全文获取类型
收费全文 | 26808篇 |
免费 | 1662篇 |
国内免费 | 3803篇 |
专业分类
化学 | 22057篇 |
晶体学 | 1122篇 |
力学 | 246篇 |
综合类 | 215篇 |
数学 | 3894篇 |
物理学 | 4739篇 |
出版年
2024年 | 15篇 |
2023年 | 189篇 |
2022年 | 673篇 |
2021年 | 827篇 |
2020年 | 609篇 |
2019年 | 712篇 |
2018年 | 652篇 |
2017年 | 627篇 |
2016年 | 684篇 |
2015年 | 619篇 |
2014年 | 934篇 |
2013年 | 2034篇 |
2012年 | 1407篇 |
2011年 | 1638篇 |
2010年 | 1613篇 |
2009年 | 1838篇 |
2008年 | 1771篇 |
2007年 | 1805篇 |
2006年 | 1722篇 |
2005年 | 1505篇 |
2004年 | 1484篇 |
2003年 | 1219篇 |
2002年 | 1113篇 |
2001年 | 805篇 |
2000年 | 769篇 |
1999年 | 591篇 |
1998年 | 581篇 |
1997年 | 471篇 |
1996年 | 414篇 |
1995年 | 417篇 |
1994年 | 385篇 |
1993年 | 351篇 |
1992年 | 328篇 |
1991年 | 237篇 |
1990年 | 145篇 |
1989年 | 170篇 |
1988年 | 154篇 |
1987年 | 103篇 |
1986年 | 75篇 |
1985年 | 77篇 |
1984年 | 98篇 |
1983年 | 27篇 |
1982年 | 53篇 |
1981年 | 74篇 |
1980年 | 60篇 |
1979年 | 54篇 |
1978年 | 39篇 |
1977年 | 27篇 |
1976年 | 21篇 |
1975年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
171.
Synthesis and herbicidal activity of O,O-dialkyl phenoxyacetoxyalkylphosphonates containing fluorine
Ting Chen 《Journal of fluorine chemistry》2006,127(2):291-295
A series of substituted phenoxyacetoxyalkylphosphonates bearing fluorine were designed and synthesized. All the new compounds were identified by elemental analysis, IR, 1H NMR and MS and were tested for herbicidal activity in greenhouse at a rate of 1.5 kg/ha. The results of preliminary bioassay showed that fluorine moiety introduced to the core structure could help to improve the herbicidal activity, and compounds with a 3-trifluoromethyl in benzene ring exhibited higher inhibitory activity. 相似文献
172.
Duygu Avci Aylin Ziylan Albayrak 《Journal of polymer science. Part A, Polymer chemistry》2003,41(14):2207-2217
Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003 相似文献
173.
174.
X. Y. Yang H. C. Gao X. L. Tan H. Z. Yuan G. Z. Cheng S. Z. Mao S. Zhao L. Zhang J. Y. An J. Y. Yu Y. R. Du 《Colloid and polymer science》2004,282(3):280-286
1H chemical shift changes of sodium 4-decyl naphthalene sulfonate (SDNS) at 313 K show that its critical micellar concentration lies between 0.82 and 0.92 mmol/dm3, which is in the same range as that of the previous study at 298 K. The spin–lattice relaxation time, spin–spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy experiments give information about the structure of the SDNS micelle and the dynamics of the molecules in the micelle. The size of the SDNS micelle remains almost unchanged in the temperature range from 298 to 313 K as deduced by analyzing the self-diffusion coefficient. Special arrangement of the naphthyl rings of SDNS in the micelles affects the packing of these hydrophobic chains. The methylene groups of the alkyl chain nearest the naphthalene groups penetrate into the aromatic region, which results in a more tightly packed hydrophobic micellar core than that of sodium dodecyl sulfonate. 相似文献
175.
176.
《Magnetic resonance in chemistry : MRC》2003,41(12):975-982
The reaction of 2,4‐pentanedione ( 1 ) with (R)‐(—)‐2‐phenylglycine methyl ester ( 2 ), (R)‐(—)‐2‐phenylglycinol ( 3 ) and the proteinogenic amino acids (2S,3R)‐(—)‐2‐amino‐3‐hydroxybutyric acid (L ‐threonine) ( 4 ) and (R)‐(—)‐2‐amino‐3‐mercaptopropionic acid (L ‐cysteine) ( 5 ) methyl esters was investigated. The corresponding enamines 6 , 7 and 8 were isolated and characterized spectroscopically whereas 9 , which is unstable, was transformed in situ into 13 . Treatment of 7 , 8 and 9 with boron trifluoride etherate afforded the new [1,4]oxazepines 10 , 11 and [1,4]thiazepine ( 12 ) as their BF3O? salts. The structures of the enamines and their corresponding seven‐membered heterocycles were assessed by 1D and 2D NMR spectroscopy. Variable‐temperature experiments revealed different molecular mobility behavior among these heterocycles. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
177.
Reaction of diethoxyphosphorylimine of methyl trifluoropyruvate with 1,3-C,N-and-N,N-binucleophiles led to a variety of N-phosphorylated fluorine-containing heterocycles, including the fused ones.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2176–2178, November, 2007. 相似文献
178.
Three-dimensional (3-D) ZnO random-wall nanostructures and one-dimensional (1-D) ZnO nanorods were prepared on silicon substrates by a simple solid-vapour phase thermal sublimation technique. Optical pumped random lasing has been observed in the ZnO random-wall arrays with a threshold intensity of 0.38 MW/cm2 in the emission wavelength from 380 to 395 nm. The optical gain was attributed to the closed-loop scattering and light amplification of the ZnO random-wall. The experimental result suggests that the morphology of nanostructure is the key factor to effect random lasing. 相似文献
179.
O. Maksimov P. Fisher M. Skowronski P.A. Salvador M. Snyder J. Xu X. Weng 《Journal of Crystal Growth》2008,310(11):2760-2766
MgO films were grown on (0 0 1) yttria-stabilized zirconia (YSZ) substrates by molecular beam epitaxy (MBE). The crystalline structures of these films were investigated using X-ray diffraction and transmission electron microscopy. Growth temperature was varied from 350 to 550 °C, with crystalline quality being improved at higher temperatures. The MgO films had a domain structure: (1 1 1)[1 1 2¯]MgO(0 0 1)[1 0 0]YSZ with four twin variants related by a 90° in-plane rotation about the [1 1 1]MgO axis. The observed epitaxial orientation was compared to previous reports of films grown by pulsed laser deposition and sputtering and explained as resulting in the lowest interface energy. 相似文献
180.
文献[1]引入一类具有广泛应用前景的随机过程-Markov骨架过程。借助Markov骨架过程的方法研究GI/G/1单重休假服务系统队长,及t时刻到达顾客等待时间的瞬时概率分布。 相似文献