苯酚(醌)与烯烃的不对称[3+2]环化反应: 手性二氢苯并呋喃的合成进展

二氢苯并呋喃结构单元广泛存在于具有良好生物活性和药用价值的天然产物之中, 因而引起了有机合成化学家和药物化学家们的关注. 针对该结构单元所包含的C2和C3邻二立体中心的对映选择性构建, 也是目前有机合成方法学研究的挑战性问题之一. 在众多解决方案中, 以苯酚(醌)与烯烃为底物, 具体采用催化不对称和手性辅剂诱导的[3+2]环化两种方式, 可以构建具有光学活性的二氢苯并呋喃结构单元. 本综述将不同类型的手性催化剂和手性辅剂进行分类梳理, 介绍了近年来不对称[3+2]环化反应的发展, 并重点剖析其中涉及的立体选择性控制. 同时, 简要介绍了该关键方法在二氢苯并呋喃天然产物合成中的应用. 为了启发更加高效和普适性的新催化体系出现, 最后总结和展望了不对称[3+2]环化反应的发展趋势.     

钠离子电池用高性能锑基负极材料的调控策略研究进展

锑(Sb)具有高的理论比容量、较小的电极极化、合适的Na⁺脱嵌电位、价格低廉以及环境友好的优势,而成为一种具有较大应用前景的钠离子电池负极材料。但是,Sb基负极材料的一个重要挑战是在循环过程中高比容量伴随着大的体积变化,进而导致活性材料粉化,并从集流体上脱落,这大大限制了其在钠离子电池领域的大规模应用。因此,如何解决Sb基负极材料充放电过程中体积膨胀问题对于高性能的钠离子电池设计是至关重要的。本文详细综述和讨论了Sb基材料的结构-性能关系及其在钠离子电池中的应用,详细介绍了钠离子电池Sb基负极材料在氧化还原反应机理、形貌设计、结构-性能关系等方面的最新研究进展。本综述的主要目的是探讨影响Sb基负极材料性能的决定因素,从而提出有前途的改性策略,以提高其可逆容量和循环稳定性。最后,对Sb基钠离子电池负极材料的未来发展、面临的挑战和前景进行了展望。本文可为Sb负极材料的构建和优化提供具体的观点,阐明了Sb基负极材料未来的发展方向,从而促进钠离子电池的快速发展和实际应用。     

Polyimidazolyl acetate ionic liquid grafted on cellulose filter paper as thin-film extraction phase for extraction of non-steroidal anti-inflammatory drugs from water

Recently, pharmaceuticals and personal care products in the water environment exhibited potential risks to both human and aquatic organisms. In order to improve the sensitivity and accuracy of pharmaceutical detection, the polyimidazolyl acetate ionic liquid was synthesized by Radziszewski reaction and coated on cellulose filter papers as a thin-film extraction phase for extraction of non-steroidal anti-inflammatory drugs from water. The attenuated total reflection-infrared spectrometry, thermogravimetric analysis, and scanning electron microscope analyses demonstrated that the polyimidazolyl acetate ionic liquid was successfully prepared and attached to the surface of the cellulose filter paper through chemical bonding. The adsorption capacity of the homemade thin-film extraction material for the four non-steroidal anti-inflammatory drugs was greater than 8898 ng/cm² under the optimum conditions, and the desorption rate was over 90%. Then, a paper-based thin-film extraction phase-high-performance liquid chromatography-tandem mass spectrometry method was established for the extraction of non-steroidal anti-inflammatory drugs in water. This method provided limits of detection and limits of quantification were in the range of 0.02–0.15 and 0.17–0.50 μg/L, respectively. Hence, the obtained thin-film extraction phase showed excellent recovery and reproducibility for the target non-steroidal anti-inflammatory drugs with carboxyl groups from water.     

Photophysical Study and Biological Applications of Synthetic Chalcone-Based Fluorescent Dyes

A chalcone series (3a–f) with electron push–pull effect was synthesized via a one-pot Claisen–Schmidt reaction with a simple purification step. The compounds exhibited strong emission, peaking around 512–567 nm with mega-stokes shift (∆λ = 93–139 nm) in polar solvents (DMSO, MeOH, and PBS) and showed good photo-stability. Therefore, 3a–f were applied in cellular imaging. After 3 h of incubation, green fluorescence was clearly brighter in cancer cells (HepG2) compared to normal cells (HEK-293), suggesting preferential accumulation in cancer cells. Moreover, all compounds exhibited higher cytotoxicity within 24 h toward cancer cells (IC₅₀ values ranging from 45 to 100 μM) than normal cells (IC₅₀ value >100 μM). Furthermore, the antimicrobial properties of chalcones 3a–f were investigated. Interestingly, 3a–f exhibited antibacterial activities against Escherichia coli and Staphylococcus aureus, with minimum bactericidal concentrations (MBC) of 0.10–0.60 mg/mL (375–1000 µM), suggesting their potential antibacterial activity against both Gram-negative and Gram-positive bacteria. Thus, this series of chalcone-derived fluorescent dyes with facile synthesis shows great potential for the development of antibiotics and cancer cell staining agents.     

