全文获取类型
收费全文 | 30111篇 |
免费 | 788篇 |
国内免费 | 179篇 |
专业分类
化学 | 18753篇 |
晶体学 | 229篇 |
力学 | 683篇 |
综合类 | 1篇 |
数学 | 4717篇 |
物理学 | 4344篇 |
无线电 | 2351篇 |
出版年
2022年 | 174篇 |
2021年 | 248篇 |
2020年 | 282篇 |
2019年 | 363篇 |
2018年 | 304篇 |
2017年 | 303篇 |
2016年 | 529篇 |
2015年 | 427篇 |
2014年 | 565篇 |
2013年 | 1512篇 |
2012年 | 1387篇 |
2011年 | 1678篇 |
2010年 | 907篇 |
2009年 | 778篇 |
2008年 | 1590篇 |
2007年 | 1635篇 |
2006年 | 1597篇 |
2005年 | 1578篇 |
2004年 | 1385篇 |
2003年 | 1154篇 |
2002年 | 1142篇 |
2001年 | 429篇 |
2000年 | 352篇 |
1999年 | 271篇 |
1998年 | 315篇 |
1997年 | 350篇 |
1996年 | 454篇 |
1995年 | 341篇 |
1994年 | 325篇 |
1993年 | 320篇 |
1992年 | 319篇 |
1991年 | 261篇 |
1990年 | 261篇 |
1989年 | 272篇 |
1988年 | 308篇 |
1987年 | 303篇 |
1986年 | 293篇 |
1985年 | 450篇 |
1984年 | 500篇 |
1983年 | 375篇 |
1982年 | 507篇 |
1981年 | 462篇 |
1980年 | 397篇 |
1979年 | 380篇 |
1978年 | 389篇 |
1977年 | 373篇 |
1976年 | 319篇 |
1975年 | 296篇 |
1974年 | 284篇 |
1973年 | 288篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
951.
John C. Schug 《Theoretical chemistry accounts》1979,53(2):197-201
Ab initio projected-unrestricted Hartree-Fock calculations have been carried out on a number of excited and ionic states of the water molecule. Results have been compared with large-scale CI calculations, with IVO calculations, and with those of Mrozek and Golebiewski obtained by the 2 × 2 rotation method applied to orbitals. It is concluded that the PUHF method may provide the most useful alternative to large-scale CI for calculating properties of open-shell systems. But it will not be generally useful for calculating spectral transition energies. 相似文献
952.
Metastable ion peak shapes, dimensions and relative abundances have been measured for the three fragmentations [C3H6]+· → [C3H4]+· + H2, [C3H6]+· → [C3H5]+ + H· and [C3H6]+· → [C3H3]+ + H2 + H·. [C3H6]+· ions were derived from propene, cyclopropane, tetrahydrofuran, cyclohexanone, 2-methyl but-1-ene and cis-pent-2-ene. Activation energies for these fragmentations have been evaluated. Three daughter ion dissociations ([C3H5]+ → [C3H3]+ + H2, [C3H5]+ → [C3H4]+· + H· and [C3H4]+· → [C3H3]+ + H·) have been similarly examined. Ion structures have been determined and the metastable energy releases have been correlated with the thermochemical data. It is concluded that the molecular ions of propene and cyclopropane become structurally indistinguishable prior to fragmentation and that differences in their metastable ion characteristics can be ascribed wholly to internal energy differences; the latter can be correlated with the photoelectron spectra of the isomers. The pathway for the consecutive fragmentation which generates the metastable ion peak (m/e 42 → m/e.39) has been shown to be It is likewise concluded that fragmentating [C3H6]+· ions generated from the various precursor molecules are also structurally indistinguishable and cannot be classified with either molecular ion of the isomeric C3H6 hydrocarbons. 相似文献
953.
