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   15552篇
  免费   422篇
  国内免费   328篇
化学   9808篇
晶体学   102篇
力学   422篇
综合类   30篇
数学   2037篇
物理学   3903篇
  2022年   171篇
  2021年   199篇
  2020年   182篇
  2019年   193篇
  2018年   184篇
  2017年   150篇
  2016年   344篇
  2015年   318篇
  2014年   384篇
  2013年   822篇
  2012年   691篇
  2011年   768篇
  2010年   555篇
  2009年   530篇
  2008年   731篇
  2007年   753篇
  2006年   618篇
  2005年   652篇
  2004年   636篇
  2003年   618篇
  2002年   653篇
  2001年   452篇
  2000年   412篇
  1999年   312篇
  1998年   234篇
  1997年   209篇
  1996年   223篇
  1995年   244篇
  1994年   233篇
  1993年   180篇
  1992年   177篇
  1991年   179篇
  1990年   196篇
  1989年   158篇
  1988年   142篇
  1987年   138篇
  1986年   126篇
  1985年   221篇
  1984年   246篇
  1983年   167篇
  1982年   184篇
  1981年   155篇
  1980年   155篇
  1979年   143篇
  1978年   118篇
  1977年   167篇
  1976年   145篇
  1975年   120篇
  1974年   113篇
  1973年   116篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
Mössbauer spectra of the 27.8 keV transition in129I have been measured with sources of129mTe implanted in - and -tin and - and -SiC. The spectra mainly show two single line components, just as those obtained in earlier investigations with sources of129mTe implanted in diamond, silicon and germanium. The component with isomer shift corresponding to a decreased s-electron density relative to the I ion is attributed to the substitutionally implanted impurities, that with shift corresponding to an increased s-electron density to interstitial impurities. Plots of the shifts of both component show a linear dependence on the lattice constant for diamond, silicon and germanium and -tin. For SiC, however, the shifts are considerably smaller than expected on the basis of this linear dependence. All shifts can be quantitatively understood on the basis of a simple model that attributes the shifts of the interstitial impurities to a compression in the host lattice and shifts of the substitutional impurities to the combined effect of compression and hybridized bonding.  相似文献   
92.
The reaction of various heteroarylamines with ethyl 2-benzoyl-2-bromoacetate was used to obtain some imidazo[1,2-a]pyridines, imidazo[1,2-a]pyrimidines, imidazo[2,1-b]thiazoles and imidazo[2,1-b]benzothiazoles characterized by the presence of a phenyl moiety on the imidazole ring. In the case of thiazole and benzothiazole derivatives, unexpected by-products were isolated and their structures elucidated.  相似文献   
93.
The addition of stannylcuprate reagents such as (Bu3Sn)(PhS)CuLi to alkynones has been found to proceed in high yield and with excellent stereoselectivity for the Z isomer of the product (>95%). The behavior of the stannylcuprates is thus very different from that of their "carbocuprate" counterparts such as Me2CuLi or Me2Cu(CN)Li2 which are nonstereoselective. Furthermore, in contrast to the reactions of (R3Sn)(PhS)CuLi with the corresponding alkynoates, the presence of a proton source in the reaction medium has no effect on the stereoselectivity of the reaction of alkynones.  相似文献   
94.
Mass spectra of 1-phenylethanol-1 and its analogues, specifically deuterated in the aliphatic chain, suggest that the [M? CH3]+ ion is represented partly by an α-hydroxybenzyl fragment. Moreover, the molecular ion loses successively—after scrambling of all hydrogen atoms, except those of CH3? a hydrogen atom and C6H6, generation the CH3CO+ ion. Diffuse peaks, found in the spectra of of 2-phenylethanol-1 and its analogues, specifically deuterated in the aliphatic chain and in the phenyl ring, show that the molecular ion loses C2H4O, possibly via a four-center mechanism, after an exchange of aromatic and hydroxylic hydrogens. Mass spectra of 1-phenylpropanol-2 and its analogues, specifically, deuterated in the aliphatic chain, demonstrate that in the molecular ion exclusively the hydroxyl hydrogen atom is transferred to one of the ortho-positions of the phenyl ring via a McLafferty rearrangement, generating the [M ? C2H4O]+ ion. Furtherore, an eight-membered ring structure is proposed for the [M ? CH3]+ ion to explain the loss of H2O and C2H2O from this ion after an extensive scrambling of hydrogen atoms.  相似文献   
95.
