全文获取类型
收费全文 | 2561篇 |
免费 | 67篇 |
国内免费 | 17篇 |
专业分类
化学 | 1699篇 |
晶体学 | 16篇 |
力学 | 50篇 |
数学 | 485篇 |
物理学 | 395篇 |
出版年
2022年 | 26篇 |
2021年 | 32篇 |
2020年 | 29篇 |
2019年 | 38篇 |
2018年 | 23篇 |
2017年 | 27篇 |
2016年 | 39篇 |
2015年 | 34篇 |
2014年 | 44篇 |
2013年 | 116篇 |
2012年 | 85篇 |
2011年 | 139篇 |
2010年 | 87篇 |
2009年 | 69篇 |
2008年 | 124篇 |
2007年 | 98篇 |
2006年 | 124篇 |
2005年 | 110篇 |
2004年 | 131篇 |
2003年 | 108篇 |
2002年 | 92篇 |
2001年 | 29篇 |
2000年 | 38篇 |
1999年 | 24篇 |
1997年 | 21篇 |
1996年 | 56篇 |
1995年 | 18篇 |
1994年 | 32篇 |
1993年 | 21篇 |
1992年 | 26篇 |
1991年 | 23篇 |
1990年 | 30篇 |
1989年 | 23篇 |
1988年 | 22篇 |
1986年 | 22篇 |
1985年 | 44篇 |
1984年 | 37篇 |
1983年 | 30篇 |
1982年 | 37篇 |
1981年 | 31篇 |
1980年 | 33篇 |
1979年 | 30篇 |
1978年 | 33篇 |
1977年 | 33篇 |
1976年 | 25篇 |
1975年 | 29篇 |
1974年 | 37篇 |
1973年 | 28篇 |
1970年 | 20篇 |
1968年 | 19篇 |
排序方式: 共有2645条查询结果,搜索用时 15 毫秒
41.
Louis S. Hegedus 《Angewandte Chemie (International ed. in English)》1988,27(9):1113-1126
The use of transition-metal complexes as reagents for the synthesis of complex organic compounds has been under development for at least several decades, and many extraordinary organic transformations of profound potential have been realized. However, adoption of this chemistry by the practicing synthetic organic chemist has been inordinately slow, and only now are transition-metal reagents beginning to achieve their rightful place in the arsenal of organic synthesis. Several factors contributed to the initial reluctance of synthetic organic chemists to use organometallic reagents. Lacking education and experience in the ways of elements having d electrons, synthetic chemists viewed organometallic processes as something mysterious and unpredictable, and not to be discussed in polite society. Organometallic chemists did not help matters by advertising their latest advances as useful synthetic methodology, but restricting their studies to very simple organic systems lacking any serious functionality (e.g., the “methyl, ethyl, butyl, futile” syndrome). Happily, things have changed. Organometallic chemists have turned their attention to more complex systems, and more recently trained organic chemists have benefited from exposure to the application of transition metals. This combination has set the stage for major advances in the use of transition metals in the synthesis of complex organic compounds. This review deals with one aspect of this area, the use of transition metals in the synthesis of indoles. 相似文献
42.
Ricard D L'Her M Richard P Boitrel B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(15):3291-3297
A series of iron porphyrins has been synthesized as models of cytochrome c oxidase; their activity as 4e catalysts in the reduction of dioxygen has been studied at pH 7. These compounds have been obtained by grafting very different residues onto the same iron complex, namely tripodal tetraamines, pickets, and straps, in order to change the environment of the metal center. In the case of porphyrins bearing a tripodal cap, the secondary amines have been alkylated with different substituents so as to modify the electronic environment of the distal pocket. Surprisingly, when the iron porphyrin is functionalized with four identical acrylamido pickets, the resulting complex exhibits biomimetic activity in that it catalyzes oxygen reduction with almost no production of hydrogen peroxide. The crystal structure of the redox-inactive zinc(II) analogue is reported; this shows how the metal influences the spatial arrangement of the four pickets through axial coordination and hydrogen bonding. Even a bis-strapped iron porphyrin, for which no dimerization or self-aggregation can occur at the electrode surface, acts as a 4e catalyst for O2 reduction. It is thus demonstrated that at pH close to physiological values, the iron porphyrin is an intrinsically efficient catalyst for the reduction of oxygen to water. 相似文献
43.
