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111.
Removal from air and decomposition of dimethyl methylphosphonate (DMMP) over high surface area anatase TiO(2) at ambient temperature have been quantitatively studied by employing Fourier transform infrared (FTIR) technique under static conditions. In the first scenario of air purification, DMMP underwent reactive adsorption that upon completion was followed by photocatalytic oxidation. DMMP was captured over the TiO(2) surface at the speed of external diffusion. Hydrolysis of adsorbed DMMP led to methanol and methyl methylphosphonate (MMP). At low DMMP coverage quantity, it hydrolyzed completely with the formation of completely surface-bound methanol at 1% relative humidity (RH) and mostly gaseous methanol at 50% RH. Photocatalytic oxidation generated CO(2) as the only carbonaceous gaseous product and bidentate formates as the intermediate surface product. At high DMMP coverage quantity, it was captured incompletely and hydrolyzed partially with CH(3)OH in the gas phase only, 50% RH enhancing both processes. Photocatalytic oxidation generated gaseous HCOOH, CO, and CO(2) and was incomplete due to catalyst deactivation by nonvolatile products. In the second scenario of air purification, DMMP underwent adsorption, hydrolysis, and photooxidation at the same time. It resulted in the quickest removal of DMMP from the gas phase and completion of oxidation in 30 min, suggesting this process for practical air decontamination. At least 0.8 nm(2) of TiO(2) surface per each DMMP molecule should be available for complete purification of air. 相似文献
112.
The temperature dependence of the rate of electron transfer is analyzed in the framework of a molecular theory presented recently, characterized by decoupling the total solvent reorganization energy into two contributions featuring reorganizations of permanent dipoles as well as solvent density. The inclusion of the temperature dependence of liquid density reorganization can give rise to a maximum in the Arrhenius coordinates for electron transfer in the inverted region and for exothermic reactions with small activation barriers as well. 相似文献
113.
Mit"kina T. V. Gerasko O. A. Sokolov M. N. Naumov D. Yu. Fedin V. P. 《Russian Chemical Bulletin》2004,53(1):80-85
Slow evaporation of hydrochloric acid solutions of zirconium(iv) or hafnium(iv) oxochlorides and cucurbituril in air afforded compounds with composition [M4(OH)8(H2O)16]Cl8·(C36H36N24O12)·16H2O, where M = Zr (1) or Hf (2). According to the X-ray diffraction data, complexes 1 and 2 are isostructural. Their crystal structures can be described as packings of polymer chains consisting of alternating cucurbituril molecules and tetranuclear cations [M4(OH)8(H2O)16]8+ linked to each other via an extensive network of hydrogen bonds. Compound 2 is the first structurally characterized tetranuclear hafnium aqua complex. 相似文献
114.
Dmitry S. Perekalin Pavel V. Petrovskii Bohumil Štíbr Alexander R. Kudinov 《Journal of organometallic chemistry》2005,690(11):2775-2779
The reaction of the tricarbollide salt Tl[7-tBuNH-7,8,9-C3B8H10] (Tl1) with [(cod)Rh(THF)x]+ gives the rhodium complex [1-(cod)-12-tBuNH-1,2,4,12-RhC3B8H10] in almost quantitative yield. Analogous reactions of Tl1 with [(ring)M(THF)x]2+ ((ring)M = Cp*Rh and (1,3,5-C6H3Me3)Ru) afford the corresponding metallatricarbollides [1-(ring)-12-tBuNH-1,2,4,12-MC3B8H10] in ca. 50% yield. Refluxing Tl1 with [Mn(CO)3(MeCN)3]+ in THF give the tricarbollide analogue of cymantrene, [1,1,1-(CO)3-12-tBuNH-1,2,4,12-MnC3B8H10], the structure of which was determined by single-crystal X-ray diffraction analysis. In all cases, the formation of the metallatricarbollide complexes is accompanied by polyhedral rearrangement leading to the maximum separation of the cage carbon atoms. 相似文献
115.
