Unusual Skeletal Reorganization of Oxetanes for the Synthesis of 1,2-Dihydroquinolines

Skeletal reorganization is a type of fascinating transformations owing to their intriguing mechanisms and utility in complex molecule synthesis. However, only a limited amount of examples are known for most functional groups. Herein, we describe such an unusual process of oxetanes. In the presence of In(OTf)₃ as catalyst, oxetane-tethered anilines reacted unexpectedly to form 1,2-dihydroquinolines. This process not only provides expedient access to dihydroquinolines, but also represents a new reaction of oxetane. Mechanistically, it is believed that the reaction proceeds through initial nitrogen attack rather than arene attack followed by a series of bond cleavage and formation events. Control experiments provided important insights into the mechanism.     

Transition in the waiting-time distribution of price-change events in a global socioeconomic system

The goal of developing a firmer theoretical understanding of inhomogeneous temporal processes–in particular, the waiting times in some collective dynamical system–is attracting significant interest among physicists. Quantifying the deviations between the waiting-time distribution and the distribution generated by a random process may help unravel the feedback mechanisms that drive the underlying dynamics. We analyze the waiting-time distributions of high-frequency foreign exchange data for the best executable bid–ask prices across all major currencies. We find that the lognormal distribution yields a good overall fit for the waiting-time distribution between currency rate changes if both short and long waiting times are included. If we restrict our study to long waiting times, each currency pair’s distribution is consistent with a power-law tail with exponent near to 3.5. However, for short waiting times, the overall distribution resembles one generated by an archetypal complex systems model in which boundedly rational agents compete for limited resources. Our findings suggest that a gradual transition arises in trading behavior between a fast regime in which traders act in a boundedly rational way and a slower one in which traders’ decisions are driven by generic feedback mechanisms across multiple timescales and hence produce similar power-law tails irrespective of currency type.     

Size‐Tunable Polymeric Nanoreactors for One‐Pot Synthesis and Encapsulation of Quantum Dots

Hydrophilic polymeric nanoparticles are synthesized through a Bergman cyclization‐ mediated intramolecular chain collapse of structurally well‐defined linear polymers, and then used as size‐tunable nanoreactors to fabricate and encapsulate quantum dots in a one‐pot reaction. Crystalline quantum dots are formed in all of these nanoreactors and visualized by transmission electron microscopy. Smaller nanoreactors produce one quantum dot each while larger nanoreactors form a number, resulting in fluorescence quenching. By controlling the molecular weight of the linear polymer precursor, a variable number of nanocrystals are fabricated and assembled in a single nanoreactor.     

Preparation of polymer hollow microspheres covered by polymer solid particles via two polymerization steps

A novel surface modification method for titania nanoparticles is provided via the surface‐initiated photocatalytic polymerization with the aid of acrylic acid (AA) or sodium styrene sulfonate (NaSS). The properties of modified titania nanoparticles are investigated with aqueous electrophoresis measurements, dynamic light scattering (DLS), and transmission electron microscopy (TEM). Then the modified titania is used as Pickering stabilizer for further polymerization and the morphology of the resulted polymer microspheres is characterized by TEM and field‐emission scanning electron microscopy. It is proven that the addition of AA or NaSS for the surface‐initiated polymerization can obviously affect the structure and morphology of the final polymer composite microspheres. The formation mechanism of several kinds of polymer particles is also proposed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Theoretical Investigation on the Electron and Energy Transfer between Peripheral Carrier Transport Groups and Central Chromophores in Electroluminescent Materials

The molecular materials with structures of luminescent core and peripheral carrier groups (e.g. carbazoles), have exhibited high‐performance in organic light‐emitting diodes (OLEDs). Present work is to understand the basic process of electronic and energy exchange between the peripheral functional groups and the central core through quantum chemical analysis. As an example, 4,7‐bis(9,9‐bis(6‐(9H‐carbazol‐9‐yl)hexyl)‐9H‐fluoren‐2‐yl)benzo[c]‐[1,2,5]thiadiazole (TCBzC) is investigated in regards to optoelectronic properties using density functional theory (DFT). The results suggest that the forbidden transition from peripheral carbazole to the central chromophore core makes for separated electrical and optical properties, and high performance electroluminescence (EL) is mainly attributed to the energy‐transfer from carbazoles to the fluorene derivative core     

基于预处理HLLEW格式的全速域数值算法

基于HLLEW(Harten-Lax-Van Leer-Einfeldt-Wada)格式引入预处理技术发展适合求解全速域流场的三维Navier-Stokes求解器.引入低速预处理技术,重新构造HLLEW格式的耗散项,给出预处理后的HLLEW格式,并根据预处理后的雅克比矩阵构造相应的隐式时间推进方程.利用预处理方法求解NACA 4412低速不可压流动与RAE 2822跨声速可压缩流动,并与实验结果及原有方法的计算结果对比.结果表明:预处理HLLEW格式不仅提高低速不可压缩流动的计算效率和精度,也保持了对可压缩流动的处理能力,是一种适用于全速域流场数值模拟的有效方法.     

Gas-Sensing Hollow-Core Waveguide Based on a Liquid Film

In this paper, a strategy for the fabrication of a gas-sensing hollow-core waveguide with liquid film was developed to replace the traditional solid film hollow-core waveguide. The surface morphologies of the solid film and liquid film were characterized by scanning electron microscopy, respectively. Compared with the solid film, liquid film can dissolve gas molecules and enhance the gas sensitivity, especially in the range of low concentration. An improved absorption for detecting 1000 ppm of acetylene has been achieved when liquid film was adopted instead of solid film.     

声学CT复杂温度场重建研究

为提高声学CT复杂温度场重建能力,提出一种利用Markov径向基函数逼近和Tikhonov正则化的温度场重建算法,简称MTR算法。该算法首先用Markov径向基函数的线性组合,逼近介质中的复杂声速场分布,然后利用介质中多路径声波传播时间和Tikhonov正则化法,求解声速场分布,进而利用声速与温度的关系获得温度分布。对单热点、三热点和五热点温度场模型进行了仿真重建,结果表明MTR算法热点定位精度高,重建误差小。开发了声学CT温度场重建实验系统,用电加热器在内装1200 kg大豆的实验粮仓中形成热点,MTR重建结果能正确反映热点位置,热点温度重建误差1.3%。可见,MTR算法复杂温度场重建能力强,可望用于实际储粮温度分布监测。