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   40814篇
  免费   3486篇
  国内免费   5878篇
化学   37407篇
晶体学   2837篇
力学   942篇
综合类   147篇
数学   242篇
物理学   8603篇
  2024年   61篇
  2023年   352篇
  2022年   862篇
  2021年   806篇
  2020年   1172篇
  2019年   1200篇
  2018年   1197篇
  2017年   1548篇
  2016年   1881篇
  2015年   1535篇
  2014年   1920篇
  2013年   3826篇
  2012年   2545篇
  2011年   2316篇
  2010年   2127篇
  2009年   2483篇
  2008年   2386篇
  2007年   2551篇
  2006年   2449篇
  2005年   2166篇
  2004年   2103篇
  2003年   1675篇
  2002年   1372篇
  2001年   1046篇
  2000年   1047篇
  1999年   1000篇
  1998年   864篇
  1997年   772篇
  1996年   804篇
  1995年   741篇
  1994年   653篇
  1993年   514篇
  1992年   466篇
  1991年   319篇
  1990年   229篇
  1989年   196篇
  1988年   209篇
  1987年   208篇
  1986年   121篇
  1985年   117篇
  1984年   115篇
  1983年   35篇
  1982年   65篇
  1981年   34篇
  1980年   28篇
  1979年   20篇
  1978年   9篇
  1977年   7篇
  1976年   7篇
  1973年   7篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
2.
meso-Tetra(n-hexyloxycarbonyl)porphyrin was found to be converted into porphine, the mother compound of porphyrins, in a 77% yield when heated in aqueous sulfuric acid at 180 °C over 30 min under an inert atmosphere. The observation demonstrates that the substituted porphyrin serves as a novel and useful precursor for porphine.  相似文献   
3.
4.
1 INTRODUCTION The study of heterocyclic molecules with aroma- tic rings and their absorptions on metals is of con- siderable importance from both theoretical and te- chnological points of view. These molecules are in- teresting because of their applications as corrosion inhibitors and flotation collectors, and their abilities to form self-assembly layers[1]. 2-Mercaptobenzo- thiazole (C7H5NS2, in the following MBT) is an important heterocyclic molecule, which can be used as corrosion …  相似文献   
5.
1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts.  相似文献   
6.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.  相似文献   
7.
    
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction.  相似文献   
8.
The first α‐diimine nickel(I) complex having a chloro bridge is reported. The centrosymmetric dinuclear structure of {[ArN?C(Me)C(Me)?NAr]NiCl}2[Ar?2,6?C6H3(i‐Pr)2] features two chelating α‐diimine ligands and two bridged chlorine atoms, so that a distorted tetrahedral N2Cl2 coordination geometry for nickel results. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   
9.
The title compound is a centrosymmetric dimer with each cadmium in a distorted CdS5 square pyramidal geometry. The Cd–S bond distances range from 2.5626(11) to 2.8459(11) Å. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   
10.
A lithium(I) coordination polymer has been formed from LiClO4 and the 2,2′‐bipyrimidine (bpym) ligand in which each square pyramidal lithium(I) atom is coordinated in the basal plane by four nitrogen donor atoms derived from two bpym ligands and one water molecule at the apical position. These are connected into a layer structure via hydrogen‐bonding interactions involving the perchlorate anions. Copyright © 2004 John Wiley & Sons, Ltd.  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