Kadish KM Phan TD Giribabu L Shao J Wang LL Thuriere A Van Caemelbecke E Bear JL 《Inorganic chemistry》2004,43(3):1012-1020
Eleven different Ru(2)(4+) and Ru(2)(3+) derivatives are characterized by thin-layer FTIR and UV-visible spectroelectrochemistry under a CO atmosphere. These compounds, which were in-situ electrogenerated from substituted anilinopyridine complexes with a Ru(2)(5+) core, are represented as Ru(2)(L)(4)Cl where L = 2-CH(3)ap, ap, 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, 3,5-F(2)ap, 2,4,6-F(3)ap, or F(5)ap. The Ru(2)(5+) complexes do not axially bind CO while mono- and bis-CO axial adducts are formed for the Ru(2)(4+) and Ru(2)(3+) derivatives, respectively. Six of the eleven investigated compounds exist in a (4,0) isomeric form while five adopt a (3,1) geometric conformation. These two series of compounds thus provide a large enough number of derivatives to examine trends and differences in the spectroscopic data of the two types of isomers in their lower Ru(2)(4+) and Ru(2)(3+) oxidation states. UV-visible spectra of the Ru(2)(4+) derivatives and IR spectra of the Ru(2)(3+) complexes under CO are both isomer dependent, thus suggesting that these data can be used to reliably predict the isomeric form, i.e., (3,1) or (4,0), of diruthenium complexes containing four unsymmetrical substituted anilinopyridinate bridging ligands; this was confirmed by X-ray crystallographic data for seven compounds whose structures were available. 相似文献
954.
1-Ethyl-6-fluoro-1,4-dihydro-7-methyl-4-oxo-1,8-naphthyridine-3-carboxylic acid ( 8 ) has been prepared in large quantities by a highly efficient process. It has in turn been degraded to give 7-chloro-1-ethyl-6-fluoro-1,4-dihydro-4-oxo-1,8-naphthyridine-3-carboxylic acid ( 11 ). This intermediate has been reacted with piperazine to give the known antibacterial agent, enoxacin ( 12 ). 相似文献
955.
West Douglas X. Scovill John P. Silverton J. V. Bavoso Alfonso 《Transition Metal Chemistry》1986,11(4):123-131
Summary The ligand 3-azabicyclo[3.2.2]nonane-3-thiocarboxylic acid 2-[1-(2-pyridinyl)ethylidene]hydrazide (HL), which is observed in an unusual tautomeric form in the solid state, and its selenium analogue (HLSe) have been used to prepare a series of nickel(II) complexes. Compounds of the general formula [NiLX] (X=Cl, Br, NCS, N3, NO2 or NCSe) as well as [Ni(LSe)Cl] have been found to be diamagnetic, planar complexes. A single crystal study of [NiL(NCS)] shows the deprotonated ligand bound in a tridentate mannervia its pyridyl nitrogen, imine nitrogen and the thione sulphur atom with the nitrogen atom of the thiocyanato-ligand occupying the fourth coordination position. The solids prepared from the nickel(II) salts having tetrafluoroborate, nitrate and iodide ions approximate to octahedral symmetry and have neutral HL ligands coordinated in a bidentate fashionvia the pyridine and imine nitrogens with the remaining coordination sites being occupied by the anions or water molecules. The [NiL2] solid is also octahedral with the two deprotonated ligands bonding as tridentate groupsvia the same atoms as in the [NiLX] complexes. 相似文献
956.
Induction of Chromosome Aberrations and Delayed Genomic Instability by Photochemical Processes 总被引:1,自引:0,他引:1
Charles L. Limoli Joseph P. Day John F. Ward William F. Morgan 《Photochemistry and photobiology》1998,67(2):233-238
Exponentially growing cells cultured in medium containing bromodeoxyuridine, then exposed to UVA light in the presence of the dye Hoechst 33258, show significant levels of DNA strand breaks and base damage. This dye–bromodeoxyuridine–UVA photolysis treatment is markedly cytotoxic. We now demonstrate that exposure of cells to the agents used in photolysis leads directly to the formation of chromosome aberrations. Furthermore, we demonstrate that this photochemical treatment induces delayed chromosomal instability in clonal populations derived from single progenitor cells surviving photolysis. These results suggest that photolysis-induced DNA damage leads to chromosome rearrangements that could account for the observed cytotoxicity. Furthermore, in those cells surviving photolysis, the delayed effects of this treatment can be observed several generations after exposure and are manifested as compromised genomic integrity. 相似文献
957.
