The photoisomerization of 11‐cis‐retinal protonated schiff base in gas phase: Insight from spin‐flip density functional theory

This extensive theoretical study employed the spin‐flip density functional theory (SFDFT) method to investigate the photoisomerization of 11‐cis‐retinal protonated Schiff base (PSB11) and its minimal model tZt‐penta‐3,5‐dieniminium cation (PSB3). Our calculated results indicate that SFDFT can perform very well in describing the ground‐ and excited‐state geometries of PSB3 and PSB11. We located the conical intersection (CI) point and constructed the photoisomerization reaction path of PSB3 and PSB11 by using the SFDFT method. To further verify the SFDFT results, we computed the energy profiles along the constructed linearly interpolated internal coordinate (LIIC) pathways by using high‐level theoretical methods, such as the EOM‐CCSD, CR‐EOM‐CCSD(T), CASPT2, NEVPT2, and XMCQDPT2 methods. The SFDFT method predicts that the photoisomerization of PSB3 is barrierless, in accordance with previous complete‐active‐space self‐consistent‐field (CASSCF) results. However, an energy barrier is predicted along the LIIC pathways of PSB11. This finding is different from previous CASSCF results and may indicate that the photoisomerization of PSB11 in gas phase is similar to that in solution. However, the higher spin contamination of the SFDFT method in the vicinity of the CI point caused the located CI geometry to deviate from that of the real CI. In addition, the LIIC pathways are only approximations to the minimum energy path (MEP). Thus, further experimental and theoretical studies are needed to verify the existence of an energy barrier along the photoisomerization reaction path of PSB11 in gas phase. © 2013 Wiley Periodicals, Inc.     

一种检测CO32-比率荧光探针的合成及其在细胞成像中的应用

本文设计开发了一种以2,6-二甲酰基对甲苯酚为母体的新型荧光探针HMI,可用于高效识别EtOH-H₂O (8/2, v/v, HEPES 10 mM, pH =7.4)体系中的CO_3^2-。HMI在660 nm处显示发射带,加入CO_3^2-后,在600 nm的等吸收点激发时,原来在660 nm处的荧光淬灭,而以540 nm为中心的新发射带荧光显着增加,为比率型荧光探针。HMI对CO_3^2-表现出高选择性且具有较强的抗干扰能力。此外,荧光探针HMI对CO_3^2-荧光响应的检测限较低,可达到3.938×10^_-6 M。更具有意义的是,HMI探针对CO_3^2-的检测能够在实际水样中起到很好的应用,而且细胞成像研究表明,HMI可用于活体MCF-7细胞中CO_3^2-的成像。     

Doped Zero-Dimensional Cesium Zinc Halides for High-Efficiency Blue Light Emission

All-inorganic zero-dimensional (0D) metal halides have recently received increasing attention due to their excellent photoluminescence (PL) performance and high stability. Herein, we present the successful doping of copper(I) into 0D Cs₂ZnBr₄. The incorporating of Cu⁺ cations enables the originally weakly luminescent Cs₂ZnBr₄ to exhibit an efficient blue emission centered at around 465 nm, with a high photoluminescence quantum yield (PLQY) of 65.3 %. Detailed spectral characterizations, including ultrafast transient absorption (TA) techniques, were carried out to investigate the effect of Cu⁺ dopants and the origin of blue emission in Cs₂ZnBr₄:Cu. To further study the role of the A-site cation and halogen, A₂ZnCl₄:Cu (A=Cs, Rb) were also synthesized and found to generate intense sky-blue emission (PLQY≈73.1 %). This work represents an effective strategy for the development of environmentally friendly, low-cost and high-efficiency blue-emitting 0D all-inorganic metal halides.     

Experimental indications for the response of the spectators to the participant blast

Precise momentum distributions of identified projectile fragments, formed in the reactions 238U+Pb and 238U+Ti at 1A GeV, are measured with a high-resolution magnetic spectrometer. With increasing mass loss, the velocities first decrease as expected from previously established systematics, then level off, and finally increase again. Light fragments are on the average even faster than the projectiles. This finding is interpreted as the response of the spectators to the participant blast. The reacceleration of projectile spectators is sensitive to the nuclear mean field and provides a new tool for investigating the equation of state of nuclear matter.     

