全文获取类型
收费全文 | 11964篇 |
免费 | 421篇 |
国内免费 | 51篇 |
专业分类
化学 | 7477篇 |
晶体学 | 58篇 |
力学 | 348篇 |
数学 | 2081篇 |
物理学 | 2472篇 |
出版年
2023年 | 69篇 |
2022年 | 106篇 |
2021年 | 174篇 |
2020年 | 187篇 |
2019年 | 185篇 |
2018年 | 201篇 |
2017年 | 177篇 |
2016年 | 336篇 |
2015年 | 321篇 |
2014年 | 345篇 |
2013年 | 692篇 |
2012年 | 789篇 |
2011年 | 871篇 |
2010年 | 471篇 |
2009年 | 419篇 |
2008年 | 695篇 |
2007年 | 665篇 |
2006年 | 648篇 |
2005年 | 618篇 |
2004年 | 507篇 |
2003年 | 439篇 |
2002年 | 357篇 |
2001年 | 236篇 |
2000年 | 192篇 |
1999年 | 149篇 |
1998年 | 102篇 |
1997年 | 116篇 |
1996年 | 96篇 |
1995年 | 99篇 |
1994年 | 92篇 |
1993年 | 76篇 |
1992年 | 89篇 |
1991年 | 86篇 |
1990年 | 86篇 |
1989年 | 79篇 |
1988年 | 71篇 |
1986年 | 65篇 |
1985年 | 91篇 |
1984年 | 122篇 |
1983年 | 79篇 |
1982年 | 114篇 |
1981年 | 90篇 |
1980年 | 89篇 |
1979年 | 85篇 |
1978年 | 89篇 |
1977年 | 97篇 |
1976年 | 73篇 |
1975年 | 72篇 |
1974年 | 74篇 |
1973年 | 69篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
191.
The enthalpy of oxidation of SrFe1-xCoxO3-d with x=0.33 and 0.67 has been determined by adiabatic calorimetry; average values for x=0.33 and 0.67 are -67±11 and -49.5±9 kJ (mol O2)-1. These data and the previously reported value for SrFeO3-d suggest that the enthalpy of oxidation for pure (perovskite-type) SrCoO3-d is close to zero. Earlier reported composition - partial pressure data for SrFe0.67Co0.33O3-d are reproduced when preferential oxidation of iron is assumed for low partial pressures of oxygen.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
192.
Tønder JE Olesen PH Hansen JB Begtrup M Pettersson I 《Journal of computer-aided molecular design》2001,15(3):247-258
A study of a series of compounds with agonistic effect at the alpha4beta2 nicotinic acetylcholine receptors resulted in an improved pharmacophore model as well as a CoMFA model. The pharmacophore was composed of three pharmacophoric elements: (1) a site point (a) corresponding to a protonated nitrogen atom, (2) a site point (b) corresponding to an electronegative atom capable of forming a hydrogen bond, and (3) the centre of a heteroaromatic ring or a C=O bond (c). The pharmacophoric elements were related by the following parameters: (a-b) 7.3-8.0 A, (a-c) 6.5-7.4 A, and the angle between the two distance vectors (delta bac) 30.4-35.8 degrees. In addition to this, a stereoselective CoMFA model was developed, which showed good predictability even for compound classes not present in the training set. 相似文献
193.
Franzén J Marigo M Fielenbach D Wabnitz TC Kjaersgaard A Jørgensen KA 《Journal of the American Chemical Society》2005,127(51):18296-18304
The development of a general organocatalyst for the alpha-functionalization of aldehydes, via an enamine intermediate, is presented. Based on optically active alpha,alpha-diarylprolinol silyl ethers, the scope and applications of this catalyst for the stereogenic formation of C-C, C-N, C-F, C-Br, and C-S bonds are outlined. The reactions all proceed in good to high yields and with excellent enantioselectivities. Furthermore, we will present mechanistic insight into the reaction course applying nonlinear effect studies, kinetic resolution, and computational investigations leading to an understanding of the properties of the alpha,alpha-diarylprolinol silyl ether catalysts. 相似文献
194.
Voszka I Szabó Z Csík G Maillard P Gróf P 《Journal of photochemistry and photobiology. B, Biology》2005,79(2):83-88
The effect of the symmetry and polarity of the porphyrin molecules on their membrane localization and interaction with membrane lipids were investigated by electron paramagnetic resonance (EPR). For this purpose, two glycoconjugated tetraphenyl porphyrin derivatives were selected, respectively, symmetrically and asymmetrically substituted. Small unilamellar liposomes composed of dipalmitoylphosphatidylcholine (DPPC) and spin labeled stearic acids were prepared. The spin probe was located at the 5th or 7th or 12th or 16th position of the hydrocarbon chain in order to monitor various regions of the lipid bilayer. EPR spectra of porphyrin-free and porphyrin-bound liposomes were recorded at various temperatures below and above the phase transition temperature of DPPC. The effect on membrane fluidity proved to be stronger with the asymmetrical porphyrin derivative than with the symmetrical one. The rigidity increased when the spin label was near lipid head groups. The difference observed between control and porphyrin-treated samples when measured below the main lipid transition temperature disappeared at higher temperature. When the spin label was near the end of the hydrophobic tails, the symmetrical porphyrin derivative caused increase in fluidity, while the asymmetrical one slightly decreased it. To explain this phenomenon we propose that the asymmetrical derivative exerts a stronger ordering effect caused by its fluorophenyl group located at the level of the lipid heads, which is attenuated to the hydrophobic tails. The perturbing effect of the symmetric derivative could not lead to similar extent of ordering at the head groups and looses the hydrocarbon chains deeper in the membrane. 相似文献
195.
