首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   70371篇
  免费   9866篇
  国内免费   6642篇
化学   46984篇
晶体学   659篇
力学   4661篇
综合类   515篇
数学   8449篇
物理学   25611篇
  2024年   228篇
  2023年   1399篇
  2022年   2280篇
  2021年   2468篇
  2020年   2522篇
  2019年   2422篇
  2018年   2188篇
  2017年   1939篇
  2016年   2964篇
  2015年   3078篇
  2014年   3650篇
  2013年   4843篇
  2012年   5889篇
  2011年   6015篇
  2010年   4079篇
  2009年   4018篇
  2008年   4187篇
  2007年   3788篇
  2006年   3567篇
  2005年   3092篇
  2004年   2478篇
  2003年   1895篇
  2002年   1682篇
  2001年   1520篇
  2000年   1419篇
  1999年   1563篇
  1998年   1330篇
  1997年   1169篇
  1996年   1227篇
  1995年   1071篇
  1994年   1007篇
  1993年   865篇
  1992年   768篇
  1991年   664篇
  1990年   555篇
  1989年   481篇
  1988年   366篇
  1987年   349篇
  1986年   297篇
  1985年   300篇
  1984年   202篇
  1983年   176篇
  1982年   145篇
  1981年   112篇
  1980年   82篇
  1978年   56篇
  1977年   52篇
  1976年   50篇
  1975年   57篇
  1973年   57篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
The introduction of a 5-trimethylsilyl group on the least hindered face of the diene thebaine was anticipated to favor attack by dienophiles from the alternate face, but only gave rise to a rearrangement product when treated with 3-butene-2-one at 110 °C. Reaction with the more reactive benzoquinone at lower temperature gave rise to a very slow reaction from the same face as the silyl group, indicating that a trimethylsilyl group does not sufficiently hinder this face to achieve reaction at the other face.  相似文献   
92.
用火焰原子吸收法检测了深圳市1408例13岁以下儿童发中钙,铁,镁的元素含量,并探讨了元素含量与年龄,性别的关系,结果显示,性别差异有显著意义,钙,镁含量随年龄增长有相似变化。  相似文献   
93.
The 1205 classical isomers of fullerene C58, as well as one quasi-fullerene C58 isomer with a heptagonal ring (labeled as Cs:hept) have been investigated by the quantum chemical methods PM3, HCTH/3-21G, and B3LYP/6-31G(d). Isomer C3v:0001, which has the lowest number of adjacent pentagons, is predicted to be the most stable isomer, but the quasi-fullerene isomer Cs:hept is only 2.50 kcal mol-1 higher in energy. Systematic investigations of the electronic properties of C3v:0001 and Cs:hept find that the C3v:0001 isomer has high vertical electron affinity (3.19 eV). The nucleus-independent chemical shifts (NICS) value at the center of Cs:hept (-5.1 ppm) is more negative than that of C60 (-2.8 ppm). The NICS value at the center of the heptagonal ring in Cs:hept (-2.5 ppm) indicates weakly aromatic character. In contrast, the C58(6-) and C58(8-) ions of the C3v:0001 and Cs:hept geometries possess large aromatic character, with NICS values between -14.0 and -26.2 ppm. To clarify the thermodynamic stabilities of C58 isomers at different temperatures, the entropy contributions are taken into account on the basis of the Gibbs energy at the B3LYP/6-31G(d) level. The C3v:0001 isomer prevails in a wide range of temperatures, and the Cs:hept isomer is also an important component around 2800 K. The IR spectra of C58 isomers are simulated to facilitate experimental identification of different isomers. In addition, the electronic spectra and the second-order hyperpolarizabilities are predicted by ZINDO and the sum-over-states model. The static second-order hyperpolarizability of the C3v:0001 isomer is 96.5 % larger than that of C60, and its second-order hyperpolarizabilities at external field frequencies are at least nine times larger than those of C60.  相似文献   
94.
