Nickel‐Catalyzed Decarbonylative Borylation of Amides: Evidence for Acyl C−N Bond Activation

A nickel/N‐heterocyclic carbene catalytic system has been established for decarbonylative borylation of amides with B₂nep₂ by C?N bond activation. This transformation shows good functional‐group compatibility and can serve as a powerful synthetic tool for late‐stage borylation of amide groups in complex compounds. More importantly, as a key intermediate, the structure of an acyl nickel complex was first confirmed by X‐ray analysis. Furthermore, the decarbonylative process was also observed. These findings confirm the key mechanistic features of the acyl C?N bond activation process.     

Molecular Characterization of Secondary Aerosol from Oxidation of Cyclic Methylsiloxanes

Cyclic volatile methylsiloxanes (cVMS) have been identified as important gas-phase atmospheric contaminants, but knowledge of the molecular composition of secondary aerosol derived from cVMS oxidation is incomplete. Here, the chemical composition of secondary aerosol produced from the OH-initiated oxidation of decamethylcyclopentasiloxane (D₅, C₁₀H₃₀O₅Si₅) is characterized by high performance mass spectrometry. ESI-MS reveals a large number of monomeric (300 < m/z < 470) and dimeric (700 < m/z < 870) oxidation products. With the aid of high resolution and MS/MS, it is shown that oxidation leads mainly to the substitution of a CH₃ group by OH or CH₂OH, and that a single molecule can undergo many CH₃ group substitutions. Dimers also exhibit OH and CH₂OH substitutions and can be linked by O, CH₂, and CH₂CH₂ groups. GC-MS confirms the ESI-MS results. Oxidation of D₄ (C₈H₂₄O₄Si₄) exhibits similar substitutions and oligomerizations to D₅, though the degree of oxidation is greater under the same conditions and there is direct evidence for the formation of peroxy groups (CH₂OOH) in addition to OH and CH₂OH.

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Phase behavior and Li+ Ion conductivity of styrene‐ethylene oxide multiblock copolymer electrolytes

Solid polymer electrolytes are attractive materials for use as battery separators. Here, a molecular weight series of polystyrene–polyethylene oxide (PEO) multiblock copolymers was synthesized by the thiol–norbornene click reaction. The subsequent materials were characterized both neat and with a lithium bis‐(trifluoromethane)sulfonimide salt loading [(Li)/(EO)] of 0.1. In general, neat samples demonstrated crystallinity scaling with PEO content. Lithium ion‐containing samples had broad scattering peaks, half of which displayed disordered scattering, even at the lowest block molecular weights (polystyrene = 1 kg/mol, PEO = 1 kg/mol). Fitting of disordered scattering data, using the random phase approximation, yielded χ_RPA and R_g values that were compared with recent predictive work by Balsara and coworkers. The predictions were accurate near the volume fraction f_PEO = 0.5 but deviated symmetrically with volume fraction asymmetry. Samples were also analyzed by electrochemical impedance spectroscopy for their potential to conduct lithium ions. Samples with f_PEO ≥ 0.5 demonstrated robust conductivity, whereas samples below this volume fraction conducted very poorly, with one exception (f_PEO = 0.24). This work expanded upon our recently reported approach to multiblock copolymer synthesis, demonstrating the improved access of materials to further our fundamental understanding of multiblock copolymers. Copyright © 2016 John Wiley & Sons, Ltd.     

Ortho‐hydroxyl effect and proton transfer via ion–neutral complex: the fragmentation study of protonated imine resveratrol analogues in mass spectrometry

The fragmentation pathways of protonated imine resveratrol analogues in the gas‐phase were investigated by electrospray ionization–tandem mass spectrometry. Benzyl cations were formed in the imine resveratrol analogues that had an ortho‐hydroxyl group on the benzene ring A. The specific elimination of the quinomethane neutral, CH₂ = C₆H₄ = O, from the two isomeric ions [M1 + H]⁺ and [M3 + H]⁺ via the corresponding ion–neutral complexes was observed. The fragmentation pathway for the related meta‐isomer, ion [M2 + H]⁺ and the other congeners was not observed. Accurate mass measurements and additional experiments carried out with a chlorinated analogue and the trideuterated isotopolog of M1 supported the overall interpretation of the fragmentation phenomena observed. It is very helpful for understanding the intriguing roles of ortho‐hydroxyl effect and ion–neutral complexes in fragmentation reactions and enriching the knowledge of the gas‐phase chemistry of the benzyl cation. Copyright © 2016 John Wiley & Sons, Ltd.     

