全文获取类型
收费全文 | 2035篇 |
免费 | 2篇 |
国内免费 | 11篇 |
专业分类
化学 | 1384篇 |
晶体学 | 12篇 |
力学 | 28篇 |
数学 | 340篇 |
物理学 | 284篇 |
出版年
2022年 | 11篇 |
2020年 | 14篇 |
2019年 | 7篇 |
2018年 | 13篇 |
2017年 | 9篇 |
2016年 | 13篇 |
2015年 | 11篇 |
2014年 | 21篇 |
2013年 | 105篇 |
2012年 | 81篇 |
2011年 | 98篇 |
2010年 | 72篇 |
2009年 | 41篇 |
2008年 | 103篇 |
2007年 | 105篇 |
2006年 | 123篇 |
2005年 | 134篇 |
2004年 | 113篇 |
2003年 | 96篇 |
2002年 | 79篇 |
2001年 | 18篇 |
2000年 | 25篇 |
1999年 | 22篇 |
1998年 | 20篇 |
1997年 | 32篇 |
1996年 | 33篇 |
1995年 | 16篇 |
1994年 | 36篇 |
1993年 | 32篇 |
1992年 | 15篇 |
1991年 | 21篇 |
1990年 | 24篇 |
1989年 | 19篇 |
1988年 | 21篇 |
1987年 | 18篇 |
1986年 | 16篇 |
1985年 | 30篇 |
1984年 | 32篇 |
1983年 | 16篇 |
1982年 | 54篇 |
1981年 | 41篇 |
1980年 | 36篇 |
1979年 | 34篇 |
1978年 | 32篇 |
1977年 | 38篇 |
1976年 | 27篇 |
1975年 | 19篇 |
1974年 | 19篇 |
1973年 | 13篇 |
1971年 | 8篇 |
排序方式: 共有2048条查询结果,搜索用时 31 毫秒
21.
Fe(CO)5 and a catalytic amount of sodium borohydride react with cycloheptatrienes in protic solvents to yield the corresponding tricarbonyl(eta 4-1,3-diene)iron complexes in a one-pot procedure, which has been found to be particularly efficient for the synthesis of the useful tricarbonyl(cyclo-heptadiene)iron complex. 相似文献
22.
14N-NMR. measurements using the Fourier Transform technique are presented and compared to C. W. experiments. The F. T. technique is especially advantageous for relaxation time measurements. However, since 14N-nuclei may have widely different relaxation times, it is often not possible to have optimal gain in sensitivity (as compared to C. W. measurements) in a single F. T. experiment for different 14N-nuclei contained in the same sample. Different experiments have to be performed, optimizing the spectrometer parameters for each 14N-resonance of appreciably different linewidth. The technique is applied to three different problems. 14N-relaxation in symmetrical ammonium salts is shown to arise from reorientation of the water dipoles. The use of a double spin-probe, 13C-14N, allows the determination of the electric field gradients in cyclic ammonium salts. The electronic distribution is especially distorted from tetrahedral symmetry in the highly strained N, N-dimethyl-aziridinium cation. Finally, electric and dynamic effects in ion pairing may be studied as shown on the case of tetrabutylammonium iodide in water and in benzene. 相似文献
23.
Berger A Djukic JP Pfeffer M de Cian A Kyritsakas-Gruber N Lacour J Vial L 《Chemical communications (Cambridge, England)》2003,(5):658-659
In the presence of large amounts of [Me4N]Cl, the reaction of ortho-chloromercurated 2-[(eta6-phenyl)tricarbonylchromium]pyridine with mu-chloro cyclopalladated aromatic compounds yields a series of new heteroleptic heterodinuclear cis-(C--N)2Pd(II) complexes, which are valuable precursors of planar chiral cyclopalladated (eta6-arene)Cr(CO)3 complexes. 相似文献
24.
Philippe Remuzon Daniel Bouzard Claire Clemencin Christian Dussy Munir Essiz Jean-Pierre Jacquet Jean Saint-Germain 《Journal of heterocyclic chemistry》1993,30(2):517-523
The synthesis of (1S,4S,7S)- and (1R,4R,7S)-2-(4-tolylsulfonyl>5-phenylmethyl-7-rnethyl-2,5-diazabicyclo-[2.2.1]heptanes ( 20 ) and ( 22 ) from trans 4-hydroxy-L-proline is described. 相似文献
25.
Jean-Pierre Vors 《Journal of heterocyclic chemistry》1990,27(3):579-582
A convenient route to prepare unsubstituted pyridazine-3,4-dicarboxylic acid on a preparative scale is described. The synthesis involves a hetero Diels-Alder reaction between a new 1,2-diaza-1,3-diene and ethyl vinyl ether and oxidation of the intermediate 1,4,5,6-tetrahydropyridazine as the key step. 相似文献
26.
