全文获取类型
收费全文 | 30311篇 |
免费 | 1169篇 |
国内免费 | 1438篇 |
专业分类
化学 | 19822篇 |
晶体学 | 237篇 |
力学 | 598篇 |
综合类 | 10篇 |
数学 | 5341篇 |
物理学 | 6910篇 |
出版年
2023年 | 209篇 |
2022年 | 439篇 |
2021年 | 553篇 |
2020年 | 452篇 |
2019年 | 474篇 |
2018年 | 524篇 |
2017年 | 527篇 |
2016年 | 1143篇 |
2015年 | 936篇 |
2014年 | 1038篇 |
2013年 | 2257篇 |
2012年 | 1960篇 |
2011年 | 2211篇 |
2010年 | 1302篇 |
2009年 | 1467篇 |
2008年 | 1451篇 |
2007年 | 1362篇 |
2006年 | 1108篇 |
2005年 | 1032篇 |
2004年 | 1359篇 |
2003年 | 1021篇 |
2002年 | 962篇 |
2001年 | 561篇 |
2000年 | 492篇 |
1999年 | 415篇 |
1998年 | 384篇 |
1997年 | 360篇 |
1996年 | 344篇 |
1995年 | 309篇 |
1994年 | 253篇 |
1993年 | 274篇 |
1992年 | 254篇 |
1991年 | 201篇 |
1990年 | 208篇 |
1989年 | 186篇 |
1988年 | 190篇 |
1987年 | 176篇 |
1986年 | 185篇 |
1985年 | 251篇 |
1984年 | 259篇 |
1983年 | 194篇 |
1982年 | 205篇 |
1981年 | 204篇 |
1980年 | 198篇 |
1979年 | 182篇 |
1978年 | 176篇 |
1977年 | 177篇 |
1976年 | 173篇 |
1975年 | 158篇 |
1974年 | 171篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Monika Goikoetxea María J. Barandiaran José M. Asua 《Journal of polymer science. Part A, Polymer chemistry》2007,45(24):5838-5846
The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007 相似文献
2.
F. Rubio F. García H. D. Burrows A. A. C. C. Pais A. J. M. Valente M. J. Tapia J. M. García 《Journal of polymer science. Part A, Polymer chemistry》2007,45(9):1788-1799
The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H2O and D2O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H2O and D2O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007 相似文献
3.
On‐line coupling of LC and ICP‐MS has been used for fractionation and detection of species of Cu, Fe, I, Se and Zn in human serum. It has been shown that anion exchange chromatography provided better separation capability (both intra‐ and inter‐element) than size‐exclusion chromatography. The mobile phases for ion exchange chromatography consisted of Tris–HNO3 buffer and ammonium salt (nitrate, acetate or formate). Formate was found to be the best mobile phase counter ion, enabling good chromatographic separation, and is acceptable for mass spectrometry too. The quantitative evaluation of element concentrations adhering to individual fractions was performed by the peak area normalization method. The repeatability of results ranged from 3 to 15% (depending on the element concentration level) and represented the main part of the result uncertainty. The accuracy of Cu and Zn fraction determinations was confirmed by comparison with the isotope dilution technique. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
4.
The complete set of self-consistent parameters of nominally undoped LiNbO3 crystals of congruent composition that describe the electro-optic, piezoelectric, elasto-optic, elastic, and dielectric response
has been determined by numerically evaluating available measurements. The parameters were determined at room temperature and
consist of the low-frequency clamped dielectric constants εS
ij, elastic stiffness constants at constant electric field CE
ijkl, piezoelectric stress coefficients eijk, elasto-optic constants at constant electric field pE
ijkl, and clamped electro-optic coefficients rS
ijk. It is shown that the complete set is required for calculating the effective electro-optic coefficients and dielectric constants
in photorefractive applications of LiNbO3.
Received: 4 January 2002 / Revised version: 1 February 2002 / Published online: 14 March 2002 相似文献
5.
María G. Armentano Ricardo G. Durn 《Numerical Methods for Partial Differential Equations》2003,19(5):653-664
In this article we analyze the effect of mass‐lumping in the linear triangular finite element approximation of second‐order elliptic eigenvalue problems. We prove that the eigenvalue obtained by using mass‐lumping is always below the one obtained with exact integration. For singular eigenfunctions, as those arising in non convex polygons, we prove that the eigenvalue obtained with mass‐lumping is above the exact eigenvalue when the mesh size is small enough. So, we conclude that the use of mass‐lumping is convenient in the singular case. When the eigenfunction is smooth several numerical experiments suggest that the eigenvalue computed with mass‐lumping is below the exact one if the mesh is not too coarse. © 2003 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 19: 653–664, 2003 相似文献
6.
Maximiliano A. Burgos Paci Gustavo A. Argüello Plcido García Helge Willner 《国际化学动力学杂志》2003,35(1):15-19
Thermal decomposition of bis(trifluoromethyl) peroxydicarbonate has been studied. The mechanism of decomposition is a simple bond fission, homogeneous first‐order process when the reaction is carried out in the presence of inert gases such as N2 or CO. An activation energy of 28.5 kcal mol?1 was determined for the temperature range of 50–90°C. Decomposition is accelerated by nitric oxide because of a chemical attack on the peroxide forming substances different from those formed with N2 or CO. An interpretation on the influence of the substituents in different peroxides on the O? O bond is given. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 15–19, 2003 相似文献
7.
Pedro lvarez‐Boo Jos Sergio Casas Alfonso Castieiras María Delfina Couce Eduardo Freijanes Eva Novoa Jos Sordo 《应用有机金属化学》2003,17(9):725-729
Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe2Cl2(PMP)] and [SnMe2Br2(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (1H, 13C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
8.
9.
Patricia Smichowski María Beatriz de la Calle Guntiñas Carmen Cámara 《Fresenius' Journal of Analytical Chemistry》1994,348(5-6):380-384
Summary A method is described for antimony preconcentration based on retention on a column of activated alumina. Recovery is 80% when no pH-control and 4 mol/l HCl as eluent are used. The preconcentration factor is 400. The method was applied to the determination of antimony in spiked tap and sea water. The analytical performance of the method is discussed. 相似文献
10.
Ll Abia X. L. Armesto M. Canle L. M. V. García M. Losada J. A. Santaballa 《国际化学动力学杂志》1994,26(10):1041-1053
This article analyzes the kinetics of the decomposition of N-Cl-Valine in aqueous solution, which is formed rapidly by chlorination of Valine with sodium hypochlorite. A general-base catalyzed process not yet described is reported. The experimental evidence shows two competitive decomposition paths: an unimolecular concerted fragmentation process (k = (1.8 ± 0.1) · 10?4 s?1 at 298 K) and the other one is an E2 elimination process whose importance increases with pH and depends on the nature and the concentration of the bases present in the medium. © 1994 John Wiley & Sons, Inc. 相似文献