The effects of ultrasonic irradiation on transport and reactions in several flow-injection manifolds are described. The influences of ultrasound on the physical dispersion of the injected plug is considered. Its effects on systems involving homogeneous (catalytic and non-catalytic) and heterogeneous (liquid/liquid extraction, precipitation) reactions are critically evaluated. In general, greater sensitivity is obtained, especially for heterogeneous systems, slow reactions and low analyte concentrations. Finally, practical considerations and potential uses of the combination of ultrasonic irradiation with flow-injection analysis are discussed.  相似文献   
96.
For 13 isotopes, the resonance integral to thermal crosssection ratio was studied. The results of two different methods, applied in two different laboratories, are compared. One method consists in a direct determination of I00-values from Cd-ratio measurements, the other is based on the evaluation of literature data, using accurately determined k0-factors from two irradiation channels with largely different thermal-to-epithermal flux ratios.  相似文献   
97.
The structures of three compounds with potential anti­malarial activity are reported. In N,N‐diethyl‐N′‐(7‐iodo­quinolin‐4‐yl)ethane‐1,2‐diamine, C15H20IN3, (I), the mol­ecules are linked into ribbons by N—H⋯N and C—H⋯N hydrogen bonds. In N‐(7‐bromo­quinolin‐4‐yl)‐N′,N′‐diethyl­ethane‐1,2‐diamine dihydrate, C15H20BrN3·2H2O, (II), two amino­quino­line mol­ecules and four water mol­ecules form an R54(13) hydrogen‐bonded ring which links to its neighbours to form a T5(2) one‐dimensional infinite tape with pendant hydrogen bonds to the amino­quinolines. The phosphate salt 7‐chloro‐4‐[2‐(diethyl­ammonio)ethyl­amino]quinolinium bis­(dihydrogen­phosphate) phospho­ric acid, C15H22ClN32+·2H2PO4·H3PO4, (III), was prepared in order to establish the protonation sites of these compounds. The phosphate ions form a two‐dimensional hydrogen‐bonded sheet, while the amino­quino­line cations are linked to the phosphates by N—H⋯O hydrogen bonds from each of their three N atoms. While the conformation of the quinoline region hardly varies between (I), (II) and (III), the amino side chain is much more flexible and adopts a significantly different conformation in each case. Aromatic π–π stacking inter­actions are the only supramolecular inter­actions seen in all three structures.  相似文献   
98.
A method is described for determining traces of boron in water, fertilizers, geological and biological (reference) materials by isotope-dilution mass spectrometry after separation on an Amberlite IRA-743 borate-selective ion-exchange column. Boron (–250 ng g?1) in water can be determined with an accuracy of 5–20% (computed on a 2s basis). After correction for weighing errors and for moisture, content, which varied from 0 to 8% for the samples tested, 1–35 μg g?1 boron in “dry” fertilizer, biological or geological sample can be assayed with an accuracy of 5–30% (2s). In an IAEA interlaboratory program on a simulated fresh water, the method yielded a value of 24.3 +? 2 μg l?1, compared to the make-up value of 25 μg l?1.  相似文献   
99.
100.
S.H. Schei  A. De Meijere 《Tetrahedron》1985,41(10):1973-1978
A gas phase electron diffraction investigation of 1-chloro-1-(trichlorovinyl)cyclopropane at 65° showed the existence of one conformer having a perpendicular arrangement of the cyclopropyl- and the trichlorovinylgroup, with torsional angle τ = 91(3)° relative to τ = 180° for the antiperiplanar conformer (CCl-CClanti arrangement). Both the experimental data and a molecular mechanics calculation indicate the lower barrier toward the antiperiplanar form,less than 40 kJ · mol-1. The second barrier was by molecular mechanics calculated to 60 kJ · mol-1.  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