N.M.R. Spectroscopic Studies of 15N Labelled N-Phosphorylphosphazenes and Imidodiphosphoric Acid Derivatives 15N labelled compounds were prepared and investigated by means of 31P- and 15N-NMR spectroscopy. The chemical shift values δP and δN, and the coupling constants 1JPN and 2JPP are discussed and interpreted qualitatively by semiempirical quantumchemical calculations (CNDO/2) using POPLE 'S ΔE-model. 相似文献
958.
John Phillips 《Journal of Functional Analysis》1983,51(3):259-267
Let B be a unital C1-algebra and A = Γ(E) be the C1-algebra of sections of a bundle over the separable compact space X with fibre B and structure group Inn B. If B is the quotient of an AW1-algebra, then an exact sequence: 0 → Inn A → PInn A →ηH2(X, G), where PInn A is the group of pointwise inner automorphisms of A and G=H°(Z(B)^, ) is obtained. The map η is onto whenever A = C(X, B) and B is the quotient of a purely infinite AW1-algebra. An essential part of the analysis is the result that Ad: U(B) → Inn B is a fibre bundle if and only if the space of inner derivations of B is norm closed. These results extend and clarify previous joint work with I. Raeburn (Indiana Univ. Math. J.29 (1980), 799). 相似文献
959.
The reactions of [Co(η-C5H5)(L)I2] with Na[S2CNR2] (R = alkyl or phenyl) give [Co(η-C5H5)(I)(S2CNR2)] (I) when L = CO and [Co(η-C5H5)(L)(S2CNR2)]I (II) when L is a tertiary phosphine, phosphite or stibine, or organo-isocyanide ligand. In similar reactions [Co(η-C5H5)(CO)(C3F7)I] gives [Co(η-C5H5)(C3F7)(S2CNMe2)] and [Mn(η-MeC5H4)(CO)2(NO)]PF6 forms [Mn(η-MeC5H4)(NO)(S2CNR2)]. The iodide ligands in I may be displaced by L, to give II, or by other ligands such as [CN]?, [NCS]?, H2O or pyridine whilst SnCl2 converts it to SnCl2I. The iodide counter-anion in II may be replaced by others to give [BPh4]?, [Co(CO)4]? or [NO3]? salts. However [CN]? acts differently and displaces (PhO)3P from [Co(η-C5H5){P(OPh)3}(S2CNMe)]I to give [Co(η-C5H5)(CN)(S2CNMe2)] which may be alkylated reversibly by MeI and irreversibly by MeSO3F to [Co(η-C5H5)(CNMe)(S2CNMe2)]+ salts. Conductivity measurements suggest that solutions of I in donor solvents are partially ionized with the formation of [Co(η-C5H5)(solvent)(S2CNR2)]+ I? species. The IR and 1H NMR spectra of the various complexes are reported. They are consistent with pseudo-octahedral “pianostool” molecular structures in which the bidentate dithiocarbamate ligands are coordinated to the metal atoms through both sulphur atoms. 相似文献
960.
John Raymond O'Lear Larry Gene Wright John Nathan Louris R. Graham Cooks 《Journal of mass spectrometry : JMS》1987,22(6):348-358
A new scan is described which responds to ions that are intermediates in the dissociation of a mass-selected parent ion (mp) to give a mass-selected daughter ion (md). The scan gives a simple mass v. abundance output for ions which satisfy this condition. It is implemented here on a BEQQ hybrid mass spectrometer using, in sequence, collision-induced dissociation occurring at high energy in the first reaction region, and low-energy collisional activation in the collision quadrupole. The experiment provides information on reaction sequences not available from single scans of other types. In the several cases examined, it is demonstrated that, among many conceivable fragmentation routes connecting a parent ion with a particular fragment ion, only a few are significant. Examination of reaction intermediate spectra also appears to be a fruitful new approach to mechanistic questions, as illustrated by consideration of the behavior of several isomeric octanones. These new spectra also have analytical value: they show good signal-to-noise ratios and allow ready distinction between isobaric and isomeric ions. A comparison of the reaction intermediate spectrum with a daughter spectrum obtained by the B/E linked-scanning technique reveals the contributions of artifact peaks which result from poor parent ion mass resolution in the latter. Reaction intermediate spectra combine information from the daughter spectra of mp and the parent spectra of md and, as a specified portion of this data domain, have unique characteristics. 相似文献