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排序方式: 共有813条查询结果,搜索用时 15 毫秒
31.
32.
By extending the Levy wavefunction constrained search to Fock Space,one can define a wavefunction constrained search for electron densities in systems having noninteger number of electrons.For pure-state v-representable densities,the results are equivalent to what one would obtain with the zero-temperature grand canonical ensemble.In other cases,the wavefunction constrained search in Fock space presents an upper bound to the grand canonical ensemble functional.One advantage of the Fock-space wavefunction constrained search functional over the zero-temperature grand-canonical ensemble constrained search functional is that certain specific excited states(i.e.,those that are not ground-statev-representable) are the stationary points of the Fock-space functional.However,a potential disadvantage of the Fock-space constrained search functional is that it is not convex. 相似文献
33.
34.
Alexis Morales Jochem Struppe Enrique Meléndez 《Journal of inclusion phenomena and macrocyclic chemistry》2008,60(3-4):263-270
The possible inclusion complexes of Cp2NbCl2 into α-, β-, and γ-CD hosts have been investigated. The existence of a true inclusion complex in the solid state was confirmed
by a combination of thermogravimetric analysis, FTIR, PXRD, and 13C CP-MAS NMR spectroscopies. The solid-state results demonstrated that α-cyclodextrin does not form inclusion complexes with
Cp2NbCl2 whereas β- and γ-cyclodextrins do form such complexes. PXRD, NMR, and thermal analysis showed that the organometallic molecules
of Cp2NbCl2OH are included in the cavities of β- and γ-cyclodextrins, possibly adopting a symmetrical conformation in the complex, with
each glucose unit in a similar environment. In solution, 1H NMR experiments suggest that niobocene has a shallow penetration on the β-CD leading to upfield shift on H-3 signal with
a minor perturbation on the H-5 proton while for γ-CD, both H-3 and H-5 are shifted upfield substantially. This suggests that
niobocene penetrates deeper into the γ-CD cavity than in the β-CD cavity, as a result of the cavity size.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
35.
36.
Laurens van Gelderen Gadi Rothenberg V. Roberto Calderone Karen Wilson N. Raveendran Shiju 《应用有机金属化学》2013,27(1):23-27
Copper immobilized on a functionalized silica support is a good catalyst for the homocoupling of terminal alkynes. The so‐called Glaser–Hay coupling reaction can be run in air with catalytic amounts of base. The copper catalyst is active for multiple substituted alkynes, in both polar and non‐polar solvents, with good to excellent yields (75–95%). Depending on the alkyne, full conversion can be achieved within 3–24 h. The catalyst was characterized by TGA, inductively coupled plasma and X‐ray photoelectron spectroscopy. Leaching tests confirm that the catalyst is and remains heterogeneous. Importantly, the overall reaction requires only alkyne and oxygen (in this case, air) as reagents, making this a clean catalytic oxidative coupling reaction. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
37.
N. A. Mel’nikova V. N. Postnov O. V. Glumov I. V. Murin 《Russian Journal of Electrochemistry》2013,49(7):676-679
The surface of aerosilogel and macroporous and microporous glasses was modified with aromatic sulfo groups (≡Si(CH2)2-C6H4-SO3H) by the chemical assembly method. Composite solid electrolytes containing Nafion were prepared from the silica matrices with a chemically modified surface. The proton conductivity of the materials was studied by impedance spectroscopy. Composite materials based on Nafion and aerosilogel matrices and macroporous glasses with grafted ≡Si(CH2)2-C6H4-SO3H groups showed the highest proton conductivity. 相似文献
38.
The reaction of 2-amino-2-(trichloromethyl)tetrahydro-4-pyrone-5-spirocyclohexane with ethylenediamine afforded 6-amino-2,3-dihydro-4-pyrone-3-spirocyclohexane, whereas 2-amino-5,5-dimethyl-2-(trichloromethyl)tetrahydro-4-pyrone gave 2-(3-hydroxy-2,2-dimethylpropionylmethylene)imidazolidine in low yield. 相似文献
39.
Torres-Valencia JM Meléndez-Rodríguez M Alvarez-García R Cerda-García-Rojas CM Joseph-Nathan P 《Magnetic resonance in chemistry : MRC》2004,42(10):898-902
A Monte Carlo random search using molecular mechanics, followed by geometry optimization of each minimum energy structure employing density functional theory (DFT) calculations at the B3LYP/6-31G* level and a Boltzmann analysis of the total energies, generated accurate molecular models which describe the conformational behavior of the antispasmodic bicyclic sesquiterpene valeranone (1). The theoretical H-C-C-H dihedral angles gave the corresponding 1H, 1H vicinal coupling constants using a generalized Karplus-type equation. In turn, the 3J(H,H) values were used as initial input data for the spectral simulation of 1, which after iteration provided an excellent correlation with the experimental 1H NMR spectrum. The calculated 3J(H,H) values closely predicted the experimental values, excepting the coupling constant between the axial hydrogen alpha to the carbonyl group and the equatorial hydrogen beta to the carbonyl group (J(2beta, 3beta)). The difference is explained in terms of the electron density distribution found in the highest occupied molecular orbital (HOMO) of 1. The simulated spectrum, together with 2D NMR experiments, allowed the total assignment of the 1H and 13C NMR spectra of 1. 相似文献
40.
Clay A. Henry Mel Judy Barbara Dyer Martin Wagner James L. Matthews 《Photochemistry and photobiology》1995,61(4):410-413
Abstract— The phototoxicity of argon laser irradiation was studied in aqueous suspensions of Porphyromonas endodontalis (American Type Culture Collection [ATCC] 35406), Porphyromonas gingivalis (ATCC 33277), Prevotella denticola (ATCC 33184) and two strains of Prevotella intermedia (ATCC 15033 and 49046), all "black-pigmented bacteria," BPB, that accumulate cellular porphyrins. Several of these species have been implicated in the etiology of Periodontol disease. Non-black-pigmented bacteria were also studied to test the specificity of irradiation as a potential photodynamic treatment for Periodontol infections. Cell suspensions were irradiated with an argon laser at fluences of 20–200 J/cm2 . When cultured in hemin-supplemented media, ATCC 15033 was the most sensitive to irradiation. However, a second strain of the same species (ATCC 49046) was resistant. The photosensitivity of other species ranked ATCC 33277 > 35406 = 33184 = 35496. When hemin was replaced in media by hemoglobin, ATCC 33277 became resistant to irradiation. Protoporphyrin IX content in BPB cells was shown not to be a major factor determining photosensitivity. Oxygen was required during irradiation for BPB species to be affected. Non-black-pigmented bacteria were much less sensitive to irradiation than BPB. 相似文献