XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp3−H Functionalization

An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved.     

Synthesis and the effect of alkyl chain length on photochromic properties of diarylethene derivatives

A new class of photochromic diarylethenes bearing pyrrole and thiophene units with different length of alkyl chains at 2-position of thiophene rings have been synthesized. Their characteristics, including photochromism and fatigue resistance were investigated systematically, and each diarylethene derivative showed good photochromic properties whether in solution or in PMMA films. The alkyl group moiety was connected directly to the central cyclopentene ring as a heteroaryl unit and availably participated in photoisomerization reaction. And some properties, for example, the conversion ratio in the photostationary state(PSS) and the absorption coefficient of the ring-closed isomers in acetonitrile were significantly affected by the alkyl chain length. The results revealed that substituents of alkyl chain played an important role in the photoisomerization process of diarylethenes.     

Novel multi-responsive fluorescence switch for Hg2+ and UV/vis lights based on diarylethene-rhodamine derivative

A new multi-responsive fluorescent switch DTE-Pip-Rho 1O has been designed and synthesized in this study. For this molecule, the reactive site of spirolactam ring is far away from the diarylethene unit through the intramolecular piperazine. It exhibited high selectivity and sensitivity to Hg²⁺ in addition to obvious color change (colorless-pink) and fluorescence “off-on” (dark-orange) during this process. It is believed that the color change is due to Hg²⁺-assisted hydrolysis of rhodamine hydrazide. Therefore, the new molecule can be used as colorimentric and fluorescent chemosensor for Hg²⁺ with high selectivity. The detection limits of absorbance and fluorescence for Hg²⁺ were calculated to be 1.15?μM and 1.16?μM, respectively. The resulting DTE-Pip-Rho 1O-Hg²⁺ could also function as a reversible fluorescence photo-switch in response to UV/vis light owing to FRET mechanism. Moreover, it has been demonstrated that the photo-switchable system displayed excellent fatigue resistance and remarkable anti-photobleaching capability.     

Molecular design for a write-by-light/erase-by-heat recording system using photochromic diarylethenes with thermal cycloreversion

We designed and synthesized photochromic diarylethenes for a write-by-light/erase-by-heat recording system. The introduction of polar substituents at both sides of the diarylethene maintained the photocyclization and photocycloreversion reactivities, but significantly affected the thermal cycloreversion reactivity. The introduction of electron-withdrawing substituents accelerated the thermal reaction and the introduction of electron-donating substituents suppressed the thermal reaction. The rate constants of the thermal reaction were well correlated with Brown-Okamoto's substituent constant σ⁺ that is a modified value of Hammett's substituent constant σ. The large rate constants are ascribed to the lower activation energy for the thermal reaction. These results provide new knowledge for the molecular design of diarylethenes for a write-by-light/erase-by-heat recording system.     

基于自发瑞利-布里渊散射测量空气的温度

瑞利-布里渊散射的散射截面比拉曼散射大，因而其在大气散射中实现对大气对流层温度廓线的准确测量方面具有一定的优势，同时利用瑞利-布里渊散射实现高压环境下温度的准确测量对于航天飞机主引擎状态的监测和超燃发动机燃烧室参数测量方面具有重要意义。基于自发瑞利-布里渊散射分别采用反卷积方法和卷积方法来实现空气在不同压力条件下的温度反演，研究引起温度反演误差的原因，并对利用两种方法获得的温度测量结果进行了比较。在利用基于维纳滤波器的反卷积方法对测量光谱直接处理实现温度反演之前，首先利用反卷积方法对由自发瑞利-布里渊散射模型与仪器函数卷积得到的卷积光谱进行处理获得反卷积光谱，将反卷积光谱与未经卷积的理论计算光谱进行比较实现温度反演, 并基于温度反演误差小于1.0 K，光谱拟合误差相对较小，光谱处理时间短的参数优化原则对反卷积方法中的关键参数奇异值叠加数进行了优化处理，得到优化后的奇异值叠加数为150。随后实验测量了由532 nm波长的连续激光激发的纯净空气在温度为294.0 K，压强为1～7 bar条件下的自发瑞利-布里渊散射光谱，并结合理论计算光谱和最小χ2值原理对光谱信号散射角进行优化，优化值为90.7°，同时利用反卷积和卷积方法分别对实验测量光谱进行处理实现空气在不同压强下的温度反演。实验结果表明反卷积方法在一定程度上可以提高信号光谱分辨率，而且利用反卷积和卷积方法均可以实现空气在不同压力（1～7 bar）条件下温度的准确测量，温度测量的最大误差均小于2.0 K；利用反卷积方法的温度反演结果随着气体压强的增大随之得到改善，实现温度反演测量所需要的光谱处理时间减少；在空气压强较低（≤2 bar）时，由卷积方法获得的温度反演结果要优于反卷积方法，压强较高（>2 bar）时，两种方法的温度反演结果相近, 其绝对误差均小于1.0 K。通过分析得到引起两种方法温度反演误差的原因主要包括环境温度的波动（±0.2 K），散射角存在一定的不确定度以及气体的各已知参数的微量偏差对温度测量结果的影响以及反卷积对光谱噪声的非线性放大引起的光谱扰动对温度测量结果的影响。在实验中可以通过提高测量光谱的信噪比、提高散射角的优化精度及改善反卷积方法来获得更加准确的参数测量结果。     

Kinetics and isothermal adsorption of U(VI) in aqueous solution by nano-Ni0

Journal of Radioanalytical and Nuclear Chemistry - The nanoscale zero-valent nickel (nano-Ni0) was prepared by liquid-phase reduction method and characterized by BET, XPS, FT-IR and XRD and be used...     

Copper quinolate: A simple and efficient catalytic complex for coupling reactions

We describe an effective and novel method to prepare N-aryl imidazoles via the copper quinolate-catalyzed N-arylation of aryl halides and imidazoles. A wide range of products were obtained in moderate to excellent yields under the optimal reaction conditions. Applying standard conditions, the model reaction could be performed on a gram scale. This method also presents a new avenue to the “click” reaction of terminal alkynes, benzyl bromide, and sodium azide and to the construction of C–C bonds by homocoupling of phenylboronic acid or phenylacetylene derivatives with the aid of copper quinolate.     

Crosslinked polyaniline nanorods coupled with molybdenum disulfide on functionalized carbon cloth for excellent electrochemical performance

Journal of Solid State Electrochemistry - In this work, the binary nanocomposite of crosslinked polyaniline nanorods (CPANINRs) and molybdenum disulfide (MoS2) is first synthesized by in situ...