Unsaturation and variable hapticity in binuclear azulene manganese carbonyl complexes

Azulene is reported to react with Mn(2)(CO)(10) to give trans-C(10)H(8)Mn(2)(CO)(6), which has been shown by X-ray crystallography to have a bis(pentahapto) structure with no metal-metal bond. This structure is found by density functional theory to be the lowest energy C(10)H(8)Mn(2)(CO)(6) structure. However, a corresponding bis(pentahapto) cis-C(10)H(8)Mn(2)(CO)(6) structure, also without an Mn···Mn bond, lies within ~1 kcal mol(-1) of this global minimum. The lowest energy C(10)H(8)Mn(2)(CO)(5) structure is singlet cis-η(5),η(5)-C(10)H(8)Mn(2)(CO)(5) with an Mn→Mn dative bond from the Mn(CO)(3) group to the Mn(CO)(2) group. However, a singlet cis-η(6),η(4)-C(10)H(8)Mn(2)(CO)(5) structure with a normal Mn-Mn single bond lies within ~6 kcal mol(-1) of this global minimum. The lowest energy structures of the more highly unsaturated C(10)H(8)Mn(2)(CO)(n) (n = 4, 3, 2) systems all have cis geometries and manganese-manganese bonds of various orders. The corresponding global minima are triplet cis-η(5),η(3)-C(10)H(8)Mn(2)(CO)(3)(η(2)-μ-CO) for the tetracarbonyl with a four-electron donor bridging carbonyl group, singlet cis-η(5),η(5)-C(10)H(8)Mn(2)(CO)(3) for the tricarbonyl, and triplet cis-η(6),η(4)-C(10)H(8)Mn(2)(CO)(η(2)-μ-CO) for the dicarbonyl.     

高效阴离子交换色谱-铜/铂修饰电极安培法测定大观霉素

采用阴离子交换色谱分离,在CuSO4溶液中加入少量镧系化合物,经电沉积制备La3+-Cu/pt/CME工作电极,建立了直流安培电化学法(DC)直接检测硫酸大观霉素的方法。考察了流动相浓度、测定电位等参数对色谱分离和测定的影响。在固定相为CarboPac PA10阴离子交换柱、流动相为26mmol/L NaOH,流速为0.6mL/min的色谱条件下,检测电位为0.68V时,硫酸大观霉素峰面积与其浓度在0.12～12mg/L(r=0.9991)和12～280mg/L(r=0.9995)两个范围内呈线性。本方法不需要柱前和柱后衍生化,能同时测定硫酸大观霉素中的主要组分和杂质。修饰电极制作方法简单,催化稳定性好,可作为电化学传感器测定硫酸大观霉素中的各组分。     

高效液相色谱的4种商品手性柱对38种手性化合物的拆分研究

采用纤维素-三(3,5-二甲基苯基氨基甲酸酯)涂敷型手性固定相(Chiralcel OD柱)、直链淀粉-三(3,5-二甲基苯基氨基甲酸酯)涂敷型手性固定相(Chiralpak AD柱)、直链淀粉-三(3,5-二甲基苯基氨基甲酸酯)键合型手性固定相(Chiralpak IA柱)和Pirkle型的(S,S)-Whelk-01手性固定相对38种外消旋体化合物进行手性拆分。实验结果表明,4种固定相的手性识别能力为:OD>AD>IA>(S,S)-Whelk-01,OD固定相的手性识别率达到60%,并且它们之间的手性识别性能还具有一定的互补性。本研究对4种常用手性固定相的拆分能力进行了对比,为拆分手性化合物时有的放矢地选择手性固定相提供了参考。     

