红外光谱法观察二茂镧系氯化物与氧及水蒸气的反应

用实时红外光谱法在特制的收池中分别观察了一些二茂镧系氯化物Ｃｐ２ＬｎＣｌ（Ｃｐ＝Ｃ５Ｈ５，Ｌｎ＝Ｈｏ，Ｇｄ，Ｌｕ）和Ｃｐ＇Ｌｕ（Ｃｐ＝Ｃ５Ｈ４ＣＨ２ＯＣＨ３）与干燥氧气及水蒸气的反应，结果证实这些二茂镧系配合物在室温干燥氧气氛中很稳定，但在水蒸气中很快水蒸气的反应，结果证实这些二茂镧系配合物在室温干燥氧气氛中很稳定，但在水蒸气中很快水解。从水解反应的最初始阶段和较后期采得的红外光谱提示可能存在...     

Organometallic Compounds of the Lanthanoides. LXVI. Synthesis and X-ray crystal structure of [O(CH2CH2C5H4)2Y(μ-OH]2 and (MeC5H4)3Ho(H2O), two unusual products of the hydrolysis of organolanthanoide compounds

The partial hydrolysis of [O(CH₂CH₂C₅H₄)₂]Y(C₅H₄CH₃) 1 , [O(CH₂CH₂C₅H₄)₂]Y(C₅H₅) 3 , and [O(CH₂CH₂C₅H₄)₂]Ho(C₅H₄CH₃) 5 results in the formation of [O(CH₂CH₂CH₂C₅H₄)₂Y(μ-OH)₂]₂ 2 , (C₅H₅)₃Y(OH₂) 9 and (MeC₅H₄)₃Ho(OH₂) 11 . The new compounds have been characterized by elemental analyses, IR and NMR spectra. The X-ray structural analyses shows 2 to be monoclinic, space group P2₁/n with a = 1146.0(3), b= 1046.6(3), c = 1514.9(3) pm, β = 94.83(2)°. The molecular structure shows bridging hydroxyl groups with a mean distance Y? O = 223.8(3) pm. 11 crystallizes in the cubic space group 14 3d with a = 1847.9(3)pm with Z = 16 molecules per unit cell. The molecules posses symmetry C₃-3, the coordination is trigonal pyramidal with three methylcyclopentadienyl anions and one water molecule as ligands. The distance Ho? O is 231 pm.     

Chemoenzymatic synthesis of β-carboline derivatives using McbA,a new ATP-dependent amide synthetase

McbA was characterized in vitro as a novel amide synthetase in the marinacarbolines A–D biosynthetic pathway, catalyzing amide bond formation between 1-acetyl-3-carboxy-β-carboline (1a) and substituted-β-phenethylamines (1b, 2b, 3b) and tryptamine (4b) in an ATP-dependent manner. Enzyme kinetic analyses highlight β-phenethylamine as the most suitable amine donor. McbA showed broad substrate compatibility with substituted amines; 10 new β-carboline analogues were chemoenzymatically generated.     

Ultrabroadband superoscillatory lens composed by plasmonic metasurfaces for subdiffraction light focusing

Conventional optics is diffraction limited due to the cutoff of spatial frequency components, and evanescent waves allow subdiffraction optics at the cost of complex near‐field manipulation. Recently, optical superoscillatory phenomena were employed to realize superresolution lenses in the far field, but suffering from very narrow working wavelength band due to the fragility of the superoscillatory light field. Here, an ultrabroadband superoscillatory lens (UBSOL) is proposed and realized by utilizing the metasurface‐assisted law of refraction and reflection in arrayed nanorectangular apertures with variant orientations. The ultrabroadband feature mainly arises from the nearly dispersionless phase profile of transmitted light through the UBSOL for opposite circulation polarization with respect to the incident light. It is demonstrated in experiments that subdiffraction light focusing behavior holds well with nearly unchanged focal patterns for wavelengths spanning across visible and near‐infrared light. This method is believed to find promising applications in superresolution microscopes or telescopes, high‐density optical data storage, etc.

