全文获取类型
收费全文 | 7432篇 |
免费 | 466篇 |
国内免费 | 21篇 |
专业分类
化学 | 5671篇 |
晶体学 | 44篇 |
力学 | 129篇 |
数学 | 782篇 |
物理学 | 1293篇 |
出版年
2023年 | 64篇 |
2022年 | 59篇 |
2021年 | 117篇 |
2020年 | 211篇 |
2019年 | 200篇 |
2018年 | 84篇 |
2017年 | 103篇 |
2016年 | 287篇 |
2015年 | 264篇 |
2014年 | 331篇 |
2013年 | 388篇 |
2012年 | 508篇 |
2011年 | 563篇 |
2010年 | 338篇 |
2009年 | 273篇 |
2008年 | 433篇 |
2007年 | 394篇 |
2006年 | 372篇 |
2005年 | 285篇 |
2004年 | 282篇 |
2003年 | 222篇 |
2002年 | 231篇 |
2001年 | 146篇 |
2000年 | 122篇 |
1999年 | 108篇 |
1998年 | 94篇 |
1997年 | 103篇 |
1996年 | 95篇 |
1995年 | 103篇 |
1994年 | 104篇 |
1993年 | 77篇 |
1992年 | 66篇 |
1991年 | 70篇 |
1990年 | 51篇 |
1989年 | 68篇 |
1988年 | 47篇 |
1987年 | 50篇 |
1986年 | 31篇 |
1985年 | 37篇 |
1984年 | 35篇 |
1983年 | 33篇 |
1982年 | 29篇 |
1981年 | 39篇 |
1980年 | 50篇 |
1979年 | 34篇 |
1978年 | 33篇 |
1977年 | 29篇 |
1976年 | 26篇 |
1974年 | 21篇 |
1973年 | 23篇 |
排序方式: 共有7919条查询结果,搜索用时 15 毫秒
101.
102.
103.
Martina Dotzler Astrid Schmidt Jochen Ellermann Falk A. Knoch Matthias Moll Walter Bauer 《Polyhedron》1996,15(24):4425-4433
BiBr3 or SbI3 react at 20°C with LiN(PPh2)2 (1) to give elementary Bi or Sb and the P---P coupled phosphazene ligand Ph2P---N=PPh2---PPh2=N---PPh2 (2). The reaction of AsI3 with 1 at room temperature formed yellow needles of the eight-membered heterocycle
(3), whereas AsI3 interacted at 80°C with 1 in the molar ratio of 1:3 to give elementary arsenic and 2. Treatment of AsI3 and 1 at 20°C in a 1:2 stoichiometry yielded the seven-membered, cyclic arsenium(I) salt I·4THF (5·4THF), which was characterized by elemental analysis, conductivity, mass, IR and NMR spectroscopy and single-crystal X-ray structural analysis. 相似文献
104.
105.
Matthias Deppner 《Journal of organometallic chemistry》2005,690(12):2861-2871
The synthesis is described of symmetric alkylidene bridged dinuclear zirconocene complexes. The influence of structural parameters and different cocatalysts such as methylaluminoxane (MAO), triphenyl tetrakis(pentafluorophenyl)borate- or tris(pentafluorophenyl)borane has been investigated for homogeneous propylene polymerization. The dinuclear catalysts show highest polymerization activities by activation with MAO. Activation with triphenyl tetrakis(pentafluorophenyl)borate results in polypropylenes with the highest degree of isotacticity. Compared to the mononuclear reference catalyst the dinuclear MAO activated complex achieved higher propylene polymerization activity and the polypropylene obtained from the dinuclear complex has a higher molecular weight than that one that was produced with the mononuclear complex. 相似文献
106.
The mechanism of reductive etherification reactions between aromatic aldehydes and alcohols has been investigated with the DFT(B3LYP)/6-31G method. One or two BH(3) molecules have been used to simulate the role of the catalyst and reducing agent. The solvent effects of the title reactions have been studied by the PCM model. It is found that the reactions between aromatic aldehydes and primary, secondary, and tertiary alcohols can proceed more easily in a polar solvent such as acetonitrile. The results provide evidence in theory to broaden the applications of reductive etherification reactions for the optimization of the radiochemical synthesis process of (18)F-labeled ether radiotracers. 相似文献
107.
