全文获取类型
收费全文 | 3589篇 |
免费 | 363篇 |
国内免费 | 242篇 |
专业分类
化学 | 2706篇 |
晶体学 | 36篇 |
力学 | 125篇 |
综合类 | 4篇 |
数学 | 380篇 |
物理学 | 943篇 |
出版年
2024年 | 8篇 |
2023年 | 56篇 |
2022年 | 114篇 |
2021年 | 111篇 |
2020年 | 130篇 |
2019年 | 110篇 |
2018年 | 86篇 |
2017年 | 91篇 |
2016年 | 162篇 |
2015年 | 151篇 |
2014年 | 149篇 |
2013年 | 233篇 |
2012年 | 287篇 |
2011年 | 283篇 |
2010年 | 192篇 |
2009年 | 175篇 |
2008年 | 226篇 |
2007年 | 229篇 |
2006年 | 174篇 |
2005年 | 196篇 |
2004年 | 132篇 |
2003年 | 98篇 |
2002年 | 101篇 |
2001年 | 65篇 |
2000年 | 73篇 |
1999年 | 52篇 |
1998年 | 44篇 |
1997年 | 38篇 |
1996年 | 56篇 |
1995年 | 48篇 |
1994年 | 49篇 |
1993年 | 38篇 |
1992年 | 36篇 |
1991年 | 37篇 |
1990年 | 30篇 |
1989年 | 25篇 |
1988年 | 16篇 |
1987年 | 13篇 |
1986年 | 11篇 |
1985年 | 11篇 |
1984年 | 11篇 |
1983年 | 6篇 |
1982年 | 8篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1937年 | 1篇 |
排序方式: 共有4194条查询结果,搜索用时 15 毫秒
81.
Won Sick Woo Sam Sik Kang Otto Seligmann V. Mohan Chari Hildebert Wagner 《Tetrahedron letters》1980,21(44):4255-4258
From the seeds of Phytolacca americana two new lignans, Americanin B and D, have been isolated and their structures elucidated mainly by spectroscopic methods 相似文献
82.
Reza Dabestani Robert D. Hall Robert H. Sik Colin F. Chignell 《Photochemistry and photobiology》1990,52(5):961-971
The photochemistry (Type I and II) of anthralin and its photo-oxidation product 1,8-dihydroxyanthraquinone (1,8-DHAQ) has been studied in ethanol, acetonitrile and dimethylsulfoxide using spin-trapping and direct detection of singlet oxygen (1O2) luminescence techniques. In ethanol, where it exists in its neutral form (AN), anthralin does not undergo either Type I or II reactions upon UV-irradiation. In contrast, irradiation of anthralin in acetonitrile, a solvent in which anthralin is partially converted to its corresponding mono-anion (AN-), generates both superoxide and singlet oxygen. Irradiation of anthralin in dimethylsulfoxide, where the AN- form is present in substantial quantity, generates superoxide and solvent derived radicals but no detectable singlet oxygen. UV-irradiation of 1,8-DHAQ in ethanol and acetonitrile produces both superoxide and singlet oxygen in significant yields. In dimethylsulfoxide, on the other hand, only superoxide and solvent derived radicals are observed. The 1O2 quantum yield for AN- and 1,8-DHAQ in acetonitrile were determined to be 0.14 and 0.88 relative to rose bengal in the same solvent. These findings suggest that the AN photosensitization occurs via Type I and II pathways, is solvent dependent and involves AN- as well as its oxidation product 1,8-DHAQ, which is a more potent generator of both singlet oxygen and superoxide. 相似文献
83.
