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   26987篇
  免费   5037篇
  国内免费   4432篇
化学   20655篇
晶体学   579篇
力学   1445篇
综合类   389篇
数学   3062篇
物理学   10326篇
  2024年   49篇
  2023年   437篇
  2022年   602篇
  2021年   828篇
  2020年   1019篇
  2019年   1134篇
  2018年   925篇
  2017年   931篇
  2016年   1236篇
  2015年   1374篇
  2014年   1537篇
  2013年   1982篇
  2012年   2551篇
  2011年   2603篇
  2010年   2045篇
  2009年   1910篇
  2008年   2177篇
  2007年   1855篇
  2006年   1798篇
  2005年   1603篇
  2004年   1299篇
  2003年   1064篇
  2002年   1172篇
  2001年   902篇
  2000年   682篇
  1999年   552篇
  1998年   350篇
  1997年   264篇
  1996年   252篇
  1995年   234篇
  1994年   220篇
  1993年   163篇
  1992年   112篇
  1991年   129篇
  1990年   98篇
  1989年   64篇
  1988年   53篇
  1987年   29篇
  1986年   33篇
  1985年   47篇
  1984年   25篇
  1983年   21篇
  1982年   14篇
  1981年   19篇
  1980年   10篇
  1979年   13篇
  1978年   7篇
  1977年   7篇
  1957年   5篇
  1936年   4篇
排序方式: 共有10000条查询结果,搜索用时 25 毫秒
991.
The effect of ß-cyclodextrin (ß-CD) on cetyltrimethylammonium bromide (CTAB) micellar properties was studied by the determination of the diffusion coefficient, D. When the CTAB micelles have a spherical structure, D firstly increased and then remained unchanged, while the micellar aggregation number, N, decreased with the addition of ß-CD. When the CTAB concentration was less than the first critical micellar concentration, CTAB molecules could be included into ß-CD cavities with the molar ratio of CTAB to ß-CD being about 1:1. However, when the CTAB concentration was higher than the first critical micellar concentration, mixed spherical micelles were formed with the molar ratio of CTAB to ß-CD being 9:1.  相似文献   
992.
Infrared (1.2-1.6 microm) luminescence in a ytterbium aluminium garnet (YbAG) crystal, doped with Cr (0.05at.%) ions, was investigated under CW laser diode pumping (lambda=940 nm). The Cr4+ emission band was observed with its peak at 1.34 microm and measured to be about 1.3 times with respect to Yb3+ IR luminescence (lambda=1.03 microm). We demonstrate that for the excitation wavelength of 940 nm Yb3+ ions act as sensitizers of the 3B2(3T2)-3B1(3A2) emission of Cr4+ ions. This crystal is promising as a high-efficient system for tunable laser (1.2-1.6 microm) output.  相似文献   
993.
SrCu2(PO4)2 was prepared by the solid-state method at 1153 K. Its structure was solved by direct methods in the space group Pccn (No. 56) with Z = 8 from synchrotron X-ray powder diffraction data measured at room temperature. Structure parameters were then refined by the Rietveld method to obtain the lattice parameters, a = 7.94217(8) A, b = 15.36918(14) A, and c = 10.37036(10) A. SrCu2(PO4)2 presents a new structure type and is built up from Sr2O16 and Cu1Cu2O8 units with Cu1...Cu2 = 3.256 A. The magnetic properties of SrCu2(PO4)2 were investigated by magnetic susceptibility, magnetization up to 65 T, Cu nuclear quadrupole resonance (NQR), electron-spin resonance, and specific heat measurements. With spin-dimer analysis, it was shown that the two strongest spin-exchange interactions between Cu sites result from the Cu1-O...O-Cu2 and Cu2-O...O-Cu2 super-superexchange paths with Cu1...Cu2 = 5.861 A and Cu2...Cu2 = 5.251 A, and the superexchange associated with the structural dimer Cu1Cu2O8 is negligible. The magnetic susceptibility data were analyzed in terms of a linear four-spin cluster model, Cu1-Cu2-Cu2-Cu1 with -2J(1)/kB = 82.4 K for Cu1-Cu2 and -2J(2)/k(B) = 59 K for Cu2-Cu2. A spin gap deduced from this model (Delta/kB = 63 K) is in agreement with that obtained from the Cu NQR data (Delta/kB = 65 K). A one-half magnetization plateau was observed between approximately 50 and 63 T at 1.3 K. Specific heat data show that SrCu2(PO4)2 does not undergo a long-range magnetic ordering down to 0.45 K. SrCu2(PO4)2 melts incongruently at 1189 K. We also report its vibrational properties studied with Raman spectroscopy.  相似文献   
994.
