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81.
多氮杂大环与许多金属离子能形成稳定的络合物。由于氮原子是三价的,因而多氮杂大环比冠醚具有更有利的结构;如果再导入羧基、膦酸基以及其他的亲水基团,则可得到一系列能形成水溶性金属络合物的配体。其中某些金属(如铜、钇等)的络合物在人体生理条件下表现出很好的稳定性,结合单原抗体技术的应用,这炎络合物在医疗、诊断方面有实用性。本文简单介绍某些代表性络合物的制备方法、物理性能和可能的应用。 相似文献
82.
S. F. Malysheva N. K. Gusarova N. A. Belogorlova A. V. Afonin S. N. Arbuzova B. A. Trofimov 《Russian Chemical Bulletin》1997,46(10):1799-1801
Diorganylvinylphosphine oxides were synthesized in 31–38% yields on heating (50°C) diorganylphosphine oxides with vinyl sulfoxides
or divinyl sulfone in the presence of KOH.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1895–1896, October, 1997. 相似文献
83.
The surface and materials science of tin oxide 总被引:3,自引:0,他引:3
The study of tin oxide is motivated by its applications as a solid state gas sensor material, oxidation catalyst, and transparent conductor. This review describes the physical and chemical properties that make tin oxide a suitable material for these purposes. The emphasis is on surface science studies of single crystal surfaces, but selected studies on powder and polycrystalline films are also incorporated in order to provide connecting points between surface science studies with the broader field of materials science of tin oxide. The key for understanding many aspects of SnO2 surface properties is the dual valency of Sn. The dual valency facilitates a reversible transformation of the surface composition from stoichiometric surfaces with Sn4+ surface cations into a reduced surface with Sn2+ surface cations depending on the oxygen chemical potential of the system. Reduction of the surface modifies the surface electronic structure by formation of Sn 5s derived surface states that lie deep within the band gap and also cause a lowering of the work function. The gas sensing mechanism appears, however, only to be indirectly influenced by the surface composition of SnO2. Critical for triggering a gas response are not the lattice oxygen concentration but chemisorbed (or ionosorbed) oxygen and other molecules with a net electric charge. Band bending induced by charged molecules cause the increase or decrease in surface conductivity responsible for the gas response signal. In most applications tin oxide is modified by additives to either increase the charge carrier concentration by donor atoms, or to increase the gas sensitivity or the catalytic activity by metal additives. Some of the basic concepts by which additives modify the gas sensing and catalytic properties of SnO2 are discussed and the few surface science studies of doped SnO2 are reviewed. Epitaxial SnO2 films may facilitate the surface science studies of doped films in the future. To this end film growth on titania, alumina, and Pt(1 1 1) is reviewed. Thin films on alumina also make promising test systems for probing gas sensing behavior. Molecular adsorption and reaction studies on SnO2 surfaces have been hampered by the challenges of preparing well-characterized surfaces. Nevertheless some experimental and theoretical studies have been performed and are reviewed. Of particular interest in these studies was the influence of the surface composition on its chemical properties. Finally, the variety of recently synthesized tin oxide nanoscopic materials is summarized. 相似文献
84.
Kang Y Zyryanov GV Rudkevich DM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(6):1924-1932
The use of simple calix[4]arenes for chemical conversion of NO2/N2O4 gases is demonstrated in solution and in the solid state. Upon reacting with these gases, calixarenes 1 encapsulate nitrosonium (NO+) cations within their cavities with the formation of stable calixarene-NO+ complexes 2. These complexes act as encapsulated nitrosating reagents; cavity effects control their reactivity and selectivity. Complexes 2 were effectively used for nitrosation of secondary amides 5, including chiral derivatives. Unique size-shape selectivity was observed, allowing for exclusive nitrosation of less crowded N-Me amides 5 a-e (up to 95 % yields). Bulkier N-Alk (Alk>Me) substrates 5 did not react due to the hindered approach to the encapsulated NO+ reagents. Robust, silica gel based calixarene material 3 was prepared, which reversibly traps NO2/N2O4 with the formation of NO+-storing silica gel 4. With material 4, similar size-shape selectivity was observed for nitrosation. The N-Me-N-nitroso derivatives 6 d,e were obtained with approximately 30 % yields, while bulkier amides were nitrosated with much lower yields (<8 %). Enantiomerically pure encapsulating reagent 2 d was tested for nitrosation of racemic amide 5 t, showing modest but reproducible stereoselectivity and approximately 15 % ee. Given high affinity to NO+ species, which can be generated by a number of NOX gases, these supramolecular reagents and materials may be useful for NOX entrapment and separation in the environment and biomedical areas. 相似文献
85.
