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   2445篇
  免费   231篇
  国内免费   192篇
化学   528篇
晶体学   9篇
力学   321篇
综合类   26篇
数学   1263篇
物理学   721篇
  2024年   3篇
  2023年   21篇
  2022年   45篇
  2021年   44篇
  2020年   76篇
  2019年   67篇
  2018年   71篇
  2017年   81篇
  2016年   71篇
  2015年   69篇
  2014年   79篇
  2013年   280篇
  2012年   69篇
  2011年   114篇
  2010年   103篇
  2009年   109篇
  2008年   137篇
  2007年   134篇
  2006年   147篇
  2005年   125篇
  2004年   112篇
  2003年   100篇
  2002年   92篇
  2001年   75篇
  2000年   88篇
  1999年   72篇
  1998年   57篇
  1997年   55篇
  1996年   38篇
  1995年   41篇
  1994年   43篇
  1993年   26篇
  1992年   37篇
  1991年   28篇
  1990年   20篇
  1989年   12篇
  1988年   16篇
  1987年   10篇
  1986年   12篇
  1985年   15篇
  1984年   11篇
  1983年   5篇
  1982年   9篇
  1981年   5篇
  1980年   6篇
  1979年   11篇
  1978年   10篇
  1977年   5篇
  1976年   6篇
  1957年   2篇
排序方式: 共有2868条查询结果,搜索用时 15 毫秒
101.
A new method is applied to prepare stable aqueous dispersion of magnetic iron oxide nanoparticles (MNPs) by biocompatible maleate polymers. Fe3O4 magnetic core–shell nanoparticles are obtained via forming an inclusion complex between carboxylic acid groups of maleated biocompatible polymers shell and Fe3O4 MNPs core surface. Maleate polymers are synthesized via esterification of poly(ethylene glycol), poly(vinyl alcohol) and starch with maleic anhydride (MA). The Fe3O4 magnetic core–shell nanoparticles are characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy and vibrating sample magnetometer. The obtained magnetic core–shell nanoparticles exhibit superparamagnetic property and reveal long‐term aqueous stability. This work represents a valid methodology to produce highly stable aqueous dispersion of Fe3O4 MNPs ferrofluids which can be expected to have great potential as contrast agent for magnetic resonance imaging. Furthermore, the shell composition of biocompatible maleate polymers with double bond of MA as crosslinker agent allows the polymerization with other monomers to design preferred drug delivery systems. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
102.
Development of highly functional cesium selective adsorbents for the decontamination of high-activity-level water(HALW) from the Fukushima NPP-1 accident is very urgent. In order to selectively adsorb the radioactive cesium, three kinds of novel porous silica gels loaded with insoluble ferrocyanides(SLFC) were prepared using a successive impregnation/precipitation method. Based on the results of previous research, the SLFC composites have relatively large uptake ratio above 95%, distribution coefficients(Kd) above 103 cm3/g, and excellent adsorption kinetics even in seawater. The solidification results also indicate that zeolites have an excellent Cs immobilization characteristic, gas-trapping and self-sintering abilities, and low leachability. We chose three kinds of SLFC composites to achieve the optimization of solidification by mixing with nine kinds of additives at high temperatures(up to 1200 °C). The Cs contents in the three composites were estimated to be below 30% of the initial contents and decreased with the three stages at calcination temperatures ranging from 25 to 1200 °C. By contrast, the Cs immobilization ratio was markedly lowered by mixing with additives: of those, allophane had the best immobilization result. By increasing the additive ratio to 50 wt%, the Cs immobilization ratio became almost 100% and no volatilization of Cs was detected even after calcination at 1200 °C. This result indicates that calcination of the mixture of SLFC composites after adsorbing Cs+ ions and specific additives under appropriate ratio is effective for stable solidification.  相似文献   
103.
The demand for more efficient methods of establishing the undetermined stereochemistries of peptidic natural products continues unabated. A new method for microscale stereochemical determination was devised by integrating solid-phase synthesis, split-and-mix randomization, 18O/16O-encoding of d /l -configurations, tandem mass spectrometry, and biological evaluation. Here we applied gramicidin A as the molecule for a blind test. Gramicidin A and its 31 diastereomers were randomly prepared in microgram scale with 18O/16O-stereochemical encoding and subjected to MS/MS-structural determination and cytotoxicity assay. Only the parent gramicidin A was selected from among the 32 stereoisomers, validating the high reliability of the present strategy.  相似文献   
104.