Dénes Szabó István Kapovits Árpád Kucsman Mátyás Czugler Vilmos Fülöp Alajos Kálmán 《Structural chemistry》1991,2(5):529-535
1-[2-(N-methylcarbamoyl)phenyl]-3H-2,1-naphto-(1,8-d,e)-oxathiin-1-ium chloride (2), 1-[2-(N-methylcarbamoyl)-phenyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (3), 1-[8-(N-methylcarbamoyl)naphtyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (4) and 1-(8-carboxylatonaphtyl)-2-methyl-3-oxo-3H-1,2-naphto-(1,8-d,e)-thiazin-1-ium dipolar ion (5) cyclic sulfonium salts were prepared and their chemical properties investigated (spirosulfurane-formation, hydrolysis). The molecular structures obtained from x-ray diffraction can be described with a considerably distorted trigonal bipyramidal arrangement of the ligands about the sulfonium center, with O/N—S ... O=apical angles of 173.9, 164.9, 156.6, and 159.0°, as well as with S—O/N apical bond lengths of 1.648, 1.671, 1.664, and 1.682 Å. The structures exhibit relatively short S ... O close contacts with interatomic distances of 2.253, 2.448, 2.795, and 2.619 Å. 相似文献
196.
197.
Melinda Fekete Pál Kolonits Ngo Thi Hien Lajos Novák 《Central European Journal of Chemistry》2005,3(4):792-802
New tryptamine 5, 7 and β-carboline derivatives 3 were preparated by palladium-catalyzed coupling reaction of 5-bromotryptamine 1 with aryl boronic acids.
Dedicated to Professor András Lipták on his 70th birthday. 相似文献
198.
Nielsen CB Johnsen M Arnbjerg J Pittelkow M McIlroy SP Ogilby PR Jørgensen M 《The Journal of organic chemistry》2005,70(18):7065-7079
[reaction: see text] The synthesis and characterization of water-soluble singlet oxygen sensitizers with a phenylene-vinylene motif is presented. The principal motivation for this study was to better understand specific features of a water-soluble molecule that influence the photosensitized production of singlet oxygen upon nonlinear, two-photon excitation of that molecule. To achieve water solubility, sensitizers were synthesized with ionic as well as nonionic substituents. In the ionic approach, salts of N-methylated pyridine, benzothiazole, and 1-methyl-piperazine moieties were used, as were aryl-substituted sulfonic acid moieties. In the nonionic approach, aryl-substituted triethylene glycol moieties were used. Selected photophysical properties of the compounds synthesized were determined, including singlet oxygen quantum yields. Of the molecules examined, the most efficient singlet oxygen sensitizers had triethylene glycol units as the functional group that imparted water solubility. Molecules containing the ionic moieties did not make singlet oxygen in appreciable yield nor did they efficiently fluoresce. Rather, for these latter molecules, rapid charge-transfer-mediated non-radiative processes appear to dominate excited state deactivation. 相似文献
199.
[reaction: see text] The regioselectivity of the Birch reductive alkylation of polysubstituted biaryls has been investigated. Results indicate that regioselectivity is affected by the electronic nature of substituents on both aromatic rings. The electron-rich 3,5-dimethoxyphenyl moiety is selectively reduced and then alkylated, while phenols and aniline are not dearomatized under these conditions. Biaryls possessing a phenol moiety are alkylated on the second ring, providing that the acidic proton has been removed prior to the Li/NH3 reduction. 相似文献
200.
Marie-Noelle Avettand-Fènoël N. David G. Reumont J. -M. Fiorani M. Vilasi P. Perrot 《Journal of Thermal Analysis and Calorimetry》2007,90(2):329-332
The Fe-Sn-Zn system is of interest because Sn is one element added to the Zn galvanizing bath to overcome the drawbacks due
to the presence of Si in semi-killed steels. This work has been undertaken with the aim to understand the tin effect on the
microstructure and the layers growth in batch galvanized coatings on low alloyed steels.
Various experimental techniques such as metallography, scanning electron microscopy (SEM) coupled with X-ray energy dispersive
spectroscopy (EDX) are used in order to characterize the microstructure and the properties of such coatings elaborated in
a zinc bath enriched with tin.
Solidification phenomena and layers growth mechanisms during galvanization are explained by means of the ternary phase diagram
Fe-Sn-Zn at 450°C. The Calphad method allows to obtain this phase diagram from the three optimized binary phase diagrams Fe-Sn,
Fe-Zn and Sn-Zn and some experimental data inside the ternary Fe-Sn-Zn system. 相似文献