Syntheses,homeomorphic and configurational isomerizations,and structures of macrocyclic aliphatic dibridgehead diphosphines; molecules that turn themselves inside out

The diphosphine complexes cis- or trans- PtCl₂(P((CH₂)_n)₃P ) (n = b/12, c/14, d/16, e/18) are demetalated by MC X nucleophiles to give the title compounds (P((CH₂)_n)₃)P (3b–e, 91–71%). These “empty cages” react with PdCl₂ or PtCl₂ sources to afford trans- MCl₂(P((CH₂)_n)₃P ). Low temperature ³¹P NMR spectra of 3b and c show two rapidly equilibrating species (3b, 86 : 14; 3c, 97 : 3), assigned based upon computational data to in,in (major) and out,out isomers. These interconvert by homeomorphic isomerizations, akin to turning articles of clothing inside out (3b/c: ΔH^‡ 7.3/8.2 kcal mol⁻¹, ΔS^‡ −19.4/−11.8 eu, minor to major). At 150 °C, 3b, c, e epimerize to (60–51) : (40–49) mixtures of (in,in/out,out) : in,out isomers, which are separated via the bis(borane) adducts 3b, c, e·2BH₃. The configurational stabilities of in,out-3b, c, e preclude phosphorus inversion in the interconversion of in,in and out,out isomers. Low temperature ³¹P NMR spectra of in,out-3b, c reveal degenerate in,out/out,in homeomorphic isomerizations (ΔG^‡_Tc 12.1, 8.5 kcal mol⁻¹). When (in,in/out,out)-3b, c, e are crystallized, out,out isomers are obtained, despite the preference for in,in isomers in solution. The lattice structures are analyzed, and the D₃ symmetry of out,out-3c enables a particularly favorable packing motif. Similarly, (in,in/out,out)-3c, e·2BH₃ crystallize in out,out conformations, the former with a cycloalkane solvent guest inside.

It’s not a magic trick. Molecules can turn themselves inside out, just like articles of clothing or other familiar household objects. This behavior is demonstrated for the title compounds through a combination of synthesis, rate, and NMR studies.     

Isolation and Purification of Polysaccharides from Cordyceps minlitaris and Its Inhibition on the Proliferation of Rat Glomerular Mesangial Cells

The crude polysaccharide was obtained by means of the decolorization of porphyrized Cordyceps minlitaris stroma with organic solvent, extraction with hot water, precipitation in 80% ethanol, and protein removal with the Sevag method. After purification with Sephadex G-75, two of its components, CMP-1 and CMP-2, were obtained. Through the assay of gel chromatography and polarimetry, CMP-1 was identified as pure polysaccharide. The results demonstrated that CMP-1 had favorable oxidation resistance activity, which could scavenge not only oxygen-free radicals in the self-oxidation system of pyrogallic acid, but also the hydroxide-free radicals in the Fenton system. The study focused on the effects of low, medium, and high dosages of CMP-1 in rat blood serum on the proliferation of glomerular mesangial cells in vitro. Through MTT Colorimetric analysis, the activities were compared among the blank control group and the Niaoduqing positive control group CMP-1 and CMP-2. The results shows that CMP-1 was able to inhibit the proliferation of rat glomerular mesangial cells effectively. Therefore, CMP-1, one component of polysaccharides of Cordyceps minlitaris, was certainly a potential remedy for hyperplastic glomerular nephritis, whose antioxidant activity could slow down the process of chronic renal failure（CRF） to some extent.     

离子交换聚合物固定三联吡啶钌电玫化学发光传感器的研究进展

将可电化学再生的电致化学发光试剂-三联吡啶钌固定于电极表面制备得到可再生的电致化学发光(ECL)传感器.综述了近年来使用离子交换聚合物膜固定三联吡啶钌ECL传感器的研究进展,简要介绍了不同离子交换聚合物的固定方法及其相关的应用情况.同时展望了该领域未来的发展方向和前景.     

Conversion of Methane to Ethylene with BaCe_(0.9)Y_(0.1)Co_xO_(3-δ) Hydrogen Permeation Membrane

Dehydrogenation coupling of methane (DCM),which can be effectively used to produce low carbon alkenes,has the advantages of rich raw materials,simple reaction device,low energy consumption,etc.Herein,we report a series of Co doped perovskite porous-dense Ba Ce_(0.9)Y_(0.1)Co_xO_(3-δ)(BCYCx) membrane for DCM.After treatment in a reduced atmosphere,a large number of Co nanoparticles will exsolute on the surface of BCY.The metal-oxide interface is helpful to activate the C–H bonds,inhibit the carbon deposition,and so on.The XRD,SEM and XPS prove that Co nanoparticles homogeneously distributed on the BCYCx porous layers,which will create a large quantity of catalytic active sites.At 1100℃,the highest concentration of C_2 product was 5.66%(5.25%ethane+0.41%ethylene)in output gas when methane conversion reaches a maximum value of 24.8%,and the C_2 selectivity gets to 45.6%.We further demonstrate the catalytic performance of high-temperature DCM without obvious decrease after running for 30hours.     

