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   1828篇
  免费   144篇
  国内免费   108篇
化学   1171篇
晶体学   24篇
力学   82篇
综合类   8篇
数学   386篇
物理学   409篇
  2023年   29篇
  2022年   69篇
  2021年   65篇
  2020年   61篇
  2019年   70篇
  2018年   64篇
  2017年   61篇
  2016年   99篇
  2015年   81篇
  2014年   95篇
  2013年   127篇
  2012年   119篇
  2011年   141篇
  2010年   89篇
  2009年   71篇
  2008年   86篇
  2007年   74篇
  2006年   79篇
  2005年   69篇
  2004年   49篇
  2003年   32篇
  2002年   33篇
  2001年   20篇
  2000年   27篇
  1999年   23篇
  1998年   16篇
  1997年   22篇
  1996年   26篇
  1995年   28篇
  1994年   18篇
  1993年   16篇
  1992年   21篇
  1991年   20篇
  1990年   11篇
  1989年   5篇
  1987年   9篇
  1986年   10篇
  1985年   15篇
  1984年   14篇
  1983年   11篇
  1982年   9篇
  1981年   12篇
  1980年   8篇
  1979年   4篇
  1978年   10篇
  1977年   12篇
  1976年   10篇
  1975年   8篇
  1974年   8篇
  1973年   10篇
排序方式: 共有2080条查询结果,搜索用时 0 毫秒
961.
Qun Dang  Yan Liu 《Tetrahedron letters》2009,50(49):6758-6760
Furo[2,3-d]pyrimidines were readily prepared via an inverse electron demand Diels–Alder (IDA) reaction between 2-aminofurans and 1,3,5-triazines. 2-Aminofurans proved to be productive dienophiles leading to the IDA product in moderate to good yields. This study further expanded the scope of 1,3,5-triazine IDA reactions with five-membered aromatic heterocycles as dienophiles.  相似文献   
962.
大分子单体通过两种可控聚合方法, 即开环易位聚合(ROMP)和原子转移自由基聚合(ATRP)的联用, 合成一种新型两亲性接枝聚合物刷. 具有高环张力的降冰片烯单侧链大分子单体norbornene-graft-poly(ε-caprolactone)/Br (PCL- NBE-Br)首先进行ROMP反应, 生成聚合物主链, 每个单体单元上含有一条PCL链和一个溴官能团; 然后用含溴的ROMP聚合物poly(norbornene)-graft-poly(ε-caprolactone)/Br (PCL-PNBE-Br)作为大分子引发剂引发单体2-(dimethyl- amino)ethyl methacrylate)的ATRP反应, 生成结构明确的高密度两亲性接枝聚合物刷poly(norbornene)-graft-poly(ε- caprolactone)/poly(2-(dimethylamino)ethyl methacrylate) (PCL-PNBE-PDMAEMA), 其主链每个单体单元上均含有一条疏水性PCL接枝链和一条亲水性PDMAEMA接枝链. 最后, 研究此类高密度两亲性接枝聚合物刷的自组装行为, 用动态激光光散射(DLS)研究其在混合溶剂(THF/H2O)中的胶束行为, 考察胶束溶液的浓度以及不同长度的亲水性接枝链对胶束尺寸的影响; 利用透射电镜(TEM)观察胶束为球形, 具有类似线团或草莓状的形态.  相似文献   
963.
The impacts of membrane degradation due to chlorine attack on the rejection of pharmaceutically active compounds (PhACs) by nanofiltration and reverse osmosis membranes were investigated in this study. Membrane degradation was simulated by soaking the membranes in a sodium hypochlorite solution of various concentrations over 18 h. Changes in membrane surface properties were characterised by contact angle measurement, atomic force microscopy analysis, and streaming potential measurement. The impacts of hypochlorite exposure to the membrane separation processes were ascertained by comparing the rejection of PhACs by virgin and chlorine-exposed membranes. Overall, the reverse osmosis BW30 membrane and the tight nanofiltration NF90 membrane were much more resilient to chlorine exposure than the larger pore size TFC-SR2 and NF270 nanofiltration membranes. In fact, rejection of all three PhACs selected in this study by the BW30 remained largely unchanged after hypochlorite exposure and further characterisation did not reveal any evidence of compromised separation capability. In contrast, the effects of chlorine exposure to the two loose nanofiltration membranes were quite profound. While chlorine exposure generally resulted in reduced rejection of PhACs, a small increase in rejection was observed when a more dilute hypochlorite solution was used. Changes in the membrane surface morphology as well as observed rejection of inorganic salts and PhACs were found to be consistent with mechanisms of chlorine oxidation of polyamide membranes reported in the literature. Chlorine oxidation consistently resulted in a more negative zeta potential of all four membranes investigated in this study. Conformational alterations of the membrane polyamide active skin layer were also evident as reflected by changes in surface roughness before and after chlorine exposure. Such alterations can either loosen or tighten the effective membrane pore size, leading to either a decrease or an increase in rejection. Both of these phenomena were observed in this study, although the decrease in the rejection of PhACs was overwhelming from exposure to highly concentrated hypochlorite solution.  相似文献   
964.