Yoshihisa Kurasawa Tomoyoshi Hosaka Kazue Ikeda Yuko Matsumoto Aiko Ishikura Atsushi Takada Ho Sik Kim Yoshihisa Okamoto 《Journal of heterocyclic chemistry》1994,31(2):527-533
The 3-(arylhydrazono)methyl-2-oxo-1,2-dihydroquinoxalines 9–11 were synthesized by the reaction of the quinoxalines 6–8 with various p-substituted benzenediazonium salts. Compounds 9–11 showed the tautomeric equilibria between the hydrazone imine A and diazenyl enamine B forms in dimethyl sulfoxide media. The substituent effect on the tautomer ratios of A to B was studied by the nmr spectroscopy to clarify that the presence of the ester group R2 on the hydrazone carbon and electron-donating p-substituent R1 on the side chain benzene ring exhibited a tendency to increase the ratios of the tautomer A . 相似文献
84.
Wong DM Greenblatt HM Dvir H Carlier PR Han YF Pang YP Silman I Sussman JL 《Journal of the American Chemical Society》2003,125(2):363-373
Acetylcholinesterase (AChE) inhibitors improve the cognitive abilities of Alzheimer patients. (-)-Huperzine A [(-)-HupA], an alkaloid isolated from the club moss, Huperzia serrata, is one such inhibitor, but the search for more potent and selective drugs continues. Recently, alkylene-linked dimers of 5-amino-5,6,7,8-tetrahydroquinolinone (hupyridone, 1a), a fragment of HupA, were shown to serve as more potent inhibitors of AChE than (-)-HupA and monomeric 1a. We soaked two such dimers, (S,S)-(-)-bis(10)-hupyridone [(S,S)-(-)-2a] and (S,S)-(-)-bis(12)-hupyridone [(S,S)-(-)-2b] containing, respectively, 10 and 12 methylenes in the spacer, into trigonal TcAChE crystals, and solved the X-ray structures of the resulting complexes using the difference Fourier technique, both to 2.15 A resolution. The structures revealed one HupA-like 1a unit bound to the "anionic" subsite of the active-site, near the bottom of the active-site gorge, adjacent to Trp84, as seen for the TcAChE/(-)-HupA complex, and the second 1a unit near Trp279 in the "peripheral" anionic site at the top of the gorge, both bivalent molecules thus spanning the active-site gorge. The results confirm that the increased affinity of the dimeric HupA analogues for AChE is conferred by binding to the two "anionic" sites of the enzyme. Inhibition data show that (-)-2a binds to TcAChE approximately 6-7- and > 170-fold more tightly than (-)-2b and (-)-HupA, respectively. In contrast, previous data for rat AChE show that (-)-2b binds approximately 3- and approximately 2-fold more tightly than (-)-2a and (-)-HupA, respectively. Structural comparison of TcAChE with rat AChE, as represented by the closely related mouse AChE structure (1maa.pdb), reveals a narrower gorge for rat AChE, a perpendicular alignment of the Tyr337 ring to the gorge axis, and its conformational rigidity, as a result of hydrogen bonding between its hydroxyl group and that of Tyr341, relative to TcAChE Phe330. These structural differences in the active-site gorge explain the switch in inhibitory potency of (-)-2a and 2b and the larger dimer/(-)-HupA potency ratios observed for TcAChE relative to rat AChE. The results offer new insights into factors affecting protein-ligand complementarity within the gorge and should assist the further development of improved AChE inhibitors. 相似文献
85.
Jang MJ Lee MJ Park HY Bae YS Min DS Ryu SH Kwak JY 《Experimental & molecular medicine》2004,36(2):172-178
Agents that elevate cellular cAMP are known to inhibit the activation of phospholipase D (PLD). We investigated whether PLD can be phosphorylated by cAMP-dependent protein kinase (PKA) and PKA-mediated phosphorylation affects the interaction between PLD and RhoA, a membrane regulator of PLD. PLD1, but not PLD2 was found to be phosphorylated in vivo by the treatment of dibutyryl cAMP (dbcAMP) and in vitro by PKA. PKA inhibitor (KT5720) abolished the dbcAMP-induced phosphorylation of PLD1, but dibutyryl cGMP (dbcGMP) failed to phosphorylate PLD1. The association between PLD1 and Val14RhoA in an immunoprecipitation assay was abolished by both dbcAMP and dbcGMP. Moreover, RhoA but not PLD1 was dissociated from the membrane to the cytosolic fraction in dbcAMP-treated cells. These results suggest that both PLD1 and RhoA are phosphorylated by PKA and the interaction between PLD1 and RhoA is inhibited by the phosphorylation of RhoA rather than by the phosphorylation of PLD1. 相似文献
86.
