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   2047篇
  免费   134篇
  国内免费   554篇
化学   2454篇
晶体学   51篇
力学   46篇
综合类   17篇
数学   2篇
物理学   165篇
  2024年   5篇
  2023年   28篇
  2022年   46篇
  2021年   74篇
  2020年   59篇
  2019年   70篇
  2018年   54篇
  2017年   73篇
  2016年   103篇
  2015年   86篇
  2014年   102篇
  2013年   210篇
  2012年   110篇
  2011年   103篇
  2010年   120篇
  2009年   116篇
  2008年   119篇
  2007年   124篇
  2006年   106篇
  2005年   112篇
  2004年   108篇
  2003年   101篇
  2002年   90篇
  2001年   76篇
  2000年   68篇
  1999年   61篇
  1998年   54篇
  1997年   39篇
  1996年   48篇
  1995年   37篇
  1994年   43篇
  1993年   35篇
  1992年   37篇
  1991年   26篇
  1990年   15篇
  1989年   25篇
  1988年   14篇
  1987年   8篇
  1986年   3篇
  1985年   5篇
  1984年   2篇
  1983年   3篇
  1982年   2篇
  1980年   2篇
  1979年   3篇
  1975年   1篇
  1974年   2篇
  1973年   1篇
  1972年   1篇
  1959年   1篇
排序方式: 共有2735条查询结果,搜索用时 265 毫秒
111.
A highly-efficient preparative procedure for ( R, S )- and ( S, S)-pyrroHdine-2-carboxyHc acid 3,5-dioxa-4-boracyclohepta[2, 1-α ; 3,4-α′] dlnaphthalen-4-yl esters [ namely ( R, S )-BNBAP and (S, S )-BNBAP] is described and the crystal structure of (R, S )-BNBAP was obtained. The data indicate that ( R, S )-BNBAP is a spirocyclic inner borate salt with almost normal te-trahedral configuration. This structural form may be the basic reason for their high chemical, optical and thermodynamic sta-bility.  相似文献   
112.
碱金属盐对ZSM-5分子筛晶化的影响   总被引:7,自引:0,他引:7       下载免费PDF全文
Effect of different alkali metal salts on the crystal size and the crystallization rate of ZSM-5 zeolite was de-tailedly investigated in this paper. The samples prepared by adding the different alkali metal salts were character-ized by using XRD, TEM, TG-DSC, BET and IR techniques. The XRD results showed that, for the nanosized ZSM-5 zeolite, the characteristic peaks broadened on the XRD patterns in comparison with the microsized ZSM-5 zeolite. The SEM results verified that the crystal size of zeolites prepared by adding different alkali metal salts had different results, and adding NaCl, NaC2H3O2 and KCl showed the better effect of reducing crystal size, which are about of 40~60nm size. The crystallization curve of adding the different alkali metal salts suggested that the crystallization rate was significantly affected by the anions in the alkali metal salt besides the cations. Moreover, the crystal size likewise depended on the anion in the alkali metal salt. In addition, the BET results suggested that the nanosized ZSM-5 zeolite possessed a larger outer surface area in comparison with the microsized ZSM-5 zeolite. The thermostability of the samples was determined by TG-DSC technique, indicating that the nanosized ZSM-5 zeolite had a poor thermostability as compared with the microsized ZSM-5 zeolite. The possible difference of the samples with different crystal sizes on IR spectra was also given.  相似文献   
113.
A new and green method for the synthesis of α,β-unsaturated arylsulfones had been achieved through the condensation of aromatic aldehydes,chloroacetonitrile,benzenesulfinic acid sodium salt in the presence of l-butyl-3-methyl imidazolium hydroxide([bmim]OH) in EtOH under reflux.The ionic liquid was recovered and recycled for subsequent reactions.The advantages of this protocol were non-toxic,easy work-up and good yields.  相似文献   
114.
There is much enthusiasm now-a-days for efforts to improve membrane performances. Membrane modification is one of the critical approaches needed for the development of membrane science and technology. The beauty of research in this orientation is that it is a dynamic process that moves forward slowly and recommendations are made based on the science available. In this regard sulfonation of polysulfones is an excellent move. The present review demonstrates different sulfonation strategies of polysulfones as well as promoting applications in pressure driven separation sciences (viz. salt, macromolecule, organic separation from water). It shows that marked path is promising one.  相似文献   
115.
A series of ammonium monosubstituted H-phosphonate salts were synthesized by combining H-phosphonate diesters with amines in the absence of solvent at 80 °C. Variation of the ester substituent and amine produced a range of ionic liquids with low melting points. The products and by-products were analyzed by spectroscopic and spectrometric techniques in order to get a better mechanistic picture of the dealkylation and formal dearylation observed. For dialkyl H-phosphonate diesters, (RO)2P(O)H (R=alkyl), the reaction proceeds via direct dealkylation with the reactivity increasing in the order R=iPr<Et<Me corresponding to DFT calculated activation enthalpies of 22.6, 20.8, and 17.9 kcal mol−1. For the diphenyl H-phosphonate diesters, (PhO)2P(O)H, the dearylation was found to proceed via phenol-assisted formation of a 5-coordinate intermediate, (PhO)3PH(OH), from which P(OPh)3 and water were eliminated. The presence of an equivalent of water then facilitated the formation of P(OH)2OPh and the amine, R'NH2, subsequently abstracted a proton from it to yield [(PhO)PH(O)O]-[R'NH3]+.  相似文献   
116.
117.
Alkyl α-chloroacrylates and p-substituted α-methylstyrenes were investigated for the effect of polymerization conditions on tacticity, molecular weight, and distribution, and for the relationship between tacticity, glass temperature, and crystalline properties.  相似文献   
118.
The palladium-catalyzed cross-coupling reaction of diaryliodonium salts with organozirconium compounds was achieved for about 1–1.5 hrs at room temperature and the reaction proceeded with retention of configuration to provide a new convenient method for the synthesis of (E)-disubstituted alkenes.  相似文献   
119.
Yi Zhou  Renjie Ni  Gaowen Yang 《合成通讯》2013,43(17):2624-2632
The [3 + 2] cycloaddition reaction between sodium azide and various organic nitriles proceeds smoothly in the presence of amine salts as catalyst in dimethylformamide. The corresponding 5-substituted 1-H tetrazoles were obtained under mild condition in good to excellent yields. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.  相似文献   
120.
Use of the calcium-ethylenediamine and sodium-liquid ammonia reduction systems for the ring opening of dihydropyran derivatives was studied. (Z)-Alkenyl alcohols and (E)-alkenyl alcohols were stereoselectively synthesized respectively.  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