     

圆形重力式网箱锚碇系统的受力研究

依据Stokes二阶波浪理论和莫里森(Morison)方法,对圆形重力式网箱的浮架结构分别与工程上常用的两种锚碇系统(折线形与直线形)相结合情况下,锚碇系统的受力进行了数值计算及相应的物理模型试验。结果表明相同波况下折线形锚碇系统承受张力较小,在相同波浪周期条件下,波高越大锚碇点受力越大;相同波高下,锚碇点最大受力随周期变化不显著。将计算结果与模型试验对比,结果显示计算数值与试验数据较接近,表明了此计算方法的可行性,为进一步模拟浮架结构的运动变形打下基础。     

荧光纳米材料在病原微生物检测中的应用

病原菌污染给人类的健康带来极大的安全隐患,对病原菌快速、准确和灵敏的检测是减少污染的重要手段。传统检测病原菌的方法存在耗时长和操作繁琐等缺点。荧光纳米材料具有荧光强度高、稳定性好以及良好的生物相容性等优势,为应用其构造传感器用于病原菌检测提供了新的研究途径。本文对近年来常见荧光纳米材料,包括半导体量子点、金属纳米簇、碳纳米材料、上转换纳米粒子和荧光硅纳米颗粒,在病原菌检测方面的应用进行了概述,着重将不同类别荧光纳米材料的光学性质和检测机理进行了分析和比较。纳米材料的生物修饰是实现病原菌特异性识别的重要环节,本文对抗体、适配体、噬菌体和抗生素等病原菌识别方式的特点及其与纳米材料的连接方式进行了介绍。最后对不同荧光纳米材料在检测病原菌中具有的优势和局限性进行了总结,并对其在未来的应用与研究重点进行了展望。     

Copolymerization of ethylene with cycloolefins by titanium complexes containing tridentate [o−NSR] ligands

A family of titanium complexes of the general formula [N‐(3,5‐di‐tert‐butylsalicylidene)‐2‐alkylsulfanylanilinato]Ti(IV)Cl₃ 5a – f was prepared from the reaction of TiCl₄ with the potassium salts of the corresponding ligands. These complexes were fully characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 5b and 5e were further confirmed by single‐crystal X‐ray analyses. Complexes 5a – f (except for 5c ) exhibited good to high catalytic activities in ethylene copolymerization with cycloolefins such as norbornene, cyclopentene, dicyclopentadiene in the presence of modified methylaluminoxane. The reaction conditions and the steric hindrance of the alkyl substituents on sulfur atom in the precatalysts influenced strongly the copolymerization behaviors and the structures of the resultant copolymers. Complex 5c with bulky tert‐butylthio sidearm showed both low catalytic activity and comonomer incorporation ratio. The n‐alkylthio complexes 5a , 5d – f all exhibited good ethylene copolymerization capabilities with cycloolefins, which is superior to the corresponding phenylthio complex 5g . © 2008 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 46: 2807–2819, 2008     

Reaction of dicyclopentadienylyttrium chloride with aldehydes and ketones. A novel cleavage reaction of Cp---Y π-bond

Dicyclopentadienylytrrium chloride reacts with aldehydes and ketones at 80°C in DME, generating fulvenes in excellent yields, while at lower temperature affording, after hydrolysis, cyclopentadienyl substituted alcohols.     

顺磁性镧系金属有机配合物的~1H核磁共振研究

顺磁类的核磁共振研究大多是简单化合物,偏重理论方面的研究,对镧系配合物曾有报道。由于这类样品对空气和湿气极为敏感,在国内外研究顺磁性~1H谱甚少。本文研究了含氯桥的醚基取代环戊二烯镧系配合物二聚体的~1H化学位移,线宽,弛豫时间T_1和磁化率,从中找出了顺磁类有机镧系配合物~1H NMR的规律。     

手性稀土配合物催化的亚膦酸酯对醛的不对称加成（Pudovik）反应研究

手性稀土配合物催化的亚膦酸酯对醛的不对称加成（Ｐｕｄｏｖｉｋ）反应研究钱长涛黄太生（中国科学院上海有机化学研究所金属有机化学开放实验室上海２０００３２）关键词对映选择性加成Ｐｕｄｏｖｉｋ反应手性镧配合物α－羟基膦酸酯分类号Ｏ６４３．３２光学纯的α－羟...