a too large self-diffusion coefficient. The self-diffusion coefficient decreases remarkably with increasing strength of electric field, and the self-diffusion coefficient is anisotropic.

Study of Imidazolium Ionic Liquids:Temperature-dependent Fluorescence and Molecular Dynamics Simulation

The steady-state fluorescence spectra and molecular dynamics simulations were explored to investigate the temperature dependent organization in some imidazolium ionic liquids：1-butyl-3-methylimidazolium hexafluo-rophosphate（[bmim][PF6]）,1-ethyl-3-methylimidazolium ethylsulfate（[emim][EtSO4]） and 1-butyl-3-methylimida-zolium tetrafluoroborate（[bmim][BF4]）.The pure room temperature ionic liquids（ILs） exhibit a large red shift at more than an excitation wavelength of around 340 nm,which demonstrates the heterogeneous nature of the liquids.Furthermore,the fluorescence spectra of the ionic liquids were found to be temperature-dependent.The emission intensity gradually decreased with increasing temperature for the neat ionic liquids and the mixed solutions of [bmim][BF4]-H2O,which was the special phenomena induced by not only the local structure but also the viscosity.The molecular dynamics simulation further confirms that the structures of ionic liquids are sensitive to the surroun-ding environment because of the aggregation degree of ILs.

Molecular Simulation of Transesterification of Ethylene Carbonate and Methanol Catalyzed by Ionic Liquids

Four ionic liquids [BMIM]OH, [BMIM]IM, [BMIM]Br, and [BMIM]PF6 were synthesized and characterized by infrared spectroscopy. Then the effects of ionic liquids(ILs), cocatalysts, and reaction temperature on the catalytic performance for transesterification of ethylene carbonate and methanol were investigated with orthogonal experiments. The influence of cations and anions of ILs on catalytic activity was revealed by the density functional theory(DFT). The reaction mechanism was proposed based on the experimental results and DFT. The results demonstrated that the optimal catalyst was [Bmim]PF6/CaO, which exhibited the advantages of high activity, excellent stability, and easy recycling. Under the optimized conditions covering a catalytic temperature of 130 °C, an ionic liquid/cocatalyst mass ratio of 5:1, and a catalyst dosage of 4.0%, the conversion rate could reach 65.23% with a dimethyl carbonate selectivity of 98.95%. No significant loss of catalyst activity was detected after 7 recycle times.

Relationship between Multi-Phase Formation and Molecular Structure for Liquid Crystal System

4 mechanical model of liquid crystals （ LCs ） was used to explain the phase formation and thermal properties . The LC plusses in the model are micro- machine systems consisting of an ensemble of molecular rotors, and some dynamie parameters in a semi-experiment molecular orbit method. A novel explanation on the multi-phase formation of LC system is obtained. It is found that the value of the critical rotational velueity is a key parameter for the characterization of each homologous series. The dipole moment of the molecules was also discussed.

Ionic Interactions in Molecular and Liquid States ofPolyvalent Metal Halides

Progress in the development of phenomenological models for the microscoplc interactions in the halides of polyvalent metals is reviewed, with main attention to neutral and ionized molecular states and to the melts of these materials. The following physical problems are discussed: (1)bond bending in the molecules of the alkaline-earth halides, (2) binding of molecular dimers and halogen transfer reactions relevant to the melts of trivalent metal halides, (3) stability of molecular ions in liquid mixtures of polyvalent metal halides and alkali halides, and (4) stabilityof molecular ions and reduced-valence states in molten cryolite under addition of sodium metal.

PREDICTION OF THE MIXING ENTHALPIES OF BINARY LIQUID ALLOYS BY MOLECULAR INTERACTION VOLUME MODEL

The mixing enthalpies of 23 binary liquid alloys are calculated by molecular interaction volume model （MIVM）, which is a two-parameter model with the partial molar infinite dilute mixing enthalpies. The predicted values are in agreement with the experimental data and then indicate that the model is reliable and convenient.

PREPARATION OF MICROPOROUS ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE (UHMWPE) BY THERMALLY INDUCED PHASE SEPARATION OF A UHMWPE/LIQUID PARAFFIN MIXTURE

Ultra-high molecular weight polyethylene (UHMWPE) with a microporous structure was prepared via thermally induced phase separation (TIPS).Liquid paraffin (LP) was used as a diluent in the preparation of microporous UHMWPE. Small angle laser light scattering (SALLS) and differential scanning calorimetry (DSC) were used to determine the phase separation temperatures,i.e.the cloud points and the dynamic crystallization temperatures,respectively.It was found that the cloudI points were coincident with the cryst...