Sokolov MN Gushchin AL Virovets AV Peresypkina EV Kozlova SG Fedin VP 《Inorganic chemistry》2004,43(25):7966-7968
Black single crystals of Ta(4)Se(9)I(8) are obtained in a high yield by heating Ta, Se, and I(2) at 300 degrees C in 1:2.2:1.0 molar ratio. In the structure, the tantalum atoms form a square, with four Se(2) ligands bridging the Ta-Ta edges and one capping the square. Each Ta atom has two terminal iodine atoms. The compound is diamagnetic and has only two electrons for metal-metal bonding. 相似文献
116.
Inclusion complexes of poly(ethylene oxide) with α-cyclodextrin are the key compounds in the synthesis of polyrotaxanes. These
complexes prepared in aqueous solutions contain free cyclodextrin, which cocrystallizes with the major reaction product. These
complexes dissociate upon dissolution in DMF and DMSO to form cyclodextrin and pseudopolyrotaxanes with a low cyclodextrin
content. Polyrotaxane was synthesized with the use of poly(ethylene oxide)-α,ω-bis-amine as a linear component. The end-groups
of the polymer in the inclusion complex were modified by the reaction with 2,4-dinitrofluorobenzene. A procedure was developed
for purification of a polyrotaxane with high cyclodextrin content.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1914–1918, August, 2005. 相似文献
117.
S. V. Trepalin A. V. Yarkov V. B. Sokolov A. N. Ivanov 《Russian Chemical Bulletin》1990,39(3):476-480
The potential function has been constructed for internal rotation of the NO-group in (CH3)2CClNO, CH3CCl2NO, and their deuterium analogs. It has been established that the N=O bond in the cisCl conformer of CH3CCl2NO does not eclipse the C-Cl bond, rather forming an angle of approximately 30. It has been shown that a change in substitutent on the -carbon atom may produce a substantial change in the form of the potential function of internal rotation (PFIR) of the NO group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 550–555, March, 1990. 相似文献
118.
A very large diversity space of synthetically accessible compounds for use with drug design programs
Nikitin S Zaitseva N Demina O Solovieva V Mazin E Mikhalev S Smolov M Rubinov A Vlasov P Lepikhin D Khachko D Fokin V Queen C Zosimov V 《Journal of computer-aided molecular design》2005,19(1):47-63
We have constructed a very large virtual diversity space containing more than 1013 chemical compounds. The diversity space is built from about 400 combinatorial libraries, which have been expanded by choosing sizeable collections of suitable R-groups that can be attached to each link point of their scaffolds. These R-group collections have been created by selecting reagents that have drug-like properties from catalogs of available chemicals. As members of known combinatorial libraries, the compounds in the diversity space are in general synthetically accessible and useful as potential drug leads. Hence, the diversity space can be used as a vast source of compounds by a de novo drug design program. For example, we have used such a program to generate inhibitors of HIV integrase enzyme that exhibited activity in the micromolar range. 相似文献
119.
120.
Chelsea N. Widener Alexandria N. Bone Mykhaylo Ozerov Rachael Richardson 路正光 Komalavalli Thirunavukkuarasu Dmitry Smirnov 陈学太 薛子陵 《无机化学学报》2020,36(6):1149-1156
最近Ruamps和同事发现三角双锥构型的Ni(Ⅱ)配合物[Ni(Me6tren)Cl]ClO4(1,Me6tren=tris(2-(dimethylamino)ethyl)amine)具有大的单轴磁各向异性(J.Am.Chem.Soc.,2013,135:3017-3026)。他们利用HF-EPR研究获得横向零场分裂(ZFS)参数E=1.56(5)cm-1但未能确定轴向零场分裂参数D。在本工作中,我们利用0~17.5 T和5 K的变磁场远红外光谱(FIRMS)来检测自旋基态S=1中的MS=±1和MS=0态之间的磁跃迁。在FIRMS中直接观察到Zeeman分裂态之间的跃迁,得出轴向ZFS参数D=-110.7(3)cm-1。我们对1的晶体结构进行了Hirshfeld表面分析,揭示了1分子中的阳离子与阴离子之间以及分子之间的相互作用。 相似文献