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   17986篇
  免费   2402篇
  国内免费   2710篇
化学   11544篇
晶体学   391篇
力学   1171篇
综合类   366篇
数学   2266篇
物理学   7360篇
  2025年   52篇
  2024年   277篇
  2023年   444篇
  2022年   621篇
  2021年   645篇
  2020年   789篇
  2019年   763篇
  2018年   620篇
  2017年   627篇
  2016年   716篇
  2015年   903篇
  2014年   972篇
  2013年   1305篇
  2012年   1442篇
  2011年   1469篇
  2010年   1224篇
  2009年   1211篇
  2008年   1353篇
  2007年   1197篇
  2006年   1106篇
  2005年   964篇
  2004年   699篇
  2003年   541篇
  2002年   541篇
  2001年   433篇
  2000年   441篇
  1999年   280篇
  1998年   146篇
  1997年   145篇
  1996年   126篇
  1995年   128篇
  1994年   106篇
  1993年   100篇
  1992年   85篇
  1991年   61篇
  1990年   71篇
  1989年   53篇
  1988年   59篇
  1987年   37篇
  1986年   41篇
  1985年   24篇
  1984年   28篇
  1983年   28篇
  1982年   21篇
  1981年   13篇
  1980年   20篇
  1979年   18篇
  1978年   25篇
  1973年   8篇
  1971年   9篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
1.
Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.  相似文献   
2.
Hydrogen peroxide is determined by a chemiluminescence method with a reagent containing 100 μM luminol and 3 μM microperoxidase at pH 10 (carbonate buffer). Microperoxidase is superior to hematin as a catalyst. The method uses an automated flow injection system with a throughput of 2 samples per minute. The log—log calibration plot is linear (slope 1.3) from the detection limit, 3 × 10-9 M up to 10-5 M H2O2. The background emission is low. Impurities in the carrier stream and from some plastics may cause elevated background unless precautions are taken.  相似文献   
3.
A cDNA for human TNF-α (615bp) was isolated by means of polymerase chain reaction (PCR) using first strand cDNA from PMA-induced HL-60 cells as template. The result from sequencing the 615 bp cDNA fragment indicated that it corresponded to the entire sequence of mature human TNF coding region. Direct expression of mature human TNF was achieved using a plasmid pHT-1 constructed by ligation of the cDNA and a synthetic DNA. The IPTG-induced bacterial product (hTNF) showed cytotoxicity to mouse L-929 cells. The TNF activity was further identified by neutralization of a specific monoclonal antibody against human TNF-α. Approximately 80,000 units of activity were detected per ml of culture at A600=2.  相似文献   
4.
The surface basicity of Ti-La-Li multicoinponent oxides has been investigated by means of CO2-TPD. The experiment results show that C2 (C2H6 C2H4) selectivity is related to surface basic strength. The surface active oxygen species have also been characterized by means of XPS, O2-TPD and so on. It has been indicated that C2 selectivity and CH4 conversion are correlated with lattice oxygen and the adsorbed oxygen on the surface of the catalyst respectively In the O2-TPD experiments, it has also been found that there are three kinds of oxygen species on the surface of the series catalvsts, which are a (100℃ 750℃) Among them α-oxvgen causes deep oxidation whileβand γ oxygen species are related to oxidalive coupling of methane (OCM).  相似文献   
5.
Zusammenfassung Bei der Umsetzung von Methylphenylacetat mit Dialkylamiden der Zimtsäure in Gegenwart von NaNH2 wurden Amidester der (±)-erythro-2,3-Diphenylglutarsäure hergestellt. Die Konfiguration der erhaltenen Verbindungen wurde durch Hydrolyse mit HCl (1:1) zu der entsprechenden Säure und im Falle der Umsetzung mit dem Zimtsäuredimethylamid durch eine mehrstufige Synthese aus demerythro-Säurenitril-ester festgestellt. Es wurden auch Bedingungen gefunden, unter welchen nur die Estergruppe hydrolysiert werden kann, wobei Mono-dimethylamid entsteht, das mit CH2N2 den Ausgangs-Amidester liefert.  相似文献   
6.
Highly crystalline anatase TiO2 nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials.  相似文献   
7.
A new 2D metal coordination polymer(MCP),[Mn(pzdc)_(0.5)(L)]_n(1,pzdc=pyrazine-2,3-dicarboxylic acid,HL=3-(2-pyridyl)pyrazole),was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TG,fluorescence and elemental analysis techniques.Pale yellow crystals crystallize in orthorhombic system,space group Fdd2 with a=11.2368(6),b=38.280(2),c=10.5682(6) A,V=4545.9(4) A~3,C_(11)H_7MnN_4O_2,M_r=282.15,D_c=1.649 g/cm~3,μ(MoKα)=1.159 mm~(-1),F(000)=2272,Z=16,the final R=0.0613 and wR=0.1773 for 2856 observed reflections(I 2σ(I)).It shows a two-dimensional network structure and is further assembled into a three-dimensional supramolecular framework via hydrogen bonds and abundant π-π interactions.In addition,we analyzed natural bond orbital(NBO) of 1 in using the PBE0/LANL2DZ method established in Gaussian 03 Program.There is obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ions.  相似文献   
8.
于凤军  袁英 《大学物理》2006,25(12):23-24
指出了一篇相关文献中的疏漏,讨论了卫星近日点的旋进现象,得出了在一般情况下卫星近日点旋进的快慢程度与近日点本身所处的位置有关的结论.  相似文献   
9.
针对大学物理实验教学目前存在的问题,考虑到物理学科的发展趋势及高等教育改革的基本要求,本着更新物理实验教师的教育思想和教育观念、加强教师的培养、调整教学体系和教学内容、改革传统的教学方法和现有的大学物理实验考核体系和评价体系以及加强实验室管理等原则,对大学物理实验教学进行了研究和实践。  相似文献   
10.
Transient photovoltage of ITO/organic/Al cells is studied under different bias polarities and voltages.It is found that for an ITO/NPB/Al cell,light incidence on the Al side induces more bias-dependent transient photovoltage variation when the photovoltage is positive than when it is negative.However,for an ITO/C60 /Al cell,the variation characteristics of transient photovoltage is reversed.These results support the previously proposed mechanism that Al could inject charges into the organic layer upon photon excitation,indicating that the absorption of electrode can also contribute to photovoltaic effect.  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