Computational studies on two novel energetic nitrogen‐rich compounds based on tetrazolone

Two novel energetic nitrogen‐rich compounds 1,4‐diaminotetrazol‐5‐one ( DATO ) and 1,4‐dinitrotetrazol‐5‐one ( DNTO ) were proposed first and studied by quantum chemistry method with B3LYP/6‐31G* level of theory. The optimized geometry, IR predicted spectrum and thermochemical parameters, frontier molecular orbitals and molecular electrostatic potential were calculated for inspecting the electronic structure, molecular stability and chemical reactivity. The important macroscopic properties including density, enthalpy of formation, detonation parameters and impact sensitivity have been predicted as well. As a result, two designed compounds DATO and DNTO possess positive enthalpy of formation (395.79 and 342.77 kJ/mol), impressive detonation parameters (D = 8.80 km/s, P = 33.69 GPa; D = 8.89 km/s, P = 34.98 GPa) superior to the remarkable explosive RDX, acceptable sensitivities and might be promising candidates of energetic materials. Copyright © 2015 John Wiley & Sons, Ltd.     

Frequency dependence of phase-synchronization time in nonlinear dynamical systems

It has been found recently that the averaged phase-synchronization time between the input and the output signals of a nonlinear dynamical system can exhibit an extremely high sensitivity to variations in the noise level. In real-world signal-processing applications, sensitivity to frequency variations may be of considerable interest. Here we investigate the dependence of the averaged phase-synchronization time on frequency of the input signal. Our finding is that, for typical nonlinear oscillator systems, there can be a frequency regime where the time exhibits significant sensitivity to frequency variations. We obtain an analytic formula to quantify the frequency dependence, provide numerical support, and present experimental evidence from a simple nonlinear circuit system.     

Back contact–absorber interface modification by inserting carbon intermediate layer and conversion efficiency improvement in Cu2ZnSn(S,Se)4 solar cell

Carbon layers have been employed as intermediate layers between Mo back contact and Cu₂ZnSn(S_1–xSe_x)₄(CZTSSe) absorber film prepared by sol–gel and post‐selenization method. Carbon layers with appropriate thickness can significantly inhibit the formation of MoSe₂ and voids at bottom region of the absorber, and therefore reduce the series resistance remarkably. The conversion efficiency can be boosted by the introducing of the carbon layer from 6.20% to 7.24% by enhancement in short current density, fill factor and open voltage in comparison to the reference sample without carbon layer. However, excess thickness of carbon layer will worse device performance due to the deteriorated absorber crystallinity. In addition, the time‐resolved photoluminescence analysis shows that inserting the carbon layer with suitable thickness does not introduce recombination and lower minority lifetime. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Theoretical kinetic study on the decomposition of 1,5‐diaminotetrazole

1,5‐Daminotetrazole (DAT) is of much interest because of the practical significance and the diversity of characteristics. The study on the decomposition pathway and the kinetics of DAT has been performed based on the quantum chemistry theory. The minimum energy path (MEP) calculation has shown that NH₂N₃ and NH₂CN are the initially detected products of DAT. And the structures of reactant, products and transition state were optimized with MP2 methods using 6‐311G** basis sets, and the energies were refined using CCSD(T)/6‐311G** levels of theory. The calculated rate constants were obtained using the conventional transition‐state theory (TST) and the canonical variational transition‐state theory (CVT) methods. The calculation results indicated that the energy barrier of decomposition reaction is 47.98 kcal mol^?1 and the variational effect is small. In addition, the rate constants and the Arrhenius experience formula of DAT decomposition have been obtained between 200 and 2500 K temperature regions. The fitted three‐parameter expressions calculated using the TST and CVT methods are (TST) and (CVT). This work may provide the theoretical support for further experimental synthesis and testing. Copyright © 2015 John Wiley & Sons, Ltd.     

Comparison of cadmium manganese telluride crystals grown by traveling heater method and vertical Bridgman method

In this paper, the CdMnTe crystals were grown by the Travelling Heater Method (THM) and the Vertical Bridgman (VB) method, respectively. The crystal properties, including the Mn axial distribution, impurity concentrations, resistivity, Hall effects and energy response spectra, were characterized and compared. The results shown that the CdMnTe crystal grown by the THM had more uniform Mn distribution and lower impurity concentrations compared to the crystal grown by VB method. The resistivity of CdMnTe grown by THM was (1.5 ∼ 8) × 10¹⁰ Ω.cm, while the resistivity of CdMnTe grown by VB was 10⁷∼10⁸ Ω.cm. The In dopant distributed uniformly throughout the crystal ingot grown by THM with the doping concentration of 0.6–0.7 ppm, while the In dopant concentration throughout the crystal grown by VB method is in the range of 1.31–2.4 ppm. Hall measurements revealed that the conductivity of the THM grown crystal was weak n‐type conductivity and the VB grown crystal was p‐type conductivity. A planar CdMnTe detector from the THM grown crystal showed a resolution of 8% of the ²⁴¹Am radiation at 59.5 keV peak, however, no energy response was revealed with the CdMnTe detector by the VB method. The results demonstrate that CdMnTe crystal grown by THM have better crystal quality and detector properties compared to that by VB method.     

[B30]−: A Quasiplanar Chiral Boron Cluster

Chirality is vital in chemistry. Its importance in atomic clusters has been recognized since the discovery of the first chiral fullerene, the D₂ symmetric C₇₆. ¹ A number of gold clusters have been found to be chiral, ² raising the possibility to use them as asymmetric catalysts. The discovery of clusters with enantiomeric structures is essential to design new chiral materials with tailored chemical and physical properties. ³ Herein we report the first inherently chiral boron cluster of [B₃₀]^? in a joint photoelectron spectroscopy and theoretical study. The most stable structure of [B₃₀]^? is found to be quasiplanar with a hexagonal hole. Interestingly, a pair of enantiomers arising from different positions of the hexagonal hole are found to be degenerate in our global minimum searches and both should co‐exist experimentally because they have identical electronic structures and give rise to identical simulated photoelectron spectra.