ZnSm2O4稀土复合氧化物的结构与光谱学性质

报道了以流变相-先驱物法制备稀土复合氧化物ZnSm2O4的软化学方法.首先用流变相法合成了草酸盐先驱物,然后用差热分析(DTA)和热重分析(TG)研究了先驱物在空气中的热分解过程;用X射线粉末衍射和红外光谱表征了热分解固体产物;最后研究了ZnSm2O4固体紫外-可见吸收光谱.结果表明,ZnSm2O4为尖晶石结构,晶胞参数a=0.921 453 nm,晶胞体积V=0.782 38 nm3,化合物在紫外-可见范围内存在吸收.其中,236.2 nm为Sm3+-O2-电荷转移跃迁,而383.4,405.2,495.4 nm为Sm3+的4G5/2→7HJ/2(J=5,7,9)的电子跃迁.     

噻唑并[3,2-a]嘧啶衍生物的合成及其在水介质中识别Fe3 的性能

噻唑[3,2-a]并嘧啶衍生物具有多种生物活性,但其较差的溶解性限制了其应用。本文在7-(3-氨基苯并呋喃-2-基)-噻唑并[3,2-a]嘧啶-5-酮的芳香环上引入三乙二醇单甲醚,成功合成了化合物L,并利用核磁、质谱对其结构进行了表征。在pH 3.4~6.4范围内,化合物L可在HEPES水溶液中荧光"开-关"识别Fe~(3+),其他金属离子对识别作用没有干扰,该荧光探针具有较高的选择性和较低的检测限。     

方便、实用的化学作图软件ISIS/DRAW

随着科技的飞速发展 ,计算机在化学化工中的应用越来越广泛深入 ,其中一个重要方面就是用计算机来绘制各种化学、化工的专业图形。在众多的化学制图软件中 ,ＩＳＩＳ Ｄｒａｗ以其完善的制绘多种化学分子结构式、化学反应方程式及化工流程图的功能 ,引起了广大化学工作者的注意。ＩＳＩＳ Ｄｒａｗ是 1 990年由ＭＤＬ公司开发的一个化学制图软件 ,它的较新版本为 2 2 1 ,是 1 999年4月升级后的第五代产品。该软件可从下列网址方便地免费下载 :ｈｔｔｐ : ｗｗｗ .ｍｄｌｉ.ｃｏｍ ｃｇｉ ｄｙｎａｍｉｃ ｄｏｗｎｌｏａｄｓｅｃｔｈｔｍ…     

抗污染高分子分离膜研究进展

高分子分离膜已广泛应用于水处理、食品、生物医药等领域。然而,常用的膜材料如聚醚砜(PES)、聚砜(PSf)、聚偏氟乙烯(PVDF)等容易吸附蛋白质和微生物形成膜污染,进而影响膜的性能和使用寿命。膜污染尤其是膜的生物污染成为限制膜广泛应用的主要瓶颈之一。本文从亲水改性、抗菌改性及亲水抗菌双功能改性三方面综述了控制膜污染的研究进展和现状,并对其未来发展方向进行了展望。     

一种基于喹唑啉酮衍生物的荧光探针对次氯酸根离子的识别

次氯酸根(ClO~-)在人体免疫系统中发挥着重要的作用,其识别与检测备受关注。本文设计合成了一种含有喹唑啉酮骨架的腙型荧光探针(HEMQ),并通过~1H NMR、~(13)C NMR、高分辨质谱(HRMS)表征了其结构。探针HEMQ在V(乙醇)∶V(水)=1∶1(c(PBS)=0.02 mol/L,pH=8.7)溶液中对ClO~-具有良好的选择性且响应快速,荧光发生显著猝灭。探针HEMQ对ClO~-具有较高的灵敏度,检测限为1.0×10-4mol/L。此外,ClO~-可引起探针溶液由黄色到无色的颜色变化,因此HEMQ可作为比色、荧光双通道响应的ClO~-探针。