Indandione-Terminated Quinoids: Facile Synthesis by Alkoxide-Mediated Rearrangement Reaction and Semiconducting Properties

A series of 1,3-indandione-terminated π-conjugated quinoids were synthesized by alkoxide-mediated rearrangement reaction of the respective alkene precursors, followed by air oxidation. This new protocol allows access to quinoidal compounds with variable termini and cores. The resulting quinoids all show LUMO levels below −4.0 eV and molar extinction coefficients above 10⁵ L mol⁻¹ cm⁻¹. The optoelectronic properties of these compounds can be regulated by tuning the central cores as well as the aryl termini ascribed to the delocalized frontier molecular orbitals over the entire molecular skeleton involving aryl termini. n-Channel organic thin-film transistors with electron mobility of up to 0.38 cm² V⁻¹ s⁻¹ were fabricated, showing the potential of this new class of quinoids as organic semiconductors.     

Alloyed Crystalline CdSe1-xSx Semiconductive Nanomaterials – A Solid State 113Cd NMR Study

Solid-state NMR analysis on wurtzite alloyed CdSe_1−xS_x crystalline nanoparticles and nanobelts provides evidence that the ¹¹³Cd NMR chemical shift is not affected by the varying sizes of nanoparticles, but is sensitive to the S/Se anion molar ratios. A linear correlation is observed between ¹¹³Cd NMR chemical shifts and the sulfur component for the alloyed CdSe_1−xS_x (0<x<1) system both in nanoparticles and nanobelts (δ_Cd=169.71⋅X_S+529.21). Based on this correlation, a rapid and applied approach has been developed to determine the composition of the alloyed nanoscalar materials utilizing ¹¹³Cd NMR spectroscopy. The observed results from this system confirm that one can use ¹¹³Cd NMR spectroscopy not only to determine the composition but also the phase separation of nanomaterial semiconductors without destruction of the sample structures. In addition, some observed correlations are discussed in detail.     

Counter‐Intuitive Gas‐Phase Reactivities of [V2]+ and [V2O]+ towards CO2 Reduction: Insight from Electronic Structure Calculations

[V₂O]⁺ remains “invisible” in the thermal gas‐phase reaction of bare [V₂]⁺ with CO₂ giving rise to [V₂O₂]⁺; this is because the [V₂O]⁺ intermediate is being consumed more than 230 times faster than it is generated. However, the fleeting existence of [V₂O]⁺ and its involvement in the [V₂]⁺ → [V₂O₂]⁺ chemistry are demonstrated by a cross‐over labeling experiment with a 1:1 mixture of C¹⁶O₂/C¹⁸O₂, generating the product ions [V₂¹⁶O₂]⁺, [V₂¹⁶O¹⁸O]⁺, and [V₂¹⁸O₂]⁺ in a 1:2:1 ratio. Density functional theory (DFT) calculations help to understand the remarkable and unexpected reactivity differences of [V₂]⁺ versus [V₂O]⁺ towards CO₂.     

Host–Guest Complexation of Amphiphilic Molecules at the Air–Water Interface Prevents Oxidation by Hydroxyl Radicals and Singlet Oxygen

The oxidation of antioxidants by oxidizers imposes great challenges to both living organisms and the food industry. Here we show that the host–guest complexation of the carefully designed, positively charged, amphiphilic guanidinocalix[5]arene pentadodecyl ether (GC5A‐12C) and negatively charged oleic acid (OA), a well‐known cell membrane antioxidant, prevents the oxidation of the complex monolayers at the air–water interface from two potent oxidizers hydroxyl radicals (OH) and singlet delta oxygen (SDO). OH is generated from the gas phase and attacks from the top of the monolayer, while SDO is generated inside the monolayer and attacks amphiphiles from a lateral direction. Field‐induced droplet ionization mass spectrometry results have demonstrated that the host–guest complexation achieves steric shielding and prevents both types of oxidation as a result of the tight and “sleeved in” physical arrangement, rather than the chemical reactivity, of the complexes.     

Photoactivated Fluorescence Enhancement in F,N‐Doped Carbon Dots with Piezochromic Behavior

Photoactivation in CdSe/ZnS quantum dots (QDs) on UV/Vis light exposure improves photoluminescence (PL) and photostability. However, it was not observed in fluorescent carbon quantum dots (CDs). Now, photoactivated fluorescence enhancement in fluorine and nitrogen co‐doped carbon dots (F,N‐doped CDs) is presented. At 1.0 atm, the fluorescence intensity of F,N‐doped CDs increases with UV light irradiation (5 s–30 min), accompanied with a blue‐shift of the fluorescence emission from 586 nm to 550 nm. F,N‐doped CDs exhibit photoactivated fluorescence enhancement when exposed to UV under high pressure (0.1 GPa). F,N‐doped CDs show reversible piezochromic behavior while applying increasing pressure (1.0 atm to 9.98 GPa), showing a pressure‐triggered aggregation‐induced emission in the range 1.0 atm–0.65 GPa. The photoactivated CDs with piezochromic fluorescence enhancement broadens the versatility of CDs from ambient to high‐pressure conditions and enhances their anti‐photobleaching.     

