Diastereo- and enantioselective palladium-catalyzed dearomative [4+2] cycloaddition of 3-nitroindoles

A Pd-catalyzed asymmetric decarboxylative [4+2] cycloaddition of 3-nitroindoles and vinyl benzoxazinanones is developed through a dearomatization approach. The reaction provides an efficient protocol for constructing a series of chiral tetrahydro-5H-indolo[2,3-b]quinolines in high yields and with excellent diastereo- and enantioselectivities.     

缺陷石墨烯吸附Au、Ag、Cu的第一性原理计算

采用基于密度泛函理论的投影缀加波方法研究了Au、Ag、Cu吸附在缺陷石墨烯单侧和双侧的体系,对吸附体系的吸附能、磁性、电荷转移和电子结构进行了计算和分析. 缺陷石墨烯吸附Au、Ag、Cu体系的吸附能比本征石墨烯增加2 eV以上,说明三种金属原子更容易吸附在缺陷位置;吸附体系的电荷密度差分和电子结构的结果表明,Au、Ag、Cu与缺陷石墨烯之间均为化学吸附. 计算吸附体系的磁性发现,单侧吸附时三种吸附体系均有磁性,磁矩大约为1μ_B;双侧吸附时,三种吸附体系磁矩大约为2μ_B.     

有机半导体薄膜生长原位实时测量方法的研究

针对原位实时监测有机半导体薄膜生长情况的需求, 提出了差分反射光谱法与场效应晶体管法结合的光电联合测量方法, 设计研制了测量系统. 以并五苯有机分子为例, 通过自制底栅底接触式场效应管微结构, 实验测试了热蒸发法生长导电膜层过程中光电信号的演变与相互关联. 光谱信号显示, 并五苯以薄膜态结构进行生长, 光谱随生长进程变化显著. 实验数据与四相结构模型仿真结果的良好吻合, 表明因薄膜增厚引起干涉条件的改变是光谱变化的主因, 由此推算出薄膜生长速率为0.23 nm/min. 当薄膜等效厚度达到28 nm时, 场效应管的导电性显著增强, 标志着并五苯有效传输层的形成. 此后, 薄膜厚度持续增加, 但测试电流增长缓慢, 说明该结构进入电学特性饱和区. 光电联合法不仅有助于研究有机半导体薄膜的光谱信息、电学特性和薄膜结构之间的相互对应关系, 也为发展原位监测有机半导体薄膜制备过程, 探索最佳工艺提供了新的研究手段.     

高效频率转换下双波长外腔共振和频技术研究

基于外腔的高效频率转换, 尤其是当系统运行在抽运不消耗近似机理下, 信号光可实现大于90%的转换, 因此无法通过信号光直接获得其到腔模频率锁定的误差信号. 本文通过对信号光调制、和频光解调的方法获得了该误差信号, 实现了双波长激光到外腔腔模的级联锁定. 实验中外部环形腔将1.3 W的1064 nm抽运光放大到约14.3 W. 当1583 nm信号光从10 μW变化到50 mW, 其到636 nm和频光的转化效率约为73%; 当从50 mW变化到295 mW时, 转换效率呈线性降低到60%, 最终获得了440 mW的636 nm激光.     

太阳大气中不可忽视的爆发活动——喷流

人类第一次注意到太阳大气中发生的喷流现象,是在20 世纪20 年代的Mt. Wilson观测台站发现的Hα冲浪。尽管已经过去了接近一个世纪,由于喷流本身并没有表现出像太阳耀斑那样的耀眼增亮,也没有像日冕物质抛射那样能够直接影响到近地空间环境,太阳大气喷流一直没能引起人们足够的重视。然而,近些年的一些研究进展表明,喷流不仅在分析太阳磁场拓扑结构和演化、与磁流体力学波(如类阿尔芬波)的相互作用、加热局地日冕以及加速太阳风等方面可能起着十分重要的作用,也与耀斑、日冕物质抛射等太阳上的极端爆发活动有着密切的关系。文章首先简要回顾太阳大气喷流的理论和观测成果,然后介绍作者在喷流触发高速日冕物质抛射方面最新的研究成果。最后简述喷流研究中亟待解决的一些问题和未来的研究方向。     

Tuning Redox Active Polyoxometalates for Efficient Electron-Coupled Proton-Buffer-Mediated Water Splitting

