首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   2658篇
  免费   299篇
  国内免费   165篇
化学   2012篇
晶体学   26篇
力学   114篇
综合类   2篇
数学   261篇
物理学   707篇
  2024年   10篇
  2023年   97篇
  2022年   195篇
  2021年   142篇
  2020年   168篇
  2019年   179篇
  2018年   162篇
  2017年   110篇
  2016年   174篇
  2015年   167篇
  2014年   191篇
  2013年   235篇
  2012年   274篇
  2011年   255篇
  2010年   169篇
  2009年   132篇
  2008年   142篇
  2007年   115篇
  2006年   61篇
  2005年   38篇
  2004年   20篇
  2003年   13篇
  2002年   19篇
  2001年   6篇
  2000年   15篇
  1999年   4篇
  1998年   9篇
  1997年   2篇
  1996年   2篇
  1995年   2篇
  1993年   2篇
  1991年   1篇
  1990年   6篇
  1987年   2篇
  1986年   1篇
  1985年   2篇
排序方式: 共有3122条查询结果,搜索用时 31 毫秒
941.
For chiral gels and related applications, one of the critical issues is how to modulate the stereoselective interaction between the gel and the chiral guest precisely, as well as how to translate this information into the macroscopic properties of materials. Herein, we report that this process can also be modulated by nonchiral solvents, which can induce a chiral‐interaction reversion for organogel formation. This process could be observed through the clear difference in gelation speed and the morphology of the resulting self‐assembly. This chiral effect was successfully applied in the selective separation of quinine enantiomers and imparts “smart” merits to the gel materials.  相似文献   
942.
Biologically significant clavilactones A, B, and the previously proposed D have been synthesized through iron‐catalyzed carbonylation–peroxidation of a 1,5‐diene. Three steps from aldehydes, alkenes, and tert‐butylhydroperoxide build up α,β‐epoxy‐γ‐butyrolactone skeleton as a key building block for synthesis of clavilactone family and its derivatives. Based on our results, the structure of the proposed clavilactone D is not correct and requires revision.  相似文献   
943.
Monodispersed mesoporous phenolic polymer nanospheres with uniform diameters were prepared and used as the core for the further growth of core–shell mesoporous nanorattles. The hierarchical mesoporous nanospheres have a uniform diameter of 200 nm and dual‐ordered mesopores of 3.1 and 5.8 nm. The hierarchical mesostructure and amphiphilicity of the hydrophobic carbon cores and hydrophilic silica shells lead to distinct benefits in multidrug combination therapy with cisplatin and paclitaxel for the treatment of human ovarian cancer, even drug‐resistant strains.  相似文献   
944.
In the field of oriented‐attachment crystal growth, one‐dimensional nanocrystals are frequently employed as building blocks to synthesize two‐dimensional or large‐aspect‐ratio one‐dimensional nanocrystals. Despite recent extensive experimental advances, the underlying inter‐particle interaction in the synthesis still remains elusive. In this report, using Ag as a platform, we investigate the van der Waals interactions associated with the side‐by‐side and end‐to‐end assemblies of one‐dimensional nanorods. The size, aspect ratio, and inter‐particle separation of the Ag precursor nanorods are found to have dramatically different impacts on the van der Waals interactions in the two types of assemblies. Our work facilitates the fundamental understanding of the oriented‐attachment assembling mechanism based on one‐dimensional nanocrystals.  相似文献   
945.
Four new charge‐neutral ruthenium(II) complexes containing dianionic Schiff base and isoquinoline or 4‐picoline ligands were synthesized and characterized by NMR and ESI‐MS spectroscopies, elemental analysis, and X‐ray diffraction. The complexes exhibited excellent chemical water oxidation activity and high stability under acidic conditions (pH 1.0) using (NH4)2Ce(NO3)6 as a sacrificial electron acceptor. The high catalytic activities of these complexes for water oxidation were sustained for more than 10 h at low concentrations. High turnover numbers of up to 3200 were achieved. A water nucleophilic attack mechanism was proposed. A RuV?O intermediate was detected during the catalytic cycle by high‐resolution mass spectrometry.  相似文献   
946.
A Lewis acid in the presence of an anionic phosphate ligand enables the addition of alkenes to α,β‐enones. The ligand facilitates selective β‐proton elimination by suppressing competing pathways, thus leading to vinylation adducts in high yields (up to 99 %) for a broad range of substrates.  相似文献   
947.
