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   1898篇
  免费   23篇
  国内免费   11篇
化学   1307篇
晶体学   41篇
力学   72篇
综合类   3篇
数学   181篇
物理学   328篇
  2024年   29篇
  2023年   22篇
  2022年   108篇
  2021年   96篇
  2020年   90篇
  2019年   72篇
  2018年   71篇
  2017年   49篇
  2016年   84篇
  2015年   60篇
  2014年   99篇
  2013年   186篇
  2012年   102篇
  2011年   121篇
  2010年   86篇
  2009年   72篇
  2008年   59篇
  2007年   65篇
  2006年   59篇
  2005年   43篇
  2004年   42篇
  2003年   37篇
  2002年   44篇
  2001年   15篇
  2000年   7篇
  1999年   10篇
  1998年   10篇
  1997年   18篇
  1996年   21篇
  1995年   13篇
  1994年   9篇
  1993年   15篇
  1992年   9篇
  1991年   4篇
  1990年   7篇
  1989年   7篇
  1988年   7篇
  1987年   5篇
  1986年   4篇
  1985年   10篇
  1984年   5篇
  1983年   3篇
  1982年   10篇
  1981年   7篇
  1980年   5篇
  1979年   6篇
  1976年   5篇
  1975年   6篇
  1974年   4篇
  1960年   3篇
排序方式: 共有1932条查询结果,搜索用时 15 毫秒
991.
    
The crystal structures of the dispiro compounds 1,3,4,8,10,11‐Hexaphenyl‐13‐methyl‐1,2,8,9,13‐pentaazadispiro[4.1.4.3]tetradeca‐2,9‐dien‐6‐one ( 3a ) and 4,11‐Bis(4‐methoxyphenyl)‐13‐methyl‐1,3,8,10‐tetraphenyl‐1,2,8,9,13‐pentaazadispiro‐[4.1.4.3]tetradeca‐2,9‐dien‐6‐one ( 3b ) have been determined at room temperature from X‐ray powder diffraction data using the method of simulated annealing as implemented in the programs DASH and TOPAS. Subsequent Rietveld refinements using the data collected to 1.5 Å resolution yielded R‐Bragg values of 2.2% for ( 3a ) and 3.7% for ( 3b ). It was found, that both compounds crystallize in the monoclinc space group P 21/n with lattice parameters of a = 17.1656(5) Å, b =13.8128(3) Å, c = 16.1016(5) Å, and β = 103.7330(2)° for ( 3a ) and a = 17.2529(8) Å, b = 13.8729(5) Å, c =16.1287(10) Å, and β = 103.6910(3)° for ( 3b ). Both compounds exhibit a distorted hexagonal close type of packing (hcp) of the molecular centers of gravity. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
992.
    
The compounds 6,7‐dihydro‐2‐methoxy‐4‐(4‐methylphenyl)‐5H ‐benzo[6.7]cyclohepta[1,2‐b ]pyridine‐3‐carbonitrile (compound IIIa) and 4‐(4‐chlorophenyl)‐6,7‐dihydro‐2‐methoxy‐5H ‐benzo[6,7]cyclohepta[1,2‐b ]pyridine‐3‐carbonitrile (compound IIIb) were synthesized and their structures have been determined from three dimensional X‐ray data using direct method and refined by full matrix least squares with anisotropic thermal parameters for non‐hydrogen atoms to conventional R(gt) of 0.036 and 0.038 for the two compounds respectively. For compound (IIIa) the crystals are monoclinic, space group Cc, with a=11.2909 (5) Å, b=17.7755(8) Å, c=9.1437(4) Å and β=95.428(3)°, while the crystals of the second compound (IIIb) are triclinic, space group P1, with a=8.7465(3)Å, b=10.3958(3)Å, c=10.9011(4)Å, α= 108.3870(10)°, β=101.3741(12)°, γ=97.9594(12)°. The molecular structure of the two compounds have nearly the same configuration, where the cyclohepta ring takes the boat shape and the methoxy and the carbonitrile groups are attached at the same position C2 and C8. The difference occurs only at the position C4, where the substituent is methylphenyl for compound (IIIa) and chlorophenyl for the other. The bond lengths, valency angles and the hydrogen bonding were calculated and fully discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
993.
994.
Channeling phenomena are observed for positive particles of momentum up to 250 GeV/c in a germanium crystal. The polar angular distributions of the channeled particles are compared with theoretical predictions based on a diffusion model. The results indicate that at high particle energy there may be additional mechanisms besides those operative at low energy leading to dechanneling of the particles. In spite of this, channeling effects are observed for particles incident at up to several times the critical angle, in contrast with the results from low energy channeling. Statistical equilibrium in the azimuthal angular distribution has also been observed at all measured beam momenta to about twice the calculated channeling critical angle. The breakdown of statistical equilibrium for the 2 cm crystal used occurs at an incident angle 2–3 times smaller than predicted theoretically.  相似文献   
995.
