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排序方式: 共有197条查询结果,搜索用时 15 毫秒
191.
Polukeev AV Kuklin SA Petrovskii PV Peregudova SM Smol'yakov AF Dolgushin FM Koridze AA 《Dalton transactions (Cambridge, England : 2003)》2011,40(27):7201-7209
Palladium fluorophenyl complexes with different pincer ligands Pd(Ar)[2,6-(tBu(2)PCH(2))(2)C(6)H(3)] (13), Pd(Ar)[2,6-(tBu(2)PO)(2)C(6)H(3)] (14), Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Fe(C(5)H(5))] (15), and Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Ru(C(5)H(5))] (16) were synthesized by the reaction of LiAr (Ar = C(6)H(4)F-4) with the respective trifluoroacetate palladium pincer complexes 9-12. The molecular structures of 14 and 16 were determined by an X-ray crystallographic method. Complexes 13-16 and {Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Fe(C(5)H(5))]}PF(6) (17) were studied by multinuclear NMR spectroscopy and cyclic voltammetry. On the basis of (19)F NMR chemical shifts and (1)J((13)C-(19)F) coupling constants, as well as Pd(II)/Pd(IV) oxidation potentials, electronic characteristics of the corresponding pincer ligands were elucidated. 相似文献
192.
193.
We present a quantum-chemical analysis of the relationship between the bond length alteration (BLA) and the static first hyperpolarizability of a series of one-dimensional (1D) chromophores with donor-bridge-acceptor (D-B-A) structures. The calculated results show that the parameter BLA can be considered as an indicator to evaluate the molecular first hyper- polarizability. Along the direction of molecular ground-state dipole moments, the evolutions of BLA can be classified into three categories: the first is a non-monotonic line, which represents most chromophores; the second is monotonic increasing; and the third, contrarily, is monotonic decreasing. On the whole, the first hyperpolarizabilities of these studied chromophores are the monotonic functions of BLA along the direction of dipole moments. Therefore, the first hyperpolarizability of these 1D chromophores can be preliminarily evaluated in terms of the development of BLA without a rigorous computation. In other words, one can roughly estimate the relative magnitude of the first hyperpolarizability according to the optimized geometry. 相似文献
194.
The interaction of Cd2+ with uracil,2-thiouracil,4-thiouracil and 2,4-dithiouracil have been investigated by the density functional theory(DFT) calculations.For uracil and 2,4-dithiouracil,where the two basic sites are the same,Cd2+ attachment to the heteroatom at position 4 is preferred.However,for the systems where both types of basic centers,a carbonyl and a thiocarbonyl groups,are present,Cd2+ association with sulfur is favorable.The enhanced stability of these enolic and thiol forms comes from Cd2+ interaction with two basic sites simultaneously,which thereby triggers a significant aromatization of the ring.More significantly,the Cd2+ binding energy with uracil and its thio-derivatives is larger than the tautomerization barriers connecting the diketo-like forms with the corresponding enolic-like tautomers.Consequently,when associated with Cd2+,all tautomers are energetically accessible and should be observed in the gas phase. 相似文献
195.
Kuklin V. N. Mikhailov L. E. Mironova G. A. Ivin B. A. 《Russian Journal of General Chemistry》2009,79(10):2212-2219
Reactions of 2-aryl-4-chloro-6H-1,3-thiazin-6-ones with sodium sulfide in aqueous alcohol at 18–20°C led to the formation of a readily separable mixture
of 2-aryl-4-sulfanyl-6H-1,3-thiazin-6-one sodium salts (yield >70%) and bis(2-aryl-6-oxo-6H-1,3-thiazin-4-yl) sulfides (<10%). The latter can also be obtained in more than 50% yield by treatment of 2-aryl-4-sulfanyl-6H-1,3-thiazin-6-one sodium salts with 2-aryl-4-chloro-6H-1,3-thiazin-6-ones. Methylation of 2-aryl-4-sulfanyl-6H-1,3-thiazin-6-ones afforded the corresponding methylsulfanyl derivatives (yield >90%) regardless of the alkylating agent,
solvent, temperature, reactant concentration, and their ratio. 2-Aryl-4-sulfanyl-6H-1,3-thiazin-6-ones in the crystalline state and in solutions in polar and nonpolar protic and aprotic solvents exist preferentially
as 4-sulfanyl-6-oxo tautomers, and they undergo almost complete ionization in neutral aqueous, alcoholic, and aqueous-alcoholic
media (pK
a = 4.3). Reactions of 4-sulfanyl-2-phenyl-6H-1,3-thiazin-6-one with ammonia, amines, and difunctional N-centered nucleophiles involve cleavage of the C6-S bond in the thiazine ring and subsequent recyclization of linear intermediates to pyrimidines and diazole derivatives.
The structure of the isolated compounds was confiirmed by 1H and 13C NMR, IR, and UV spectra. 相似文献
196.
S. N. Kuklin T. M. Shneidman G. G. Adamian N. V. Antonenko 《The European Physical Journal A - Hadrons and Nuclei》2012,48(8):1-11
A model of the cluster radioactivity of even-even nuclei is presented. In this model, the zero-point vibrations in the charge-asymmetry coordinate determine the cluster formation (spectroscopic factor), while the tunneling in the coordinate of the relative separation of the centers of mass of the cluster and the daughter nucleus determines the penetrability of the barrier of the nucleus-nucleus potential. The quality of the model is demonstrated for describing cluster decay half-lives and the fine structure in alpha decays of even-even U isotopes. The model is applied to describe the alpha decays in the isotopic chains of Po, Rn, and U. The correspondence of the calculated half-lives to the Geiger-Nuttall law is discussed. 相似文献
197.
Valentin Borshchevskiy Ekaterina Moiseeva Alexander Kuklin Georg Büldt Masakatsu Hato Valentin Gordeliy 《Journal of Crystal Growth》2010,312(22):3326-3330
Here we report a successful use of a recently developed isoprenoid-chained lipid family for in meso crystallization of membrane proteins. The isoprenoid-chained lipid 1-O-(3,7,11,15-tetramethylhexadecyl)-β–d-xyloside (β-XylOC16+4) used as a host lipid for in meso crystallization provided high quality bacteriorhodopsin (bR) crystals (P63 space group) diffracting to high resolution and characterized by low twinning ratio. β-XylOC16+4 has an isoprenoid chain with methyl branches at each 4th position and a xylose group in the water-soluble part. These peculiarities make the lipid clearly distinguishable in the bR crystalline lattice and provides a unique opportunity to study the role of the host lipid in the in meso crystallization. We conclude that β-XylOC16+4 may have a general application for in meso crystallization for a wide range of membrane proteins. The cubic phase of β-XylOC16+4 is present over a wide range of temperatures and is stable at low temperature (down to about 8 °C). This opens up the possibility of using temperature as a tool for the optimization of in meso crystallization with additional advantages for the crystallization of membrane proteins at lower temperatures where the proteins of interest may be more stable. 相似文献