微波器件微放电阈值计算的蒙特卡罗方法研究

为了精准快速地计算微波器件中微放电效应的阈值,在传统蒙特卡罗方法的基础上,提出了三种不同的蒙特卡罗方法,分别对二次电子的初始能量、出射角度和初始相位等参数进行随机,结合四阶龙格-库塔法和Furman模型计算电子的运动轨迹和单次碰撞产生的二次电子发射系数,然后应用不同的方法计算有效二次电子发射系数作为微放电效应的判据.以平板传输线TEM模式为研究对象,采用四种不同的蒙特卡罗方法计算微放电阈值,并与统计模型结果进行对比.结果表明单电子-多碰撞蒙特卡罗方法误差最小,而且稳定性最好.     

固体核磁共振定量表征方法及其在高分子结构研究中的应用

高分子材料拥有众多优良的特性,使其广泛应用于现代社会的生产、生活及高新科技等领域。对于高分子特性的研究离不开微观物理、化学结构的定量表征。在众多表征高分子结构定量信息的实验技术中,固体核磁共振（SSNMR）发挥着重要的作用。它可以定量表征高分子的化学结构、材料体系的相成分及共混组分等,从而实现了难溶高分子产物的结构鉴定,以及高分子微观物理、化学结构关联材料性能的研究。然而,传统的SSNMR定量方法（直接激发法,DD）往往需要耗费十几个小时甚至数天的实验时间。交叉极化方法（CP）虽然大大缩短了实验时间,却往往无法提供定量的信息。基于此,研究者们提出了多个定量CP的实验方法,同时满足了方法定量性和实验耗时短的需求。本文综述了传统SSNMR定量方法及几种定量的CP方法,简单介绍了每个方法的基本原理,并平行阐述了实验方法的应用范围及特点,通过部分实例展示了SSNMR定量方法在高分子材料领域的应用价值,为研究者研发新型的高分子材料提供可靠并有效的结构表征手段。     

La4-x(P2O5)3:Eux的合成及光谱性质

制备;La4-x(P2O5)3:Eux的合成及光谱性质     

Research on mechanical and dielectric properties of XLPE cable under accelerated electrical‐thermal aging

Research into the electrical‐thermal aging properties of cross‐linked polyethylene (XLPE) cable has great significance, because of its wide application. This study conducted accelerated electrical‐thermal aging tests on 10‐kV XLPE cable in order to assess the cable's mechanical and dielectric properties. After being aged by applying 34.8‐kV AC voltage at the four temperatures of 90, 103, 114, and 135°C, the cable samples were taken out in five stages according to the aging time and cut into slices. The slices were conducted experiments to test the breaking elongation, tensile strength, gel content, breakdown voltage, and frequency spectrums of the dielectric constant and dielectric loss. The results demonstrate that the mechanical strength and gel content of XLPE vary greatly under different aging temperatures, a finding that is associated with the crystallization characteristics of the material. The breakdown voltage shows a slight decreasing trend with aging time. The dielectric constant decreases with aging time in high‐frequency areas (10³–10⁶ Hz), while the dielectric loss factor increases with aging time at low frequencies (10^?2–0 Hz). These two parameters can be used to characterize the degree of aging in cable. Copyright © 2016 John Wiley & Sons, Ltd.     

Modular Customization and Regulation of Metal–Organic Frameworks for Efficient Membrane Separations

Metal–organic frameworks (MOFs) are considered ideal membrane candidates for energy-efficient separations. However, the MOF membrane amount to date is only a drop in the bucket compared to the material collections. The fabrication of an arbitrary MOF membrane exhibiting inherent separation capacity of the material remains a long-standing challenge. Herein, we report a MOF modular customization strategy by employing four MOFs with diverse structures and physicochemical properties and achieving innovative defect-free membranes for efficient separation validation. Each membrane fully displays the separation potential according to the MOF pore/channel microenvironment, and consequently, an intriguing H₂/CO₂ separation performance sequence is achieved (separation factor of 1656–5.4, H₂ permeance of 964–2745 gas permeation unit). Taking advantage of this strategy, separation performance can be manipulated by a non-destructive modification separately towards the MOF module. This work establishes a universal full-chain demonstration for membrane fabrication-separation validation-microstructure modification and opens an avenue for exclusive customization of membranes for important separations.     

