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   1262篇
  免费   46篇
  国内免费   6篇
化学   877篇
晶体学   13篇
力学   36篇
数学   142篇
物理学   246篇
  2024年   5篇
  2023年   12篇
  2022年   33篇
  2021年   29篇
  2020年   28篇
  2019年   29篇
  2018年   40篇
  2017年   21篇
  2016年   54篇
  2015年   37篇
  2014年   46篇
  2013年   101篇
  2012年   83篇
  2011年   93篇
  2010年   52篇
  2009年   55篇
  2008年   98篇
  2007年   77篇
  2006年   82篇
  2005年   71篇
  2004年   45篇
  2003年   35篇
  2002年   29篇
  2001年   6篇
  2000年   11篇
  1998年   11篇
  1997年   5篇
  1996年   8篇
  1995年   12篇
  1994年   8篇
  1992年   5篇
  1991年   9篇
  1990年   3篇
  1989年   3篇
  1988年   6篇
  1987年   4篇
  1986年   3篇
  1985年   3篇
  1983年   3篇
  1982年   6篇
  1981年   8篇
  1980年   4篇
  1979年   3篇
  1978年   5篇
  1977年   5篇
  1976年   6篇
  1975年   3篇
  1974年   4篇
  1967年   2篇
  1963年   2篇
排序方式: 共有1314条查询结果,搜索用时 15 毫秒
41.
YAG phosphor powders doped/codoped with Er3+/(Er3+ + Yb3+) have been synthesised by using the solution combustion method. The effect of direct pumping into the 4I11/2 level under 980 nm excitation of doped/codoped Er3+/Yb3+−Er3+ in Y3Al5O12 (YAG) phosphor responsible for an infrared (IR) emission peaking at ∼1.53 μm corresponding to the 4I13/24I15/2 transition has been studied. YAG exhibits three thermally-stimulated luminescence (TSL) peaks at around 140°C, 210°C and 445°C. Electron spin resonance (ESR) studies were carried out to identify the centres responsible for the TSL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0176 is identified as O ion, while centre II with an isotropic g-factor 2.0020 is assigned to an F+ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal-annealing experiments and this centre (assigned to F+ centre) seems to originate from an F-centre (oxygen vacancy with two electrons) and these two centres appear to correlate with the observed high-temperature TSL peak in YAG phosphor.  相似文献   
42.
Palladium-catalyzed [4+2] oxidative annulation of coumarin-benzimidazoles with olefins for the synthesis of polycyclic aromatic hydrocarbons have been achieved. This synthetic protocol gives access to a wide range of structurally distinct imidazo[1,2-a]chromeno[3,4-c]pyridines in moderate to good yield with wide functional group tolerance. Further, photophysical properties of annulated scaffolds have been examined, which discloses their interesting solvatochromic emission behaviors.  相似文献   
43.
Nair V  Biju AT  Mohanan K  Suresh E 《Organic letters》2006,8(11):2213-2216
[reaction: see text] Reaction of the Huisgen zwitterion, derived from triphenylphosphine and dialkyl azodicarboxylate, with allenic esters affords highly functionalized pyrazolines and pyrazoles. The crystal structure of pyrazoline derivative 7a showed extensive C-H...O interactions. Pyrazole formation proceeds via a novel nitrogen to carbon migration of the carboalkoxy group.  相似文献   
44.
A qualitative method was developed for the determination of degraded products of nerve agents by using ion-pair liquid chromatography electrospray ionization tandem mass spectrometry (IP-LC-ESI-MS(n)). Generally, alkylphosphonic acids (APAs) and O-alkyl alkylphosphonic acids (AAPAs) give deprotonated molecular ion [M-H](-) in negative mode. Interestingly, first time we obtained the molecular radical anion [M](.-) of phosphonic acids in negative mode by using tri-n-butyl amine as an ion-pairing agent. We interpreted this observation as an indication of electrochemical reduction of phosphonic acids in electrospray needle. Three variables such as sheath gas flow, electrospray needle voltage and pH of the mobile phase were investigated to enhance the molecular radical anion [M](.-) signal of each analyte. The Doehlert design was used to obtain the region in which the optimum value of such variables is simultaneously achieved. Limit of detection achieved was 0.5 microg mL(-1) for AAPAs and 10 microg mL(-1) for APAs. Excellent precision was observed with less than 8.61% RSD. Finally, the method was applied for the detection of ethyl methylphosphonic in aqueous extract of soil sample.  相似文献   
45.