Three-dimensional time-dependent quantum wave packet calculation for the O((1)D)+HBr reaction has been carried out using an accurate ab initio global potential energy surface [K. A. Peterson, J. Chem. Phys. 113, 4598 (2000)]. The calculations show that the initial state-selected reaction probabilities are dominated by resonance structures, and the lifetime of the resonance is generally in the subpicosecond time scale. The energy dependence of the reaction cross section is computed, which manifests still resonance structures, and is a decreasing function of the translational energy. The thermal rate constants are also computed, which are nearly independent on the temperature. The calculation results are discussed and compared to similar reaction with deep well.  相似文献   
95.
A novel compound, [Co(phen)3][V10O26]·H2O, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. This compound crystallizes in the orthorhombic space group Ccca with a=13.447(3), b=29.936(6), c=23.252(5) Å, V=9360(3) Å3, Z=8 and R=0.0285. Data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K in the range of 1.36<θ<24.99°. The structure of the compound consists of vanadium oxide layers, which are built up from the infinite VO4 chains by corners and edges sharing. The [Co(phen)3]2+ complexes occupy the interlayer space and contact each other via ππ stacking interactions of the phen groups to form infinite one-dimensional chains.  相似文献   
96.
The 2-methyloxazol-5-on-2-yl radical (3) and its deuterium labeled analogs were generated in the gas-phase by femtosecond electron-transfer and studied by neutralization-reionization mass spectrometry and quantum chemical calculations. Radical 3 undergoes fast dissociation by ring opening and elimination of CO and CH(3)CO. Loss of hydrogen is less abundant and involves hydrogen atoms from both the ring and side-chain positions. The experimental results are corroborated by the analysis of the potential energy surface of the ground electronic state in 3 using density functional, perturbational, and coupled-cluster theories up to CCSD(T) and extrapolated to the 6-311 ++ G(3df,2p) basis set. RRKM calculations of radical dissociations gave branching ratios for loss of CO and H that were k(CO)/k(H) > 10 over an 80-300 kJ mol(-1) range of internal energies. The driving force for the dissociations of 3 is provided by large Franck-Condon effects on vertical neutralization and possibly from involvement of excited electronic states. Calculations also provided the adiabatic ionization energy of 3, IE(adiab) = 5.48 eV and vertical recombination energy of cation 3(+), RE(vert) = 4.70 eV. The present results strongly indicate that oxazolone structures can explain fragmentations of b-type peptide ions upon electron capture, contrary to previous speculations.  相似文献   
97.
Zhang W  Chen CH 《Tetrahedron letters》2005,46(11):1807-1810
A solution-phase synthesis of bicyclic prolines containing four points of diversity has been developed by a two-step synthesis involving 1,3-dipolar cycloaddition of perfluoroalkylsulfonyl-protected hydroxybenzaldehydes followed by Pd-catalyzed Suzuki coupling reaction of fluorous sulfonates with boronic acids. Both reactions are conducted under microwave irradiation and reaction mixtures are purified by solid-phase extractions without performing chromatography.  相似文献   
98.
A novel micro-injector has been fabricated for capillary electrophoresis (CE). It was successfully used for the determination of some indole derivatives for example melatonin (MT), serotonin (5-HT), tryptophan (Trp), and 5-hydroxy-tryptophane (5-HTrp) in the rat pineal gland by capillary electrophoresis with electrochemical detection (CE-EC). CE was performed in 0.20 mol L(-1) phosphate buffer (pH 8.0). The compounds investigated can be well separated and detected within 15 min. The working electrode used was a 300-microm diameter carbon electrode positioned opposite the outlet of the capillary. The relationship between peak current and analyte concentration was highly linear in the range from 0.10 to 500 micromol L(-1); detection limits (S/N = 3) were 0.03-0.13 micromol L(-1). The proposed method has been successfully used to analyze real biological samples.  相似文献   
99.
In this paper, we deal with the nonlinear second-order differential equation with damped vibration term involving p-Laplacian operator. Of particular interest is the resolution of an open problem. An interesting outcome from our result is that we can obtain the fast homoclinic solution with general superlinear growth assumption in suitable Sobolev space. To our knowledge, our theorems appear to be the first such result about damped vibration problem with p-Laplacian operator.  相似文献   
100.
Methodology and Computing in Applied Probability - Risk measures for tail risk have an important application in the dynamic portfolio insurance strategies. We propose a new risk measure called...  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号