全文获取类型
收费全文 | 53255篇 |
免费 | 4485篇 |
国内免费 | 3693篇 |
专业分类
化学 | 28365篇 |
晶体学 | 532篇 |
力学 | 2679篇 |
综合类 | 350篇 |
数学 | 11636篇 |
物理学 | 17871篇 |
出版年
2024年 | 86篇 |
2023年 | 507篇 |
2022年 | 867篇 |
2021年 | 901篇 |
2020年 | 1003篇 |
2019年 | 1032篇 |
2018年 | 2037篇 |
2017年 | 2253篇 |
2016年 | 1970篇 |
2015年 | 1842篇 |
2014年 | 1877篇 |
2013年 | 2536篇 |
2012年 | 5260篇 |
2011年 | 4611篇 |
2010年 | 3370篇 |
2009年 | 3155篇 |
2008年 | 2218篇 |
2007年 | 2044篇 |
2006年 | 1989篇 |
2005年 | 5622篇 |
2004年 | 4861篇 |
2003年 | 3099篇 |
2002年 | 1326篇 |
2001年 | 937篇 |
2000年 | 707篇 |
1999年 | 684篇 |
1998年 | 512篇 |
1997年 | 431篇 |
1996年 | 349篇 |
1995年 | 362篇 |
1994年 | 313篇 |
1993年 | 234篇 |
1992年 | 338篇 |
1991年 | 287篇 |
1990年 | 265篇 |
1989年 | 206篇 |
1988年 | 163篇 |
1987年 | 115篇 |
1986年 | 98篇 |
1985年 | 76篇 |
1984年 | 54篇 |
1983年 | 56篇 |
1976年 | 80篇 |
1975年 | 43篇 |
1974年 | 44篇 |
1973年 | 53篇 |
1972年 | 40篇 |
1970年 | 36篇 |
1969年 | 38篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
61.
The reaction of a new fluorinated unsymmetrical allenylazine with dimethyl acetylenedicarboxylate and phenylacetylene affords the combined intra-intermolecular criss-cross cycloaddition products, 2,3-disubstituted-1,10-diazatricyclo[5.2.1.04,10]deca-2,6-diene derivatives. The products contain three fused five-membered rings with two nitrogen atoms within an unsaturated heterocyclic system. The structures were assigned using 2D NMR correlations and in the case of the phenylacetylene adduct by X-ray structure analysis. 相似文献
62.
Parameters of Gaussian multivariate models are often estimated using the maximum likelihood approach. In spite of its merits, this methodology is not practical when the sample size is very large, as, for example, in the case of massive georeferenced data sets. In this paper, we study the asymptotic properties of the estimators that minimize three alternatives to the likelihood function, designed to increase the computational efficiency. This is achieved by applying the information sandwich technique to expansions of the pseudo-likelihood functions as quadratic forms of independent normal random variables. Theoretical calculations are given for a first-order autoregressive time series and then extended to a two-dimensional autoregressive process on a lattice. We compare the efficiency of the three estimators to that of the maximum likelihood estimator as well as among themselves, using numerical calculations of the theoretical results and simulations. 相似文献
63.
In this paper, by using elementary analysis, we establish some new Lyapunov-type inequalities for nonlinear systems of differential equations, special cases of which contain the well-known equations such as Emden-Fowler-type and half-linear equations. The inequalities obtained here can be used as handy tools in the study of qualitative behaviour of solutions of the associated equations. 相似文献
64.
E. Beinrohr M. Németh P. Tsch?pel G. T?lg 《Fresenius' Journal of Analytical Chemistry》1992,344(3):93-99
Summary Flow-through electrochemical cells with porous working electrodes made of crushed reticulated vitreous carbon and plated with mercury were used for absolute analysis of trace amounts of lead by anodic stripping coulometry with collection (ASCWC) in a flow system. The role of mercury coating, flow rate and pH were investigated. The coulombic content of the collection peak corresponded to the theoretical values calculated by Faraday's law in a concentration range from about 10–9 to 10–6 mol/l. The relative error and the relative standard deviation was +0.15% and 0.8%, respectively for 2×10–6 mol/l analyte concentration. The absolute detection limit (3 s) was 0.1 ng of Pb, the linear response range 7×104.
One leave from: Department of Analytical Chemistry, Slovak Technical University, CS-812 37 Bratislava, Czechoslovakia 相似文献
65.
Celik Tarimci Anda? Karamustafa Kutalmi? Güven Mehmet Kabak Akgül Ye?ilada 《Analytical sciences》2003,19(9):1347-1348
The crystal structure of 1-[3-(3,4-dimethoxyphenyl)-2-propenoyl]pyrrolidine (C15H19NO3) (I) has been determined by X-ray analysis. It crystallizes orthorhombic space group Pbca with a = 24.295(3), b = 15.086(3), c = 7.552(3)A, V = 2768(1)A3, Z = 8, Dcalc = 1.254 g/cm3, mu = (Mo K(alpha)) = 0.87 cm(-1). The title compound has analgesic activity of cycloaliphatic amine part. The molecule is deviated from planar configuration. 相似文献
66.
The kinetics of the hydrolysis of p-nitrophenyl esters of three types of single-chain carboxylic acids, namely, saturated, olefinic and acetylenic, was investigated in two aquiorgano binary solvent systems, DMSO-H2O and dioxane (DX)-H2O. The ester probes used are: octanoic (C8), dodecanoic (C12) , stearic (C18) , oleic (C18-ol) , elaidic (C18-el ) and stearolic (C18-st). The order of measured CAgC values is: C18-ol>C18-el>C18>C18-st, whereas the order of decreasing magnitude of the observed hydrolytic rate constants of the monomeric species (km) is: C18>C18-el>C18-ol> C18-st. These rather unanticipated results are discussed. 相似文献
67.
68.
超软X射线流气式正比计数管 总被引:2,自引:0,他引:2
介绍了一种用于测量183~933eV超软X射线的圆柱形、侧窗式、流气式正比计数管,工作气体是0.11MPa的P-10气体或氦气-丙烷混合气体。计数管内径为φ25mm,直径为φ0.3mm的入射窗是由厚度80~90μgcm~2聚乙烯甲醛制成的。该计数管的特点:(1)薄窗,对软X射线透过率高。(2)流气式,工作寿命长。(3)能量分辨率好。(4)计数率高(1×10~(14)个/s)。(5)可测能区宽(0.183~10keV)。(6)可以方便更换窗膜材料、厚度及窗口直径。近几年来该计数管已经为高强度低能X光源提供较好监测。 相似文献
69.
70.
P E S?rensen R A McClelland R D Gandour 《Acta chemica Scandinavica (Copenhagen, Denmark : 1989)》1991,45(6):558-566
The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate. 相似文献