We present strategies to tune the redox properties of polyoxometalate clusters to enhance the electron-coupled proton-buffer-mediated water splitting process, in which the evolution of hydrogen and oxygen can occur in different forms and is separated in time and space. By substituting the heteroatom template in the Keggin-type polyoxometalate cluster, H₆ZnW₁₂O₄₀, it is possible to double the number of electrons and protonation in the redox reactions (from two to four). This increase can be achieved with better matching of the energy levels as indicated by the redox potentials, compared to the ones of well-studied H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀. This means that H₆ZnW₁₂O₄₀ can act as a high-performance redox mediator in an electrolytic cell for the on-demand generation of hydrogen with a high decoupling efficiency of 95.5 % and an electrochemical energy efficiency of 83.3 %. Furthermore, the H₆ZnW₁₂O₄₀ cluster also exhibits an excellent cycling behaviour and redox reversibility with almost 100 % H₂-mediated capacity retention during 200 cycles and a high coulombic efficiency >92 % each cycle at 30 mA cm⁻².     

Special Issue: Theory and Simulation of Macromolecules

Chinese Journal of Polymer Science -     

Chemical Bonding as a New Avenue for Controlling Excited-State Properties and Excitation Energy-Transfer Processes in Zinc Phthalocyanine–Fullerene Dyads

Whether chemical bonding can regulate the excited-state and optoelectronic properties of donor–acceptor dyads has been largely elusive. In this work, we used electronic structure and nonadiabatic dynamics methods to explore the excited-state properties of covalently bonded zinc phthalocyanine (ZnPc)-fullerene (C₆₀) dyads with a 6–6 (or 5–6) bonding configuration in which ZnPc is bonded to two carbon atoms shared by the two hexagonal rings (or a pentagonal and a hexagonal ring) in C₆₀. In both cases, the locally excited (LE) states on ZnPc are spectroscopically bright. However, their different chemical bonding differentiates the electronic interactions between ZnPc and C₆₀. In the 5–6 bonding configuration, the LE states on ZnPc are much higher in energy than the LE states on C₆₀. Thus, the excitation energy transfer from ZnPc to C₆₀ is thermodynamically favorable. On the other hand, in the 6–6 bonding configuration, such a process is inhibited because the LE states on ZnPc are the lowest ones. More detailed mechanisms are elucidated from nonadiabatic dynamics simulations. In the 6–6 bonding configuration, no excitation energy transfer was observed. In contrast, in the 5–6 bonding configuration, several LE and charge-transfer (CT) excitons were shown to participate in the energy-transfer process. Further analysis reveals that the photoinduced energy transfer is mediated by a CT exciton, such that electron- and hole-transfer processes take place in a concerted but asynchronous manner in the excitation energy transfer. It is also found that high-level electronic structure methods including exciton effects are indispensable to accurately describe photoinduced energy- and electron-transfer processes. Furthermore, this work opens up new avenues for regulating the excited-state properties of molecular donor–acceptor dyads by means of chemical bonding.     

基于新能源材料与器件专业的理论教学*——绝对电位和相对电位

为培养新能源材料与器件专业学生的科研与创新能力,以新能源热点前沿“电化学还原CO₂”作为切入点,引导学生明晰绝对电位和相对电位,掌握参比电极,揭示实际电位的意义,探索将基础理论教学与科研前沿相结合。融合专业研究前沿和基础理论能激发学生的专业兴趣,让学生重视科学严谨性和前沿性,为培养能用于新能源方向、具有综合素质的专门人才奠定基础。     

Cyclodextrin-micellar electrokinetic chromatography of apolipoproteins on human very low-density lipoprotein

The apolipoproteins (APOs) of human very low-density lipoprotein (VLDL) were investigated by an optimized cyclodextrin-micellar electrokinetic chromatography (CD-MEKC) method. The separation buffer consisted of 20 mM sodium phosphate, 40 mM bile salts (50% sodium cholate and 50% sodium deoxycholate), 25 mM carboxymethyl-β-cyclodextrin (CM-β-CD) (pH 7.0). For CD-MEKC separation, a sample injection time of 12 s, a separation voltage of 15 KV, and a capillary temperature of 15°C were chosen. The optimal CD-MEKC method showed good resolution and repeatability for VLDL APOs. Identification and quantitation of VLDL APOs CI, CIII, and E were based on comparison with human APO standards. Good linear relationships with correlation coefficient (R²) 0.99 were obtained for APOs CI, CIII, and E standards. For these three APOs, the linear ranges were within 0.01-0.54 mg/mL, and the concentration limits of detection (LODs) were lower than 0.02 mg/mL. Moreover, VLDL APOs from four uremic patients and four healthy subjects were compared. The uremic and healthy CD-MEKC profiles showed dramatic difference. The levels of APO CIII were significantly higher for two patients, and the level of APO E was significantly higher for one patient. This study might be helpful for following the disease development of uremia and cardiovascular disease (CVD) in the future.