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   4475篇
  免费   686篇
  国内免费   632篇
化学   3672篇
晶体学   40篇
力学   266篇
综合类   61篇
数学   606篇
物理学   1148篇
  2024年   2篇
  2023年   64篇
  2022年   78篇
  2021年   96篇
  2020年   141篇
  2019年   153篇
  2018年   133篇
  2017年   115篇
  2016年   215篇
  2015年   198篇
  2014年   275篇
  2013年   346篇
  2012年   387篇
  2011年   346篇
  2010年   323篇
  2009年   277篇
  2008年   273篇
  2007年   248篇
  2006年   257篇
  2005年   205篇
  2004年   190篇
  2003年   192篇
  2002年   302篇
  2001年   257篇
  2000年   136篇
  1999年   120篇
  1998年   87篇
  1997年   51篇
  1996年   47篇
  1995年   38篇
  1994年   46篇
  1993年   13篇
  1992年   17篇
  1991年   27篇
  1990年   27篇
  1989年   18篇
  1988年   18篇
  1987年   17篇
  1986年   11篇
  1985年   11篇
  1984年   9篇
  1982年   5篇
  1981年   5篇
  1980年   5篇
  1979年   3篇
  1977年   3篇
  1975年   1篇
  1974年   1篇
  1972年   2篇
  1971年   1篇
排序方式: 共有5793条查询结果,搜索用时 15 毫秒
111.
The preparation and potentiometric pH response properties of membranes formulated with various aminated-poly(vinyl chloride) (PVC-NH2) products are described. Products containing secondary and/or primary amino functional groups are obtained by modifying PVC with mono- and/or diamines, respectively. Blank membranes prepared with either type of aminated-polymer exhibit nearly Nernstian potentiometric pH responses over different pH ranges. In general, membranes based on diamino products exhibit pH response over a wider range (5–10.5) than membranes formulated with monoamino products (<8.0). These potentiometric results are used to estimate the basicity of the various primary and secondary amino sites in the membrane phases.Dedicated to Professer W. Simon on the occasion of his 60th birthday  相似文献   
112.
Ginseng, the underground parts of plants of Panax species, has been used in oriental traditional medicine for centuries. Unfortunately, because of extensive exploitation over thousands of years, the natural source of these species has been almost exhausted. Recently, we have found a wild ginseng growing in Myanmar. Here, by a combination of chemical composition study and gene sequence analysis, we unambiguously demonstrate that the wild ginseng is actually P. zingiberensis, commonly known as ginger ginseng. This ginseng was an indigenous to the southwestern China. However, now it is seriously threatened to brink of extinction and is put on the highest level of protection in China. Therefore, an appropriate protection measure is highly recommended to preserve this valuable resource, since this Myanmar ginseng might turn out to be the last P. zingiberensis, which could ever be seen in the planet.  相似文献   
113.
A novel, highly active immobilized ruthenium catalyst, which can be successfully used in oxidation of alcohols to aldehydes and ketones, has been developed. In contrast to most immobilized catalysts, the Ru catalyst has activity that is higher than that of the original non-immobilized catalyst. In a batch system, the Ru catalyst was recovered and reused several times without loss of activity. The catalyst was also applied to a flow system, in which excellent conversions and yields were demonstrated. No leaching of Ru was observed in both cases.  相似文献   
114.
合成了标题卟啉配体及其钴,镍,铜,锌和铁的五种配合物,对它们进行了元素分析,UV,IR和荧光光谱等结构表征。用DTA,TG,DSC等手段研究了这些新化合物的热稳定性及热分解机理,实验结果与HMO方法计算的结果一致。  相似文献   
115.