We investigate the solvation structure of aqueous potassium ions, using a combination of electronic structure calculations, statistical mechanical simulations with a derived polarizable empirical potential and experimental measurement of the extended X-ray absorption fine structure (EXAFS) spectra. The potassium K-edge (at 3,608 eV) EXAFS spectra were acquired on the bending magnet of sector 20 at the Advanced Photon Source, at ambient conditions and for the concentrations of 1 and 4 m KCl. We focus on the coordination distances and the degree of disorder of the first hydration shell as determined by electronic structure calculations, molecular dynamics simulations and experimental measurement. Finally, we characterize the changes of the structure in the first hydration shell with increasing temperature as predicted by molecular simulation  相似文献   
965.
Four new (1-4) and seven known (5-11) benzaldehyde derivatives were characterized from the liquid fermentation cultures of Eurotium rubrum, an endophytic fungus that was isolated from the inner tissue of stems of the mangrove plant Hibiscus tiliaceus. The structures of these compounds were determined by extensive analysis of their spectroscopic data. Among these metabolites, compound 1, which was named as eurotirumin, possesses a new carbon skeleton with a cyclopentabenzopyran ring system.  相似文献   
966.
Abstract

Cardanol-formaldehyde resin (CF) and cardanol glycidylether (CGE) have been synthesized for reinforcing natural rubber (NR), a blend of NR and styrene-butadiene rubber (SBR), and nitrile-butadiene rubber (NBR). The novolac CF resin reinforced the NR, SBR, and NBR. The resolic CF is not only a reinforcing agent but also a hardener (crosslinking agent) for NBR by means of the methylol groups of CF with the CN- group of NBR. The CGE resin was synthesized by the epoxidation of cardanol by epichlorohydrin; it could be used as a reinforcing agent for NR and for crosslinking maleinized NR. The results of estimates of the physical properties of the vulcanisate, their DSC diagrams, and SEM showed the enhanced properties of the final products.  相似文献   
967.
We report here studies on the influence of oxygen pressure on the electroresistance behavior of La0.9Sr0.1MnO3 thin films fabricated by laser molecular beam epitaxy. It was found that the film deposited at lower oxygen pressure shows larger c-axis parameter, higher resistance, and more distinct electroresistance. These results reveal that the electroresistance of manganite thin films can be tuned by the conditions of film fabrication. Supported by the National Natural Science Foundation of China (Grant No. 10334070) and the National Key Basic Research Program of China (Grant No. 2004CB619004)  相似文献   
968.
We designed and fabricated an arrayed-waveguide grating (AWG) in silicon oxynitride as a spectrometer for spectral domain optical coherence tomography (SD-OCT). The AWG has a footprint of only 3.0 cm × 2.5 cm, operates at a center wavelength of 1300 nm, and has 78 nm free spectral range. OCT measurements are performed that demonstrate imaging up to a maximum depth of 1 mm with an axial resolution of 19 μm, both in agreement with the AWG design parameters. Using the AWG spectrometer combined with a fiber-based SD-OCT system, we demonstrate cross-sectional OCT imaging of a multilayered scattering phantom.  相似文献   
969.
Recently, there has been an increasing need of efficient synthetic protocols using eco-friendly conditions including low costs and green chemicals for production of metal nanoparticles. In this work, silver nanoparticles (silver NPs) with average particle size about 10 nm were synthesized by using a thermal decomposition technique. Unlike the colloidal chemistry method, the thermal decomposition method developed has advantages such as the high crystallinity, single-reaction synthesis, and easy dispersion ability of the synthesized NPs in organic solvents. In a modified synthesis process, we used sodium oleate as a capping agent to modify the surface of silver NPs because the oleate has a C18 tail with a double bond in the middle, therefore, forming a kink which is to be effective for aggregative stability. Importantly, the as-synthesized silver NPs have demonstrated strong antimicrobial effects against various bacteria and fungi strains. Electron microscopic studies reveal physical insights into the interaction and bactericidal mechanism between the prepared silver NPs and tested bacteria in question. The observed excellent antibacterial and antifungal activity of the silver NPs make them ideal for disinfection and biomedicine applications.  相似文献   
970.
Xiang J  Geng C  Yi L  Dang Q  Bai X 《Molecular diversity》2011,15(4):839-847
A practical strategy was developed for the preparation of highly substituted 2,3-dihydropyrimido[4,5-d]pyrimidin-4(1H)-ones from 4,6-dichloro-5-formylpyrimidine, primary amines, and aldehydes. The key step for this synthesis entails a cyclization reaction involving an intramolecular amide addition to an iminium intermediate formed in situ from 4-amino-pyrimidine-5-carboxamide 2 and aldehydes to form the pyrimido[4,5-d]pyrimidine core with a strategically placed 5-Cl group for further derivatization. The utility of this methodology was demonstrated through the preparation of a 27-membered library of representative 2,3-dihydropyrimido[4,5-d]pyrimidin-4(1H)-ones in moderate to good yields.  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