深海不平海底对声场水平纵向相关性的影响

海底地形变化对与海底作用的声反射区声场空间相关性有重要影响。利用南中国海某深海海域的一次声学实验数据,对深海海底反射区的声场空间相关性进行了分析。实验观测到,在距离声源约29 km至35 km距离范围处,不平海底环境下的水平纵向相关性出现了一些不同于平坦海底环境下的振荡结构,利用射线声学理论分析并解释了这两种不同海底环境产生水平纵向相关差异的原因。结果表明,在深海平坦海底方向一次海底反射到达区,对声场起主要贡献的经过一次海底反射声线间的到达时间差随着水平距离的增加而逐渐减少,从而干涉叠加后的相位差在[0,2π]内发生周期性变化,导致该区域声场的水平纵向相关性随着间距增加呈周期性振荡现象;而不平海底方向的海底小山丘恰对一次海底反射声线的阻挡影响,不仅使得与平坦海底方向相同区域的声传播损失明显增大,而且由于相对更多的本征声线路径的复杂多途干涉,该区域水平纵向相关性不再呈现明显的振荡周期,相关系数也有所下降。研究结果对于分析在深海复杂海底地形环境下的声呐阵列探测性能具有重要意义。     

有序介孔材料:历史、现状与发展趋势

有序介孔材料是指孔径在2~50 nm之间的多孔材料, 是一类具有均匀孔径、 高有序度纳米孔道和高比表面积的新材料. 在过去30年里, 有序介孔材料的研究取得了长足的进步, 在可控合成、 结构设计和调控及功能化等方面形成了系统的理论. 同时, 其应用领域也不断被拓展, 包括能源存储与转化、 催化、 生物医药和传感等方面. 本文首先回顾了有序介孔材料的发展历史, 简要介绍发展过程中“里程碑式”的研究工作; 然后根据构效关系总结了其在不同领域应用的最新进展; 最后讨论了有序介孔材料领域进一步发展所面临的挑战与机遇, 并对未来前景进行了展望.     

基于遗传算法的同步感应线圈发射装置参数优化

发射速度和能量转换效率是同步感应线圈型电磁发射装置（SICEML）最重要的两项指标。驱动线圈和电枢的结构参数、驱动线圈匝数以及电枢初始触发位置都会对这两项指标产生影响。以上述参数为变量,以发射速度和能量转换效率之积为目标函数,引入遗传算法对单级SICEML参数进行了优化设计,并利用有限元软件进行了仿真验证。结果表明：在储能与发射装置总体体积不变的前提下,优化后的系统效率由5.38%提高到13.6%,出口速度由38 m/s提高到61 m/s,系统性能得到明显改善。利用单级SICEML样机进行了堵驻试验,结果与仿真结果吻合较好,验证了本文提出的遗传算法的可行性。     

浅海中利用单水听器的声源被动测距

针对浅海声波导中远距离脉冲声源被动测距问题,提出了一种利用单水听器接收信号自相关函数进行warping变换的声源被动测距方法。理想水下声波导中,接收信号warping变换输出的傅里叶变换频谱中具有不变性频率特征,即与声源距离无关的各简正波截止频率;信号自相关函数中不同简正波相干成分也存在不变性频率特征;推导了未知声源距离时特征频率提取值与不变性频率特征之间的近似关系式。这些规律可推广到实际浅海声波导,并用于声源被动测距。利用声场计算模型来提供具有不变性频率特征的频谱,对2011年12月北黄海海域水声实验中单水听器接收的脉冲声数据进行了处理,验证了方法的有效性,测距结果和实际距离符合良好,平均测距误差在10%以内。     

空间层叠矩形阵列式角多路解码光路设计

根据角多路技术原理,提出了一种矩形阵列空间层叠形式的解码光路结构和先分组解码再组内解码的两步解码方式,并针对本实验室的高功率准分子激光系统给出了具体的解码光路设计实例。该方法具有解码精度高,设计误差小,与光路准直、激光参数测量系统等兼容性好,便于加工制作和安装调试等优点。