双吡啶化合物3，7-di(3-pyridyl)-1，5-dioxa-3，7-diazacyclooctane构建的四个过渡金属配合物的合成、结构及热稳定性

采用准刚性的双吡啶化合物3,7-di(3-pyridyl)-1,5-dioxa-3,7-diazacyclooctane(L),合成了4个过渡金属配合物[Co(NO3)(H2O)2(L)2]NO3(1)、[Co2Cl4(L)2]·CH2Cl2(2)、[Cd2(AcO)4(L)2]·4CH3OH(3)和[Cd2(NO3)2(CH3OH)2(H2O)2(L)2](NO3)2·2H2O(4)。单晶衍射分析表明,配合物1是单核结构,配合物2是24-元环状双核结构,而配合物3和4为多边形双核结构。在这些配合物中,双吡啶配体分别采用了单齿、trans-和cis-桥连3种不同配位方式。配合物经过了元素分析、红外、热重和X射线单晶结构分析表征。     

Calculation Methods of Solution Chemical Potential and Application in Emulsion Microencapsulation

Several new biased sampling methods were summarized for solution chemical potential calculation methods in the field of emulsion microencapsulation. The principles, features, and calculation efficiencies of various biased Widom insertion sampling methods were introduced, including volume detection bias, simulation ensemble bias, and particle insertion bias. The proper matches between various types of solution in emulsion and biased Widom methods were suggested, following detailed analyses on the biased insertion techniques. The volume detection bias methods effectively improved the accuracy of the data and the calculation efficiency by inserting detection particles and were suggested to be used for the calculation of solvent chemical potential for the homogeneous aqueous phase of the emulsion. The chemical potential of water, argon, and fluorobenzene (a typical solvent of the oil phase in double emulsion) was calculated by a new, optimized volume detection bias proposed by this work. The recently developed Well-Tempered(WT)-Metadynamics method skillfully constructed low-density regions for particle insertion and dynamically adjusted the system configuration according to the potential energy around the detection point, and hence, could be used for the oil-polymer mixtures of microencapsulation emulsion. For the macromolecule solutes in the oil or aqueous phase of the emulsion, the particle insertion bias could be applied to greatly increase the success rate of Widom insertions. Readers were expected to choose appropriate biased Widom methods to carry out their calculations on chemical potential, fugacity, and solubility of solutions based on the system molecular properties, inspired by this paper.     

Reentrant 2D Nanostructured Liquid Crystals by Competition between Molecular Packing and Conformation: Potential Design for Multistep Switching of Ionic Conductivity

Reentrant phenomena in soft matter and biosystems have attracted considerable attention because their properties are closely related to high functionality. Here, we report a combined experimental and computational study on the self-assembly and reentrant behavior of a single-component thermotropic smectic liquid crystal toward the realization of dynamically functional materials. We have designed and synthesized a mesogenic molecule consisting of an alicyclic trans,trans-bicyclohexyl mesogen and a polar cyclic carbonate group connected by a flexible tetra(oxyethylene) spacer. The molecule exhibits an unprecedented sequence of layered smectic phases, in the order: smectic A-smectic B-reentrant smectic A. Electron density profiles and large-scale molecular dynamics simulations indicate that competition between the stacking of bicyclohexyl mesogens and the conformational flexibility of tetra(oxyethylene) chains induces this unusual reentrant behavior. Ion-conductive reentrant liquid-crystalline materials have been developed, which undergo the multistep conductivity changes in response to temperature. The reentrant liquid crystals have potential as new mesogenic materials exhibiting switching functions.     

Non-Markovianity and Indivisible Quantum dynamics of a Apin-S System

Using a measure for the divisibility of a dynamical map, we study the non-Markovian character of a quantum evolution of a spin-S system, which is in an external field and weakly coupled to a bosonic bath with a certain temperature. The finite-temperature dynamics of the open system is obtained by the time-convolutionless master equation in the secular approximation. Besides the influence of the environmental spectral density function, the external field and low temperatures can affect the quantum non-Markovianity. It is found out that the non-Markovian feature of a dynamical map of a high-dimensional spin system is noticeable in contrast to that of a low-dimension spin system.     

三嗪类双极性蓝色磷光主体材料的合成及性能

设计合成了一种基于三嗪类的新型双极性蓝色磷光主体材料[4-(4,6-二-α-萘氧基-1,3,5-三嗪-2-基)苯基]9-咔唑(NOTPC),并对其结构进行了表征。通过紫外-可见(UV-Vis)吸收、荧光、低温磷光、循环伏安法、热重分析(TGA)、差热分析(DSC)和密度泛函理论(DFT)对其性能及结构进行了研究。结果表明,NOTPC在CH₂Cl₂稀溶液中的吸收峰位于341和374 nm;发射峰位于478 nm;NOTPC的低温(77 K)磷光光谱的第一发射峰位于442 nm,其三线态能级为2.80 eV,与蓝色磷光材料FIrpic(2.62 eV)的能级相匹配;NOTPC的HOMO主要分布在苯基咔唑单元,而LUMO主要定域在三嗪环上。其HOMO能级为-5.40 eV,与阳极ITO的功函(-4.5~-5.0 eV)相匹配,LUMO能级为-2.32 eV,接近于电子传输材料PBD(-2.82 eV),NOTPC表现出双极传导性能, 且热稳定性良好。     