The chitosan-microparticles reinforced cellulose biocomposite sponges regenerated from ionic liquid were prepared and characterized. Fourier transform infrared (FTIR) spectroscopy confirmed that the cellulose dissolved in 1-allyl-3-methylimidazolium chloride without derivatization. Chitosan particles as reinforcement were incorporated into the cellulose matrix. FTIR spectra indicated hydrogen bonding between hydroxyl groups of cellulose and chitosan. The biocomposite sponges showed uniform three-dimensional interconnected porous structures. The breaking strength of the sponges increased significantly, from 0.09 to 0.32 MPa with the addition of 1.0 wt% chitosan. The sponges also demonstrated excellent antibacterial activity against S. aureus and E. coli with the average inhibition zone diameters >2 mm and the inhibition rate higher than 80 %. Furthermore, the biocomposite sponges exhibited good moisture penetrability and high porosity. The water uptake ability of the sponge was >25 times of its weight in water with a fast swelling. The chitosan/cellulose composite sponge is expected to be a promising material for potential applications as wound dressing.  相似文献   
948.
A novel hyphenated method based on ultrasound‐assisted dispersive liquid–liquid microextraction coupled to precolumn derivatization has been established for the simultaneous determination of bisphenol A, 4‐octylphenol, and 4‐nonylphenol by high‐performance liquid chromatography with fluorescence detection. Different parameters that influence microextraction and derivatization have been optimized. The quantitative linear range of analytes is 5.0–400.0 ng/L, and the correlation coefficients are more than 0.9998. Limits of detection for soft drinks and dairy products have been obtained in the range of 0.5–1.2 ng/kg and 0.01–0.04 μg/kg, respectively. Relative standard deviations of intra‐ and inter‐day precision for retention time and peak area are in the range of 0.47–2.31 and 2.76–8.79%, respectively. Accuracy is satisfactory in the range of 81.5–118.7%. Relative standard deviations of repeatability are in the range of 0.35–1.43 and 2.36–4.75% for retention time and peak area, respectively. Enrichment factors for bisphenol A, 4‐octylphenol, and 4‐nonylphenol are 170.5, 240.3, and 283.2, respectively. The results of recovery and matrix effect are in the range of 82.7–114.9 and 92.0–109.0%, respectively. The proposed method has been applied to the determination of bisphenol A, 4‐octylphenol, and 4‐nonylphenol in soft drinks and dairy products with much higher sensitivity than many other methods.  相似文献   
949.
Tl(I)in water even at a trace level is fatal to human beings and the ecosystem.Here we fabricated a new polymer-supported nanocomposite(HMO-001)for efficient Tl(I)removal by encapsulating nanosized hydrous manganese dioxide(HMO)within a polystyrene cation exchanger(D-001).The resultant HMO-001 exhibited more preferable removal of Tl(I)than D-001 and IRC-748,an iminodiacetic chelating polymer,particularly in the presence of competing Ca(II)ions at greater levels in solution.Such preference was ascribed to the Donnan membrane effect caused by D-001 as well as the specific interaction between Tl(I)and HMO.The adsorbed Tl(I)was partially oxidized into insoluble Tl(III)by HMO at acidic pH,while negligible oxidation was observed at circumneutral pH.The exhausted HMO-001 was amenable to efficient regeneration by binary NaOH-NaClO solution for at least 10-cycle batch runs without any significant capacity loss.Fixed-bed column test of Tl(I)-contained industrial effluent and natural water further validated that Tl(I)retention on HMO-001 resulted in a conspicuous concentration drop from 1.3 mg/L to a value lower than 0.14 mg/L(maximum concentration level for industrial effluent regulated by US EPA)and from 1–4?g/L to a value lower than 0.1?g/L(drinking water standard regulated by China Health Ministry),respectively.  相似文献   
950.
Hexagonal β-Co(OH)2 nanosheets with edge length of 50 nm and thickness of 10 nm were hydrothermally synthesized with the aid of triethylamine.Upon calcination at 350°C in air,the β-Co(OH)2 nanosheets was converted into Co3O4 nanosheets with a similar dimension.Structural analyses during the calcination process identified that the β-Co(OH)2 precursor was initially dehydrated to HCoO2 and subsequently transferred into Co3O4.When being applied to catalyze CO oxidation at room temperature,the Co3O4 nanosheets exhibited a higher activity than the conventional spherical nanoparticles.This was perhaps related to the partial exposure of the{112}planes over the Co3O4 nanosheets.The porous structure generated during the calcination process also provided significant amounts of surface defects,which might contribute to the enhanced catalytic activity as well.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号