Cleavage of the N-(1-phenylethyl) unit of carboxamides using less than 1 equiv of MsOH in refluxing toluene was found to be simple and very efficient leading to the desired amides in good to excellent yields, and also proved to be more effective compared with reductive methods using hydrogen sources, or acid hydrolysis reagents such as TFA and TsOH. The method selectively cleaved only the N-(1-phenylethyl) group of N-benzyl-N-(1-phenylethyl)amides.  相似文献   
995.
The mass spectrometric behavior of phenanthroindolizidine alkaloids has been investigated in detail by positive ion fast atom bombardment tandem mass spectrometry (FAB-MS/MS) combined with collision-induced dissociation (CID). The fragmentation has been correlated with the skeleton structure and positions of substituents. The product ions arising from retro-Diels-Alder cleavages differ clearly for compounds with different skeletons. The substituents at C-14 were observed to markedly influence the fragmentation pathway of [M + H](+) ions. A diversity of dissociation behavior initiated by the variation of substituents on the aromatic ring was also observed in the CID spectra. Product ions resulting from loss of CH(4) were obtained for compounds in which both C-6 and C-7 are occupied by methoxy groups. FAB-MS/MS spectra can reflect the connection between the fragmentation behavior and structural features of these phenanthroindolizidine alkaloids rapidly and effectively, and should prove to be a powerful method to determine the structures of related compounds.  相似文献   
996.
侧链液晶离聚物对PA1010/PP共混体系的增容作用   总被引:2,自引:0,他引:2  
将聚酰胺(PA1010)、聚丙烯(PP)和热致型侧链液晶离聚物(SLCI)进行熔融共混,采用FTIR,SEM,DSC,WAXD研究测定了共混物中的相互作用,用形态结构,热行为和结晶行为,系统地研究了SLCI对PA101/PP共混物的增容作用。结果表明,SLCI有效地改善了PA1010/PP共混物的形态结构,增强了PA1010与PP链间的相互作用,使PA1010/PP熔点升高,结晶度提高。  相似文献   
997.
Two new diterpenoids, pedunculatic acid A (= (4R,5α,7α)‐7‐ethoxy‐9β,13β‐dioxyabiet‐8(14)‐en‐18‐oic acid; 1 ) and pedunculatic acid B (= (4S,5α,12β)‐8β,14β‐epoxy‐12‐hydroxy‐11‐oxototaran‐19‐oic acid; 2 ), together with three known sesquiterpenoids, were isolated from the Chinese medicinal herb Callicarpa pedunculata R. Brown . Their structures were elucidated by spectroscopic analyses, including 1D‐ and 2D‐NMR, and by high‐resolution mass spectrometry.  相似文献   
998.
The effects of alkali metals (Na+,K+) on the exchange degree of Hβ zeolite under different conditions and the conversion of α(or β)-methylnaphthalene over the alkalized zeolites were studied. The results showed that the H+ of Hβ zeolite is totally replaced by the Na+ of NaCl solution, while partially exchanged by the K+ of KC1 solution, there is an exchange equilibrium between the H+ and K+ for Hβ zeolite (Si/Al=17.23) and the value of equilibrium is 88.39. The exchange degree also increases with increasing the Si/Al of the samples. It was suggested that these resluts are attributed to the electrostatic field in the pore of Hβ zeolite and the nature of zeolite and the properties of alkali metal. The isomerization of α(or β)-methylnaphthalene is the main reaction over the samples and it is more favour on the proper acid-base sites of KHβ zeolite.  相似文献   
999.
A gauche-gauche interaction is proposed as a powerful controlling factor for the stereochemistry in the intramolecular nitrile oxide cycloaddition reaction derived from N-protected 3-(N-allylamino)propionaldehyde and 2-(N-homoallylamino)acetaldehyde oximes. High levels of stereoselectivity (76% de to perfect) were obtained from the reaction involving nitrile oxides with substituents at the adjacent carbon atom to the tether nitrogen.  相似文献   
1000.
The title compound, [Sr(C7H5O4)2(C12H8N2)2(H2O)2]·2C12H8N2·4H2O, consists of an SrII complex, uncoordinated phenanthroline (phen) molecules and solvent water molecules. The SrII ion is located on a twofold axis and is coordinated by two phen ligands, two dihydroxybenzoate anions and two water molecules in a distorted tetragonal antiprismatic geometry. Partially overlapped arrangements exist between parallel coordinated and parallel uncoordinated phen rings; the face‐to‐face separations between the former (coordinated) and the latter (uncoordinated) rings are 3.436 (13) and 3.550 (14) Å, respectively. This difference suggests the effect of metal coordination on π–π stacking between phen rings.  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