高效传质与电子转移的全纳米线光催化燃料电池自驱动净水同步产氢

分别以三维分级碳布基底上组装的TiO₂纳米线阵列和铂化的硅纳米线阵列作为光阳极和光阴极,构建了具有高效传质和电子转移特征的全纳米线光催化燃料电池。在光照作用下,光阳极微流道内的光生空穴能有效氧化降解有害污染物,这同时增强了光电子还原水产氢的活性。与传统的平面式光电极相比,全纳米线光催化燃料电池在不需要外部偏压条件下即可高效降解模拟印染废水和同步生成氢气新能源。     

等效零折射率材料微腔中均匀化腔场作用下的简正模劈裂现象

研究了零折射率材料微腔中人造原子与腔模的相干耦合现象.首先通过数值模拟的方法研究了在二维光子晶体微腔中填充阻抗匹配的零折射率材料后腔模的场分布.结果表明零折射率材料的引入使得原本以驻波场形式存在的腔模分布在整个微腔中变得近似均匀且值最大.其次,将人造原子放入腔中的不同位置并与腔模耦合,结果从频谱上观察到腔模的劈裂与人造原子在腔中的位置无关.最后,利用微波实验,通过开口谐振环等效的人造原子与一维复合左右手传输线等效的零折射率材料微腔之间的耦合验证了仿真结果的准确性.该结果为腔量子电动力学中量子点对位难的问题提供了新的方案,同时零折射率材料微腔也为今后研究原子与光子之间的相互作用提供了一个新的平台.     

9，10-二杂环取代蒽衍生物制备与三线态-三线态湮灭上转换性能研究

弱光上转换是基于三线态-三线态湮灭机制将低能量(长波长)的光转换为高能量(短波长)光的一种现象,是通过光敏剂与发光剂之间能量转移实现的。针对当前上转换体系中的光敏剂研究备受关注,而对于同等重要作用的发光剂的研究甚少的现状,利用Suzuki偶联反应制备了两个新的杂环取代蒽衍生物：9,10-二(3-呋喃)蒽(DFA)和9,10-二(3-噻吩)蒽(DTA)并通过结构表征;以9,10-二杂环取代蒽为发光剂、四苯基卟啉钯衍生物(PdTPPMe和PdTPPCOOH)为三线态光敏剂,研究所构成的光敏剂/发光剂双组分体系中,三线态-三线态能量转移效率(k_Q)、发光剂的延迟荧光寿命(τ_DF)及发光剂荧光量子产率(Φ_f)等因素对上转换效率(Φ_UC)的影响。结果表明,高效三线态-三线态能量效率(Φ_TTT)、快速延迟荧光寿命和大荧光量子产率将有利于提高上转换效率。进一步研究发现,含氧发光剂(DFA)与含羧基的光敏剂(PdTPPCOOH)之间可借助氢键发生有效耦合,有利于光敏剂与发光剂之间的三线态能量转移,导致弱光上转换效率显著提高。在半导体激光器(532 nm,70 mW·cm-2)激发下获得强的绿-转-蓝上转换效率最大可达10.11%。所获得的绿-转-蓝上转换荧光可使Pt/WO₃复合半导体受激;产生氧自由基并可促使香豆素转化为7-羟基香豆素。     

Ag3PO4/rectorite nanocomposites: Ultrasound-assisted preparation,characterization and enhancement of stability and visible-light photocatalytic activity

To overcome the drawback of low stable brought by the transformation of Ag⁺ into Ag, a highly efficient and stable photocatalyst Ag₃PO₄/rectorite composite was successfully synthesized by ultrasound-assisted precipitation method. The as-prepared samples were characterized by field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, N₂ adsorption-desorption, room-temperature photoluminescence spectra, Fourier transform infrared spectrum measurements and UV–vis diffuse reflectance spectra. The absorption edges of the Ag₃PO₄/rectorite display a noticeable shift to the visible light region as compared to that of the Ag₃PO₄. Compared with bare Ag₃PO₄, the Ag₃PO₄/rectorite composite by ultrasound-assisted precipitation process exhibits significantly enhanced photocatalytic activity and stable for methyl orange (MO) degradation under visible light irradiation. The improved activity of the Ag₃PO₄/rectorite photocatalyst could be attributed to the expanded visible light absorption, the enhanced interfacial charge transfer and the inhibited recombination of electron-hole pairs. Therefore, the facile ultrasound-assisted preparation process provides some insight into the application of Ag₃PO₄/rectorite nanocomposites in photocatalytic degradation of organic pollutants.     

Ring-closing metathesis protocol for a diastereocontrolled preparation of the C28–C34 segment of FK-506

A new synthesis of the C₂₈–C₃₄ segment of FK-506 has been developed using a chiral building block having a 6,8-dioxabicyclo[3.2.1]octane framework by employing a ring-closing metathesis reaction as the key step.