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   4620篇
  免费   226篇
  国内免费   20篇
化学   3292篇
晶体学   44篇
力学   150篇
数学   353篇
物理学   1027篇
  2024年   5篇
  2023年   22篇
  2022年   35篇
  2021年   104篇
  2020年   99篇
  2019年   88篇
  2018年   66篇
  2017年   55篇
  2016年   153篇
  2015年   146篇
  2014年   176篇
  2013年   271篇
  2012年   378篇
  2011年   419篇
  2010年   216篇
  2009年   212篇
  2008年   305篇
  2007年   277篇
  2006年   268篇
  2005年   253篇
  2004年   187篇
  2003年   171篇
  2002年   160篇
  2001年   100篇
  2000年   96篇
  1999年   85篇
  1998年   59篇
  1997年   40篇
  1996年   49篇
  1995年   48篇
  1994年   50篇
  1993年   45篇
  1992年   32篇
  1991年   21篇
  1990年   30篇
  1989年   21篇
  1988年   7篇
  1987年   10篇
  1986年   12篇
  1985年   12篇
  1984年   6篇
  1983年   6篇
  1982年   9篇
  1980年   8篇
  1979年   5篇
  1977年   8篇
  1976年   7篇
  1975年   6篇
  1974年   7篇
  1973年   5篇
排序方式: 共有4866条查询结果,搜索用时 203 毫秒
61.
Nitroarenes are reductively cyclized with 3‐amino‐1‐propanols in dioxane/H2O in the presence of a ruthenium catalyst and tin(II) chloride dihydrate together with isopropanol to afford the corresponding quinolines. A reaction pathway involving initial reduction of nitroarenes to anilines, propanol group transfer from 3‐amino‐1‐propanols to anilines, N‐alkylation of anilines by 3‐anilino‐1‐propanols and heteroannulation of 1,3‐dianilinopropanes is proposed.  相似文献   
62.
T cells are the central mediators of both humoral and cellular adaptive immune responses. Highly specific receptor-mediated clonal selection and expansion of T cells assure antigen-specific immunity. In addition, encounters with cognate antigens generate immunological memory, the capacity for long-term, antigen-specific immunity against previously encountered pathogens. However, T-cell receptor (TCR)-independent activation, termed “bystander activation”, has also been found. Bystander-activated T cells can respond rapidly and secrete effector cytokines even in the absence of antigen stimulation. Recent studies have rehighlighted the importance of antigen-independent bystander activation of CD4+ T cells in infection clearance and autoimmune pathogenesis, suggesting the existence of a distinct innate-like immunological function performed by conventional T cells. In this review, we discuss the inflammatory mediators that activate bystander CD4+ T cells and the potential physiological roles of these cells during infection, autoimmunity, and cancer.Subject terms: T cells, CD4-positive T cells  相似文献   
63.
A novel oligothiophene derivative containing the triphenylamine moiety with high glass transition temperature (Tg; 135 °C), 5,5′‐{bis[4‐di(4‐thiophenyl)amino]phenyl}‐2,2′‐bithiophene (TTPA‐dimer) was synthesized by the dimerization of tris[4‐(2‐thienyl)phenyl]amine (TTPA) with a palladium catalysis. Some types of electroluminescent (EL) devices that use the amorphous material for a hole‐ and an electron‐transporting with an emitting layer were fabricated. These devices emitted a bright green‐yellowish light (λemi; around 510 nm) with a small full width at half maximum (FWHM) rather than that of Alq3. The single layer EL device showed a maximum luminance of 221 cd/m2 at 8 V (0.06 lm/W at 100 cd/m2). On the other hand, the double layer (TTPA‐dimer/Alq3) EL device that used Alq3 as the electron transport material was increased up to 10830 cd/m2 at 12 V (0.89 lm/W at 300 cd/m2) and with a lower turn‐on voltage (3.2 V at 0.1 cd/m2) than other types of EL devices. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
64.
The energy and temperature dependence of the reaction cross section for CH3I + K → CH3 + KI have been calculated using the reaction probability obtained from the idealized model of collinear, impulsive interaction between the atoms K and I and between the group CH3 and I. Calculated values of the cross section agree very closely with the postmaximum data by Gersh and Berastein.  相似文献   
65.