Molecular dynamics simulation of supercritical CO2 microemulsion with ionic liquid domains: Structures and properties

Supercritical carbon dioxide microemulsions are great medium to combine two immiscible substances through forming nanoscale polar cores in nonpolar continuous phase with the help of proper surfactants. The properties of microemulsions could be significantly affected by their constituents and structures. In this work, molecular dynamics simulation was implemented to study supercritical carbon dioxide microemulsions containing ionic liquid [bmim][PF6] and water by adding surfactant Ls-36. Results showed that the above components could form spherical aggregates in CO2 bulk phase with [bmim][PF6] and some water as the inner core, surfactant headgroups and water as the intermediate shell, and surfactant tails as the outer shell. The microstructure information about the outer shell was further investigated by defining an angle between the surfactant tail and the normal direction of the aggregate outer surface, which ranged from 78° to 125°. The influence of the ionic liquid content on the size and structure of microemulsions was explored and the best molar ratio between the ionic liquid and surfactant was around 1.25 for getting maximum water solubility.

Molecular dynamics simulation of self-diffusion coefficients for liquid metals

The temperature-dependent coefficients of self-diffusion for liquid metals are simulated by molecular dynamics meth ods based on the embedded-atom-method （EAM） potential function. The simulated results show that a good inverse linear relation exists between the natural logarithm of self-diffusion coefficients and temperature, though the results in the litera ture vary somewhat, due to the employment of different potential functions. The estimated activation energy of liquid metals obtained by fitting the Arrhenius formula is close to the experimental data. The temperature-dependent shear-viscosities obtained from the Stokes-Einstein relation in conjunction with the results of molecular dynamics simulation are generally consistent with other values in the literature.

Rotational viscosity of a liquid crystal mixture: a fully atomistic molecular dynamics study

Fully atomistic molecular dynamics （MD） simulations at 293, 303 and 313 K have been performed for the four- component liquid crystal mixture, E7, using the software package Material Studio. Order parameters and orientational time correlation functions （TCFs） were calculated from MD trajectories. The rotational viscosity coefficients （RVCs） of the mixture were calculated using the Nemtsov-Zakharov and Fialkowski methods based on statistical-mechanical approaches. Temperature dependences of RVC and density were discussed in detail. Reasonable agreement between the simulated and experimental values was found.

INFLUENCE OF THE SOLVENT SWELLING ON MACROMOLECULAR CHOLESTERIC LIQUID CRYSTALLINE STRUCTURE

Ethyl-cyanoethyl cellulose [(E-CE)C]/cross-linked polyacrylic acid [PAA] molecular composites with cholesteric order were prepared. It was found that the macromolecular cholesteric structure was changed with the swelling of PAA in the composites. The selective reflection of the cholesteric phase shifted to the longer wavelength and the X-ray diffraction angle shifted to the high angle direction during swelling, which suggested that the cholesteric pitch and the number of the layers of ordered (E-CE)C chains in the cholesteric phase were increased.

INFLUENCE OF MOLECULAR WEIGHT OF CHITIN AND ITS THREE DERIVATIVES ON CRITICAL CONCENTRATION OF LYOTROPIC LIQUID CRYSTALLINE PHASE TRANSITION

The critical concentration of lyotropic liquid crystalline phase transition for chitin derivatives was determined using a polarization microscope. The influence of molecular weight on critical concentration of liquid crystalline solution for chitin, chitosan, cyanoethyl chitosan and propionyl chitin successively increases as the chain rigidity decreases. Therefore it can be used as an indicator of the chain rigidity.

MOLECULAR DYNAMICS SIMULATIONS OF FILLED AND EMPTY CAGE-LIKE WATER CLUSTERS IN LIQUID WATER AND THEIR SIGNIFICANCE TO GAS HYDRATE FORMATION MECHANISMS

Molecular dynamics simulations are performed to observe the evolutions of 512 and 51262 cage-like water clusters filled with or without a methane molecule immersed in bulk liquid water at 250 K and 230 K. The lifetimes of these clusters are calculated according to their Lindemann index δ (t) using the criteria of δ≥0.07. For both the filled and empty clusters, we find the dynamics of bulk water determines the lifetimes of cage-like water clusters, and that the lifetime of 512 62 cage-like cluster is the same as that of 512 cage-like cluster. Although the methane molecule indeed makes the filled cage-like cluster more stable than the empty one, the empty cage-like cluster still has chance to be long-lived compared with the filled clusters. These observations support the labile cluster hypothesis on the formation mechanisms of gas hydrates.