Chemical modification of silica surface by immobilization of functional groups for extractive concentration of metal ions 总被引:11,自引:0,他引:11
Increased utilization of mechanically stable synthetic matrices particularly silica gel as a solid support and its surface modification either by impregnation of organic ligands directly or covalent grafting through spacer unit for extractive concentration of trace elements are highlighted in the present article. Experimental evidences for existence of surface silanol and its chemical nature have explored the idea of silica surface modification. Recent methods of development in functionalized silica synthesis by attachment of various ligands or organic reagents to the silica surface and techniques of characterization of the modified surface have been reported. Analytical applications of various modified silica surfaces, in particular, adsorption of trace elements taking separation and preconcentration into account from complex synthetic mixture as well as natural water is presented. 相似文献
86.
Metal (M) oxide (M: Ir, Os, Pd, Pt, Rh, Ru) together with MaO2 and MnO2 alone, were coated on SnO2 films and the anode behavior was examined in 1.0 N H2SO4, 1.0 N NaOH and 1.0, N NaCl aqueous solutions at 25°. The results are compared with those of DSA and of metallic Pt. 相似文献
87.
含Cu复合氧化物对NO和CO吸附和活化的TPSR研究 总被引:2,自引:2,他引:2
利用MS-TPD法并结合XRD、化学分析等对催化剂进行了表征,探讨了K2NiF4结构La2-x(Sr,Th)xCuO4±λ系催化剂中三个典型样品LaSrCuO4、La2CuO4和La1.7Th0.3CuO4对NO、CO及CO+NO等小分子的吸附性能和活化规律。结果表明:NO吸附量的大小与催化剂中氧空位含量有关,吸附强度和脱附峰种类与金属离子氧化态有关。CO在氧缺陷复合氧化物催化剂上的吸附是首先变为碳酸根,并在高温以CO2物种脱出.在NO和CO的共吸附过程中,有关NO的吸、脱性能与单独NO-TPD中NO的吸脱附规律相似,表明NO在NO+CO共吸附的竞争吸附过程中,优先吸附起决定作用,而受CO的影响较小.NO的吸附是NO活化分解的必要条件. 相似文献
88.
V. A. Startseva L. E. Nikitina N. P. Artemova S. A. Dieva V. V. Plemenkov 《Chemistry of Natural Compounds》2000,36(6):587-589
Ethanedithiol and di(mercaptoethyl)sulfide react regio- and stereoselectively with (+)-3-carene and -hydroxy(-)--pinene -oxides in the presence of sodium ethoxide to give the corresponding bis- and tris-sulfides with two terpene fragments 相似文献
89.
Zr0.5Ti0.5O2(ZT) and Zr0.25Ti0.25Al0.5O2(ZTA) mixed oxides were prepared by co-precipitation method and characterized by low temperature adsorption-desorption, XRD and NH3-TPD. The activity of Pt/Zr0.5Ti0.5O2 and Pt/ Zr0.5Ti0.5Al0.5O2 catalysts was evaluated using the simulated gases. The results show that ZTA samples exhibit higher specific surface area, larger pore volume and proper surface acidic amount and acidity in comparison with ZT. The results of the catalytic test indicate that Pt/ZT and Pt/ZTA catalysts exhibit excellent low-temperature catalytic activity and lower light-off temperatures of hydrocarbon, carbon monoxide and nitrogen oxides, especially better conversion for nitrogen oxides (NOx). The addition of Al2O3 into ZT enhanced the anti-aging property of Pt/ ZTA catalysts due to the excellent textural, structural, surface acidity and thermal stability. 相似文献
90.
Fabrication of high performance thin films from metal fluorocomplex aqueous solution by the liquid phase deposition 总被引:1,自引:0,他引:1
Hnin Yu Yu Ko Minoru Mizuhata Akihiko Kajinami Shigehito Deki 《Journal of fluorine chemistry》2003,120(2):157-163
The hetro-structured oxide thin films from metal fluorocomplex solution have been prepared by the liquid phase deposition (LPD) method. The Pt/Nb2O5 and Au/Nb2O5 composite films can be prepared from a mixed solution of niobium source, H3BO3, Pt(NH3)4Cl2 and HAuCl4 aqueous solutions under the ambient temperature and atmosphere. In the case of Au/SiO2 composite film, (NH4)2SiF6 solution is used as a mother solution. The Pt and Au ionic species are deposited in Nb2O5 and SiO2 matrices. They are reduced to their metallic state after treatment above 200 °C. The size of dispersed particles can be controlled by heat treatment temperature. It is also clear that, gold nanoparticles are also found to interact with SiO2, although the interaction is smaller than that with Nb2O5 showing the size of Au nanoparticles remain smaller in Nb2O5 that in SiO2. 相似文献