Attractive natural products with strained cyclopropane and/or cyclobutane ring systems

The strained cyclopropane and/or cyclobutane subunits occurred in many complex natural products including terpenoids, steroids and alkaloids. Natural products with cyclopropane and/or cyclobutane motifs not only furnished fascinating structures, but also exhibited versatile biological activities, such as cytotoxic, anti-HIV, antimicrobial, antiviral, and immunosuppressive effects. This review covered a large array of structurally unique natural products with strained cyclopropane and/or cyclobutane motifs and summarized their structural features, distributions, biological activities, as well as biogenetic considerations.     

Progress of Jinping Underground laboratory for Nuclear Astrophysics (JUNA)

Jinping Underground laboratory for Nuclear Astrophysics(JUNA) will take the advantage of the ultra-low background of CJPL lab and high current accelerator based on an ECR source and a highly sensitive detector to directly study for the first time a number of crucial reactions occurring at their relevant stellar energies during the evolution of hydrostatic stars. In its first phase, JUNA aims at the direct measurements of~(25)Mg(p,γ)~(26)Al,~(19)F(p,α)~(16)O,~(13)C(α,n)~(16)O and ~(12)C(α,γ)~(16)O reactions. The experimental setup,which includes an accelerator system with high stability and high intensity, a detector system, and a shielding material with low background, will be established during the above research. The current progress of JUNA will be given.     

Three New Polyoxygenated Steroids from Two Species of the South China Sea Gorgonian Muricella flexuosa and Menella verrucosa Brundin

Three new polyoxygenated steroids, muricesteroid ( 1 ), and menellsteroids A ( 2 ) and B ( 3 ), were isolated from two species of the South China Sea gorgonian Muricella flexuosa and Menella verrucosa Brundin , respectively. The structures of these new compounds were elucidated on the basis of extensive spectroscopic analysis, chemical methods and comparison with known related compounds.     

恒流应力下E2PROM隧道氧化层的退化特性研究

在电容测量的基础上研究了薄隧道氧化层在恒定Fowler-Nordheim(F-N)隧穿电流下的退化情况. 这种退化是恒流应力和时间的函数，对恒流应力大小的依赖性更加强烈，隧道氧化层在F-N电流下的退化是注入电荷密度(Q_inj)的函数. 在较低Q_inj下氧化层中发生正电荷俘获，在较高Q_inj下发生负电荷俘获，导致栅压变化的反复. 关键词： 2PROM')" href="#">E²PROM 隧道氧化层 退化 恒流应力     

金属薄膜制备及物性测量系列实验

介绍了由模拟真空实验和“金属薄膜的制备”、“金属薄膜厚度的测量”、“金属薄膜电阻率的测量”,以及“金属薄膜生长过程的动态监测”等4个实验组成的金属薄膜制备与物性测量系列实验.这组实验与现代科学技术发展联系紧密,仪器设备可靠,操作简单,适合于普通物理实验阶段的研究性教学.     

量子位Heisenberg XX开链中边界量子位之间的纠缠

Heisenberg 开链对研究量子态在自旋链上的传递有重要的意义.本文研究了五量子位Heisenberg XX 开链中边界量子位之间的纠缠，在该系统中引入了磁杂质和系统杂质且它们之间满足线性关系时，该系统可以精确求解，此时边界量子位之间存在纠缠.选择合适的杂质参数和磁场参数，该边界纠缠的最大值可达到0.5. 关键词： Heisenberg XX开链 边界纠缠 杂质