全文获取类型
收费全文 | 18899篇 |
免费 | 3594篇 |
国内免费 | 3007篇 |
专业分类
化学 | 14442篇 |
晶体学 | 285篇 |
力学 | 1062篇 |
综合类 | 248篇 |
数学 | 2215篇 |
物理学 | 7248篇 |
出版年
2024年 | 44篇 |
2023年 | 366篇 |
2022年 | 535篇 |
2021年 | 758篇 |
2020年 | 882篇 |
2019年 | 815篇 |
2018年 | 682篇 |
2017年 | 734篇 |
2016年 | 973篇 |
2015年 | 1017篇 |
2014年 | 1213篇 |
2013年 | 1518篇 |
2012年 | 1803篇 |
2011年 | 1855篇 |
2010年 | 1377篇 |
2009年 | 1307篇 |
2008年 | 1420篇 |
2007年 | 1258篇 |
2006年 | 1184篇 |
2005年 | 920篇 |
2004年 | 733篇 |
2003年 | 532篇 |
2002年 | 539篇 |
2001年 | 424篇 |
2000年 | 359篇 |
1999年 | 336篇 |
1998年 | 300篇 |
1997年 | 262篇 |
1996年 | 224篇 |
1995年 | 203篇 |
1994年 | 171篇 |
1993年 | 158篇 |
1992年 | 117篇 |
1991年 | 104篇 |
1990年 | 98篇 |
1989年 | 67篇 |
1988年 | 50篇 |
1987年 | 42篇 |
1986年 | 28篇 |
1985年 | 36篇 |
1984年 | 13篇 |
1983年 | 12篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1975年 | 2篇 |
1959年 | 2篇 |
1936年 | 1篇 |
1916年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 500 毫秒
991.
An efficient and practical method for the synthesis of cyano, sulfonyl and phosphoryl substituted naphthalene derivatives via the rearrangement aromatization of benzo[c]oxepine has been developed. The system holds the advantages of metal catalysts free, and mild reaction conditions. 相似文献
992.
A direct DDQ-mediated dehydrogenative intramolecular cyclization of (Z)-1,2,3-triaryl substituted propylenes promoted by Cu(OAc)2 was developed, providing 1,2-diarylindene derivatives in moderate to good yields (up to 92%) under mild conditions. This protocol provides a straightforward access to 1,2-diarylindenes via DDQ-mediated benzylic/allylic sp3 C–H bond activation. 相似文献
993.
Feng-Peng Wang Dong-Lin Chen Hong-Ying Deng Qiao-Hong Chen Xiao-Yu Liu Xi-Xian Jian 《Tetrahedron》2014
We have corrected (Tetrahedron2013, 69, 5859–5866) the structures of diterpenoid alkaloids reported in the Journal of Natural Products2012, 75, 1145–1159. Our follow-up experiments compel us to present further revisions and clarifications on the diterpenoid alkaloids: 相似文献
994.
The NMR spin–spin scalar coupling constants (JHH's) of closely contacting, but non-bonded hydrogen atoms in a series of highly strained molecules (including a new in,in-cyclophane made specifically for this study) have been examined both experimentally and computationally. The experimental JHH's are invariably quite small (0.1–0.6 Hz), but common DFT methods with modest basis sets nearly always overestimate these values, by factors of 10–30, and even with quite large basis sets (up to cc-pVQZ) the JHH's of two of the molecules are overestimated by a factor of 10 or more. Possible reasons for these discrepancies are discussed. 相似文献
995.
Li-Xia Wang Ben-Quan Hu Jun-Feng Xiang Jie Cui Xiang Hao Tong-Ling Liang Ya-Lin Tang 《Tetrahedron》2014
Hydrogen bonding interaction as one type of non-covalent force has proven itself to be highly efficient for constructing structurally unique artificial secondary structures. Here, the structure of Naryl-substituted anthranilamide in solution is demonstrated by various NMR technique, the intramolecular hydrogen bonds between amide attached to arylamine of the same ring is proposed, which is supported by its crystal structure in the solid phase. The substituent on the nitrogen atom of arylamine plays an important role in forming the presence of intramolecular hydrogen bonds. The chemical shift of the Naryl-H downfield changes obviously, due to the formation of intramolecular hydrogen bonds and the deshielding effect of oxygen, and the neighboring C–H is activated and shows downfield protonic signal too. The presence of intramolecular hydrogen bonds probably provides the explanation for the transformation from Naryl-substituted anthranilamide to imine, which could be converted into 2-aryl quinazolinone finally. 相似文献
996.
