Gold‐Catalyzed Tandem Cycloisomerization–Halogenation of Chiral Homopropargyl Sulfonamides

Two new gold‐catalyzed tandem cycloisomerization–halogenation reactions of chiral homopropargyl sulfonamides have been developed. Various enantioenriched 3,3‐diiodopyrrolidin‐2‐ols and 3‐fluoropyrrolidin‐2‐ols were obtained in moderate‐to‐good yields with excellent enantio‐ and diastereoselectivity.     

Temperature memory effect and its stability revealed via differential scanning calorimetry in ethylene‐vinyl acetate within glass transition range

In this article, we reveal the temperature memory effect (TME) in a commercial thermoplastic polymer, namely ethylene‐vinyl acetate (EVA), within its glass transition range via a series of differential scanning calorimeter (DSC) tests. In addition, we investigate the influence of heating holding time and also compare the observed TME in current study with that of shape memory alloys (SMAs). It is concluded that the TME via DSC (without any macroscopic shape change) is achievable within the glass transition range of a polymer. Conversely, although the observed TME shares the many similar features as those in SMAs, due to the nature of micro‐Brownian motion in the glass transition of polymers, the resulted TME is strongly affected by the heating holding time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1731–1737     

High‐Nuclear Organometallic Copper(I)–Alkynide Clusters: Thermochromic Near‐Infrared Luminescence and Solution Stability

Cu(CF₃COO)₂ reacts with tert‐butylacetylene (tBuC≡CH) in methanol in the presence of metallic copper powder to give two air‐stable clusters, [Cu^I₁₅(tBuC≡C)₁₀(CF₃COO)₅]?tBuC≡CH ( 1 ) and [Cu^I₁₆(tBuC≡C)₁₂(CF₃COO)₄(CH₃OH)₂] ( 2 ). The assembly process involves in situ comproportionation reaction between Cu²⁺ and Cu⁰ and the formation of two different clusters is controlled by reactants concentration. The clusters consist of Cu₁₅ and Cu₁₆ cores co‐stabilized by strong by σ‐ and π‐bonded tert‐butylethynide and CF₃COO^? (together with methanol molecule in 2 ). Their stabilities in solution were confirmed using electrospray ionization mass spectrometry in which the cluster core remains intact for 1 in chloroform and acetone, and for 2 in acetonitrile. Strong thermochromic luminescence in the near infrared (NIR) region was observed in the solid‐state. Of particular interest, the emission maximum of 1 is red‐shifted from 710 nm at 298 K to 793 nm at 93 K, along with a 17‐fold fluorescence enhancement. In contrast, 2 exhibits red shift from 298 to 123 K followed by blue shift from 123 to 93 K. The emission wavelength was correlated with the structural parameters using variable‐temperature X‐ray single‐crystal analyses. The rich cuprophilic interaction plays a significant role in the formation of ³LMCT (tBuC≡C→Cu_x) excited state mixed with cluster‐centered (³CC) characters, which can be considerably influenced by temperature, leading to thermochromic luminescence. The present work provides 1) a new synthetic protocol for the high‐nuclear Cu^I–alkynyl clusters; 2) a comprehensive insight into the mechanism of thermochromic luminescence; 3) unusual emissive materials with the characters of NIR and thermochromic luminescence simultaneously.     

Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes

Two polymorphic structures have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs showed distinct thermal‐ and photomagnetic behavior, and are thus ideal for studying the “pure” intermolecular factors to VT transitions. In polymorph 1A , the VT cations are arranged head‐to‐waist with their neighbors and exhibit weak π???π interactions, resulting in a gradual and incomplete thermal VT transition. In contrast, the cations in polymorph 1B are arranged head‐to‐tail and exhibit relatively strong π???π interactions, leading to an abrupt and complete thermal VT transition with adjustable hysteresis loop at around room temperature. The VT process for both polymorphs can be induced by light, but the light‐excited state of 1B? 2H₂O has a higher thermal relaxation temperature than that of 1A? 3H₂O.     

An Analytical Model for Fluid Imbibition in Organic Nanopores

Transport in Porous Media - Estimating the fluid imbibition flow in natural system composed of nanopores is challenging due to the strong fluid/rock molecular scale interaction and the invalidation...     

等离子体激励器的静特性与高速特性仿真研究

A parametric study of high-frequency plasma jet actuator was carried out, using the experiment- tally measured energy distribution law of arc discharge as an ideal heat source. The influence of the exit angle of the actuator on the flow field was explored. The jet flow field characteristics of the spark discharge actuator under supersonic flow (Ma0=2.0) were investigated. The results show that the energy density of heat flux increases and the jet front and forward shock wave moves faster with the decrease of discharge region, and the smaller the exit angle of the jet is, the stronger the momentum injection ability of the actuator along the flow direction is. The rule still applies under high-speed air flow conditions. Compared to the static condition, the momentum injection capability of the jet is stronger and the influence domain is larger under supersonic flow conditions.     

窄线宽光纤激光器在1030 nm波段实现3 kW近衍射极限输出

基于大模场面积掺镱光纤搭建了全光纤1030 nm高功率窄线宽光纤激光主振荡功率放大系统,实现了3004 W的最高功率输出,斜率效率69.27%,是目前报道的输出功率最高的1030 nm波段近衍射极限光纤激光器。最高输出功率时,x,y方向的光束质量因子分别为1.169,1.174,3 dB光谱宽度为0.18 nm,放大自发辐射抑制比达到37 dB。     

紫外熔石英元件高精度低缺陷控形控性制造技术研究进展

传统的紫外熔石英元件加工方法本身会引入各类制造缺陷,需要后期加工来消除前期加工带来的缺陷,限制了熔石英元件的加工质量和加工效率。针对这些问题,课题组提出了采用磁流变、离子束、保形光顺和流体动压抛光等可控柔体加工技术提升熔石英元件的加工效果,并开展了相关研究。主要介绍了课题组在关键技术上取得的重要进展,包括亚纳米精度表面控形制造技术、纳米精度本征表面控性生成方法、熔石英元件高精度低缺陷组合工艺与设备等一系列关键技术。通过探讨关键技术及其发展现状,为未来紫外熔石英元件高精度低缺陷制造技术的发展提供参考。     

Ti0.33WO3电子结构和太阳辐射屏蔽性能第一性原理研究

节能减排已成为当今社会发展的主题,对节约能源、提高太阳能的高效综合利用的新型窗用透明隔热材料的理论设计和研究尤其重要.本文采用基于密度泛函理论的计算方法,研究了六方相三氧化钨Ti掺杂前、后的晶格参数、电子能带结构、形成能和光学性质.研究结果表明,Ti掺杂后晶格体积增大,系统能量降为负值,体系具有更好的稳定性;掺杂后电子能带结构发生很大的变化,但材料仍保持n型电导率;随之,其光学性质也发生改变,掺杂前h-WO3无近红外吸收性能,掺杂后的Ti0.33WO3具有很强的近红外吸收性能.在此基础上研究了Ti掺杂h-WO3前、后的太阳辐射屏蔽性能,掺杂前无太阳辐射屏蔽性能;掺杂后的Ti0.33WO3薄膜具有可见光高透明、近红外屏蔽的性能.计算结果为Ti掺杂h-WO3在窗用透明隔热材料方面的研究提供了理论依据.