Baier J Maier M Engl R Landthaler M Bäumler W 《The journal of physical chemistry. B》2005,109(7):3041-3046
Singlet oxygen was generated by energy transfer from the photoexcited sensitizer, Photofrin or 9-acetoxy-2,7,12,17-tetrakis-(beta-methoxyethyl)-porphycene (ATMPn), to molecular oxygen. Singlet oxygen was detected time-resolved by its luminescence at 1270 nm in an environment of increasing complexity, water (H2O), pure phosphatidylcholine, phosphatidylcholine in water (lipid suspensions), and aqueous suspensions of living cells. In the case of the lipid suspensions, the sensitizers accumulated in the lipids, whereas the localizations in the cells are the membranes containing phosphatidylcholine. By use of Photofrin, the measured luminescence decay times of singlet oxygen were 3.5 +/- 0.5 micros in water, 14 +/- 2 micros in lipid, 9 +/- 2 micros in aqueous suspensions of lipid droplets, and 10 +/- 3 micros in aqueous suspensions of human colonic cancer cells (HT29). The decay time in cell suspensions was much longer than in water and was comparable to the value in suspensions of phosphatidylcholine. That luminescence signal might be attributed to singlet oxygen decaying in the lipid areas of cellular membranes. The measured luminescence decay times of singlet oxygen excited by ATMPn in pure lipid and lipid suspensions were the same within the experimental error as for Photofrin. In contrast to experiments with Photofrin, the decay time in aqueous suspension of HT29 cells was 6 +/- 2 micros when using ATMPn. 相似文献
108.
The source of the effect of N-alkylation on the redox properties of Ni(II/I) and Cr(III/II) cyclam complexes has been investigated using DFT calculations. The structures of the anhydrous and hydrated complexes were optimized in the gas phase, and single point calculations were performed in a polarized continuum. The main results are the following: the decrease in outer sphere solvation upon N-alkylation is the major source of the relative stabilization of the lower oxidation state complexes by the tertiary amine ligands; tertiary amine nitrogen donors are stronger sigma-donors than the secondary amines, as predicted from the inductive effect of alkyls; steric strain elongates the metal-nitrogen bonds in the tertiary complexes and decreases the ligand strain energies; and the site of water binding to the complexes differs because of their different electronic structures (i.e., in the Ni complexes, the water molecules bind to the M[bond]N[bond]H sites, whereas in the Cr complexes they bind to the central metal cation). Outer sphere hydrogen bonding of water to the ligands in the coordination sphere lowers the ionization potentials by charge delocalization. 相似文献
109.
Annals of Global Analysis and Geometry - In the present paper, we consider star-shaped mean convex hypersurfaces of the real, complex and quaternionic hyperbolic space evolving by a class of... 相似文献
110.
M. Gorska H. Grawe D. Foltescu D. B. Fossan R. Grzywacz J. Heese K. H. Maier M. Rejmund H. Roth R. Schubart Ö. Skeppstedt K. Spohr 《Zeitschrift für Physik A Hadrons and Nuclei》1995,353(3):233-234
The neutron deficient nucleus94Pd was identified and studied for the first time by in-beam spectroscopy. An I=(14+) isomer with t1/2=0.8 (2) s was observed in a recoil catcher setup inside the multi-detector -array OSIRIS. Filter detectors for neutrons and charged particles were used to identify the (2p2n) exit channel of the reaction58Ni+40Ca, populated with only 0.06% of the total evaporation residue cross section. The structure of the isomer is discussed within the frame work of shell model calculations in the (p1/2,g9/2) model space with emphasis on the g
9
2/2
T=0, I=1,9 pairing two-body matrix elements.Communicated by: D. Schwalm 相似文献