Christiane Santelli-Rouvier Maurice Santelli Jean-Pierre Zahra 《Tetrahedron letters》1985,26(9):1213-1216
(+)-2-carene heated neat with iron pentacarbonyl leads to α-phellandrene-Fe(CO)3 complex ( ~15 % ), p. cymene ( ~15 % ), (-)-(1S)-3,8,8-trimethylbicyclo (4.1.1) oct-3-ene-7-one ( ~50 % ) and (+)-(1S,7S)-3,8,8-trimethylbicyclo (4.1.1.) oct-3-ene-7-ol ( ~20 % ). 相似文献
27.
Haberichter T Roux E Marhl M Mazat JP 《Bioelectrochemistry (Amsterdam, Netherlands)》2002,57(2):129-138
In airway myocytes, like in many cells, Ca(2+) signaling is controlled by inositol 1,4,5-trisphosphate (InsP(3)) via InsP(3) receptors (InsP(3)R) located in the sarco-endoplasmic reticulum. Three types of InsP(3)R exist, labeled Types 1, 2, and 3, which differ in their gating kinetics. We analyze a possible impact of the different gating kinetics of Type 1 and Type 3 InsP(3)R on the time course of cytosolic Ca(2+) concentration in tracheal smooth muscle cells upon agonist stimulation. Previous experimental data in rat tracheal myocytes showed that upon gradually increased stimulation with acetylcholine (ACh), a contractile agonist that acts via InsP(3) production, signal spikes, several spikes with declining maxima, and sustained oscillations appear. Our model reproduces the time courses of cytosolic Ca(2+) measured in tracheal myocytes. Moreover, by postulating slight variations in the model parameters which determine the total number of receptors expressed and the ratio between Type 1 and Type 3 InsP(3)R, it offers an explanation to the experimental observation of qualitatively different responses of cells within a presumably homogeneous tissue. 相似文献
28.
Several biaryls bearing various substituents on both rings were synthesized in a preparative fashion, and in yields up to 88% by a technical improvement on the classical Ullmann reaction. All these biaryls bear reactive functional groups (i.e. formyl, methoxycarbonyl, dimethoxycarbonylpropyl and butanolidylmethyl) in both the o and o′ positions. The biaryls 9, 13, 21 and 26–33 are plausible synthons for bisbenzocyclooctadiene lignans such as schizandrin and steganacin. 相似文献
29.
Pegaz B Debefve E Borle F Ballini JP van den Bergh H Kouakou-Konan YN 《Journal of photochemistry and photobiology. B, Biology》2005,80(1):19-27
In the present work, we performed a preclinical inter-comparison study using several photosensitizers with the goal of optimizing photodynamic therapy (PDT) for the treatment of choroidal neovascularization (CNV) associated with age-related macular degeneration. The tested molecules were the porphyrins meso-tetraphenylporphyrin (TPP) and meso-tetra-(4-carboxyphenyl)-porphyrin (TCPP), and the chlorins pheophorbide-a (Pheo-a) and chlorin e(6) (Ce(6)). Each of these molecules was entrapped in biodegradable nanoparticles (NP) based on poly(d,l-lactic acid). The influence of the degree of lipophilicity on the incorporation efficiency of the drug in the NPs, and on the dye leakage from blood vessels as well as on the photothrombic efficiency was investigated using the chick chorioallantoic membrane (CAM) as in vivo model. NP characterization showed that the dye was more effectively entrapped in the polymeric matrix when its degree of lipophilicity increased. While less lipophilic compounds (TCPP, Ce(6)) extravasate rather easily, the more lipophilic dyes (TPP, Pheo-a) tend to remain inside the blood vessels. After injection of a drug dose of 1 mg/kg body weight and a drug-light application interval of 1 min, irradiation with light doses ranging from 5 to 20 J/cm(2) led to the highest photothrombic efficiency when using the NPs loaded with the most lipophilic molecule (TPP). The latter induced vascular damage, which was significantly higher than that observed with the other molecules tested. Thus, in addition to minimal leakage from blood vessels, the TPP in NP formulation exhibited photothrombic efficiency similar to Visudyne which was also tested in the CAM model. 相似文献
30.
Regioselectivite de la reaction des dialkyl cuprates de magnesium sur des aldehydes α,β-ethyleniques
Monique Bourgain-Commerçon Jean-Pierre Foulon Jean François Normant 《Journal of organometallic chemistry》1982,228(3):321-326
Various magnesium organocuprates give conjugative addition products with α,β-ethylenic aldehydes, and even with acrolein. The enolates may be trapped with bromine or trimethylsilyl chloride. 相似文献