方酸菁荧光探针的应用研究进展

功能性方酸菁染料具有独特的D-A-D共轭结构,其在可见光和近红外区域有强烈的吸收和荧光发射。方酸菁染料作为近红外荧光探针母体被应用于蛋白质、氨基酸、一些生物小分子、环境污染物及金属离子等的检测。本文结合课题组近几年工作综述了方酸菁染料在蛋白质、氨基酸、生物小分子、阳离子和其它物质检测方面的应用。     

Naphthalimide-rhodamine based fluorescent probe for ratiometric sensing of cellular pH

The pH values of lysosomes in cancer cells is slightly lower than that in normal cells, which can be used to distinguish cancer cells from normal cells. According to this, a naphthalimide-rhodamine based fluorescent probe(hereafter referred to as RBN) with a pK_a of 4.20 was designed and synthesized for ratiometric sensing of cellular pH via fluorescence resonance energy transfer(FRET), which can respond to different pH precisely through ratiometric fluorescence intensity(Ⅰ_(577)/Ⅰ_(540)). RBN can be employed to distinguish cancer cells from normal cells on the basis of different fluorescent response, in particular, RBN showed excellent water solubility and low cell toxicity, all these are quite significant for potential application in cancer diagnose and therapy.     

Rational Design of an Ultrasensitive and Highly Selective Chemodosimeter by a Dual Quenching Mechanism for Cysteine Based on a Facile Michael‐Transcyclization Cascade Reaction

Differentiation of biologically important thiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH) is still a challenging task. Herein, we present a novel fluorescent chemodosimeter capable of selectively detecting Cys over other biothiols including Hcy and GSH and other amino acids by a facile thiol‐Michael addition/transcyclization rearrangement cascade click process. The unique transcyclization step is critical for the selectivity as a result of the kinetically favorable formation of a six‐membered ring with the Cys Michael adduct. Moreover, the probe adopts a distinctive dual quenching mechanism—photoinduced electron transfer (PET) and photoinduced intramolecular charge transfer (ICT) to deliver a drastic turn‐on fluorescence response only at the Cys‐selective transcylization step. The judicious selection of strong electron‐withdrawing naphthalimide fluorophore with maleimide group enhances the electrophilicity and thus reactivity for the cascade process leading to fast detection and ultrasensitivity with a detection limit of 2.0 nm (S/N=3). The probe has demonstrated its practical utility potential in Cys imaging in live cells.     

Thermochemical process in preparation of ZnO film by TFA-MOD method

The excess weight loss due to the evaporation of zinc compound is observed in the growth of ZnO film by trifluoroacetate metalorganic deposition (TFA-MOD) method. Higher temperature (>90 °C) aging and/or addition of monoethanolamine (MEA) are effective to prevent the evaporation of zinc compound and increase the yield of ZnO. The mechanism of preventing evaporation is that zinc trifluoroacetate is hydrolyzed into Zn₄O(CF₃COO)₆. A three-dimensional structure of Zn₄O(CF₃COO)₆ is proposed. It is shown that higher temperature aging does harm to the surface morphology of ZnO films. The addition of MEA reduces the required aging temperature thus improves the surface morphology.     

Chemical Synthesis,Structure Characterization,and Optical Properties of Hollow PbSx–Solid Au Heterodimer Nanostructures

Heterodimer nanostructures have attracted extensive attention, owing to an increasing degree of complexity, functionality, and then importance. So far, all the reported ones are built from solid nanoparticles. Herein, nearly monodisperse heterodimer nanostructures are constructed by hollow PbS_x and solid Au domains simultaneously through a mild reaction between PbS nanocrystals and the gold species in the presence of dodecylamine. Control experiments clearly reveal the underlying formation mechanism of the hollow PbS_x–solid Au heterodimers. The Au^III species in the solution, lead to the etching of PbS nanocrystals and the Au^I species facilitate the control of the number of gold domains per nanoparticle. Dodecylamine molecules not only work as a stabilizer in the reaction, but also act as a reducing agent that could greatly affect the morphology of the product. The optical properties of the heterodimers are investigated based on UV/Vis absorption spectroscopy and Raman spectroscopy. This novel heterodimer nanostructure pushes the development of complex nanocrystal‐based architectures forward, and also provides many opportunities for potential applications.     

Unexpected hydrobromic acid-catalyzed C-C bond-forming reactions and facile synthesis of coumarins and benzofurans based on ketene dithioacetals

Hydrobromic acid was found to be a unique catalyst in C? C bond‐forming reactions with ketene dithioacetals. Distinctly different from other acids (including Lewis and Brønsted acids), the remarkable catalytic performance of hydrobromic acid in catalytic amounts was observed in the “acid”‐catalyzed reactions of readily available functionalized ketene dithioacetals 1 with various electrophiles. Under the catalysis of 0.1 equivalents of hydrobromic acid, the reaction of 1 with carbonyl compounds 2 a – l gave polyfunctionalized penta‐1,4‐dienes 3 or conjugated dienes 4 in good to excellent yields. The reaction tolerated a broad range of substituents on both the ketene dithioacetals 1 and the carbonyl compounds 2 . Application of this efficient C? C bond‐forming method generated coumarins 5 and benzofurans 7 under mild, metal‐free conditions by hydrobromic acid‐catalyzed reactions of 1 with salicylaldehydes 2 m – o and p‐quinones 6 a – d , respectively. A new reactive species, a sulfur‐stabilized carbonium ylide, formed depending on the nature of the counterion, and this was proposed as the key intermediate in the unique catalysis of hydrobromic acid.     

关于SOL流形具有常平均曲率旋转曲面的注记

研究非欧流形SOL 空间上共形平均曲率方程的可解性,通过研究轮廓曲线对具有平均曲率的旋转曲面进行分类。当这些旋转曲面的平均曲率为给定函数时,计算出相应轮廓曲线的微分方程。通过求解这些微分方程,给出旋转函数是其上共形平均曲率的充分条件。     

ESTIMATION OF ACTIVATED ENERGY OF DESORPTION OF n-HEXANE ON ACTIVATED CARBONS BY TPD TECHNIQUE

1. INTRODUCTION In some cities of China, cancer and breath system diseases caused by the pollution of volatile organic compounds (VOCs) have been obviously increasing. The VOCs includes BTEX (benzene, toluene, ethylbenzene, and xylene), aldehydes, cresol, phenol, acetic acid, polynuclear aromatic hydrocarbons (PAHs), which have long-term human health implications. Emission of the VOCs has threatened the health of people seriously [1,2]. The pollution of the VOCs mostly hails from…     

稳态条件下气溶胶粒子在口腔模型中的沉淀率

以实际人体解剖学数据为基础,利用流体力学软件构建了口腔模型。由于口腔形状不规则,流场中会有湍流产生,所以本文选用的是k-ω方程。在此基础上,假设吸入空气流量为一个常量,改变吸入气体、气溶胶粒子的物理参数,以调整St数的变化,模拟不同情况下气溶胶粒子运动情况。由模拟结果可知:气溶胶粒子在口腔中的沉淀率受粒子半径、密度、及流速的影响,并随这些量的增加而增加;沉淀率可以视作St数的函数,并随St数的增加而增加;气溶胶粒子在口腔中的沉淀分布受模型几何形状和湍流的影响,在喉部附近沉淀较为明显;粒子在口腔中将沿怎样的轨迹运动则取决于粒子在入口处的初始位置。     

雷达隐身与反隐身技术的发展与现状

讨论现代战场环境中出现的雷达隐身与反隐身课题。阐述当今世界上雷达隐身与反隐身技术的现状及主要代表形式，分析其技术实现途径及发展方向。