Synthesis of a Nine-atom Germanium Cluster K_(0.5)[K(18-crown-6)]_(1.5)Ge_9·1.5en with Unprecedented “up” and “down” Chain Arrangement of Unit [-(Ge_9-K-Ge_9)~(3-)-]

A new complex K0.5[K(18-crown-6)]1.5Ge9·1.5en(1) which contains unprecedented "up" and "down" chain arrangement of unit [-(Ge-9-K-Ge9)3-] has been prepared by the reaction of K4Ge9 with HgS in ethylenediamine(en) in the presence of 18-crown-6(1,4,7,10,13,16-hexaoxacyclooctadecane), and characterized by X-ray structure analysis. The color of the title crystals(black), which is darker than that of the reported three compounds with chains of germanium clusters, may result from the naked K+ and their interactions with the chain. And the structure differences between 1 and the reported three compounds with chains of germanium have also been discussed.     

CO2-3掺杂纳米羟基磷灰石晶体的合成与表征

CO2-3掺杂是提高纳米羟基磷灰石（n-HA）生物活性的有效方法之一。以 Ca（NO3）2·4H2O 和Na3PO4·12H2O为主要原料，Na2CO3作为CO2-3来源，合成纳米碳羟基磷灰石（n-CHA）晶体。采用TEM ， XRD ，FTIR ，RS对合成晶体形貌和结构进行表征。结果表明：合成的n-HA晶体长度约为60～80 nm ，宽度在20～30 nm之间，形状为针状，具有良好的结晶度，与自然骨磷灰石形貌相似；n-CHA晶体随CO2-3掺入量的增加，结晶度降低；合成的 n-CHA晶体的晶胞参数 a值随着CO2-3加入量的增大不断收缩，但 c值增大，参数比c/a值增大，符合B型取代（取代PO3-4）的晶胞参数变化规律。红外谱图中，872 cm -1附近出现AB混合型取代（同时取代O H -，PO3-4）的CO2-3面外弯曲振动特征红外峰，同时CO2-3的不对称伸缩振动红外峰在1454和1420 cm -1附近出现分裂峰，1540 cm -1附近出现弱CO2-3峰；1122 cm -1附近出现CO2-3对称伸缩振动拉曼峰，1071 cm -1附近出现CO2-3的B型替代特征拉曼峰，通过计算PO3-4，CO2-3，O H -拉曼峰的积分面积比PO3-4/CO2-3，O H -/CO23，PO3-4/O H -，表明CO2-3在替换时，先以B型为主，随着CO2-3掺入量的增加，发生A型替代（取代O H -）。实验结果表明，合成的磷灰石晶体为B型取代（取代PO3-4）为主的AB混合型取代的 n-CHA。与人骨磷灰石晶体在形态、尺寸、晶体结构和生长方式上具有相似性，可称为类骨磷灰石。     

多酸基金属-有机框架的构筑及其催化性能

在水热条件下合成了两个基于Keggin型磷钨酸盐的金属-有机框架化合物(MOFs)[Er_2H(μ-O)_2(dpdo)_4(H_2O)_2][PW_(12)O_(40)]·3H_2O(1)和[Tm_2H(μ-O)2(dpdo)4(H_2O)_2][PW_(12)(O_(40)]·3H_2O(2)(dpdo=4,4′-bis(pyridine-N-oxide),并通过元素分析、红外光谱(IR)、紫外光谱(UV)及单晶X射线衍射(XRD)的方法对其进行了结构表征.此外,通过紫外-可见分光光度法,在EPPS缓冲溶液中,考察了两种化合物在非均相体系中催化DNA模型磷酸二酯双(对硝基苯酚)磷酸二酯(BNPP)的水解进程.催化结果表明,在50℃,pH=4的条件下,两种催化剂对BNNP催化的一级水解裂解速率为10-7~10-6 s-1,最终产物为无机磷酸盐和对硝基苯酚.此外,该催化体系具有很好的重现性,并且催化剂可循环使用.     

基于“标准-3”动能拦截弹的顺轨拦截方法研究

提出了针对大气层外机动目标的顺轨拦截方法,能够大幅度降低目标与拦截器之间的相对速度,缓和拦截器的过载需求,避免脱靶现象。采用“标准-3”拦截弹的公开参数建立数学模型,对大气层外机动弹头的顺轨拦截过程进行了仿真研究,仿真综合考虑了助推器和拦截器的质量变化、末制导初始对准误差、导引头的测量误差和盲区、动力学系统的响应延迟和过载约束。结果表明,在处于速度劣势的情况下,拦截器能够对机动目标进行精准碰撞,验证了顺轨拦截方法的工程实践意义。     

3d-4f异金属修饰的缺位Lindqvist型同多酸化合物的合成与表征

在水热条件下,成功合成了一例新的异金属修饰的有机-无机杂化型多金属同多酸簇合物[Cu(en)_2(H_2O)]_4[Ce(W_5O_(18))_2]·4H_2O(1)(en=乙二胺),采用X射线单晶衍射、元素分析、X射线粉末衍射及热重分析对化合物进行了结构分析和基本表征.化合物1属于单斜晶系,P2_1/c空间群,单胞参数为a=2.736 1(2)nm,b=1.452 52(7)nm,c=1.634 53(9)nm,β=97.153(6)°.结构解析表明,化合物1中的中心离子Ce~(4+)与两个同多酸簇块的O原子结合形成八配位的四方反棱柱体,并通过游离的及支撑的[Cu(en)_2(H_2O)]~(2+)进行修饰.值得注意的是,化合物1是首例基于{W_5O_(18)}型同多酸簇块的Cu-Ce异金属修饰型有机-无机杂化的孤立结构.     

