全文获取类型
收费全文 | 1951篇 |
免费 | 269篇 |
国内免费 | 142篇 |
专业分类
化学 | 1510篇 |
晶体学 | 22篇 |
力学 | 68篇 |
综合类 | 8篇 |
数学 | 191篇 |
物理学 | 563篇 |
出版年
2023年 | 31篇 |
2022年 | 48篇 |
2021年 | 48篇 |
2020年 | 51篇 |
2019年 | 78篇 |
2018年 | 67篇 |
2017年 | 48篇 |
2016年 | 80篇 |
2015年 | 93篇 |
2014年 | 104篇 |
2013年 | 146篇 |
2012年 | 173篇 |
2011年 | 186篇 |
2010年 | 123篇 |
2009年 | 95篇 |
2008年 | 135篇 |
2007年 | 115篇 |
2006年 | 130篇 |
2005年 | 103篇 |
2004年 | 89篇 |
2003年 | 59篇 |
2002年 | 65篇 |
2001年 | 23篇 |
2000年 | 21篇 |
1999年 | 36篇 |
1998年 | 21篇 |
1997年 | 25篇 |
1996年 | 32篇 |
1995年 | 11篇 |
1994年 | 11篇 |
1993年 | 10篇 |
1992年 | 13篇 |
1991年 | 8篇 |
1990年 | 10篇 |
1989年 | 6篇 |
1988年 | 8篇 |
1987年 | 8篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1974年 | 3篇 |
1969年 | 2篇 |
1968年 | 2篇 |
1962年 | 1篇 |
1960年 | 1篇 |
1938年 | 1篇 |
排序方式: 共有2362条查询结果,搜索用时 31 毫秒
31.
[reaction: see text] We have investigated the olefin metathesis from alkenyl Baylis-Hillman adducts using second-generation Grubbs catalyst. In the experiment, the ring-closing metathesis (RCM) product could not be found, while the cross-metathesis (CM) products were found. The computational studies provided consistent explanations for the experimental result. The most limiting factor for the RCM process using second-generation Grubbs catalyst is caused by the high strain and steric effect in the metallacyclobutane intermediates. 相似文献
32.
Polyacrylamide (PAL) was physically adsorbed onto a hydroxylated silicon surface to form a uniform PAL film and the up-top PAL thin film was treated by nitrogen (N2) plasma for surface modification. The atomic composition of the modified surface of the PAL film adsorbed on silicon substrate was analyzed with Fourier Transform Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The surface energy of PAL film was calculated from the data of contact angle of three-probe liquid. The FTIR results show an increase of peak intensity at 1214 cm−1 (NH2 stretch vibration) after the nitrogen plasma treatment, which confirms that the nitrogen was grafted to the PAL surface in the process of N2-plasma treatment. The XPS results show that the ratio of relative intensity of N1s to O1s increases with increasing the plasma treatment time, which further affirms the formation of the amine groups on the PAL surface after the nitrogen plasma treatment. The surface tension increases with increasing the plasma grafting time. However, the surface energy decreases rapidly at the early stage when stored in air and approaches to an equilibrium value. It suggests that some physically-adsorbed ions and alkyl radicals on PAL surface can rapidly lose their activities. The increase of the surface tension of the plasma treated PLA films is due to the amine groups covalently grafted to PAL surface. 相似文献
33.
用ICP-AES法测定了东太平洋深海锰结核样品中二十多种主,次及微量元素,结果表明,表面瘤状和表面光滑两种类型锰结核的化学元素含量有较明显的区别,如表面光滑的锰结核TiO2含较高,而表面瘤状的锰结核Mn/Fe之值较高等。 相似文献
34.
Mi Jung Lee 《Tetrahedron》2006,62(13):3128-3136
A new and regioselective [4+2] benzannulation protocol toward polysubstituted benzenes was developed. A nitroalkane derivative, which was prepared from Baylis-Hillman adduct, served as the four-carbon unit and a Michael acceptor as a two-carbon unit. Vinyltriphenylphosphonium salt could also be used as a Michael acceptor efficiently. 相似文献
35.
Annaraj J Suh Y Seo MS Kim SO Nam W 《Chemical communications (Cambridge, England)》2005,(36):4529-4531
A mononuclear nonheme ferric-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [(TMC)Fe(III)-O2]+, was prepared and used in mechanistic studies of aldehyde deformylation; a catalytic aldehyde deformylation by a nonheme iron(II) complex, [Fe(II)(TMC)]2+, and molecular oxygen is reported as well. 相似文献
36.
There is a need for a better characterization of sludges from wastewater treatment plants which are destined to be spread on agricultural lands. Inorganic pollutants are regularly controlled but organic pollutants have received few attention up to now. On this paper, we have been interested on the analysis of the 16 polycyclic aromatic hydrocarbons (PAHs) listed in the US Environmental Protection Agency (US EPA) priority list and more particularly of the six PAHs listed in the European community list (fluoranthene, benzo[b and k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene). The analysis step consists on liquid chromatography with both fluorescence and UV detections as described in the EPA Method 8310. As for the extraction step, several techniques such as supercritical fluid extraction, pressurized liquid extraction, focused microwave extraction in open vessels, Soxhlet and ultrasonic extractions are compared after optimization of the experimental conditions (solvent nature and quantity, temperature, pressure, duration, ... ) and validation with certified sludges. When optimized, these five extraction techniques are as much efficient with similar relative standard deviation. Whatever the extraction techniques used, the whole analysis protocol permits to quantify PAHs in the range of 0.09 to 0.9 mg/kg of dried sludges. 相似文献
37.
38.
为提高小檗碱的水溶性以及降糖活性,对其C-9位进行了结构修饰,合成了6个9-O-小檗碱酯类衍生物(3a~3f),其中3b~3d和3f为新化合物,其结构经1H NMR, IR和HR-MS(ESI)表征。选用人肝癌细胞(HepG2)建立胰岛素抵抗模型(HepG2-IR),通过MTT法研究了3a~3f的体外降糖活性。结果表明:3a~3f均具有不同程度的降糖活性,其中化合物3a(IC50=0.044 ±0.97 mg·L-1)在低浓度0.08 mg·L-1时,对HepG2-IR细胞葡萄糖消耗量为3.5 mM,优于小檗碱(2.75 mM)。 相似文献
39.
Kang EJ Cho EJ Ji MK Lee YE Shin DM Choi SY Chung YK Kim JS Kim HJ Lee SG Lah MS Lee E 《The Journal of organic chemistry》2005,70(16):6321-6329
(+)-SCH 351448 (Na+ salt A) was synthesized employing ring-closing olefin metathesis reaction of an open diene diester intermediate for construction of the 28-membered macrodiolide structure. The open diene diester was prepared from the monomeric hydroxy carboxylic acid and two different olefin fragments. The monomeric hydroxy acid was synthesized via Julia-Julia coupling reaction of intermediates derived from the same olefinic fragments. Oxane units in these fragments were prepared by radical cyclization reactions of beta-alkoxyacrylates. Analogous SCH 351448 salts incorporating other mono- and divalent cations may be prepared. Under acidic conditions, SCH 351448 (Na+ salt A) was the most stable complex, but SCH 351448 (Ca2+ salt) and (Na+ salt B) appear to be physiologically important species. 相似文献
40.
A new synthetic route for biologically interesting benzochromenes was developed starting from naphthalenols and α,β‐unsaturated aldehydes in the presence of ethylenediamine diacetate. This methodology was applied for the total synthesis of the biologically important natural products lapachenole, dihydrolapachenole, and mollugin with a benzochromene moiety. 相似文献