全文获取类型
收费全文 | 5176篇 |
免费 | 804篇 |
国内免费 | 570篇 |
专业分类
化学 | 3497篇 |
晶体学 | 48篇 |
力学 | 368篇 |
综合类 | 32篇 |
数学 | 683篇 |
物理学 | 1922篇 |
出版年
2024年 | 27篇 |
2023年 | 105篇 |
2022年 | 169篇 |
2021年 | 212篇 |
2020年 | 209篇 |
2019年 | 199篇 |
2018年 | 189篇 |
2017年 | 142篇 |
2016年 | 286篇 |
2015年 | 236篇 |
2014年 | 265篇 |
2013年 | 397篇 |
2012年 | 497篇 |
2011年 | 482篇 |
2010年 | 326篇 |
2009年 | 302篇 |
2008年 | 320篇 |
2007年 | 257篇 |
2006年 | 251篇 |
2005年 | 218篇 |
2004年 | 191篇 |
2003年 | 162篇 |
2002年 | 138篇 |
2001年 | 113篇 |
2000年 | 97篇 |
1999年 | 113篇 |
1998年 | 81篇 |
1997年 | 81篇 |
1996年 | 80篇 |
1995年 | 64篇 |
1994年 | 52篇 |
1993年 | 47篇 |
1992年 | 30篇 |
1991年 | 39篇 |
1990年 | 37篇 |
1989年 | 28篇 |
1988年 | 13篇 |
1987年 | 12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6550条查询结果,搜索用时 0 毫秒
91.
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
92.
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
93.
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
94.
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
95.
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
96.
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
97.
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
98.
Long Tang Liang Bai Yaping Duan Wei Xia Wenwen Dong Dongsheng Li 《无机化学与普通化学杂志》2014,640(11):2268-2273
Three ZnII and CdII complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L1)(2,2′‐bpy)2(H2O)] · 2H2O ( 1 ), [Zn(L1)(bpp)(H2O)] ( 2 ), and [Cd(L1)(H2O)] · H2O ( 3 ) [H2L1 = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.82). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated. 相似文献
99.
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
100.
Rapid separation and characterization of diterpenoid alkaloids in processed roots of Aconitum carmichaeli using ultra high performance liquid chromatography coupled with hybrid linear ion trap‐Orbitrap tandem mass spectrometry 下载免费PDF全文
Jing Zhang Dayuan Zhu Juan Huang Zhihai Huang Junqi Bai Xiaohui Qiu 《Journal of separation science》2014,37(20):2864-2873
The lateral root of Aconitum carmichaeli, a popular traditional Chinese medicine, has been widely used to treat rheumatic diseases. For decades, diterpenoid alkaloids have dominated the phytochemical and biomedical research on this plant. In this study, a rapid and sensitive method based on ultra high performance liquid chromatography coupled with linear ion trap‐Orbitrap tandem mass spectrometry was developed to characterize the diterpenoid alkaloids in Aconitum carmichaeli. Based on an optimized chromatographic condition, more than 120 diterpenoid alkaloids were separated with good resolution. Using a systematic strategy that combines high resolution separation, highly accurate mass measurements and a good understanding of the diagnostic fragment‐based fragmentation patterns, these diterpenoid alkaloids were identified or tentatively identified. The identification of these chemicals provided essential data for further phytochemical studies and toxicity research of Aconitum carmichaeli. Moreover, the ultra high performance liquid chromatography with linear ion trap‐Orbitrap mass spectrometry platform was an effective and accurate tool for rapid qualitative analysis of secondary metabolite productions from natural resources. 相似文献