A novel electrospray interface, which has distinct advantages over conventional pulled silica emitters, has been developed. This novel interface can be easily fabricated by forming a porous polymer monolith (PPM) at the end of a fused-silica capillary that facilitates a stable electrospray over a wide range of flow rates with only a modest increase in back-pressure. A comparison was made between the PPM-assisted electrospray and a commercial nanosprayer in terms of sensitivity, stability and robustness. A PPM-filled electrospray tip produced a day-to-day signal variation of 23% relative standard deviation (RSD) over a 3-day period when spraying a 1.0 microM test peptide solution. Furthermore, three different capillaries fabricated by the same process produced a signal variation of 17% RSD, indicating that the fabrication process shows good reproducibility. The multiple flow paths of the PPM function to split the flow and reduce clogging. Even following the accumulation of debris after prolonged use, a stable spray could still be generated with the PPM-filled capillary while the commercial nanosprayer ceased to function properly. In terms of sensitivity, PPM-assisted electrospray showed an enhancement in sensitivity at infusion flow rates between 100 to 1000 nL/min while commercial nanosprayers performed slightly better at flow rates below 100 nL/min. A sample purification step can be combined with the PPM-assisted sprayer, using the PPM as a stationary phase to desalt and preconcentrate samples prior to mass spectrometric detection.  相似文献   
116.
研磨法合成α,β-不饱和酮   总被引:5,自引:1,他引:5  
将苯乙酮、芳香醛与KF Al2 O3 置于研钵中 ,在无溶剂条件下 ,室温研磨 5min后放置一定时间 ,得到收率 94%~ 98%的α ,β 不饱和酮 .该法反应条件温和 ,操作简便 ,KF Al2 O3 可回收再利用  相似文献   
117.
草酸电还原制取乙醛酸的研究   总被引:2,自引:4,他引:2  
研究了由草酸电解还原制备乙醛酸时,温度、草酸纯度、电解时间、电极状态和电解产物对电流效率和产率的影响。实验发现,除温度和原料纯度是重要的影响因素外,电极表面的有机物吸附和电解产物-乙醛酸的浓度具有更大的影响。  相似文献   
118.
The increasing demand to produce enantio-pure pharmaceuticals, flavors, and other fine chemicals has advanced the field of asymmetry catalytic technologies. Among all asymmetry catalytic methods, catalytic enantioselective hydrogenation of unsaturated bonds such as olefins, ketones, and imines, which employs dihydrogen and small amounts of transition-metal complexes modified intrinsically by chiral ligands, is now recognized as being the most promising strategy for the synthesis of large amount…  相似文献   
119.
The keto–enol tautomerism of cyameluric acid, both in gas phase and in water and methanol solution, has been studied at the B3LYP/6-31++g(d,P) level of theory in this paper. The harmonic frequencies of all the structures are calculated. The results show that the transition states of the tautomerism are 4-membered ring conformations in gas phase, whereas 6-membered ring conformations in solution. In the first proton transfer, activation energy ΔE# is 56.4 and 50.9 kJ/mol for water and methanol solution, respectively, which is much lower than that in gas phase (163.2 kJ/mol). Solvent molecules (water and methanol) produce an important catalytic effect in the tautomerism, especially for methanol-solvated system. NBO analysis shows that there is a strong interaction between cyameluric acid and solvent molecules in transition states. AIM charge analysis indicates that the keto–enol tautomerism shows a certain degree of proton transfer character. From the reaction enthalpy and reaction rate point of view, keto–enol tautomerism in water-solvated and methanol-solvated system is easier than that in gas phase. The keto–enol tautomerisms are endothermic both in gas phase and in solution, so the enol forms are less stable than the keto ones.  相似文献   
120.
Eleven (S)-(-)-bishydrocarbyl-(l-alkanoylpyrrolidin-2_yl)_methanol derivatives of three types were synthesized from L-proline.asymmtncally selective alkylation products were obtained oy LDA treatment and alkylation using methyl 2-bromoethyl ether, and three types of chiral α-Substituted-γ-butyrolactones were obtained by hydrolyzing the alkylation products, with %e.e. beijing up to 89 percent.  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