Study of nano‐Cu/SiO2 catalysts for highly selective hydrogenation of acetophenone

Hydrogenation of acetophenone over nano‐Cu/SiO₂ catalysts was investigated. The catalysts, prepared by a liquid precipitation method using various precipitating agents, were characterized using low‐temperature nitrogen adsorption, X‐ray diffraction, temperature‐programmed desorption of ammonia, hydrogen temperature‐programmed reduction, transmission electron microscopy and X‐ray photoelectron spectroscopy. It was found that the catalysts prepared by a homogeneous precipitation method had better activity and stability than those prepared by a co‐precipitation method. The catalyst prepared using urea as precipitating agent had well‐dispersed copper species, high surface area and abundant pore structure. The catalytic performance and mechanism of the Cu/SiO₂ catalysts were further studied. It was found that the activity and stability of the catalysts could be improved by adjusting the proportion of Cu⁺/(Cu⁺ + Cu⁰). The sample prepared using urea as precipitating agent presented higher activity and selectivity. Also, the catalyst prepared using urea maintained a high catalytic performance while being continuously used for 150 h under the optimal reaction conditions.     

Topotactic Conversion of Alkali-Treated Intergrown Germanosilicate CIT-13 into Single-Crystalline ECNU-21 Zeolite as Shape-Selective Catalyst for Ethylene Oxide Hydration

The conversion of the alkali-treated intergrowth germanosilicate CIT-13 into the single-crystalline high-silica ECNU-21 (named after East China Normal University) zeolite, with a novel topology and a highly crystalline zeolite framework, has been realized through a creative top-down strategy involving a mild alkaline-induced multistep process consisting of structural degradation and reconstruction. Instead of acid treatment, hydrolysis in aqueous ammonia solution not only readily cleaved the chemically weak Ge(Si)−O−Ge bonds located within the interlayer double four ring (D4R) units of CIT-13, but also cleaved the metastable Si−O−Si bonds therein. This led to extensive removal of the D4R units, and also generated silanol groups on adjacent silica-rich layers, which then condensed to form a novel daughter structure upon calcination. Individual oxygen bridges in the reassembled ECNU-21 replaced the germanium-rich D4R units in CIT-13, thereby eliminating the original intergrowth phenomenon along the b axis. With an ordered crystalline structure of 10-ring (R) channels as well as suitable germanium-related Lewis acid sites, ECNU-21 serves as a stable solid Lewis acid catalyst for the shape-selective hydration of ethylene oxide (EO) to ethylene glycol (EG) at greatly reduced H₂O/EO ratios and reaction temperature in comparison with the noncatalytic industrial process.     

Monodisperse Six-Armed Starbursts based on Truxene-Cored Multibranched Oligofluorenes: Design,Synthesis, and Stabilized Lasing Characteristics

A series of monodisperse six-armed conjugated starbursts ( Tr1F , Tr2F , and Tr3F ) containing a truxene core and multibranched oligofluorene bridges capped with diphenylamine (DPA) units has been designed, synthesized, and investigated as robust gain media for organic semiconductor lasers (OSLs). The influence of electron-rich DPA end groups on their optoelectronic characteristics has been discussed at length. DPA cappers effectively raise HOMO levels of the starbursts, thus enhancing the hole injection and transport ability. Solution-processed electroluminescence devices based on the resulting six-armed starbursts exhibited efficient deep-blue electroluminescence with clear reduced turn-on voltages (3.2–3.5 V). Moreover, the resulting six-armed molecules showed stabilized electroluminescence and amplified spontaneous emission with low thresholds (27.4–63.9 nJ pulse⁻¹), high net gain coefficients (80.1–101.3 cm⁻¹), and small optical loss (2.6–4.4 cm⁻¹). Distributed feedback OSLs made from Tr3F exhibited a low lasing threshold of 0.31 kW cm⁻² (at 465 nm). The results suggest that the construction of truxene-centered six-armed conjugated starbursts with the incorporation of DPA units can effectively enhance EL properties by precisely regulating the HOMO energy levels, and further optimizing their optical gain properties.     

In Situ Anchoring of Pyrrhotite on Graphitic Carbon Nitride Nanosheet for Efficient Immobilization of Uranium

Enrichment of U^VI is an urgent project for nuclear energy development. Herein, magnetic graphitic carbon nitride nanosheets were successfully prepared by in situ anchoring of pyrrhotite (Fe₇S₈) on the graphitic carbon nitride nanosheet (CNNS), which were used for capturing U^VI. The structural characterizations of Fe₇S₈/CNNS-1 indicated that the CNNS could prevent the aggregation of Fe₇S₈ and the saturation magnetization was 4.69 emu g⁻¹, which meant that it was easy to separate the adsorbent from the solution. Adsorption experiments were performed to investigate the sorption properties. The results disclosed that the sorption data conformed to the Langmuir isotherm model with the maximum adsorption capacity of 572.78 mg g⁻¹ at 298 K. The results of X-ray photoelectron spectroscopy (XPS) demonstrated that the main adsorption mechanism are as follows: U^VI is adsorbed on the surface of Fe₇S₈/CNNS-1 through surface complexation initially, then it was reduced to insoluble U^IV. Thereby, this work provided an efficient and easy to handle sorbent material for extraction of U^VI.     