中空纤维协同液相微萃取在4种莨菪碱分析中的应用

利用协同液相微萃取方法初步探讨氢溴酸山莨菪碱、硫酸阿托品、氢溴酸东莨菪碱和丁溴酸东莨菪碱的优势构象;阐明有机溶剂对4种莨菪碱的萃取选择性和协同萃取作用机理;探讨中空纤维与莨菪碱形成电荷转移超分子对萃取效果的影响以及4种莨菪碱结构中N原子的亲电能力;结合高效液相色谱技术测定药物制剂中4种莨菪碱的含量。4种莨菪碱的线性范围均为0.05～5mg/L(r0.99),方法RSD小于7%,消旋山莨菪碱片和颠茄片中平均回收率分别为95.0%～119.0%和93.0%～95.0%,氢溴酸山莨菪碱和丁溴酸东莨菪碱检出限为0.03mg/L,硫酸阿托品和氢溴酸东莨菪碱检测出限为0.01mg/L。     

气相色谱-质谱法测定玩具中的4种阻燃剂

建立了玩具中三(2-氯乙基)磷酸酯、磷酸三邻甲苯酯、2,2′,4,4′,5-五溴联苯醚、2,2′,3,3′,4,4′,6,6′-八溴联苯醚等4种阻燃剂的气相色谱-质谱分析方法。玩具样品以V(正己烷):V(二氯甲烷)=1:1混合溶液为提取溶剂,超声提取30min,提取液以DB-5HT石英毛细管色谱柱(15m×0.25mm×0.10μm)分离后进行选择离子监测模式下的定性及定量分析。4种阻燃剂的定量限为0.1mg/kg,在低、中、高3个添加水平范围内,4种阻燃剂的平均回收率为93.5%～97.3%,相对标准偏差在2.4%～4.1%之间。     

基于GUI的阿贝-波特滤波实验的计算机仿真

介绍了阿贝-波特空间滤波的实验原理,在Matlab环境下建立了带有图形用户界面（GUI）的计算机仿真平台.不仅可以准确地完成针对不同输入图像、不同滤波要求的滤波过程,还可以通过调整滤波器参数观察滤波效果的差异,形象地展现光学空间滤波过程的物理本质,提高教学效果.     

Calibration of a multiple axes 3-D laser scanning system consisting of robot, portable laser scanner and turntable

A multiple axes 3-D laser scanning system consisting of a portable 3-D laser scanner, a industrial robot and a turntable is demonstrated. By using a criterion sphere, a robot tool center point (TCP) calibration approach is proposed to calibrate the relation between the laser 3-D scanner and the robot end-effector. In this approach, two different translational motions of robot are first made to determine the rotation part, and then at least three different rotational motions are made to determine the translation part. Meanwhile, by using the criterion sphere, a turntable approach is proposed to calibrate the pose of the turntable relative to the robot. In this approach, several rotational angles of turntable and two different heights of the sphere are made to determine the rotational axis of turntable. Experiment is performed on a portable laser scanner mounted on an industrial robot ABB IRB4400 with a turntable. The experiment results show that the two proposed calibration algorithms are stable and flexible. The application of 3-D measurement is also given to demonstrate the effectiveness and stability of the multiple axes 3-D laser scanning system.     

基于光纤布拉格光栅的智能服装人体测温模型研究

根据热量传递机理建立了智能服装中光纤布拉格光栅人体测温的热传递物理模型,对人体、空气层和服装之间的热传递进行了有限元建模和稳态热分析,确定了智能服装中光纤布拉格光栅温度场的数学模型,利用该数学模型对光纤布拉格光栅测量温度值进行了修正.在多点加权皮肤平均温度的基础上,提出了由左右胸、左右腋和后背五处皮肤温度构成的智能服装...     

拓展小尺寸离心压气机级失速裕度机匣处理方案的数值研究

为提高一小尺寸离心压气机级的失速裕度,首先为其设计了进气回流和周向槽两种机匣处理方案,对实壁机匣和处理机匣压气机级总体性能的分析表明;进气回流并没有起到拓展压气机级失速裕度的效果,周向槽机匣处理对压气机级失速裕度的改进量也只有约2.41%。因此考虑了一种新的机匣处理方案,即同时采用进气回流和周向槽机匣处理。计算结果表明:压气机级失速裕度得到了明显的提高,提高幅度达13.25%。