Qiong Ye Hong Zhao Xiang Xue Shie-Ming Pang 《Journal of organometallic chemistry》2005,690(2):286-290
Solvothermal treatments of W(CO)6 with 2,2′-bipyridine and 1,10-phenanthroline give [W(CO)4(bipy)] (1) and [W(CO)4(phen)] (2), respectively, which both crystallize in noncentrosymmetric space groups, suggesting that they meet the requirement of second harmonic generation (SHG) investigations. The preliminary experiment indicates that they are SHG active, and approximately estimated to be that of urea. 相似文献
87.
The covalent immobilization of DNA onto self-assembled monolayer (SAM) modified gold electrodes (SAM/Au) was studied by X-ray photoelectron spectrometry and electrochemical method so as to optimize its covalent immobilization on SAMs. Three types of SAMs with hydroxyl, amino, and carboxyl terminal groups, respectively, were examined. Results obtained by both X-ray photoelectron spectrometry and cyclic voltammetry show that the largest covalent immobilization amount of dsDNA could be gained on hydroxyl-terminated SAM/Au. The ratio of amount of dsDNA immobilized on hydroxyl-terminated SAMs to that on carboxyl-terminated SAMs and to that on amino-terminated SAMs is (3-3.5): (1-1.5): 1. The dsDNA immobilized covalently on hydroxyl-terminated SAMs accounts for 82.8-87.6% of its total surface amount (including small amount of dsDNA adsorbed). So the hydroxyl-terminated SAM is a good substrate for the covalent immobilization of dsDNA on gold surfaces. 相似文献
88.
Yoon MS Ahn KH Cheung RW Sohn H Link JR Cunin F Sailor MJ 《Chemical communications (Cambridge, England)》2003,(6):680-681
Free-standing porous Si multilayer dielectric mirrors, prepared by electrochemical etching of crystalline Si, are treated with a ruthenium ring-opening metathesis polymerization (ROMP) catalyst followed by norbornene to produce flexible, stable composite materials in which poly(norbornene) is covalently attached to the porous Si matrix. 相似文献
89.
2-Iodoaniline reacts with α,β-unsaturated carbonyl compounds in DMF at 100 °C in the presence of a catalytic amount of a palladium catalyst along with a base to afford the corresponding quinolones or quinolines in moderate to good yields. 相似文献
90.
Yuyin Wang Yan Wang Li Zhang Prof. Dr. Chun‐Sen Liu Prof. Dr. Huan Pang 《化学:亚洲杂志》2019,14(16):2790-2795
To realize the effective conversion of renewable energy through water decomposition, efficient electrocatalysts for the oxygen evolution reaction (OER) are essential. In this article, PBA@POM was successfully prepared with a Prussian blue analogue (PBA) as the initial structure. A facile hydrothermal process is reported for obtaining PBA@POM by etching the cubic PBA with a strong Brønsted acid, H3PMo12O40 (HPMo). The hollow cube structure not only exposes more active sites but also promotes electron transport, which results in excellent electrocatalytic activity for the OER. Compared with the PBA, which initially simply adhered to POM, the optimum PBA@POM hybrids display remarkably enhanced OER catalytic activity, with an almost constant overpotential of 440 mV at a current density of 10 mA cm?2 and a small Tafel slope (23.45 mV dec?1). The facilely prepared PBA@POM with good electrochemical activity and stability promises great potential for the OER. 相似文献