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   29964篇
  免费   3719篇
  国内免费   3265篇
化学   21600篇
晶体学   369篇
力学   1519篇
综合类   243篇
数学   3664篇
物理学   9553篇
  2024年   80篇
  2023年   468篇
  2022年   836篇
  2021年   925篇
  2020年   957篇
  2019年   986篇
  2018年   852篇
  2017年   802篇
  2016年   1191篇
  2015年   1239篇
  2014年   1453篇
  2013年   2008篇
  2012年   2384篇
  2011年   2584篇
  2010年   1816篇
  2009年   1788篇
  2008年   1962篇
  2007年   1786篇
  2006年   1613篇
  2005年   1424篇
  2004年   1127篇
  2003年   912篇
  2002年   888篇
  2001年   748篇
  2000年   635篇
  1999年   592篇
  1998年   506篇
  1997年   450篇
  1996年   480篇
  1995年   387篇
  1994年   379篇
  1993年   348篇
  1992年   325篇
  1991年   277篇
  1990年   233篇
  1989年   191篇
  1988年   167篇
  1987年   129篇
  1986年   143篇
  1985年   155篇
  1984年   101篇
  1983年   64篇
  1982年   71篇
  1981年   53篇
  1980年   52篇
  1979年   58篇
  1978年   40篇
  1976年   37篇
  1974年   40篇
  1973年   45篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Three new pavine N-oxide alkaloids, (-)-isocaryachine-N-oxide B, (+)-caryachine-N-oxide, (-)-caryachine-N-oxide, and a new isoquinoline alkaloid, 6,7-methylenedioxy-N-methylisoquinoline together with 11 known alkaloids were isolated and characterized from the stem bark of Cryptocarya chinensis. The structures of the isolated compounds were determined by spectral methods. The stereochemistry of pavine-N-oxide alkaloids is also discussed.  相似文献   
82.
C.S. Lin 《Chemical physics》1974,3(1):125-130
Accurate vibrational wave functions and a state-dependent model interaction potential were used in the study, within the framework of a semi-classical theory, of the vibrational excitation and dissociation of the hydrogen molecule in collinear collisions with the helium atom. A molecule initially in the excited state is shown to be very efficient in energy transfer and twice more likely to be further excited than to be de-excited. The change in the population distribution among the vibrational states at the first few collisions was analyzed. It is shown that the population of the first vibrational excited state ψ1 reaches its maximum after the very first collision and that of ψ2 after the second. It is also found that at a sufficiently high collision energy, ψ5 is the most efficient state in dissociation at the second collision while ψ6 contributes most at the third collision.  相似文献   
83.
MCM-48 membranes have been prepared on alumina supports of different pore sizes. A battery of characterization techniques has been used to study the physical properties and the quality of the membranes prepared. The highest quality membranes were prepared on supports with pore size of up to 60 nm. The MCM-48 membranes were tested in the separation of gas phase mixtures and a cyclohexane/O2 selectivity higher than 270 was obtained. The selective separation of organic compounds from inert components is a result of the cooperative effects of capillary condensation in MCM-48 pores and of the specific interactions of the permeating compounds and the membrane material.  相似文献   
84.
To explore the properties of cyclodextrins (CDs) as an optical sensing phase, the behavior of immobilized CD in interaction with analytes was studied in this work. CDs having different cavity sizes were immobilized onto the surface of infrared (IR) internal reflection-sensing element (IRE) to kinetically monitor the behavior of CD in interaction with analytes. Several aromatic compounds having various molecular sizes and functional groups were used to characterize the interaction mechanism. A two-layer modification method was proposed in this work, which utilized a thin hydrophobic film (polyvinyl benzyl chloride) to stick on the IRE and to covalently bond to the CDs through an ethylene diamine linker. The synthesized CD phases exhibited high stability in aqueous solution. To analyze the behavior during the formation of complexes between the guest molecules and the CD phases, we modeled the interaction behavior and treated the kinetic data with the theoretical equations developed in this work. The results indicate that the behavior of the interaction between guest molecules and CDs was explained by considering the formation of two types of complexes: adsorbed complexes and inclusion complexes. The formation of the inclusion complexes was relatively fast, the time required to reach equilibrium could be shorter than a few minutes. The adsorbed complexes were also observed, but their rate of formation was relatively slow; equilibrium could be reached at times greater than 60 min. Based on the signals observed under equilibrium conditions, the concentration of inclusion complexes was approximately three times than that of the adsorbed complexes.  相似文献   
85.
This study investigated the visible-light catalysis mediated by zeolite NaY on the oxidation of dyes with H2O2. The results demonstrated that zeolite NaY acts as a sink for the electron from the photo-excited dye in the heterogeneous catalysis. Furthermore, the electron can effectively activate H2O2 to produce ·OH radical that is a powerful oxidant for the oxidation of dye at room temperature. The effects of the framework topology, Si/Al ratio, and exchangeable cation of the zeolite on the oxidation of various dyes were also shown.  相似文献   
86.
Summary The spectrochemical, electrochemical and electrocatalytic properties of Co[15]aneN4 ([15]aneN4 = 1,4,8,12-tetraazacyclopentadecane) have been investigated. The results show that, in aqueous solution, this compound mainly exists as three species whose axial coordination positions are occupied by water and/or hydroxy ligands; it is marginal whether other substrates such as Cl and NO inf3 sup– interact with the central ion in acid-base solutions. The approximate Pourbaix diagram of CoIII/II[15]ane N4 was determined. There is an electrochemically-induced isomerization between two trans conformational isomers of the Co[15]aneN4 complexes in acid and netural solutions. The Co[15]aneN4 complex has electrocatalytic properties for reduction of nitrate and nitrite only in strong alkaline solution.  相似文献   
87.
二氢茉莉酮酸甲酯的简便合成方法   总被引:1,自引:0,他引:1  
本文报道二氢茉莉酮酸甲酯的简便合成方法。先由丁二酸和庚酰氯反应得到2-戊基-1,3-环戊二酮(1),再用甲醇醚化1,可得到2-戊基-3-甲氧基-环戊-2-烯酮(2)。2与丙二酸二甲酯反应生成(2-戊基-3-酮-1-环戊烯-)基乙酸甲酮(3)。最后,催化氢化3,便可得到二氢茉莉酮酸甲酯(4)。  相似文献   
88.
Parallel synthesis of β-carbolines on soluble polyethylene glycol (PEG-OH) support is demonstrated. One-pot condensation of polymer-bound tryptophan residues with various aldehydes and ketones has been carried out in the presence of p-TSA as a catalyst to deliver immobilized 1,2,3,4-tetrahydro-β-carbolines. Subsequent disengagement of the appendant from the polymer support afforded the desired products in good yield and acceptable purity.  相似文献   
89.
Addition of an aldehyde and zinc chloride to a cyclobutanone enolate, prepared by the reaction of an α-chlorocyclobutanone with dimethylcopperlithium, gave an aldol adduct in good yield.  相似文献   
90.
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