Chiral gold clusters stabilised by enantiopure thiolates were prepared, size-selected and characterised by circular dichroism and mass spectrometry. The product distribution is found to be ligand dependent. Au(25) clusters protected with camphorthiol show clear resemblance of their chiroptical properties with their glutathionate analogue.  相似文献   
46.
The poor pharmacokinetics, side effects and particularly the rapid emergence of drug resistance compromise the efficiency of clinically used anticancer drugs. Therefore, the discovery of novel and effective drugs is still an extremely primary mission. Naphthalimide family is one of the highly active anticancer drug based upon effective intercalator with DNA. In this article, we review the discovery and development of 1,8‐naphthalimide moiety, and, especially, pay much attention to the structural modifications and structure activity relationships. The review demonstrates how modulation of the moiety affecting naphthalimide compound for DNA binding that is achieved to afford a profile of antitumor activity. The DNA binding of imide and ring substitution at naphthalimide, bisnaphthalimide, naphthalimide‐metal complexes is achieved by molecular recognition through intercalation mode. Thus, this synthetic/natural small molecule can act as a drug when activation or inhibition of DNA function, is required to cure or control the cancer disease. The present study is a review of the advances in 1,8‐naphthalimide‐related research, with a focus on how such derivatives are intercalated into DNA for their anticancer activities.  相似文献   
47.
Pharmaceuticals, especially fluoroquinolone antibiotics, have received increasing global concern, due to their intensive use in the environment and potential harm to ecological system as well as human health. Degradation of antibiotics, such as oxidative degradation by metal oxides, often plays an important role in the elimination of antibiotics from the environment. The kinetics of oxidation of levofloxacin by water-soluble manganese dioxide has been studied in aqueous acidic medium at 25 °C temperature. The stoichiometry for the reaction indicates that the oxidation of 1 mol of levofloxacin requires 1 mol of manganese dioxide. The reaction is second order, that is first order with respect to manganese dioxide and levofloxacin. The rate of reaction increases with the increasing [H+] ion concentration. A probable reaction mechanism, in agreement with the observed kinetic results, has been proposed and discussed. The energy and enthalpy of activation have been calculated to be 30.54 and 28.07 kJ mol?1, respectively.  相似文献   
48.
Journal of Thermal Analysis and Calorimetry - This paper presents the comprehensive thermodynamic modelling to compare the performance and optimization of single-stage NH3–H2O-type absorption...  相似文献   
49.
Research on Chemical Intermediates - The synthesis of a new series of triazole-biscoumarin conjugates by using a molecular hybridization approach is described. The newly synthesized compounds...  相似文献   
50.
Nitrile metabolizing enzymes, i.e., aldoxime dehydratase, hydroxynitrile lyase, nitrilase, nitrile hydratase, and amidase, are the key catalysts in carbon nitrogen triple bond anabolism and catabolism. Over the past several years, these enzymes have drawn considerable attention as prominent biocatalysts in academia and industries because of their wide applications. Research on various aspects of these biocatalysts, i.e., sources, screening, function, purification, molecular cloning, structure, and mechanisms, has been conducted, and bioprocesses at various scales have been designed for the synthesis of myriads of useful compounds. This review is focused on the potential of nitrile metabolizing enzymes in the production of commercially important fine chemicals such as nitriles, carboxylic acids, and amides. A number of opportunities and challenges of nitrile metabolizing enzymes in bioprocess development for the production of bulk and fine chemicals are discussed.  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