全文获取类型
收费全文 | 4931篇 |
免费 | 820篇 |
国内免费 | 548篇 |
专业分类
化学 | 3406篇 |
晶体学 | 46篇 |
力学 | 349篇 |
综合类 | 24篇 |
数学 | 623篇 |
物理学 | 1851篇 |
出版年
2024年 | 24篇 |
2023年 | 103篇 |
2022年 | 165篇 |
2021年 | 196篇 |
2020年 | 200篇 |
2019年 | 195篇 |
2018年 | 187篇 |
2017年 | 139篇 |
2016年 | 277篇 |
2015年 | 230篇 |
2014年 | 261篇 |
2013年 | 382篇 |
2012年 | 478篇 |
2011年 | 456篇 |
2010年 | 308篇 |
2009年 | 290篇 |
2008年 | 307篇 |
2007年 | 250篇 |
2006年 | 248篇 |
2005年 | 211篇 |
2004年 | 185篇 |
2003年 | 162篇 |
2002年 | 132篇 |
2001年 | 111篇 |
2000年 | 94篇 |
1999年 | 100篇 |
1998年 | 75篇 |
1997年 | 74篇 |
1996年 | 74篇 |
1995年 | 61篇 |
1994年 | 45篇 |
1993年 | 45篇 |
1992年 | 27篇 |
1991年 | 38篇 |
1990年 | 35篇 |
1989年 | 26篇 |
1988年 | 12篇 |
1987年 | 13篇 |
1986年 | 14篇 |
1985年 | 18篇 |
1984年 | 9篇 |
1983年 | 10篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1974年 | 2篇 |
1944年 | 4篇 |
1943年 | 1篇 |
1942年 | 3篇 |
1941年 | 1篇 |
1940年 | 1篇 |
排序方式: 共有6299条查询结果,搜索用时 12 毫秒
201.
Yongzhi Bai Changyu Li Jinghui Zhao Peihe Zheng Yali Li Yongqi Pan Yingping Wang 《Chromatographia》2013,76(11-12):635-642
A high yield method to extract alkaloids from Aconitum coreanum using pulsed electric field (PEF) was developed, and the optimized extraction method compared to the other four extraction methods, consisting of cold maceration extraction, percolation extraction, heat reflux extraction (HRE), and ultrasonic-assisted extraction (UE). The experimental factors of the extraction methods such as electric field intensity, pulse frequency and solid-to-solvent ratio were evaluated. The content of Guanfu base A (GFA) was quantified by liquid chromatography coupled with electrospray ionization tandem mass spectrometry. The results indicated that the highest yield of GFA was 3.94 mg g?1 by PEF with conditions of 20 kV cm?1 electric field intensity, 8 pulse, 1:12 solid-to-solvent ratio, and 90 % ethanol–water solution. Meanwhile, the extraction time of PEF was <1 min, which is much less than the HRE of 10 h and even the newly used technique UE of 40 min. Moreover, the results of PEF extraction method showed obvious advantages, with the highest efficiency (120 L h?1), the shortest extraction time (0.5–1 min), and the lowest energy costs, which could be applied in the industrial production of alkaloids from A. coreanum. Therefore, the application of the PEF extraction method is a promising and constructive method for extraction of GFA. 相似文献
202.
Xiaodong Xu Siwei FengYuanqi Zhu Han LiXiande Shen Chunhong ZhangJianwei Bai Lili Zhang 《European Polymer Journal》2013
The effects of Lewis acids, namely, rare earth metal trifluoromethanesulfonates, on the radical polymerization of (S)-N-(2-hydroxy-1-phenylethyl) methacrylamide were examined under various conditions. In the absence of Lewis acids, syndiotactic-rich polymers (r = 84%) were obtained, whereas in the presence of a catalytic amount of Lewis acids, the polymerization proceeded in an isotactic-specific manner (m up to 64%). Polymerization solvents strongly influenced the effect of the Lewis acids. The polymerization in n-butyl alcohol showed the highest isotactic selectivity, whereas the polymerization in DMSO showed no isotacticity-enhancing effect. Further increases in the Lewis acid concentration and the polymerization temperature did not produce clear effects on the tacticity of the polymers. The interaction between the monomer and Lewis acids was investigated, and the plausible mechanism of stereocontrol in the radical polymerization of (S)-HPEMA was analyzed based on the Lewis acid-monomer interaction. 相似文献
203.
Total synthesis of α-elvucitabine was achieved in 26% overall yield by a concise nine-step procedure starting from L-lyxose, with trimethylsilyl trifluoromethaneoulfonate (TMSOTf)–mediated stereocontrolled α-N-glycosidation and olefination through Barton–McCombie deoxygenation being the key steps, and the stereochemistry of the product was determined by nuclear Overhauser effect spectroscopy. 相似文献
204.
Binglian Bai Xiyue Mao Zhanhu Xi Jie Ma Xiaolong Lin Haitao Wang 《Liquid crystals》2013,40(2):214-221
Two series of dissymmetric hydrazide derivatives containing alkoxyazobenzene with nitro terminal group and octyloxy terminal group, N-4-alkoxyphenyl-N′-4-((4-nitrophenyl)azophenyl) benzohydrazide (Bn-NO2, n indicates the number of carbon atoms) and N-4-octyloxyphenyl-N′-4-((4-octyloxyphenyl)azophenyl) benzohydrazide (B8-B8), were designed and synthesised, and their liquid crystalline properties were investigated by means of differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. It was found that B8-B8 with octyloxy terminal chains displayed monolayer smectic C phase, whereas Bn-NO2 with nitro terminal group displayed SmAd phase, and intermolecular hydrogen bonding was confirmed as the driving force. In addition, the effect of hydrogen bonding, dipole–dipole interactions and steric hindrance effect on the liquid crystalline structures were also discussed. 相似文献
205.