一种新颖高效的气体发生器

针对启普发生器使用过程中存在液体使用量大、反应溶液利用效率低、安全性差等问题，研制了一种新型的气体发生器。该装置由储液杯、流量调节器、排气管和反应容器组成。利用流量调节器将反应液滴加到固体药品上，固-液反应充分，排出的废液基本不含反应试剂，大大减少了液体药品的用量。实验结果表明，该新型制气装置具有液体试剂用量少、利用效率高、安全性能优良、操作方便，同时兼具随开随用等特点，可有效地应用于化学实验教学中。     

苯/二联苯为桥的噻吩-吡咯-噻吩结构:分子构型及电致变色性质

A series of multi-branched dithienylpyrrole (SNS) monomers with rigid phenyl (PhSNS) and biphenyl rings (BPhSNS) as bridges were designed and synthesized, and were fabricated to form cross-linked polymers (pPhSNS, pBPhSNS) by electrochemical polymerization. Cyclic voltammetry (CV) results showed that PhSNS and BPhSNS exhibited similar oxidative properties except for one new higher-potential oxidative peak appearing in the curves of PhSNS. Theoretical calculations indicated that it should be attributed to the different steric configuration between the two dithienylpyrrole (SNS) units in PhSNS. One SNS unit possessed a larger twist angle (40.2°) between thiophene and pyrrole rings than the other one (21.2°), which indicated that PhSNS possessed a relatively larger energy gap (~0.4 eV) between HOMO-1 and HOMO than BPhSNS, for which HOMO and HOMO-1 levels were of almost the same energy. However, both PhSNS and BPhSNS showed similar onset oxidation potentials. The CV curves of pPhSNS and pBPhSNS showed that they presented similar oxidative properties, which enabled their corresponding electrochemical polymers to exhibit similar electrochromic properties. The UV-vis spectra of the corresponding polymers showed that both pPhSNS and pBPhSNS possessed similar optical absorption and similar multicolor switching between yellow (-0.8 V), greyish-green (0.9 V) and gray (1.1 V) colors. Besides, pPhSNS and pBPhSNS showed fast switching times of 0.57 s and 0.93 s at 1100 nm, respectively and reasonable contrasts of 46% and 31% at 1100 nm, respectively. These investigations may help understand the relationship between structural configuration and the electrochemistry/electrochromic properties for polymer electrochromic (PEC) materials research.     

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In this paper, a nonparametric method for reliability of the stress-strength model is proposed when the dependent stress variable and strength variable are subject to right censoring. The dependence between variables is measured by the common Farlie-Gumbel-Morgenstern copula function and Clayton copula function. Using the empirical process theory, consistency and asymptotic normality of the proposed estimator is established in this paper. The results of numerical simulation show that the proposed method performs well in the case of finite sample. The method proposed in this paper has a wide application prospect in practice.     

线性互补问题在宽邻域下的局部二次收敛算法

艾文宝(2004)的宽邻域算法弥补了内点法在理论和实践表现之间的差异.基于这个算法的优越性,将其推广到线性互补问题中.新算法在一次迭代中,采用两个方向的线性组合作为新方向,并以满步长到达下一个点.可以证明,该算法具有O(n~(1/2)L)的理论复杂度,这是迄今为止最好的复杂度结果.同时,在假设线性互补问题存在严格互补解的前提下,证明算法具有局部二次收敛性.最后,数值实验说明算法是有效的.     

纳米金/β-环糊精复合修饰碳糊电极测定亚硝酸盐

本文研究了亚硝酸盐(NO_2~-)在纳米金和β-环糊精复合修饰碳糊电极(AuNPs-β-CD/CPE)上的电化学行为。实验结果表明,与裸CPE相比,AuNPs-β-CD/CPE对NO_2~-的电化学氧化有显著的促进作用,其氧化峰电流显著增加。同时用循环伏安法(CV)、计时电流法(CA)测定了NO_2~-在AuNPs-β-CD/CPE上的电极反应动力学参数,用线性扫描伏安法(LSV)法测得NO_2~-氧化峰电流与其浓度在6.0×10-6~8.0×10-3 mol·L-1范围内呈良好的线性关系,检出限(S/N=3)为5.7×10-7 mol·L-1。将该传感器应用于水样的检测,相对标准偏差在0.15%~1.40%之间,回收率达99.3%~104.0%,检测结果符合定量测定要求。