Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors

We herein report a method that enables the generation of glycosyl radicals under highly acidic conditions. Key to the success is the design and use of glycosyl sulfinates as radical precursors, which are bench-stable solids and can be readily prepared from commercial starting materials. This development allows the installation of glycosyl units onto pyridine rings directly by the Minisci reaction. We further demonstrate the utility of this method in the late-stage modification of complex drug molecules, including the anticancer agent camptothecin. Experimental studies provide insight into the reaction mechanism.     

氨基功能化介孔氧化硅纳米中空球负载乙酰丙酮氧钒催化苯甲硫醚选择性氧化反应

首次将乙酰丙酮氧钒固载在氨基功能化的介孔氧化硅纳米中空球以及SBA-15(直型孔道结构)和SBA-16(笼型孔道结构)上,并应用于苯甲硫醚选择氧化反应.结果表明,在温和的反应条件下,上述催化剂均可催化苯甲硫醚高选择性地转化为亚砜产物(选择性最高大于99.0%).动力学对比实验表明,相比于直型和笼型介孔氧化硅,纳米中空球负载的催化剂具有更高的转化频率.这是因为纳米空心球尺寸小,更有利于催化活性中心的暴露以及反应物和产物在催化过程中的扩散.催化剂可循环使用多次,其活性和选择性基本保持不变.     

Manipulating electromagnetic wave with the magnetic surface plasmon based metamaterials

In this work, we have investigated the optical properties of the magnetic metamaterials (MMs) consisting of periodically/randomly arranged ferrite rods. By calculating the photonic band diagrams and transmittance, we have identified a photonic band gap originating from the magnetic surface plasmon (MSP) resonance. In addition, by tuning the external magnetic field (EMF), an MM slab can be used as an optical switch. Our simulated results also suggest that the optical properties of the MMs are robust against the position disorder and the size fluctuation of the ferrite rods. Moreover, by examining the relation between the transmittance and the EMF, we can optimize the EMF to realize the best switching effect. With the retrieved effective constitutive parameters ε _eff and μ _eff obtained from the effective-medium theory, the optimal EMF can be understood in a more clear manner.     

Enantioselective carbonyl-ene reaction on BINOLate/titanium catalyst encapsulated in magnetic nanoreactors

An asymmetric multicomponent catalyst, BINOLate/titanium, successfully encapsulated in the nanocages of mesoporous silicas exhibits much higher activity than the homogeneous counterpart in quasi solvent-free enantioselective carbonyl-ene reaction, owing to the confinement effect of the nanoreactor.     

超声换能器并联谐振频率的复合式跟踪方法研究

为了使超声换能器适应变化比较剧烈的负载,本文通过分析超声换能器在并联谐振频率附近工作时的频率特性和实际需求特点,利用变压器初级匹配方法得到了更好的频率特性,并对比了换能器空载和带负荷情况下的阻抗特性曲线,提出了复合式自动频率跟踪方法,空载时找到超声换能器最小电流的对应的频率点,加载过程中利用比例积分微分算法实现频率的快速跟踪。并对超声换能器在不同负载时的功率输出进行了实验,结果表明,复合式频率跟踪方法可以稳定地跟踪到超声换能器的并联谐振频率,能实现超声换能器的功率自调节,对提高换能器的工作效率和负荷适应能力具有实际的指导意义和应用价值。     

氘氘冰层贯穿性缺陷对ICF冷冻靶内爆性能的影响

使用二维多群辐射扩散流体力学程序LARED-S, 模拟研究DD冰贯穿性缺陷在方波驱动DD冷冻靶内爆过程中的演化行为及其对内爆性能的影响。模拟结果表明: DD冰层贯穿性缺陷显著降低DD冷冻靶内爆的中子产额, 二维模拟产额仅为一维结果的23.8%。DD冰层贯穿性缺陷使靶丸CH(Si)的烧蚀层生成大幅度的尖钉, 穿透到芯部热斑区。在中子bang-time时刻, 热斑区混入了487 ng的烧蚀物质, 使芯部韧致辐射漏失功率相对一维理想内爆显著升高, 离子温度与DD核反应速度相应降低。同时, 高密度的烧蚀层尖钉把DD热斑推离球心, 显示明显的P1不对称性, 而且高温热斑具有定向流动速度, 降低了内爆动能转化为热斑内能的效率。     