Inhibition of the corrosion of carbon steel in hydrochloric acid solution by some mono- and bis-azo dyes based on 1,5-dihydroxynaphthalene was studied in relation to the concentration of inhibitors using weight loss and potentiostatic polarization techniques. The percentage inhibition efficiency calculated from two methods is in a good agreement with each other. The inhibition mechanism of the additives was ascribed to the formation of complex compound adsorbed on the metal surface. The adsorption process follows Freundlich adsorption isotherm. The formation of the complex compound was studied by conductometric and potentiometric titrations. The stability constants of the Fe-complexes were determined using the latter technique and related to the inhibition efficiency.  相似文献   
996.
Dimetridazole (DMD) is one of the significant antibiotic drugs of nitroimidazoles derivates that have attracted increasing attention in the medical field due to its pharmacological and toxicological activity. The development of high-performance sensors for continuous monitoring of DMD in food and environments is receiving increasing attention. Herein, an electrochemical platform was designed based on a dysprosium vanadate/halloysite nanotubes (DyV/HNTs) nanocomposite for the detection of DMD. The DyV/HNTs nanocomposite was examined by various spectroscopic and analytical techniques. The DyV/HNTs based electrochemical sensor reveals a distinctly higher electrocatalytic response to the reduction of DMD due to the good physiochemical properties compared to other electrodes. The DyV/HNTs based electrochemical sensor for DMD covered two linear ranges of 0.001–0.54 and 0.54–188 μM with a detection limit of 0.9 nm through the amperometric method, which is better than those previously reported. Furthermore, selectivity, stability, repeatability, and reproducibility studies were performed. Moreover, the fabricated DyV/HNTs sensor was successfully applied for the reliable discrimination of DMD in biological and water samples with satisfactory recovery values. The results indicated that this DyV/HNTs nanocomposite may be a promising electrochemical sensing platform for the determination of DMD.  相似文献   
997.
Cellulose - Herein, natural fiber (energy reeds and rice straw) reinforced with phenol formaldehyde (PF) polymeric resin biocomposites are developed and reported in this study. The dimensions of...  相似文献   
998.
Monoterpenes, linalool and thymol have been widely used in not only the treatments of several diseases but also food flavouring, dental, perfumery, and toilet products. Plants of the several Lamiaceae family are good sources of linalool and thymol. A rapid, simple, and precise high-performance thin layer chromatography (HPTLC) method was developed for the concurrent estimation of linalool and thymol, and this method was orchestrated using the essential oils extracted from two Lamiaceae plants leaves i.e. O. basilicum and T. vulgaris. Two standards were separated using pre-coated thin-layer chromatography glass plates. The developed HPTLC method was validated by following ICH guidelines (linearity; limit of detection, LOD; limit of quantitation; specificity; accuracy; precision; and robustness). The calibration curves of both the compounds were linear (100–700 ng/spot), with a correlation coefficient (r2) of >999. The developed HPTLC method was effectively applied to the concurrent detection and quantification of linalool and thymol in commercial essential oils.  相似文献   
999.
We report an optical spectroscopy study on the newly discovered superconductor Cu0.07TiSe2. Consistent with the development from a semimetal or semiconductor with a very small indirect energy gap upon doping TiSe2, it is found that the compound has a low carrier density. Most remarkably, the study reveals a substantial shift of the screened plasma edge in reflectance towards high energy with decreasing temperature. This phenomenon, rarely seen in metals, indicates either a sizable increase of the conducting carrier concentration or/and a decrease of the effective mass of carriers with reducing temperature. We attribute the shift primarily to the latter effect.  相似文献   
1000.
Previously reported experimental results indicate that photooxygenation of homochiral N-(hydroxyalkyl)-2-methylpyrroles with singlet oxygen yields trans-rather than cis-bicyclic lactams as the major product. In this study, the origin of selectivity in this reaction has been investigated with computational methods. Relative stabilities of homochiral N-(hydroxyalkyl)-2-methylpyrrole conformers and their effect on pi-facial selectivity of 1O2 were extensively studied. Stepwise and concerted reaction mechanisms, starting from the endoperoxide intermediates, were proposed and modeled in vacuum using the UB3LYP method with the 6-31+G** basis set. Solvent calculations were carried out in CH2Cl2, by means of the integral equation formalism-polarizable continuum model (IEF-PCM) at the UB3LYP/6-31+G** level of theory. Free energies of activation leading to both diastereomers were analyzed in an effort to explain the stereoselectivity and product distribution. Steric interactions among the pyrrole substituents were shown to lead to a rotational barrier higher than 10 kcal/mol. Hence, hindered internal rotation is suggested to cause one pyrrole conformer to be substantially overpopulated. This in turn has a major effect on pi-facial selectivity of 1O2, thereby favoring one endoperoxide over the other and leading to the diastereoselective synthesis of trans-pyrrolooxazolones. The importance of hindered internal rotors, for an accurate calculation of the frequency factors of a chemical reaction, has already been mentioned in the literature many times; however, in this work hindered internal rotors also seem to dictate the diastereoselective outcome of the reaction.  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