Two series 3-armed dendritic molecules with their 1,3,5-tris(4-methyloxyphenyl) benzene or 2,4,6-tris(4- hydroxylphenyl)-1,3,5-s-triazine core and triphenylene derivative shells connected by soft hydrocarbon chains have been synthesised and fully characterised. Whether liquid crystal (LC) or photoluminescence materials have been tuned by changing the length of the soft chain and they have been studied by POM, DSC, XRD, UV-Vis and PL. The results show that all the new dendritic compounds display UV to blue fluorescence in solvents such as DCM, THF and acetone. The TC3 compound bearing 1,3,5-tris(4-hydroxylphenyl) benzene core exhibits LC property with rectangular columnar phase (Colr) on cooling. 相似文献
206.
Junling Bai Toshifumi Nakatani Yuuki Sasaki Sadanobu Inoue Nobuo Takahashi 《International journal of environmental analytical chemistry》2013,93(9):856-865
Effectiveness of Pd/Mg chemical modifier for the accurate direct determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry (GF-AAS) using slurry samples was evaluated. A calibration curve prepared by aqueous zinc standard solution with addition of Pd/Mg chemical modifier is used to determine the zinc concentration in the sediment. The accuracy of the proposed method was confirmed using Certified Reference Materials, NMIJ CRM 7303-a (lacustrine sediment) from National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, Japan, and MESS-3 (marine sediment) and PACS-2 (marine sediment) from National Research Council, Canada. The analytical results obtained by employing Pd/Mg modifier are in good agreement with the certified values of all the reference sediment materials. Although for NRC MESS-3 an accurate determination of zinc is achieved even without the chemical modifier, the use of Pd/Mg chemical modifier is recommended as it leads to establishment of a reliable and accurate direct analytical method. One quantitative analysis takes less than 15 minutes after we obtain dried sediment samples, which is several tens of times faster than conventional analytical methods using acid digested sample solutions. The detection limits are 0.13?µg?g?1 (213.9?nm) and 16?µg?g?1 (307.6?nm), respectively, in sediment samples, when 40?mg of dried powdered samples are suspended in 20?mL of 0.1?mol?L?1 nitric acid and a 10?µl portion of the slurry sample is measured. The precision of the proposed method is 8–15% (RSD). 相似文献
207.
Chuan Jie Cheng Quan Lei Fu Xiong Xiong Bai Shao Jin Liu Liang Shen Wu Qin Fan Hong Xia Li 《Chemical Papers》2013,67(3):336-341
A novel cationic gemini surfactant has been readily synthesised in 70 % total yield. The functional gemini surfactant can act both as an emulsifier and an atom transfer radical polymerisation (ATRP) initiator in mini-emulsion polymerisation of methyl methacrylate (MMA), in which no other emulsifier was required. 1-(Dimethylamino)dodecane (N,N-dimethyldodecylamine, DMDA) was found to be a good ligand in the activator generated by electron transfer (AGET) ATRP reaction. Kinetic studies indicated that the polymerisation featured controlled/living radical polymerisation. 相似文献
208.
Jian Fei Yang Xiu Fang Bian Mei Ling Yuan Yan Wen Bai Yang Liu Jun Peng Fan Xiao Qian Lu Kai Kai Song 《Journal of Sol-Gel Science and Technology》2013,67(2):362-367
The metallic glass/titanium dioxide powders (MG/TiO2) with enhanced photocatalytic oxidation activity were synthesized, which exhibit a higher efficiency in decolorizing methylene blue solutions (MB). Compared with the pure TiO2 and crystalline alloy/TiO2 (CA/TiO2) under the same circumstances, its degradation rate was 60 % and 30 % higher, respectively. Furthermore, compared with the CA/TiO2, the MG/TiO2 photocatalytic rate was three times faster when decolorizing MB. Considering the excellent intrinsic high-performance photocatalytic degradation under visible light irradiation, these novel powders were proven to have potential applications in water purification industry. 相似文献
209.
以高磺化度的侧链型磺化聚芳醚酮(S-SPAEK)和聚乙烯醇(PVA)为原料,通过溶液共混的方法在120℃下制备了PVA含量不同的S-SPAEK/PVA交联膜.红外光谱图表明S-SPAEK聚合物中的磺酸基团与PVA中的羟基反应生成酯键而形成共价交联.通过对交联膜的性能测试发现PVA的引入明显降低了膜的甲醇渗透系数,改善了膜的溶胀性,提高了膜的保水能力.S-SPAEK/PVA(85/15)交联膜水的脱附系数从S-SPAEK的3.1×10-8 cm2/s降低到2.9×10-9 cm2/s.在25℃和60℃时S-SPAEK/PVA(85/15)交联膜的甲醇渗透系数分别为2.6×10-7cm2/s和3.9×10-7cm2/s,明显低于相同温度下的纯S-SPAEK膜的8.1×10-7cm2/s与14.5×10-7cm2/s,而其质子传导率虽然有所下降,但是在25℃和80℃时分别达到了0.055 S/cm和0.083 S/cm,能够满足直接甲醇燃料电池(DMFCs)对质子交换膜的要求,有望在DMFCs中得到应用. 相似文献
210.
Chemical examination of the fermentation broth of the marine-derived bacterium Bacillus sp. resulted in the isolation of seven new amicoumacin-type isocoumarin derivatives, namely bacillcoumacins A–G (1–7), together with four known analogues. Their structures were elucidated on the basis of extensive spectroscopic analysis, while the absolute configurations of the new compounds were determined by CD, Mosher’s method, and chemical conversion. Compounds 7 and 9 showed inhibitory effects against the NO production induced by lipopolysaccharide (LPS) in mouse macrophage RAW 264.7 cells. 相似文献