展示了一台自制的电化学扫描隧道显微镜. 这台电化学STM具有很高的稳定性,它在XY平面和Z方向的漂移速率分别为每分钟67和55.6 pm/min. 另外,特殊设计的扫描管部件有效地避免了在高湿度的环境中大漏电电流的产生. 详细描述了这台电化学STM的机械结构.通过在硫酸铜溶液中测量STM图像证明这套系统的优异性能,得到了大范围干净有序的Au(111)表面和高分辨的高聚石墨原子图像.  相似文献   
105.
陈义 《色谱》2020,38(10):1217-1223
毛细管电泳经常遭受结果不稳定、不重现的困扰。该文从理论上推导了一些新模式并以例证说明,这些模式能在一定条件下抵抗条件变化,获得超重现电泳谱图。它们是加权淌度谱、迁移电量谱、电荷密度谱、摩尔电荷密度谱、扩散系数谱、液相质量谱,以及它们各自的比例谱等,其中前4种为实时测量模式,其余的为实验后模式。这些模式需要发展新的仪器或算法,但都有发展潜力,值得深入研究。  相似文献   
106.
Oxyallyl derivatives are typically elusive compounds. Even recently reported “stabilized” 1,3‐diaminooxyallyl species are still highly reactive and have short lifetimes at room temperature. Herein, we report the synthesis and preliminary study of mesoionic pyrimidine derivatives that feature 1,3‐bis(dimethylamino)oxyallyl patterns with an unprecedented level of stabilization. The latter are not only insensitive towards air and moisture, but they are also compatible with the formation of an ancillary stable N‐heterocyclic carbene moiety. As the oxyallyl pattern is proton‐responsive, it allows the reversible switching of the electronic properties of the carbene, as a ligand.  相似文献   
107.
We present the access to [5‐19F, 5‐13C]‐uridine and ‐cytidine phosphoramidites for the production of site‐specifically modified RNAs up to 65 nucleotides (nts). The amidites were used to introduce [5‐19F, 5‐13C]‐pyrimidine labels into five RNAs—the 30 nt human immunodeficiency virus trans activation response (HIV TAR) 2 RNA, the 61 nt human hepatitis B virus ? (hHBV ?) RNA, the 49 nt SAM VI riboswitch aptamer domain from B. angulatum, the 29 nt apical stem loop of the pre‐microRNA (miRNA) 21 and the 59 nt full length pre‐miRNA 21. The main stimulus to introduce the aromatic 19F–13C‐spin topology into RNA comes from a work of Boeszoermenyi et al., in which the dipole‐dipole interaction and the chemical shift anisotropy relaxation mechanisms cancel each other leading to advantageous TROSY properties shown for aromatic protein sidechains. This aromatic 13C–19F labeling scheme is now transferred to RNA. We provide a protocol for the resonance assignment by solid phase synthesis based on diluted [5‐19F, 5‐13C]/[5‐19F] pyrimidine labeling. For the 61 nt hHBV ? we find a beneficial 19F–13C TROSY enhancement, which should be even more pronounced in larger RNAs and will facilitate the NMR studies of larger RNAs. The [19F, 13C]‐labeling of the SAM VI aptamer domain and the pre‐miRNA 21 further opens the possibility to use the biorthogonal stable isotope reporter nuclei in in vivo NMR to observe ligand binding and microRNA processing in a biological relevant setting.  相似文献   
108.
关于微分方程解的一致非常稳定性与一致距离有界性   总被引:2,自引:0,他引:2  
湛少锋 《大学数学》2006,22(3):76-77
讨论了一般非自治方程解的一致非常稳定性与一致距离有界性.  相似文献   
109.
亚氯酸盐氧化硫脲非缓冲体系的复杂动力学行为   总被引:1,自引:0,他引:1  
王新红  高庆宇 《化学通报》2006,69(8):601-605
研究了ClO2--SC(NH2)2的非缓冲体系中的动力学行为,发现在开放体系中,体系的铂电极电位和pH呈现反相位连续的大幅度振荡,随着流速的降低,体系行为更加丰富,在高流速的混合模式之后出现了低流速的混合模式;在外部条件变化时,观察到了准周期振荡和倍周期振荡现象;考察了温度、流速、酸度以及反应物的初始浓度比等主要的影响因素,发现分叉参数的变化与体系的行为紧密相关。  相似文献   
110.
热声波数值模拟的虚假振荡研究   总被引:10,自引:4,他引:6  
采用可压缩流动的SIMPLE算法对一维封闭空腔内由边界突然加热所引起的非稳态热声波进行了数值模拟,对流-扩散项采用了中心差分、一阶迎风差分、QUICK、及MIJSCL等不同格式。计算表明各种格式均存在不同程度的虚假振荡现象,其大小与热声波的强度及离散格式的形式等多种因素有关。这些结果对热声波的进一步研究及高效可靠的对流差分格式的开发具有重要意义。  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