Woodhouse SL Ziolkowski EJ Rendina LM 《Dalton transactions (Cambridge, England : 2003)》2005,(17):2827-2829
A series of novel, dinuclear (2,2':6',2'-terpyridine)platinum(ii) complexes containing bis(thioalkyl)-dicarba-closo-dodecaborane(12)(carborane) ligands were prepared and characterised, and their preliminary anti-cancer characteristics have been determined in vitro; the complexes are the first examples of bis-intercalator complexes containing a boron-rich carborane cage. 相似文献
44.
Photoelectron spectroscopy has been explored as a tool to measure the flattening of the phosphorus pyramid in a phosphole as caused by a large, sterically demanding P-substituent. Earlier PE spectra had shown no difference in ionization energies (IE) for simple phospholes and their tetrahydro derivatives (both around 8.0-8.45 eV). Calculations of the Koopmans IE at the Hartree-Fock 6-31G level for 1-methylphospholane showed that, as is known for nitrogen, planarization at phosphorus markedly reduced the ionization energy value (8.74 to 6.29 eV). A reduction in IE also occurred on planarizing 1-methylphosphole, but to a lesser extent, being offset by increased electron delocalization (8.93 to 7.16 eV). This suggests that experimental comparison of IE for the unsaturated and saturated systems could be used to detect the presence of electron delocalization in the former. The IE experimentally determined for the crowded 1-(2,4-di-tert-butyl-6-methylphenyl)-3-methylphosphole was 7.9 eV, the lowest ever recorded for a phosphole. The corresponding phospholane had IE 7.55 eV. The difference in the values is attributed to electron delocalization in the phosphole. Calculations performed on the related model 1-(2-tert-butyl-4,6-dimethylphenyl)phosphole showed that the P-substituent adopted an angle of 55.7 degrees (DFT/6-31G level; 57.6 degrees at the HF/6-31 level) with respect to the C(2)-P-C(5) plane (for P-phenyl, 67.1 degrees and 68.3 degrees, respectively). 相似文献
45.
Starting from α-methylchalcone and diethyl ketone the title compound, II, has been synthesized in 6 steps (overall yield 26%). As an intermediate compound the gold yellow 10, 12-dioxoderivative of II was also obtained. 相似文献
46.
The biangular bis-indeno-fluorene 10,15-dihydro-5H-diindeno [l, 2-a; 2′, 1′-i]-fluorene (XII) has been synthesised in 6 steps starting from 1-(o-carboxyphenyl)-fluorenone (overall yield 21%). As an intermediate the 5,10,15-trioxoderivative of XII and, accessorily, its 5,10-dioxoderivative were also obtained. 相似文献
47.
Michele Daney Henry Bouas-Laurent Bernard Calas Louis Giral Nicole Platzer 《Journal of organometallic chemistry》1980,188(3):277-291
The structure of the 9,10-dihydroanthracenyl anion and of a series of 9-alkyl-10-lithio-9-10-dihydroanthracenes (9-R-10-LiDHA, I–V where R = H, Me, Et, i-Pr, t-Bu) was studied in solution by electronic absortion spectrometry and proton magnetic resonance. Our electronic absorption results, in addition to those of other authors, show that the contact ion pairs (c.i.p.) have an absorption at λmax}- 400 nm (I–III) and 415 nm (V) whereas the loose ion pairs (l.i.p.) absorb at λmax}- 450 nm (I–V). In the NMR the chemical shift of the proton para with respect to the carbanionic center was examined as a function of solvent (THF, THF/HMPA, and in some cases ether or pure HMPA) and temperature (+20 to ?40°C). The para proton is shielded significantly with regard to the aromatic protons of the hydrocarbon (Δδ(Hpara) ca. 1–1.7 ppm). The weakest shielding was observed in ether, in agreement with the existence of c.i.p. The largest shielding (THF/HMPA or pure HMPA) is in connection with the presence of l.i.p. where the negative charge is less localised at position 10. Moreover, in the same solvent, and at the same temperature, Δδ(Hpara) was observed to increase with the substituent bulk, up to the point that there are only l.i.p. present. As found previously (namely for the fluorenyl anion) the l.i.p./c.i.p. ratio increases when temperature decreases. The results of this structural study allow to rationalize the protonation stereochemistry of 9-alkyl-10-lithio-9,10-dihydroanthracenes in the above-mentioned solvents. 相似文献
48.
Xing L Ziener U Sutherland TC Cuccia LA 《Chemical communications (Cambridge, England)》2005,(46):5751-5753
This work describes a high-yielding, one-step synthesis of pyrizadine and naphthyridine containing macrocycles directed by intramolecular H-bonding. 相似文献
49.