氮吸附法测定纳米粒子的比表面积实验

在纳米粒子的性能表征中,比表面积是一个非常重要的参数。本文研究了用氮吸附法测定纳米粒子比表面积的实验方法。     

红外导数光谱鉴定铁系复合氧化物中的γ-Fe_(2)O_3

用于丁烯氧化脱氢的铁系复合氧化物催化剂具有复杂的相组成，可能存在着。Fe。O。、1贝。0。、Fe。0。、铁酸盐尖晶石相及尖晶石相之间形成的固溶体，这些相的鉴定对于弄清活性位／相的结构具有本质意义．由于缺乏有效的相结构表征手段，导致对于活性位／相的结构和上述各相所起的作用的观，入歧异．Misono山曾测出7－Fe。O。具有较高的活性，故认为它是该系催化剂的活性相，但XRD难以把7－Fe。O。与其它尖晶石相区分开，因而无法确认它在催化剂中是否存在及起何作用．Gillot门提出了可用红外光谱鉴定了一FeZO。：1－Fe。O。在600～…     

Improved synthesis of 2,2'-dibromo-9,9'-spirobifluorene and its 2,2'-bisdonor-7,7'-bisacceptor-substituted fluorescent derivatives

Pure 2,2'-Dibromo-9,9'-spirobifluorene was synthesized by a method that did not involve troublesome dibromination of 9,9'-spirobifluorene or Sandmeyer reaction of 2,2'-diamino-9,9'-spirobifluorene. A series of donor-acceptor orthogonally substituted 9,9'-spirobifluorene was subsequently prepared showing rich variation of fluorescence in solution and in solid state. [reaction: see text]     

Enol ethers as substrates for efficient Z- and enantioselective ring-opening/cross-metathesis reactions promoted by stereogenic-at-Mo complexes: utility in chemical synthesis and mechanistic attributes

The first examples of catalytic enantioselective ring-opening/cross-metathesis (EROCM) reactions that involve enol ethers are reported. Specifically, we demonstrate that catalytic EROCM of several oxa- and azabicycles, cyclobutenes and a cyclopropene with an alkyl- or aryl-substituted enol ether proceed readily in the presence of a stereogenic-at-Mo monopyrrolide-monoaryloxide. In some instances, as little as 0.15 mol % of the catalytically active alkylidene is sufficient to promote complete conversion within 10 min. The desired products are formed in up to 90% yield and >99:1 enantiomeric ratio (er) with the disubstituted enol ether generated in >90% Z selectivity. The enol ether of the enantiomerically enriched products can be easily differentiated from the terminal alkene through a number of functionalization procedures that lead to the formation of useful intermediates for chemical synthesis (e.g., efficient acid hydrolysis to afford the enantiomerically enriched carboxaldehyde). In certain cases, enantioselectivity is strongly dependent on enol ether concentration: larger equivalents of the cross partner leads to the formation of products of high enantiomeric purity (versus near racemic products with one equivalent). The length of reaction time can be critical to product enantiomeric purity; high enantioselectivity in reactions that proceed to >98% conversion in as brief a reaction time as 30 s can be nearly entirely eroded within 30 min. Mechanistic rationale that accounts for the above characteristics of the catalytic process is provided.     

基于表面富Cd2+的硫化镉量子点荧光增强测定半胱氨酸

采用一步法可控合成了表面富Cd2+的水溶性荧光硫化镉量子点,并成功用于半胱氨酸测定.通过控制镉-硫前驱体合适比例,使合成的量子点表面富含Cd2+,它们能与半胱氨酸分子中巯基结合引起体系量子点荧光增强,由此实现半胱氨酸的选择性定量分析检测.在pH=2.87的B-R缓冲体系中,测定半胱氨酸的线性区间分别为0.01～5.0 μmol/L和5.0～100 μmol/L;检出限(3σ)为3.3 nmol/L,且其它氨基酸干扰小,可应用于混合氨基酸合成样品、复方氨基酸注射液和人血清实际样品中半胱氨酸的检测.