全文获取类型
收费全文 | 1340篇 |
免费 | 282篇 |
国内免费 | 203篇 |
专业分类
化学 | 859篇 |
晶体学 | 27篇 |
力学 | 137篇 |
综合类 | 21篇 |
数学 | 166篇 |
物理学 | 615篇 |
出版年
2024年 | 11篇 |
2023年 | 32篇 |
2022年 | 56篇 |
2021年 | 47篇 |
2020年 | 66篇 |
2019年 | 69篇 |
2018年 | 51篇 |
2017年 | 60篇 |
2016年 | 58篇 |
2015年 | 89篇 |
2014年 | 77篇 |
2013年 | 100篇 |
2012年 | 122篇 |
2011年 | 131篇 |
2010年 | 80篇 |
2009年 | 100篇 |
2008年 | 97篇 |
2007年 | 72篇 |
2006年 | 81篇 |
2005年 | 64篇 |
2004年 | 79篇 |
2003年 | 60篇 |
2002年 | 52篇 |
2001年 | 29篇 |
2000年 | 35篇 |
1999年 | 25篇 |
1998年 | 12篇 |
1997年 | 20篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1971年 | 1篇 |
排序方式: 共有1825条查询结果,搜索用时 15 毫秒
41.
Qing Yan Li Hong Liang Hu Biao Chen Bin Wang Yu Ying Zhao 《中国化学快报》2007,18(7):843-845
One new cucurbitane-type triterpenoid saponin, 5b,19-epoxycucurbita-6,23-diene-3b,19,25-triol-3-O-b-D-allopyranoside (1), named momordicoside P was isolated from the fresh fruits of Momordica charantia. The structure of the saponin was elucidated byspectral methods, including 2D-NMR spectra. 相似文献
42.
Treatment of phenyl 2,3-O-cyclic ketene acetal- and 2,3-O-thionocarbonyl-1-thio-mannopyranosides with TMSOTf and MeOTf, respectively, gave the corresponding 2,3-O-cyclic dioxonium intermediates, which proceeded via 1→2 migration and concurrent glycosidation in the presence of alcohols to provide the corresponding 2-S-phenyl glycosides stereoselectively. While the former donors were too labile, the latter donors have proved superior for the present purpose. The X-ray crystallographic structures of phenyl 4-O-methyl-2,3-O-thiocarbonyl-1-thio-α-l-rhamnopyranoside (1), a typical donor for the present reaction, and its anomeric azide analogue (6), which could not undergo the present reaction under similar conditions, are provided. 相似文献
43.
Sulfonylation of alkenes through photoredox‐catalyzed functionalization of alkenes with thiourea dioxide under visible‐light irradiation is achieved. The reaction of alkenes, thiourea dioxide and electrophiles provides a green and efficient access to alkyl sulfones and sulfonamides. A broad reaction scope is presented with good functional group compatibility and excellent regioselectivity. A plausible mechanism involving a radical addition process with sulfur dioxide radical anion (SO2‐) derived from the oxidation of sulfur dioxide anion (SO22–) is proposed, which is supported by fluorescence quenching experiments. 相似文献
44.
[carbohydrate structure: see text] The beta-p-methoxyphenol hexadeoxysaccharide fragment of landomycin A was synthesized in a total of 33 steps and 0.5% overall yield starting from D-mannose and D-xylose, featuring the use of phenyl 2,3-O-thionocarbonyl-1-thioglycosides as 2-deoxy-beta-glycoside precursors. 相似文献
45.
皂甙的三维定量构效关系研究 总被引:7,自引:0,他引:7
针对目标分子柔性大的特点,在比较分子场分析(CoMFA)方法中采用交叉验证相关系数平方R^2引导的构象选择法。对12个皂甙分子的生物活性进行了三维定量构效关系研究。探讨了几种探针对构效关系结果的影响,并选择了一种较合理的“复合”探针方案。应用该复合探针构建CoMFA模型,发现影响药效的立体场与静电场的贡献分别为40%和40%,其它能量项的贡献为20%。该模型交叉验证的相关系数平方R^2为0.653,非交叉验证的R^2为0.991,方差比F(4,7)值130.195(即置信度99%以上),活性预计的标准偏差与极差比(s/△γ)为4.2%,表明模型具有较好的预测能力。根据该模型,预计在指定位置添加位阻较大的基团活性值提高将会比较明显。 相似文献
46.
47.
Straight-chain aliphatic terr-amine N-oxides were found to be useful oxidizing agent for epoxidation of tri- and tetra-substituted perfluoroalkenes under mild conditions in high yields.The process for epoxidation by employing tri-n-butylamine N-oxide gave the best result in the reagent survey. 相似文献
48.
The enhanced biological activities of three Zn (II) complexes based on different 1,2,4‐triazole fungicides 下载免费PDF全文
Guo‐yu Ren Jie Li Xu‐zhan Wei Jin‐hua Zhou Biao Yan Zhao‐qi Guo Ying‐hui Ren Xiao‐hong Sun Hai‐xia Ma 《应用有机金属化学》2018,32(9)
In order to screen effective fungicides, three Zn (II) complexes, [Zn L 1 4 (NO3)2]·2H2O·2EtOH ( 1 ), [Zn L 2 4 (NO3)2] ( 2 ), and [Zn L 3 4 (DMF)2](NO3)2 ( 3 ), ( L 1 = paclobutrazol, L 2 = diniconazole, and L 3 = hexaconazole), were synthesized and characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal XRD. The antifungal activities of these complexes were then evaluated against four selected fungi using the mycelial growth rate method. The resulting data indicate that all the complexes show the enhanced antifungal activities than the corresponding ligand and mixtures. And, the interactions between the metal salt and ligands in the three complexes seem to be synergistic. According to the study of the influence of the structures on the activity, complex 2 with C=C linkage and 2,4‐dichlorophenyl moieties enhances the bioactivity significantly, especially against Wheat gibberellic ( II ). Density functional theory (DFT) calculations were carried out to help explain the enhanced bioactivity of the Zn (II) complexes. Meanwhile, all complexes are excellent grow‐regulators, especially complex 3 . The resulting data show that the complexes based on triazole fungicides have the potential applications in agriculture. 相似文献
49.
A unique ultrafine full-vulcanized powdered ethyl acrylate rubber (EA-UFPR) was used as the toughening modifier for poly (lactic acid) (PLA). Largely improved tensile toughness was successfully achieved with the incorporation of only 1 wt% EA-UFPR, while the tensile strength and modulus of the blends were almost the same as pure PLA. The highly efficient toughening of PLA by UFPR is mainly ascribed to the strong interfacial interaction between PLA and UFPR and good dispersion of UFPR particles in PLA matrix. Our work provides an effective toughening method to largely improve the mechanical properties of PLA without sacrificing its stiffness, which is very important for the wide application of PLA materials. 相似文献
50.
Biao Ma Peng Wu Xing Wang Zhengyu Wang Hai‐Xia Lin Hui‐Xiong Dai 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(38):13469-13473
A rhodium(III)‐catalyzed domino annulation of simple olefins with diazo oxindoles to give spirooxindole pyrrolone products is described. This reaction can be formally viewed as the result of an anomalous tandem C?H activation, carbene insertion, Lossen rearrangement, and a nucleophilic addition process. The potential utility of this reaction was further demonstrated by the late‐stage diversification of drug molecules. 相似文献