Jang J  Cho SI  Chung DS 《Electrophoresis》2001,22(20):4362-4367
In the capillary electrophoretic separation of primary amine enantiomers using (+)-(18-crown-6)-tetracarboxylic acid (18C6H4) as a chiral selector, the presence of run buffer constituents such as tris(hydroxymethyl)aminomethane (Tris) or Na+ competing with analytes for 18C6H4, diminishes the effectiveness of 18C6H4. In order to determine appropriate buffer systems for 18C6H4, various run buffer cationic components including Tris, 1,3-bis[tris(hydroxymethyl)methylamino]propane, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, triethanolamine, tetramethylammonium, and Na+ were compared. Quantitative studies of the effects of the competitive constituents were carried out by measuring the electrophoretic mobilities of histidine as a function of the 18C6H4 concentration. We also derived a simple equation to estimate the optimal chiral selector concentration for a maximum mobility difference in the presence of a competitive inhibitor.  相似文献   
66.
Choi HJ  Park YS  Cho CS  Koh K  Kim SH  Paek K 《Organic letters》2004,6(24):4431-4433
An unusually stable molecular capsule was formed by heating phenyleneurea-spanned resorcinarene cavitand with 4-methyl-N-p-tolylbenzamide. The molecular capsule behaved as a discrete molecular entity showing a cylindrical D(4d) structure and showed no guest exchange in toluene-d(8) even at 100 degrees C. [structure: see text]  相似文献   
67.
Aerosol flame pyrolysis deposition method was applied to deposit the oxide glass electrolyte film and LiCoO2 cathode for thin film type Li-ion secondary battery. The thicknesses of as-deposited porous LiCoO2 and Li2O–B2O3–P2O5 electrolyte film were about 6 μm and 15 μm, respectively. The deposited LiCoO2 was sintered for 2 min at 700 °C to make partially densified cathode layer, and the deposited Li2O–P2O5–B2O3 glass film completely densified by the sintering at 700 °C for 1 h. After solid state sintering process the thicknesses were reduced to approximately 4 μm and 6 μm, respectively. The cathode and electrolyte layers were deposited by continuous deposition process and integrated into a layer by co-sintering. It was demonstrated that Aerosol flame deposition is one of the good candidates for the fabrication of thin film battery.  相似文献   
68.
Summary The performance of acid-treated montmorillonite catalysts in the degradation of polystyrene (PS) was investigated in this study. The degradation was carried out in a semi-batch reactor with a mixture of PS and catalyst at 400-450oC. The commercial Süd Chemie acid-treated montmorillonite clays (K-series) showed good catalytic activity for the degradation of PS. The styrene monomer and ethylbenzene were major liquid products. The increase of surface acidity enhanced further cracking of styrene dimer and trimer to produce styrene monomer. Higher production of ethylbenzene for K30 may be related to its bigger pore volume and surface area compared to those of K5. High degradation temperature favored styrene monomer production.  相似文献   
69.
Reaction of laser-ablated Zr with CH(4) ((13)CH(4), CD(4), and CH(2)D(2)) in excess neon during condensation at 5 K forms CH(2)=ZrH(2), the simplest alkylidene hydride complex, which is identified by infrared absorptions at 1581.0, 1546.2, 757.0, and 634.5 cm(-)(1). Density functional theory electronic structure calculations using a large basis set with polarization functions predict a C(1) symmetry structure with agostic C-H- - -Zr bonding and distance of 2.300 A. Identification of the agostic CH(2)=ZrH(2) methylidene complex is confirmed by an excellent match of calculated and observed isotopic frequencies particularly for the four unique CHD=ZrHD isotopic modifications. The analogous reactions in excess argon give two persistent photoreversible matrix configurations for CH(2)=ZrH(2). Finally, methane activation by CH(2)=ZrH(2) gives the new (CH(3))(2)ZrH(2) molecule.  相似文献   
70.
The thermodynamic parameters for the interaction of Cu2+, Ni2+, Co2+, Cd2+, andAg+ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag+ exhibited remarkably higher complexation selectivity.Ag+ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg+–M2+ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag+ was observed in both single and competitiveAg+–M2+ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P2N2) with silver,[Ag(P2N2)] (NO3), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P21/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) 3 and Z = 4.  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