全文获取类型
收费全文 | 24043篇 |
免费 | 1328篇 |
国内免费 | 3452篇 |
专业分类
化学 | 19553篇 |
晶体学 | 1057篇 |
力学 | 221篇 |
综合类 | 192篇 |
数学 | 3688篇 |
物理学 | 4112篇 |
出版年
2024年 | 17篇 |
2023年 | 189篇 |
2022年 | 815篇 |
2021年 | 739篇 |
2020年 | 542篇 |
2019年 | 539篇 |
2018年 | 426篇 |
2017年 | 562篇 |
2016年 | 592篇 |
2015年 | 550篇 |
2014年 | 818篇 |
2013年 | 1781篇 |
2012年 | 1291篇 |
2011年 | 1489篇 |
2010年 | 1483篇 |
2009年 | 1678篇 |
2008年 | 1625篇 |
2007年 | 1643篇 |
2006年 | 1555篇 |
2005年 | 1342篇 |
2004年 | 1309篇 |
2003年 | 1109篇 |
2002年 | 946篇 |
2001年 | 710篇 |
2000年 | 701篇 |
1999年 | 530篇 |
1998年 | 520篇 |
1997年 | 426篇 |
1996年 | 361篇 |
1995年 | 367篇 |
1994年 | 323篇 |
1993年 | 303篇 |
1992年 | 286篇 |
1991年 | 213篇 |
1990年 | 122篇 |
1989年 | 153篇 |
1988年 | 136篇 |
1987年 | 89篇 |
1986年 | 61篇 |
1985年 | 71篇 |
1984年 | 90篇 |
1983年 | 23篇 |
1982年 | 44篇 |
1981年 | 60篇 |
1980年 | 51篇 |
1979年 | 38篇 |
1978年 | 27篇 |
1977年 | 22篇 |
1976年 | 11篇 |
1975年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
Hyun Chul Choi Min Kyu Lee Hyun Joon Shin Seung Bin Kim 《Journal of Electron Spectroscopy and Related Phenomena》2003,130(1-3):85-96
To investigate the formation of a solid electrolyte interface (SEI) on the Li1+xV3O8 electrode surface in the thermodynamic stability range of the organic electrolyte, we applied scanning photoelectron microscopy (SPEM) to a pristine electrode and to an electrode after ten cycles. The F K-edge absorption spectrum of the cycled electrode showed that LiF forms on the electrode surface during the lithium insertion–extraction process in the Li1+xV3O8/Li cell. The photoelectron spectrum for the cycled electrode showed intense spectral features corresponding to Li 1s, F 2s, F 2p, and P 2p electron signals, whereas these spectral features were of negligible intensity for the pristine electrode. The above results give strong support for the formation of an SEI that consists of LiF and compounds containing phosphorus during operation of the battery. The SPEM images also revealed that the fluorine distribution on the surface of the cycled electrode was inhomogeneous. 相似文献
42.
The structure of the title adduct comprises a phenanthroline derivative 2-phenyl-imidazo[4,5-f]1,10-phenanthroline and a methanol.The composition of the crystalline adduct was characterized as C19H12N4.CH3OH.It belongs to orthorhombic system,space group Pna21 with a=1.3693(4)nm,b=2.2988(7)nm,c=0.51338(15)nm,V=1.6160(8)nm^3.Z=4,and final R1=0.0423.wR2=0.1012 .Crystal structure shows that all the 19 carbon atoms and 4 nitrogen atoms are coplanar.The bond length data indicated that a very extensive conjugation system was formed.This conjugation makes the compound being a potentially excellent energy transformer used for luminescent materials. 相似文献
43.
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
44.
V. G. Lakhtin V. L. Ryabkov A. V. Kisin V. M. Nosova M. V. Polyakova E. A. Chernyshev 《Russian Chemical Bulletin》1995,44(11):2163-2167
Liquid-phase chlorination of a number of chloro(chlorovinyl)methylsilanes was investigated. A number of novelC-chlorosilanes were characterized by IR and1H NMR spectra. Some regularities of these reactions were determined; correlations between the structure of chloro(chlorovinyl)methylsilanes and their reactivities were identified.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2256–2260, November, 1995. 相似文献
45.
Alpeshkumar K. Malde Santosh A. Khedkar Evans C. Coutinho 《Journal of Physical Organic Chemistry》2007,20(2):151-160
Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
46.
C. Bogani M. G. Gasparo A. Papini 《Journal of Optimization Theory and Applications》2007,134(1):47-59
We propose a pattern search method to solve a classical nonsmooth optimization problem. In a deep analogy with pattern search
methods for linear constrained optimization, the set of search directions at each iteration is defined in such a way that
it conforms to the local geometry of the set of points of nondifferentiability near the current iterate. This is crucial to
ensure convergence. The approach presented here can be extended to wider classes of nonsmooth optimization problems. Numerical
experiments seem to be encouraging.
This work was supported by M.U.R.S.T., Rome, Italy. 相似文献
47.
In this article, a kind of auxiliary design BSA* for constructing BSAs is introduced and studied. Two powerful recursive constructions on BSAs from 3‐IGDDs and BSA*s are exploited. Finally, the necessary and sufficient conditions for the existence of a BSA(v, 3, λ; α) with α = 2, 3 are established. © 2006 Wiley Periodicals, Inc. J Combin Designs 15: 61–76, 2007 相似文献
48.
《Magnetic resonance in chemistry : MRC》2003,41(9):660-670
Reduced forms of iso‐α‐acids (isohumulones), used in modern beer brewing were separated and characterized by 1H and 13C NMR spectroscopy. Components from mixtures of rho‐iso‐α‐acids, tetrahydro‐iso‐α‐acids, and hexahydro‐iso‐α‐acids were isolated using high‐performance liquid chromatography (HPLC) and analyzed by use of one‐ and two‐dimensional NMR experiments. The data presented assign the identities of the main peaks in the HPLC traces for the reduced iso‐α‐acids. Previous tentative assignments regarding the cis and trans configurations and the structures of the acyl residues of the reduced iso‐α‐acids were confirmed and extensive NMR assignments were made. Furthermore, the previously unknown stereochemistry in the C‐4 side‐chain of the rho‐ and hexahydro‐iso‐α‐acids was assigned. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
49.
Florence Newberger 《Geometriae Dedicata》2003,97(1):215-249
The goal of this paper is to provide a tool, the Global Measure Formula, that will facilitate the study of the limit set of discrete geometrically finite groups of isometries of the rank one symmetric spaces. We consider the shadow of a ball from a fixed reference point onto the boundary, and prove a formula that describes the measure of the shadow in terms of the center of the shadowed ball, generalizing a result from real hyperbolic geometry. 相似文献
50.
聚醚醚酮链结构与反应的模型化合物的量子化学研究 总被引:1,自引:1,他引:0
利用AM1方法对聚醚醚酮模型化合物全优化,结果为:芳环平均相互扭转角为33.0度,桥键角117.0-118.0度,其分子结构拓扑图形表明:所有苯环(核)为平面构型,但其内角扭曲;其氢原子对苯环构型无实质性贡献,在更长链的计算中,冻结苯核与氢原子也得出满意结果,根据Mulliken键序与电荷讨论了醚交换与磺化反应。 相似文献