基于2，5-双(三氟甲基)对苯二甲酸配体的锌配合物的合成、晶体结构及性质

利用2，5-双（三氟甲基）对苯二甲酸（H₂L）为主配体，氯化锌为金属盐，分别与辅助配体4，4''-联吡啶（4，4''-bipy）和2，2''-联吡啶（2，2''-bipy）通过溶剂热法反应合成了配合物[Zn（L）₂（4，4''-bipy）（H₂O）]_n（1）和[Zn（L）（2，2''-bipy）]_n（2）。通过X射线单晶衍射、红外光谱、元素分析、荧光光谱、热重分析等测试手段对其结构和性质进行了表征与研究。结果表明，配合物1是以Zn²⁺为金属节点，L^2-和4，4''-bipy作为连接体相互连接，形成无限延伸的二维网状结构，层与层之间通过O5-H5B…O1氢键作用有序堆积形成三维结构。配合物2以Zn²⁺为金属节点，配体L^2-上的每个羧基都通过双齿螯合的方式桥联锌离子并无限连接形成三维网状结构。     

Syntheses and Crystal Structures of Two One-dimensional Cobalt(Ⅱ) Compounds with the Flexible Dipyridyl Ligan

Two one-dimensional cobalt(Ⅱ) compounds {[Co(Hbpma)(H2O)4 ] 2 ·3SO 4 ·4.5H2O} n1 and {[Co(Hbpma)(NCS) 3 (H2O)]·2.85H2O}n2 (bpma = N,N -bis(3-pyridylmethyl)amine) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1 with a = 15.8780(5), b = 16.2187(5), c = 16.4858(5) , α = 91.0420(10), β = 94.5190(10), γ = 101.4360(10)°, V = 4145.7(2) 3 , C 24 H 53 Co 2 N 6 O 24.50 S 3 , M r = 1031.76, Z = 4, D c = 1.653 g/cm 3 , μ(MoKα) = 1.046 mm -1 , F(000) = 2148, S = 1.017, the final R = 0.0269 and wR = 0.0644 for 13032 observed reflections (I > 2σ(I)). For complex 2, it belongs to triclinic, space group P1 with a = 9.3761(11), b = 10.5814(13), c = 11.2972(14) , α = 85.472(2), β = 88.058(2), γ = 76.203(2)°, V = 1085.0(2) 3 , C 15 H 21.70 CoN 6 O 3.85 S 3 , M r = 502.79, Z = 2, D c = 1.539 g/cm 3 , μ(MoKα) = 1.112 mm -1 , F(000) = 519, S = 1.070, the final R = 0.0358 and wR = 0.0899 for 3466 observed reflections (I > 2σ(I)). Two complexes 1 and 2 are both found to be one-dimensional coordination polymers bridged by the protonated bpma ligands, which are assembled into three-dimensional supramolecular structures through the hydrogen bonding interactions and π-π packing interactions.     

Physical characteristics with SPP in the metallic nanowires structure

In this work,the terahertz(THz) electromotive force(EMF) of the surface plasmon(SP) electric field and field strength was investigated in its propagation direction.Based on the nanowires structure,we introduced physical models which were light wave energy of surface plasmon polariton(SPP) pulse and the variation of EMF changes in the active condition.Results of theory and verification showed SPP generated EMF with 10 2-10 V among wire radii of 5-30 nm;the electric field was up to 105-106 V/cm in the radius of 5 nm;the electric field intensity induced localization at =850 nm,and at the same time light intensity amplified 40 times.The characteristics which are femtosecond SPP pulse response and force-field amplifier in this work are significant for nonlinear spectroscopy research.     

(3S,4S)-4-氨基-3-羟基-6-甲基庚酸的合成

价廉易得的L-亮氨酸先以苄基同时保护氨基及羧基得(S)-2-(二苄胺基)-4-甲基戊酸苄酯,进而在碱性条件下与乙腈发生亲核取代反应得(S)-4-(二苄胺基)-6-甲基-3-氧代庚腈,再经硼氢化钠选择性还原羰基得(3S,4S)-4-(二苄胺基)-3-羟基-6-甲基庚腈,用双氧水氧化得(3S,4S)-4-(二苄胺基)-3-羟基-6-甲基庚酸,最后在Pd(OH)2/C-H2作用下脱掉苄基得到(3S,4S)-4-氨基-3-羟基-6-甲基庚酸,即(3S,4S)-statine。整个合成路线总产率为33.6%。     

双核芳基Os(Ⅱ)配合物的合成及诱导肿瘤铁死亡机制

本文报道了一种双核锇Os(Ⅱ)配合物[Os （η⁶-bip）（1，3-bib） Cl]₂Cl₂（bib-Os），其中η⁶-bip=η⁶-联苯，1，3-bib=1，3-二（1H-咪唑-1-基）苯。并通过¹H NMR和ESI-MS进行基础表征。配合物bib-Os具有良好的脂溶性，易在细胞中积累。配合物bib-Os对人卵巢癌A2780细胞表现出高效的抗增殖活性，可产生活性氧（ROS）并诱导线粒体损伤。脂质过氧化物（LPO）积累、谷胱甘肽（GSH）消耗和谷胱甘肽过氧化物酶4（GPX4）下调表明，配合物bib-Os诱导A2780细胞死亡的主要机制是铁死亡，bib-Os是第一例诱导肿瘤细胞铁死亡的Os金属配合物。     

超半环的广义直觉模糊理想刻画

对超半环上的直觉模糊子集进行讨论.首先在超半环上给出有边界值的直觉模糊超理想,对其部分性质进行研究.其次给出正则超半环和内禀正则超半环的概念,利用有边界值的直觉模糊超理想对这两种超半环进行刻画,得到若干刻画定理.     

Recoverable Mn~Ⅲ (salen) supported on diamine modified zirconium poly(styrene-isopropenyl phosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins

Chiral Mn Ⅲ (salen) (Jacobsen’s catalyst) was axially immobilized onto a new type of organic polymer-inorganic hybrid materialzirconium poly(styrene-isopropenyl phosphonate)-phosphate(ZPS-IPPA) with different linkage lengths and evaluated as catalysts for the epoxidation of unfunctionalized olefins. The results demonstrated that the prepared catalysts exhibited moderate to good activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the immobilized catalysts were relatively stable and could be conveniently separated from the reaction system by simple precipitation in hexane. Moreover, higher enantioselectivity was obtained with catalyst 2c than that of homogeneous counterpart catalyzed even after eight times. The excellent recycling of the catalyst was attributed to its structure feature of ZPS-IPPA which is different from either pure polystyrene or pure zirconium phosphates.     

优化背景值的GM(1,1)幂模型及其应用

GM(1,1)幂模型中幂指数的连续性,使得模型在一般的S形曲线序列的预测和拟合中具有更广泛的实用性.通过将背景值转化为相邻序列点的确定性函数建立了改进的GM(1,1)幂模型,给出了背景值序列的有关性质,借助已有文献中的算例验证了模型在拟合和预测方面的优越性.     

重力热管喷涌不稳定性调控判据

重力热管内的两相流型对其工作特性有着至关重要的影响.本文借鉴垂直圆管内两相流型转变的实验研究结果和近饱和自由降膜流始发沸腾的观测结论,通过简化分析,给出重力热管蒸发段内由泡状流向弹状流过渡的流型转变判据.在低饱和蒸汽压和高过冷度下,这种流型转变将导致周期性振荡的两相流不稳定性,这就是喷涌不稳定性;因此,流型转变判据也就是喷涌不稳定性调控判据.文中还结合数值计算实例,指出影响流型转变的重要因素.