Recent advances in asymmetric reactions catalyzed by chiral phosphoric acids

The very recent advances in chiral phosphoric acids (CPAs) catalyzed asymmetric reactions are discussed.     

Near-infrared aminocyanine dyes: synthesis,optical properties,and application to the preparation of fluorescent microspheres

Several near-infrared (NIR) fluorescent dyes based on aminocyanine have been designed, synthesized, and used for preparation of NIR fluorescent microspheres. Their spectral properties and pH-dependent optical characteristics were investigated. It was found that different substitution at the central position of the dyes led to diverse optical properties, with especially large effects on their spectroscopic properties. Spectroscopic responses of the fluorescent dyes to changes of pH were different. Under acidic conditions, the wavelengths of maximum absorption of the N-substituted cyanine dyes were clearly red shifted. Dyes with an N-substituted piperazidine ring were the most sensitive. The fluorescent microspheres retained the properties of the parent dyes, making them suitable for applications in biological studies.     

Synthesis of CF2H‐Containing Oxime Ethers Derivatives from ClCF2H,tert‐Butyl Nitrile and Indoles

Summaryof main observation and conclusion A new and intriguing methodology to access various O-difluoromethylation oxime compounds from CICF2H,TBN and indoles is developed under mild reaction conditions.This strategy can suppress N-difluoromethylation of indoles successfully,in which there are two different active species(:CF2and·NO)while indoles are unprotected,featuringsimple operation and radical involvement.     

乙醛酸和草酸的毛细管区带电泳分析

建立了同时测定乙醛酸和草酸的毛细管区带电泳法。考察了缓冲溶液的种类、浓度和pH以及分离电压等因素对分离结果的影响。在缓冲溶液为20 mmol/L硼砂-5.5 mmol/L邻苯二甲酸氢钾(pH 9.0)、分离电压20 kV、检测波长212 nm的优化条件下,11 min内即可实现对目标物的分离。乙醛酸和草酸分别在0.8～20 g/L和1.2～20 g/L范围内线性关系良好,相关系数分别为0.9993和0.9975;方法的检出限分别为0.2和0.4 g/L(信噪比为3);样品的加标回收率为98.3%～102.5%,相对标准偏差为0.35%～0.61%。该方法操作简便、快速、成本低廉,已应用于实际样品的分析,并获得了令人满意的结果。     

非球面和梯度折射率在眼光学成象中的作用

在Gullstrand-Le Grand眼模型的基础上,构造不同的眼光学模型,分别研究了角膜非球面、晶状体非球面和昌状体折射率在眼光学成象中的作用.通过比较各模型系统的Zernike标准多项式系数,分析了非球面和梯度折射率对眼光光系统各象差的影响.同时研究了不同模型调制传递函数的特性.     

Research on Flood Loss Distribution and Catastrophe Bond Pricing Based on Bayesian Inference

Taking flood catastrophe risk in China as the research background, aiming at the characteristics of flood loss ``low frequency and high loss', Bayesian inference method is used to fit the loss distribution, and Bayesian inference is used to obtain the loss frequency distribution and loss quota distribution of flood in China. On this basis, Monte Carlo simulation method is used to calculate the probability distribution of annual flood loss in China under different trigger conditions, and then CAPM is used to study the pricing of flood catastrophe bonds in China. It is concluded that under different trigger conditions, as the trigger value increases gradually, the corresponding trigger is triggered. Comparing the three types of bonds, it can be found that the price of bonds decreases with the decrease of principal guarantee ratio and the increase of principal loss ratio, that is, the investment risk is directly proportional to the return, which provides reference for issuing flood catastrophe bonds in China.     

Theoretical insights into excited-state intramolecular proton transfer in 1,8-dihydroxydibenzo[a,h]phenazine

1,8-Dihydroxydibenzo[a,h]phenazine (DHBP) is a new synthetic compound possessing two intramolecular hydrogen bonds; however, it has been found to exhibit the excited-state intramolecular single proton transfer (ESSPT) behaviour, in recent experiment. To explain the phenomenon reasonably, two combined methods of CASSCF/CASPT2 and DFT/TD-DFT have been employed to investigate the structural and spectral properties of its three tautomers, corresponding to the non-proton-transferred (E), the single-proton-transferred (SK) and the double-proton-transferred (DK) forms. These studies suggest that the E form is the global minimum in the S₀ state, while the SK form is the most stable in the S₁ state, both of which are responsible for the experimental absorption peak at 2.54 eV and emission band at 1.64 eV, respectively. Because of the relatively high energy barrier, the DK form will play no important role in the fluorescence emission of DHBP. The present results lend a good support to the experimental finding of single proton transfer (SPT).     

Palladium-Catalyzed Atroposelective Kinetic C−H Olefination and Allylation for the Synthesis of C−B Axial Chirality

The direct C−H functionalization of 1,2-benzazaborines, especially asymmetric version, remains a great challenge. Here we report a palladium-catalyzed enantioselective C−H olefination and allylation reactions of 1,2-benzazaborines. This asymmetric approach is a kinetic resolution (KR), providing various C−B axially chiral 2-aryl-1,2-benzazaborines and 3-substituted 2-aryl-1,2-benzazaborines in generally high yields with excellent enantioselectivities (selectivity (S) factor up to 354). The synthetic potential of this reaction is showcased by late-stage modification of complex molecules, scale-up reaction, and applications.     

Chaos induced by weak A-coupled-expansion of non-autonomous discrete dynamical systems

This paper focuses on chaos induced by weak A-coupled-expansion of non-autonomous discrete systems in compact subsets of metric spaces and in bounded and closed subsets of complete metric spaces, separately. A new concept of weak A-coupled-expansion for non-autonomous discrete systems, whose condition is weaker than that of A-coupled-expansion, is introduced, and several new criteria of chaos induced by weak A-coupled-expansion of non-autonomous discrete systems are established. By applying some close relationships between chaotic dynamical behaviours of the original system and its induced systems, two criteria of chaos are established. One example is provided for illustration.