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   4726篇
  免费   308篇
  国内免费   32篇
化学   3259篇
晶体学   57篇
力学   170篇
数学   751篇
物理学   829篇
  2023年   29篇
  2022年   93篇
  2021年   142篇
  2020年   97篇
  2019年   188篇
  2018年   151篇
  2017年   107篇
  2016年   240篇
  2015年   154篇
  2014年   246篇
  2013年   475篇
  2012年   280篇
  2011年   292篇
  2010年   207篇
  2009年   198篇
  2008年   213篇
  2007年   202篇
  2006年   200篇
  2005年   168篇
  2004年   153篇
  2003年   129篇
  2002年   171篇
  2001年   72篇
  2000年   109篇
  1999年   63篇
  1998年   40篇
  1997年   46篇
  1996年   35篇
  1995年   36篇
  1994年   35篇
  1993年   37篇
  1992年   32篇
  1991年   23篇
  1990年   16篇
  1989年   29篇
  1988年   27篇
  1987年   20篇
  1986年   17篇
  1985年   29篇
  1984年   24篇
  1983年   21篇
  1982年   20篇
  1981年   26篇
  1980年   16篇
  1979年   15篇
  1978年   15篇
  1977年   9篇
  1976年   13篇
  1975年   16篇
  1959年   8篇
排序方式: 共有5066条查询结果,搜索用时 15 毫秒
161.
A new Schiff base ligand (HL) was prepared via a condensation reaction of quinoline‐2‐carboxaldhyde with 2‐aminophenol in a molar ratio of 1:1. Its transition metal mixed ligand complexes with 1,10‐phenanthroline (1,10‐phen) as co‐ligand were also synthesized in a 1:1:1 ratio. HL and its mixed ligand complexes were characterized using elemental analysis, infrared, 1H NMR, mass and UV–visible spectroscopies, molar conductance, magnetic measurements, solid reflectance, thermal analysis, electron spin resonance and X‐ray diffraction. Molar conductance measurements showed that all complexes have an electrolytic nature, except Cd(II) complex. From elemental and spectral data, the formulae [M(L)(1,10‐phen)(H2O)]Clx?nH2O (where M = Cr(III) (x = n = 2), Mn(II) and Ni(II) (x = 1, n = 2), Fe(III) (x = n = 2), Co(II), Cu(II) and Zn(II) (x = 1, n = 2)) and [Cd(L)(1,10‐phen)Cl]?3H2O for the metal complexes have been proposed. The geometric structures of complexes were found to be octahedral. Powder X‐ray diffraction reflected the crystalline nature of the complexes; however, the Schiff base is amorphous. HL and its mixed ligand complexes were screened against Gram‐positive bacteria (Streptococcus pneumoniae and Bacillus subtilis) and Gram‐negative bacteria (Pseudomonas aeruginosa and Escherichia coli). Antifungal activity was determined against Aspergillus fumigatus and Candida albicans, the data showing that most complexes had activity less than that of the Schiff base while Mn(II), Fe(III) and Ni(II) complexes showed no significant antifungal activity. The anticancer activity of HL and its metal complexes was also studied against breast and colon cell lines. The metal complexes showed IC50 higher than that of HL, especially the Cu(II) complex which showed the highest IC50 against breast cell line.  相似文献   
162.
Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the AuI d10 metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of AuI–AuI interactions in 2 a , b .  相似文献   
163.
164.
165.
5-Acetyl-2-cyanomethyl-4-methylthiazole, 2-aminothiazole, and 5-N-benzoylamino-1,3,4-thiadiazole-2-yl-acetonitrile react with acetone, and malononitrile derivatives in the presence of sulfur to yield the corresponding thiophene derivatives. Also, 4-furylmethylene-2-phenyl-2-oxazolin-5-ones react with thiophenol, and/or thionaphthol to give the thiolester derivatives in one-pot synthesis. The structures of the products were based on IR, 1 H NMR, and elemental analysis.  相似文献   
166.
The first immobilization of a pyrene-tagged chromium salen complex through π-π noncovalent interactions on reduced graphene oxide (rGO) is described. A very robust supported catalytic system is obtained to promote asymmetric catalysis in repeated cycles, without loss of activity or enantioselectivity. This specific behavior was demonstrated in two different catalytic reactions (up to ten reuses) promoted by chromium salen complexes, the cyclohexene oxide ring-opening reaction and the hetero-Diels-Alder cycloaddition between various aldehydes and Danishefsky's diene. Furthermore, the chiral chromium salen@rGO has been found to be compatible with a multi-substrate type use, in which the structure of the substrate involved is modified each time the catalyst is reused.  相似文献   
167.
Zn‐Al‐salicylic nanohybrid layers have been prepared and used as fillers for polyvinyl alcohol (PVA). Nanohybrid layers of a broad absorption area in UV region were completely and uniformly dispersed in a continuous polymer matrix. PVA and PVA nanohybrid composite (NHC) films were exposed to UV irradiation. Thermal properties (diffusivity, effusivity, and conductivity) of both have been measured through photoacoustic technique before and after UV irradiation. Thermal parameters of PVA suffered from a quick deterioration with UV exposure due to reduction of the phonon mean free path as a result of molecular chain scissions. However, significant stability in such parameters of NHC has been obtained under the influence of UV irradiation. This thermal properties stability may be an important step on the way of obtaining photostable polymer NHC. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   
168.
169.
The current density (JE), the piecewise linear recursive convolution (PLRC) and the constant convolution recursive (CRC) techniques are developed and integrated into the transmission line matrix (TLM) algorithm. A comparison of these three schemes according to the criteria of accuracy and CPU time is presented. Numerical experiments show that JE provides the most accurate solution and requires the least CPU time; PLRC is nearly as accurate but consumes more CPU time than CRC.  相似文献   
170.
A highly efficient and mild transamidation of amides with amines co‐catalysed by borinic acid and acetic acid has been reported. A wide range of functionalised formamides was synthesized in excellent yields, including important chiral α‐amino acid derivatives, with minor racemisation being observed. Experiments suggested that the reaction rely on a cooperative catalysis involving an enhanced boron‐derived Lewis acidity rather than an improved Brønsted acidity of acetic acid.  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