钪—铋—三溴偶氮胂混合多核络合物显色反应及其在钪光度分析中应用研究

本文研究了钪-铋-三溴偶氮胂络合物的共显色反应。实验表明,共显色反应是由于形成混合多核络合物所致。钪络合物最大吸收峰在635nm,表观摩尔吸光系数为7.1×10~4L·mol~(-1)·cm~(-1)。钪在0～5μg/25ml遵守比尔定律。     

2－（5－Br－2－吡啶偶氮－5－二乙氨基）－酚与铑的显色反应的研究及应用

本文研究了２－（－５－Ｂｒ－２吡啶偶氮－５－二乙氨基）－酚与铑（Ⅲ）的显色反应。在ｐＨ为４．０的邻苯二甲酸氢钾缓冲液介质中，Ｒｈ（Ⅲ）与试剂形成稳定的橙红色络合物，其组成比为１：４，最大吸收波长为４９０ｎｍ，表现摩尔吸光系数为１．３×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）。铑含量在０～４μｇ／１０ｍＬ范围内服从比尔定律。     

Structural characterization of a novel self-assembly heterohexanuclear complex: [Ni2Ag4(μ-dppm)4(pymt)6](SbF6)2 · 2DMF · H2O

A novel heterohexanuclear complex [Ni₂Ag₄(μ-dppm)₄(pymt)₆](SbF ₆)₂ · 2DMF · H₂O (1), was synthesized by self-assembly with [Ag₂(μ-dppm)₂(MeCN)₂](SbF₆) ₂ and [Et₄N][Ni(pymt)₃] (dppm = bis(diphenylphosphino)methane, pymt = pyrimidine-2-thiolate) as components and characterized by IR spectra, elemental analysis, ¹H-NMR spectrum, ³¹P-NMR spectrum and Visible-Ultraviolet spectrum. Structure of the complex was determined by X-ray analysis.     

Inelastic incoherent neutron scattering measurements of intact cells and tissues and detection of interfacial water

We have previously used inelastic incoherent neutron scattering spectroscopy to investigate the properties of aqueous suspensions of biomolecules as a function of hydration. These experiments led to the identification of signals corresponding to interfacial (hydration) water at low water content. A prediction from these studies was that in the crowded environment inside living cells, a significant proportion of the water would be interfacial, with profound implications for biological function. Here we describe the first inelastic incoherent neutron scattering spectroscopy studies of living cells and tissues. We find that the interfacial water signal is similar to that observed for water interacting with purified biomolecules and other solutes, i.e., it is strongly perturbed in the librational and translational intermolecular optical regions of the spectrum at 20-150 meV. The ratio of interfacial water compared to total water in cells (approximately 30%) is in line with previous experimental data for hydration water and calculations based on simple assumptions.     

An annulation toward fused bicyclolactones

The combination of Lewis and Bronsted acids catalyzed the addition of beta-ketoesters to cyclic diene. Lactonization occurs in situ to afford fused bicyclic lactones directly. The catalysis provides an expedient route to bicylic lactones via a zip-process.     

β-Bromodifluoromethyl β-enaminoketones: versatile synthetic intermediates for synthesis of CF2-containing compounds

A series of N-aryl β-bromodifluoromethyl β-enaminoketones were regioselectively synthesized in good yield by the reaction of N-aryl bromodifluoroacetimidoyl chlorides with methyl ketones. β-Bromodifluoromethyl β-enaminoketones smoothly cyclized to give a novel class of cyclic (2,2-difluoro-5-phenyl-furan-3-ylidene)-aryl-amines under basic condition. An intramolecular halophilic substitution mechanism was proposed.     

Versatile photosensitization system for 1O2-mediated oxidation of alkenes based on nafion-supported platinum(II) terpyridyl acetylide complex

[structure: see text] Platinum(II) terpyridyl acetylide complex (1) was incorporated into Nafion membranes as a photosensitizer, and the Nafion was immersed in an aqueous or organic solution of 7-dehydrocholesterol, alpha-pinene, or cyclopentadiene. This photosensitizer system can generate singlet oxygen ((1)O(2)) in high quantum yield to oxidize the alkenes in the solution outside the Nafion and can be easily removed from the reaction vessel at the end of the photooxidation.     

Quantitative Transfer of In-Gel Digest Products to Liquid Chromatography-Electrospray Mass Spectrometry Using On-Line Coupled Extraction

A system is described for the on-line extraction of a digested protein in a gel spot. The extract obtained was on-line transferred to a precolumn, used to desalinate and preconcentrate the sample. The precolumn was switched in-line with an LC-ESI-MS system to separate the digest products prior to detection. By using this approach sample losses were minimized and the sample was quantitatively transferred. The benefits of the system were shown for the in-gel tryptic digest of several model proteins. Using this system, the sensitivity was 13-fold increased compared to the off-line extraction of in-gel digest products leading to a higher sequence coverage and thus a better identification potential. Also, the within day repeatability was a factor 2.5 improvement using the on-line procedure compared to the off-line extraction procedure.     

Imidazole facilitates electron transfer from organic reductants

In cyclic voltammetry studies at pH 8, imidazole facilitates oxidation of organic compounds that normally lose hydrogen atoms. High concentrations of imidazole shift the oxidizing wave of ascorbic acid, 2,3-dimethoxy-5-methyl-1,4-hydroquinone, and the vitamin E analogue Trolox toward lower potentials. By contrast, imidazole has no effect on the cyclic voltammogram of methyl viologen, which undergoes electron rather than hydrogen-atom transfer. The effect of imidazole is observed at pH 8.0 but only to a lesser extent at pH 5.5 indicating that imidazole must be unprotonated to facilitate oxidation. Digital simulation shows that these results are consistent with a mechanism in which imidazole acts as a proton acceptor permitting concerted proton/electron transfer by the organic reductant.     

碱金属和重金属叠氮化物的感度和导电性研究

分别用EHCO和DV－X_α方法，计算研究了α－NaN_3、β-NaN_3和AgN_3的能带结构和原子簇电子结构. AgN_3与NaN_3相比：带隙(△Eg)较小、带宽(BW)较大，因而电导率较大. 比较前沿晶体轨道(CO)和前沿分子轨道(MO)的能级、组成及电子在其间的跃迁；预示AgN_3比NaN_3更敏感、更易分解和起爆．还从电子微观层次揭示了金属叠氮化物的导电性和爆炸性之间的联系．