Chemical constituents isolated from stems of Schisandra chinensis and their antifeedant activity against Tribolium castaneum

Abstract

One new sesquiterpene (α-iso-cubebenol acetate, 8), together with 9 known compounds (1-7, 9, 10) were isolated from the stems of Schisandra chinensis (Turcz.) Baill. by repeated silica gel column chromatography. Based on the results of MS, NMR spectra and comparing with literature data, the six dibenzocyclooctadiene lignans were identified as schizandrin A to C (1-3), schizandrin (4), schisantherin A (5) and gomisin J (6), the two sesquiterpenes were identified as α-iso-cubebenol (7) and α-iso-cubebenol acetate (8), while the two triterpenic acids were identified as ganwuweizic acid (9) and kadsuric acid (10). The antifeedant activity of the 10 compounds against Tribolium castaneum adults was tested. Gomisin J (6) exhibited activity at 1500?ppm concentration with 40.3% antifeeding index percentages. As for the dibenzocyclooctene lignans (compounds 1–3, 6), the number of methylenedioxies and the position of hydroxyl groups were the main factors to affect their antifeedant activities.     

A weak cation exchanger by encapsulating silica with maleic anhydride–modified polyvinyl alcohol

A novel weak cation exchanger is described by encapsulating silica with a (or multiple) layer(s) of maleic anhydride–modified polyvinyl alcohol coating(s). The preparation method is facile and fast, which is simply performed by dipping silica particles into maleic anhydride–modified polyvinyl alcohol solution as‐synthesized, then filtering and curing thermally, and finally generating a thin coating onto silica particles. Multiple layers of maleic anhydride–modified polyvinyl alcohol coatings can be generated by repeating above steps, offering an easy way to manipulate the capacity. The obtained weak cation exchanger demonstrated high separation efficiency and good selectivity toward common inorganic cations, for example, high plate count of 81 000 per meter was obtained for NH₄⁺. Simultaneous separation of alkali and alkaline earth metals could be achieved within 14 min under isocratic conditions.     

收缩扩张管内液氮空化流动演化过程试验研究

本文基于低温空化试验平台研究了收缩扩张流道内液氮非定常空化流动的演化过程. 试验采用高时空分辨率的高速摄像机对77 K液氮在不同空化数σ下空穴结构的演变进行了精细化的分析和研究. 利用试验得到的空穴长度和面积等数据, 定量分析了液氮空化流动的非定常特性与时空演变规律. 研究结果表明: (1)在相似来流速度和温度条件下, 随着空化数的减小, 液氮空化流动呈现四种典型流型, 空穴长度在2.5 h以内为初生空化、空穴长度在2.5 h ~ 7.5 h之间为片状空化、空穴长度在7.5 h ~ 15 h之间为大尺度云状空化, 空穴长度超过15 h为双云状空化, 且在大尺度云状空化和双云状空化阶段均捕捉到了回射流现象; (2)液氮空化流动从初生空化到双云状空化, 脱落空穴的尺度逐渐增大, 空穴面积脉动的幅值和准周期均有所增加. 同时, 在大尺度云状空化与双云状空化阶段, 喉口处堵塞效应对空化流动的影响显著增强; (3)相比于初生空化, 片状空化、大尺度云状空化以及双云状空化中脱落空穴的移动距离依次增加了0.97倍、2.65倍与2.68倍, 溃灭时间依次增加了1.18倍、3.59倍与4.47倍, 但溃灭速度依次减小了0.10倍、0.20倍与0.30倍. 除此之外, 对于双云状空化阶段, 存在两种显著不同的脱落空穴演化过程.      

Nonlinear oscillation of active magnetic bearing–rotor systems with a time-delayed proportional–derivative controller

Nonlinear Dynamics - A time-delayed proportional–derivative controller is applied to suppress the nonlinear vibration of a rigid rotor suspended by the active magnetic bearing (AMB) subjected...     

一种弹体入水冲击波阴影成像可视化系统及其试验研究

扩大成像视野对于开展充水容器中弹体入水冲击波传播及弥散方面的可视化研究具有重要的实际意义。阴影成像技术适用于大视野实验,且对流场冲击波和扰动的可视化研究具有简单性和通用性,其中直接阴影成像最为简单,但可靠点光源的缺乏是阻碍其发展应用的瓶颈。因此基于国产短弧氙灯管,自制了短弧氙灯点光源,根据阴影成像原理,设计出一种弹体入水冲击波阴影成像可视化系统,详细介绍了其组成和运行原理。利用该系统对高速弹体入水进行了试验研究,获得了弹体入水冲击波的阴影成像和冲击波信号的压力时程曲线,通过阴影成像和冲击波信号相结合分析了弹体入水冲击波的传播特性,并进行了理论验证。结果表明:该弹体入水冲击波阴影成像可视化系统具有可靠性和设计的合理性。弹体高速入水后,初始冲击波的强度最大,随着冲击波的传播,冲击波强度逐渐降低,水中冲击波的传播速度不断降低,球形冲击波的半径逐渐增大。