Copper-catalysed photoinduced decarboxylative alkynylation: a combined experimental and computational study

Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C–C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac)₂. The photoexcitation of copper acetylides with electron-rich NEt₃ as a ligand provides a general strategy to generate a range of alkyl radicals from RAEs of carboxylic acids, which can be readily coupled with a variety of aromatic alkynes. The scope of this cross-coupling reaction can be further expanded to aliphatic alkynes and alkynyl silanes using a catalytic amount of preformed copper-phenylacetylide. In addition, DFT calculations revealed the favorable reaction pathway and that the bidentate acetylacetonate ligand of the copper intermediate plays an important role in inhibiting the homo-coupling of the alkyne.

Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for Cu-catalysed C–C bond formation.     

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

A new solvatomorph of [Au₃(1-Methylimidazolate)₃] (Au₃(MeIm)₃)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au₃(MeIm)₃ has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.     

模式偏置波前传感器理论模拟及实验验证

将模式偏置法与全息多重存储法波前传感器原理联系起来,通过研究模式偏置波前传感器的输出响应特性,间接得到全息模式波前传感器的运行规律.对模式偏置波前传感器进行理论分析与总结,并建立简化模型,针对若干阶Zernike像差,通过数值模拟对理论结果进行验证.模拟结果显示:传感器输出信号与各种类型待测像差系数有不同的变化关系,这...     

电感耦合等离子体发射光谱法测定铝合金中La、Ce、Pr、Nd、Sm

利用ICP—AES仪测定稀土铝合金中微量的La、Ce、Pr、Nd、Sm。试样用酸分解,直接上机测定,对光谱干扰情况和仪器参数的选择进行了研究。实验结果和推荐值核对相符。     

Hierarchically imprinted porous films for rapid and selective detection of explosives

On the basis of the combination of colloidal and mesophase templating, as well as molecular imprinting, a general and effective approach for the preparation of hierarchically structured trimodal porous silica films was developed. With this new methodology, controlled formation of well-defined pore structures not only on macro- and mesoscale but also on microscale can be achieved, affording a new class of hierarchical porous materials with molecular recognition capability. As a demonstration, TNT was chosen as template molecule and hierarchically imprinted porous films were successfully fabricated, which show excellent sensing properties in terms of sensitivity, selectivity, stability, and regeneracy. The pore system reported here combines the multiple benefits arising from all length scales of pore size and simultaneously possesses a series of distinct properties such as high pore volume, large surface area, molecular selectivity, and rapid mass transport. Therefore, our described strategy and the resulting pore systems should hold great promise for various applications not only in chemical sensors, but also in catalysis, separation, adsorption, or electrode materials.     

用任意偏向角测量三棱镜折射率

本文给出用任意偏向角测量三棱镜折射率的理论公式和实验方法，并给出与最小偏向角法测量结果的比较，具有几乎一样的误差。     

Sensing Plant Physiology and Environmental Stress by Automatically Tracking Fj and Fi Features in PSII Chlorophyll Fluorescence Induction

Following a step excitation, chlorophyll fluorescence (ChlF) from photosystem II (PSII) of a dark‐adapted photosynthetic organism exhibits the well‐known OJIP pattern. The OJIP induction has been widely used in plant science and agriculture engineering. While the J and I phases are related to transitions of photochemical reaction redox states, characteristic fluorescence intensities at the two phases (F_j and F_i) are often treated at fixed time points in routine measurement and thus do not account for variations in plant and experimental conditions, this (1) neglects the differences in the time of appearance of these phases, which is potentially useful information for characterizing plant status and environmental factors, and (2) leads to errors in measured F_j and F_i values in the many publications. In this work, an alternative method for consistent measurement of F_j and F_i was presented. The proposed method measures the curvatures in the OJIP curve and automatically tracks the characteristic transition points under variable sample and experimental conditions. Experiments were carried out to demonstrate the concept and classification capabilities of the method. This research has established a new framework to analyze ChlF and has enhanced the application capability of ChlF. It is expect useful in analysis ChlF from PSII.