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901.
Pyrochlore Y2Nb2O7 is studied with density functional calculations. In the ideal pyrochlore structure, no magnetism is found, consistent with experiments, but the band structure is metallic. The phonon dispersions show unstable modes corresponding to charge instabilities. These frustrated instabilities lead to a metal-insulator transition with the formation of "charge singlets". Partial substitution of Ti for Nb results in moment formation due to the occurrence of Ti3+. 相似文献
902.
903.
Long-term exposure to arsenic in drinking water has been linked to cancer of the bladder, lungs, skin, kidney, nasal passages, liver, and prostate in humans. It is therefore important to understand the structural aspects of arsenic in water, as hydrated arsenic is most likely the initial form of the metalloid absorbed by cells. We present a detailed experimental and theoretical characterization of the coordination environment of hydrated arsenite. XANES analysis confirms As(III) is a stable redox form of the metalloid in solution. EXAFS analysis indicate, at neutral pH, arsenite has a nearest-neighbor coordination geometry of approximately 3 As-O bonds at an average bond length of 1.77 A, while at basic pH the nearest-neighbor coordination geometry shifts to a single short As-O bond at 1.69 A and two longer As-O bonds at 1.82 A. Long-range ligand scattering is present in all EXAFS samples; however, these data could not be fit with any degree of certainty. There is no XAS detectable interaction between As and antimony, suggesting they are not imported into cells as a multinuclear complex. XAS results were compared to a structural database of arsenite compounds to confirm that a 3 coordinate As-O complex for hydrated arsenite is the predominate species in solution. Finally, quantum chemical studies indicate arsenite in solution is solvated by 3 water molecules. These results indicate As(OH)3 as the most stable structure existing in solution at neutral pH; thus, ionic As transport does not appear to be involved in the cellular uptake process. 相似文献
904.
López F Delgado A Rodríguez JR Castedo L Mascareñas JL 《Journal of the American Chemical Society》2004,126(33):10262-10263
The well-known "first generation" Grubbs metathesis complex is capable of catalyzing the intramolecular [3 + 2] cycloaddition of alk-5-ynylidenecyclopropanes. It appears that the species responsible for the catalysis is a ruthenium complex generated in situ from the Grubbs carbene in the presence of the substrate. 相似文献
905.
Marilyn Daisy Milton Sarbjot Singh Sokhi Monika Maheshwari Minakshi Asnani 《Tetrahedron letters》2004,45(48):8941-8944
A novel class of multifunctional and multinucleate chalcogen (selenium and tellurium) containing derivatives (1-10) has been developed based on sequential chloride substitution of 2,4,6-trichloro-1,3,5-triazine with chalcogen-bearing amines. The structure of compound 1 has been determined in the solid state by X-ray crystallography. 相似文献
906.
Sham M.?SondhiEmail author Nirupma?Singh Shefali?Rajvanshi 《Monatshefte für Chemie / Chemical Monthly》2004,135(2):119-150
Summary. The preparation of -isothiocyanatoketones and their reactions leading to formation of pyrimidine and bicyclic, tricyclic, tetracyclic, and pentacyclic heterocyclic compounds are reviewed. A few references concerning the rearrangement of heterocyclic compounds are also included. Some of the compounds reported have shown good antiinflammatory activity. 相似文献
907.
Ramírez A Candler J Bashore CG Wirtz MC Coe JW Collum DB 《Journal of the American Chemical Society》2004,126(45):14700-14701
The key elimination step for the formation of 3-chloro- and 3-fluorobenzyne from 2-chloro-6-fluorophenyllithium displays a pronounced solvent-dependent regioselectivity. 6Li and 13C NMR spectroscopic studies on 2-chloro-6-fluorophenyllithium reveal a single monomeric aryllithium, suggested by DFT computational studies to be a trisolvate. Rate studies indicate that the elimination of LiCl and LiF proceeds via trisolvated and disolvated monomers, respectively. 相似文献
908.
Mladenova G Singh G Acton A Chen L Rinco O Johnston LJ Lee-Ruff E 《The Journal of organic chemistry》2004,69(6):2017-2023
The photochemical pinacol reaction of a series of nonsymmetrical 9-fluorenyl-substituted vic-diols was investigated and compared with their acid-catalyzed thermal reaction. Unlike the thermal reaction, the radiation-induced processes involve only fluorenyl cations, as is reflected in differences of product distribution between the two reactions. From the product studies, substituent migratory aptitudes are reversed in the photochemical process, suggesting that kinetic control takes place under neutral conditions unlike the acid-catalyzed thermal reactions. The presence of fluorenyl cation intermediates and their lifetimes were established by laser flash spectroscopy studies. 相似文献
909.
Jeffrey J DaCunha Parmjeet K Singh 《Journal of Mathematical Analysis and Applications》2004,295(2):378-391
We prove the existence of a positive solution for the three point boundary value problem on time scale given by
910.
The remote inspection for defects in large metallic elements such as pipes, tubes and plates is a field where guided waves are being applied with success. There are a number of situations where a surface coating is added for corrosion protection or insulation purposes. Since the coating materials are usually viscoelastic, the guided wave inspection range may be severely reduced unless a proper mode and an adequate frequency range is selected. Previous authors found the existence of low-attenuated modes at certain frequency ranges, which were used to detect and locate defects at reasonably large distances. This paper studies the potential of guided waves for not only locating but also sizing defects in plates with viscoelastic coatings. A hybrid finite element-boundary element method which explicitly includes the attenuating characteristics of the coating is used to determine Lamb and SH mode conversion factors at corrosion defects under the coating. Through parametric studies and analysis of the numerical results, some trends and features are highlighted that could be used for sizing purposes. 相似文献