LC–MS/MS method for determination of kansuinine a in rat plasma and its application to a rat pharmacokinetic study

Kansuinine A is a macrocyclic jatrophane diterpene isolated from the plant Euphorbia kansui Liou. It exhibits many pharmacological activities including cytoxic, antitumor, antiallergic and proinflammatory effects. In the present study, a simple and sensitive LC–MS/MS method was established and validated for the determination of kansuinine A in rat plasma. After methanol-mediated protein precipitation, chromatographic separation was achieved on an Acquity BEH C₁₈ column (2.1 × 100 mm, 1.7 μm) using acetonitrile and 0.1% formic acid in water as mobile phase by gradient elution. Kansuinine A and IS were quantified in negative multiple reaction monitoring mode with ion transitions at m/z 731.1–693.2 for kansuinine A and m/z 723.2–623.1 for IS. The method showed excellent linearity over the range 1–500 ng/ml. The intra- and inter-day precisions (relative standard deviation) were 2.13–4.28 and 3.83–7.67%, respectively, whereas accuracy (relative error) ranged from −4.17 to 3.73%. The extraction recovery, stability and matrix effect met the requirement of the regulations issued by the US Food and Drug Administration. The validated method was successfully applied to the pre-clinical pharmacokinetic study of kansuinine A in rats after oral administration (20 mg/kg) and intravenous administration (2 mg/kg). This study provides valuable reference for the further study of E. kansui liou, especially for the drug development and clinical application of kansuinine A.     

Synthesis and memory characteristics of highly organo‐soluble hyperbranched polyimides with various electron acceptors

A series of hyperbranched polyimides (HBPIs) were synthesized by reacting a triamine monomer N ,N ′,N ″‐tris(4‐methoxyphenyl)‐N ,N ′,N ″‐tris(4‐phenylamino)?1,3,5‐benzenetriamine with various dianhydrides such as oxydiphthalic dianhydride (ODPA), 3,3′,4,4′‐diphenylsulfonetetracarboxylic dianhydride (DSDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA). The hyperbranched polyimide (6FHBPI) using 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) as dianhydride monomer was also added into the discussion. All the hyperbranched polyimides exhibited excellent organo‐solubility and high thermal stability. Memory devices with a sandwiched structure of indium tin oxide (ITO)/HBPI/Al were constructed by using these HBPIs as the active layers. All these HBPIs based memory devices exhibited favorable memory performances, with switching voltages between ?1.3 V and ?2.5 V, ON/OFF current ratios up to 10⁷ and retention times long to 10⁴ s. Tunable memory characteristics from electrical insulator to volatile memory, and then to nonvolatile memory were obtained by adjusting the electron acceptors of these HBPIs. Molecular simulation results suggested that the electron affinity and the dipole moment of these HBPIs were responsible for the conversion of the memory characteristics. With the electron affinity and dipole moment of these HBPIs increasing, the memory characteristics turned from volatile to nonvolatile. The present study suggested that tunable memory performance could be achieved through adjusting the acceptor moieties of the hyperbranched polyimides. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2281–2288     

点火黑腔二维模拟设计

基于二维激光靶耦合流体力学程序,研究设计惯性约束聚变间接驱动点火黑腔的方法.提出先调控X射线驱动温度再调控辐照均匀性的设计顺序.给出总激光功率(特别是主脉冲激光功率)的设计方法.模拟表明,填充气体密度的上限受到槽脉冲P²辐照不均匀性的限制.另外,增加腔长可以抑制靶丸烧蚀层物质的膨胀.最后给出点火黑腔二维设计结果.     

Manipulating negative-refractive behavior with a magnetic field

We demonstrated a construction of negative-index material (NIM) with epsilon(eff)=mu(eff)=-1 employing ferrites only, with no metallic components. Our design of the NIM is motivated by recent coherent potential approximation results and corroborated by exact numerical calculation demonstrating the negative refraction of an electromagnetic beam, with equal incident and refraction angles, as well as by the slab imaging phenomena, with the source-image separation twice as the slab thickness. The ferrite only based scheme furnishes the fabricated NIM with magnetically tunable working frequency, less loss and the air-matched wave impedance.