A silver(I)-catalyzed reaction of 2-alkynylaryl aldimine with trimethyl(trifluoromethyl)silane is reported. This reaction proceeds efficiently under extremely mild conditions to generate 1-(trifluoromethyl)-1,2-dihydroisoquinolines in good yields. A three-component reaction of 2-alkynylbenzaldehyde, amine, with trimethyl(trifluoromethyl)silane is presented as well. 相似文献
997.
A convenient and regioselective one-pot synthesis of 3-chloride or 3-bromide quinoline derivatives was achieved through a Grignard addition reaction by alkynyl Grignard regent to o-trifluoroacetyl aniline and a Cu(II)-catalyzed cyclization–halogenation tandem reaction with aqueous HCl or HBr as electrophilic reagent. 相似文献
998.
Yiwei Li Raymond Seekell Jie Cao Jing Jing 《Journal of Dispersion Science and Technology》2014,35(5):672-676
In this article, positively charged GVs were electroformed in a binary system of quaternary ammonium salts and egg phosphatidylcholine (EggPC) under an alternative current (AC) electric field. The diameter and charge density of the GVs is controlled by doping suitable cationic quaternary ammonium molecules into the EggPC bilayer. By developing positively charged GVs, there will be expanded the applications for phospholipids vesicles, especially the investigation of charge-induced interactions between cationic lipid membranes and macromolecules, such as colloidal particles or proteins. 相似文献
999.
Characterization of radioactive cobalt on graphene oxide by macroscopic and spectroscopic techniques
Zhongxiu Jin Jie Sheng Yubing Sun 《Journal of Radioanalytical and Nuclear Chemistry》2014,299(3):1979-1986
Graphene oxide (GO) was synthesized using the modified Hummers method and characterized by XRD and FTIR. The sorption of 60Co(II) on GO as a function of contact time, pH, polyacrylic acid, ionic strength, temperature and solution concentration was studied by batch technique. The sorption kinetics indicated that the sorption of 60Co(II) on GO could be simulated by the pseudo-second-order model very well. The maximum sorption capacities of GO for 60Co(II) calculated from Langmuir model at pH 6.40 and T = 300 K was ~62.0 mg/g. The thermodynamic parameters from the temperature-dependent sorption isotherms indicated that the 60Co(II) sorption on GO was an endothermic and spontaneous process. The interaction mechanism between GO and Co(II) were outer-sphere surface complexation or ion exchange at pH <7, whereas the inner-sphere surface complexation was observed at pH 7–9 in terms of the analysis of XPS spectra. 相似文献
1000.
Jian Deng Kaihui Huang Lin An Canhui Hu Saiqin Ju Ni Xiao 《Journal of Radioanalytical and Nuclear Chemistry》2014,300(2):835-842
In this work, a new method has been proposed to simultaneously determine V(V), Co(II) and Cu(II) ions from aqueous solution by spectrophotometry after cloud point extraction using partial least squares regression (PLS). The metal ions in 10 ml of aqueous solution (containing 0.2 M sodium acetate buffer solution, pH 3.5) were formed complexes with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP). Then, Triton X-114 (2 %, v/v) was added to the solution. By increasing the temperature of the solution up to 55 °C, a phase separation occurred. After centrifugation at 3,000 rpm for 10 min, the surfactant-rich phase was dissolved and diluted to 0.5 mL with ethanol. The metal ions were then determined using spectrophotometry. At these optimal extraction and operating conditions, linearity was obeyed in the range 7–300, 3–100 and 15–700 ng mL?1 of V(V), Co(II) and Cu(II), with the detection limit of 2.2, 1.0 and 4.5 ng mL?1, respectively. The relative predictive error for the simultaneous determination of 15 test samples of different concentrations of V(V), Co(II) and Cu(II) was 3.28, 3.64 and 4.04 %, respectively. The root mean square error of prediction for applying the PLS method to 15 synthetic samples in the linear ranges of these metal ions was 3.4, 1.6 and 18.1 ng mL?1. The interference effect of some anions and cations was also tested. The proposed method has been applied successfully to the simultaneous determination of V(V), Co(II) and Cu(II) ions in real matrix samples with the recoveries of 96.75–104.80 %. 相似文献