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141.
Horvath JD Koritnik A Kamakoti P Sholl DS Gellman AJ 《Journal of the American Chemical Society》2004,126(45):14988-14994
Kinked-stepped, high Miller index surfaces of metal crystals are chiral and, therefore, exhibit enantiospecific properties. Previous temperature-programmed desorption (TPD) spectra have shown that the desorption energies of R-3-methylcyclohexanone (R-3-MCHO) on the chiral Cu(643)(R) and Cu(643)(S) surfaces are enantiospecific (J. Am. Chem. Soc. 2002, 124, 2384). Here, a comparison of the TPD spectra from Cu(111), Cu(221), Cu(533), Cu(653)(R&S), and Cu(643)(R&S) surfaces reveals that the enantiospecific desorption occurs from the chiral kink sites on the Cu(643) surfaces. Titration of the chiral kink sites with I atoms confirms this assignment of desorption features in the TPD spectra. Finally, the enantiospecific difference in the desorption energies of R- and S-3-MCHO has been used as the basis for demonstration of an enantioselective, kinetic separation of racemic 3-MCHO into its purified components during adsorption and desorption on the Cu(643)(R&S) surfaces. 相似文献
142.
Journal of Theoretical Probability - Let $$ \{X, X_{n};~n \ge 1 \}$$ be a sequence of independent and identically distributed Banach space valued random variables. This paper is devoted to... 相似文献
143.
Ying-Sing Fung Andrew Shin-Kwan Tang 《Fresenius' Journal of Analytical Chemistry》1994,350(12):721-723
A fast, simple and reliable method for the analysis of DEHP in PVC products was developed using a one-step Soxhlet extraction prior to HPLC determination. The linear range from 1.25 /g to 250 mg/g of DEHP in PVC was found sufficient to cover the normal concentrations encountered. The reliability of the method was established by comparison with the ASTM method and no potential interferent was identified except a large concentration of DIMP. 相似文献
144.
Elliptic genera of level N have been defined by F. Hirzebruch,generalising the earlier notion of elliptic genus due to S.Ochanine. We show that there are corresponding elliptic cohomologytheories which are naturally associated to such genera and thatthese are obtained from the level 1 case by algebraic extensionof the coefficient rings from level 1 to level N modular forms. 相似文献
145.
146.
The pentacyclic marine alkaloids (-)-papuamine (1) and (-)-haliclonadiamine (2) have been prepared by total synthesis. The synthesis began with (-)-8, which was converted into diester 20 by way of bis-mesylate 17, dinitrile 18, and diacid 19. Dieckmann cyclization of 20 provided keto ester 21, which was transformed into acetal 22. After hydrolysis of the acetal, ketone 25 was subjected to reductive amination with 1,3-propanediamine and sodium triacetoxyborohydride to obtain diamines 26 and 27 as a 71:29 mixture of diastereomers, favoring the symmetrical isomer having the papuamine relative configuration. After transformation of the diamines to their t-Boc derivatives, the benzyl ethers were cleaved and the resulting diol was oxidized to dialdehyde 30. Application of the Seyferth procedure for conversion of aldehydes to alkynes gave a mixture of diynes 31 and 32. After removal of the t-Boc protecting groups from 31, diamino diyne 15 was treated with tributylstannane and azoisobutyronitrile to obtain the bis-vinylstannane 34. Treatment of this compound with Pd(II) and Cu(I) in the presence of air produced (-)-papuamine (1). (-)-Haliclonadiamine (2) was obtained from the unsymmetrical isomer, 32. The NMR spectra of the synthetic alkaloids were identical to those of authentic samples of the natural alkaloids. 相似文献
147.
In this paper we investigate the left cell representations ofthe Iwahori-Hecke algebras associated to a finite Coxeter groupW. Our main result shows that , where w0 is the element of longest length in W, acts essentiallyas an involution upon the canonical bases of a cell representation.We describe some properties of this involution, use it to furtherdescribe the left cells, and finally show how to realize eachcell representation as a submodule of . Our results rely uponcertain positivity properties of the structure constants ofthe Kazhdan-Lusztig bases of the Hecke algebra and so have notyet been shown to apply to all finite Coxeter groups. 相似文献
148.
Cheeseman M Feuillet FJ Johnson AL Bull SD 《Chemical communications (Cambridge, England)》2005,(18):2372-2374
A new way of combining chiral auxiliaries and substrate-directable reactions for asymmetric synthesis is described that employs a three-step sequence of aldol-cyclopropanation-retro-aldol reactions for the stereoselective synthesis of enantiopure cyclopropane carboxaldehydes. 相似文献
149.
Perry JM Moad AJ Begue NJ Wampler RD Simpson GJ 《The journal of physical chemistry. B》2005,109(42):20009-20026
A perturbation theory approach was developed for predicting the vibrational and electronic second-order nonlinear optical (NLO) polarizabilities of materials and macromolecules comprised of many coupled chromophores, with an emphasis on common protein secondary structural motifs. The polarization-dependent NLO properties of electronic and vibrational transitions in assemblies of amide chromophores comprising the polypeptide backbones of proteins were found to be accurately recovered in quantum chemical calculations by treating the coupling between adjacent oscillators perturbatively. A novel diagrammatic approach was developed to provide an intuitive visual means of interpreting the results of the perturbation theory calculations. Using this approach, the chiral and achiral polarization-dependent electronic SHG, isotropic SFG, and vibrational SFG nonlinear optical activities of protein structures were predicted and interpreted within the context of simple orientational models. 相似文献
150.
2-Bromopyridine derivatives 2a-2c were prepared. Compounds 2b and 2c and ammonia yielded aminopyridines 3b and 3c which were converted to imidazo[1,2-a]pyridine derivatives 4b and 4c . Compound 4b was nitrated giving the analogue 5b of metronidazole 1 . 相似文献