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.     

Nukiangendines A and B,two novel 13,14-seco-abietanes from Abies nukiangensis

From Abies nukiangensis, two novel 13,14-seco-abietane diterpenes, nukiangendines A (1) and B (2) were isolated. Their relative structures were determined by extensive NMR and HRMS spectroscopic analysis. The absolute configuration of 1 was established by ECD calculations. Compound 1 showed significant anti-hepatitis C virus (HCV) effects.     

Visible‐Light‐Driven Halogen Bond Donor Based Molecular Switches: From Reversible Unwinding to Handedness Inversion in Self‐Organized Soft Helical Superstructures

Visible‐light‐driven molecular switches endowing reversible modulation of the functionalities of self‐organized soft materials are currently highly sought after for fundamental scientific studies and technological applications. Reported herein are the design and synthesis of two novel halogen bond donor based chiral molecular switches that exhibit reversible photoisomerization upon exposure to visible light of different wavelengths. These chiral molecular switches induce photoresponsive helical superstructures, that is, cholesteric liquid crystals, when doped into the commercially available room‐temperature achiral liquid crystal host 5CB, which also acts as a halogen‐bond acceptor. The induced helical superstructure containing the molecular switch with terminal iodo atoms exhibits visible‐light‐driven reversible unwinding, that is, a cholesteric–nematic phase transition. Interestingly, the molecular switch with terminal bromo atoms confers reversible handedness inversion to the helical superstructure upon irradiation with visible light of different wavelengths. This visible‐light‐driven, reversible handedness inversion, enabled by a halogen bond donor molecular switch, is unprecedented.     

质子辐照硼硅酸盐玻璃盖片的物理效应分析

作为航天器电源系统的重要组成部分,太阳电池需要更高的转换效率和可靠性以及更长的使用寿命。通过在太阳电池表面覆盖抗辐照玻璃盖片,可以增强太阳电池对粒子辐射的防护,延长太阳电池的服役寿命,使航天器获得可靠的能源供应。硼硅酸盐玻璃就是一种理想的太阳电池玻璃盖片材料。采用蒙特卡罗方法,结合SRIM软件模拟研究质子辐照硼硅酸盐玻璃的损伤物理机理。基于粒子与物质相互作用的理论以及基本公式,通过分析不同入射能量的质子在硼硅酸盐玻璃中的阻止本领、电离能损、位移能损、空位的产生情况,对辐照损伤的物理机制进行研究。结果表明:能量为30~120 keV的质子辐照损伤主要发生在硼硅酸盐玻璃表面;质子沉积、空位分布等均为Bragg峰型分布;电离能损是能量损失的主要部分,随入射能量的增加而增大,导致电子的电离和激发;位移能损在玻璃内部随能量降低而增大,导致硼、氧和硅等空位缺陷的产生;电离效应和缺陷的产生是硼硅酸盐玻璃色心形成的重要原因。     

基于EKF的水下LD通信精对准控制算法

高速激光通信中接收机与光斑中心很难处于精对准状态,导致水下光通信链路难以稳定建立.首先采用蒙特卡洛仿真统计法分析激光光子在海水中传输的接收光强分布规律,再通过实验对接收端的光斑图像进行采样分析,利用曲线拟合得到接收器位置与接收光强的关系.仿真与实验结果表明:光束经过25 m的水下传输,接收光强分布仍近似为高斯分布.采用非线性估计算法(扩展卡尔曼滤波)与基本状态控制反馈理论,根据接收光强度估计接收器当前位置与最大光强处的距离,通过反馈算法实现接收端与光斑中心的主动跟踪对准.算法仿真结果显示,接收端对准误差在2 mm以下,稳定后接收效率超过98%.     

Preparing molecularly imprinted nanoparticles of saponins via cooperative imprinting strategy

Saponin is an important class of natural products with various pharmacological activities. The selective separation of saponins is an essential step before further analysis. Molecular imprinting has been an effective strategy for preparing antibody mimics. However, a facile and efficient imprinting strategy for saponins is still lacking owing to their amphiphilic nature. Herein, we have prepared the saponins imprinted nanoparticles via cooperative imprinting strategy. This new strategy relies on the combination of various non‐covalent interactions (hydrophobic and hydrogen bonding) and covalent boronate affinity interactions. The obtained imprinted nanoparticles could rebind specific saponins from complex matrices with good selectivity, superb tolerance to interference, and fast binding equilibrium. This method was verified to be versatile and facile. Thus, this strategy could greatly facilitate the preparation of imprinted nanoparticles for the specific recognition of saponins.