N-丁基吡啶四氟硼酸盐/水二元体系的分子动力学模拟研究

利用分子动力学模拟方法研究了离子液体N-丁基吡啶四氟硼酸盐([BPy]BF4)与Tip4p模型水分子的二元体系的微观结构.比较了各组分间的径向分布函数,结果表明随着离子液体比例的增加,水与阴离子、水与阳离子头部吡啶环、阳离子头部与阴离子上相关原子间的径向分布函数峰值都呈现递增的趋势,而阳离子上丁基链末端碳原子间的径向分布函数没有明显变化;空间分布函数则直观地反映出阴离子主要分布在阳离子的吡啶环周围,水分子在阴离子周围近似呈均等分布,且几率随离子液体比例增大而增加;另外还探讨了不同离子液体比例下的二元体系中氢键的数目和寿命,结果均呈现一定规律的变化.

电场条件下高盐溶液蒸发的分子动力学模拟

已有研究表明,外加电场能显著改变纯水蒸发过程和蒸发速率。为了探究外加电场对高盐溶液微观结构和蒸发性质的影响,采用分子动力学模拟方法对纯水和LiCl、KCl和CaCl23种盐溶液在平行液面(x方向)和垂直液面方向(z方向)上布置外加电场来观察其蒸发过程。模拟计算分析了电场对蒸发速率、水分子取向、氢键以及水合离子的影响,并且观察比较了电场下不同离子在溶液中的运动。结果显示,与纯水相反,平行液面的电场能显著提高盐溶液中自由水分子的占比,当平行液面电场强度从0变为0.3 v·nm-1时,LiCl、KCl和CaCl2溶液中用于评价蒸发的自由水分子占比分别增加了48%,38%和56%,高盐溶液蒸发速率得到有效提高。

固液界面热阻的温度依赖特性模拟研究

基于非平衡态分子动力学模拟方法,研究了系统温度及固液结合强度对固液界面传热的影响规律。模拟结果表明,固液界面热阻随着系统温度的升高而降低,并且亲水性界面的界面热阻温度依赖性较弱。基于微观热流密度计算式的分析表明,随着系统温度升高,动能项和维里项的贡献均逐渐增大,因而固液界面传热增强,但是动能项占比逐渐增大,维里项占比逐渐降低;随着固液结合强度逐渐增大,界面吸附效应增强,维里项贡献明显增大,这是较强的固液相互作用能够强化界面传热的主要原因。

Quantum chemical aided molecular design of ionic liquids as green electrolytes for electrodeposition of active metals

Quantum chemical calculation was used to estimate the reduction potentials of 25 organic cations and the oxidation potentials of 11 anions.This information was used to select promising cations and anions for the preparation of ionic liquids as green electrolytes for electrodeposition of active metals.The reasonable linear correlations between the lowest unoccupied molecular orbital(LUMO)energies and the reduction potentials of cations,and the linear relationships between the oxidation potentials and the highest occupied molecular orbital(HOMO)energies of anions were obtained.The orders of electrochemical stability for cations and anions being obtained agree well with the experimental measurements.The suitable ionic liquids with sufficiently wide electrochemical windows for electrodeposition of active metals are suggested to be[Emim]NTf2,[Bmim]NTf2,[Bmim]BF4, [Bmim]PF6,[Bmim]CTf3,[Emim]BF4,[Emim]PF6,[Emim]CTf3..

Stability in Liquid Phases of Molecular Compounds Composed of Saturated Atoms: Application with the Even-Odd Rule and a Specific Periodic Table for Liquids

Building on the idea that molecules in liquid phase associate into multi-molecular complexes through covalent bonds, the present article focuses on the possible structures of these complexes. Saturation at atomic level is a key concept to understand where connections occur and how far molecules aggregate. A periodic table for liquids with saturation levels is proposed, in agreement with the even-odd rule, for both organic and inorganic elements. With the aim at reaching the most stable complexes, meaning no other chemical reactions can occur in the liquid phase, the structure of complexes resulting from liquefaction of about 30 molecules is devised. The article concludes that complexes in liquids generally assume rounded shapes of an intermediate size between gas and solid structures. It shows that saturation and covalent bonds alone can explain the specific properties of liquids. While it is generally acknowledged that molecular energy in gases and solids are respectively linear kinetic and vibratory, we suggest that rotatory energy dominates in liquids.

纳米材料中的界面现象

在课程教学中融入科学前沿实例不仅可以阐明所学基本原理的实际意义,还可以为基本原理的灵活应用提供范例,启发学生独立思考能力。界面化学是物理化学课程中的重要学习内容,但由于在常规尺度的多相体系中界面现象并不显著,学生对该部分知识常有忽视。近年来纳米材料已成为国内外研究的热点。纳米材料由于其高界面分子比例而表现出更为显著的界面现象。将界面化学的基本原理应用于纳米材料的研究中,已取得了一系列令人瞩目的成果。本文首先对附加压力、接触角等相关界面现象的基本原理进行梳理,然后分别介绍根据这些基本原理所发展出的分子马达、光控微流控器件、液体门控技术以及超疏水表面四项科技突破。