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   395篇
  免费   5篇
  国内免费   2篇
化学   284篇
晶体学   7篇
力学   11篇
数学   13篇
物理学   87篇
  2023年   1篇
  2022年   5篇
  2021年   16篇
  2020年   12篇
  2019年   9篇
  2018年   7篇
  2017年   6篇
  2016年   11篇
  2015年   11篇
  2014年   8篇
  2013年   20篇
  2012年   20篇
  2011年   27篇
  2010年   18篇
  2009年   13篇
  2008年   23篇
  2007年   19篇
  2006年   15篇
  2005年   18篇
  2004年   15篇
  2003年   23篇
  2002年   21篇
  2001年   9篇
  2000年   9篇
  1999年   4篇
  1998年   3篇
  1997年   3篇
  1996年   3篇
  1995年   3篇
  1994年   4篇
  1993年   3篇
  1992年   5篇
  1991年   4篇
  1990年   3篇
  1989年   2篇
  1988年   4篇
  1987年   2篇
  1986年   3篇
  1985年   3篇
  1984年   4篇
  1983年   3篇
  1982年   1篇
  1981年   2篇
  1980年   1篇
  1979年   1篇
  1978年   1篇
  1977年   1篇
  1976年   2篇
  1973年   1篇
排序方式: 共有402条查询结果,搜索用时 31 毫秒
301.
302.
We report the MR imaging findings of a primary malignant mesothelioma of the liver arising from Glisson's capsule. A 54-year-old woman, presenting with acute abdominal pain and a large liver mass previously shown on CT, underwent MR imaging to characterize the lesion. The tumor was a greater than 12 cm tumor located in the right lobe of the liver, which was sharply marginated, with heterogeneous internal signal, septations and central necrosis. The tumor was considered a hepatocellular carcinoma. The diagnosis of malignant mesothelioma was established by immunohistochemical staining and electron microscopy of the resected tumor.  相似文献   
303.
Summary The molecular and crystal structure of Ru3(CO)12 has been reinvestigated on single-crystal X-ray diffraction data collected at 100 and 150 K. Thermal motion analysis on high-order diffraction data have been used to characterize the motion about equilibrium positions of the molecule as a whole and of groups of atoms. It has been shown that, while the molecule undergoes an almost isotropic rigid-body librational and translational motion, the three Ru(CO)4 units undergo different librational motions about the axes passing between each Ru atom and bisecting the opposite 615-01 bond. Packing potential energy calculations and computer graphics have been used to show that the most favoured packing motif in the experimental crystal is based on interlocking between tetracarbonyl units formed by two pairs of CO ligands at right angles along a 615-02 edge. Starting from the structure of Ru3(CO)12, alternative crystal arrangements have been generated and compared with the experimental crystal structure in terms of packing efficiency and cohesive energy.  相似文献   
304.
Infections caused by methicillin-resistant Staphylococcus aureus (MRSA) are a worldwide health problem. In a previous study, a murine monoclonal antibody (mMAB), capable of binding to PBP2a within MRSA strains, was generated. F(ab’)2 antibody fragments are widely described in the literature as immunochemical tools and reagents for diagnostics and therapeutics, particularly because of their low immunogenicity and rapid pharmacokinetics. In this study, F(ab’)2 fragments from mMAB were generated by enzymatic digestion, using pepsin. They were purified by affinity chromatography using protein A and concentrated by a MWCO 50 kDa filtration unit. The results indicate that it is possible to obtain F(ab’)2 fragments by pepsin digestion. ELISA, western blotting, and fluorescence microscopy data demonstrated that F(ab’)2 affinity for PBP2a is not lost even after the enzymatic digestion process. As expected, in the pharmacokinetics tests, F(ab’)2 presented a faster elimination (between 12 and 18 h) compared to IgG. These F(ab’)2 fragments could be used in future immunodiagnostic applications, including in vitro or in situ radiolabeling and in the treatment of infections caused by this important pathogen.  相似文献   
305.
An efficient copper (I) halotriphenylphosphine catalyzed one-pot multicomponent reaction (MCR) of 3-substituted indole derivatives has been developed using a variety of aldehydes (aromatic, aliphatic, and heteroaromatic), indole, and active methylene substrates such as malononitrile and ethyl 2-cyano acetate. This reaction proceeds smoothly and obtained good to excellent yields (68–93%) using water as green solvent under ambient conditions. The obtained products were confirmed by 1H, 13C NMR, and mass spectroscopy techniques. The one-pot MCR occurs through formation of Knoevenagel adducts then followed by Michael addition of indole.  相似文献   
306.
For a 2+1 strongly coupled (β=2/g 2 small) Wilson action lattice gauge theory with complex character we analyze the mass spectrum of the associated quantum field theory restricted to the subspace generated by the plaquette function and its complex conjugate. It is shown that there is at least one but not more than two isolated masses and each mass admits a representation of the formm(β)=?4lnβ+r(β), wherer(β) is a gauge group representation dependent function analytic inβ 1/2 orβ atβ=0. For the gauge group SU(3) there is mass splitting and the two massesm ± are given by $$m_ \pm (\beta ) = - 41n\beta + 16r^4 + \tfrac{1}{2}(2 \pm 1)\beta + \left( {d_ \pm (\beta )\sum\limits_{n = 2}^\infty {c_n^ \pm } \beta ^n } \right)$$ wherer=3 is the dimension of the representation andd ±(β) is analytic atβ=0.c n ± can be determined from a finite number of theβ=0 Taylor series coefficients of finite lattice truncated plaquette-plaquette correlation function at a finite number of points.  相似文献   
307.
-Cyclodextrin (-CD) and p-hydroxybenzaldehyde (p-HB) were studied by 1H-NMR in deuterated aqueous solution and the stoichiometry of the resulting complex (1:1) was determined by the continuous variation method. Inclusion of p-HB in -CD was confirmed by the observation of NMR shifts for the inside H5 protons of the -CD cavity. In the solid state X-ray analysis was carried out and revealed the detailed structure of the inclusion complex. Two -CDs cocrystallize with four p-HB and 9.45 water molecules[2(C6H10O5)4C7H6O9.45H2O] in the triclinic space group P1 with unit cell parameters: a = 15.262(2), b = 15.728(1), c = 16.350(1) Å, = 92.67(1)°, = 96.97(1)°, = 103.31(1)°. The anisotropic refinement of 1973 atomic parameters converged at an R-factor = 0.066 for 10157 data with Fo 2 > 2 (Fo 2). The 2:4 stoichiometry for the -CD inclusion complex with p-HB in the crystalline state is different from that obtained in solution. -CD forms dimers stabilized by direct O2(m)1O3(m)1·O2(n)2O3(n)2 hydrogen bonds (intradimer) and by indirect O6(m)1·O6(n)2 hydrogen bonds with one or two bridging water molecules joined in between (interdimer). These dimers are stacked like coins in a roll constructing infinite channels where the p-HB molecules are included. The p-HB molecules direct their polar CHO and OH groups into the nonpolar -CD cavities and are hydrogen bonded to each other, yielding infinite, antiparallel chains. In addition, crystals of the complex were also investigated with thermogravimetry, vibrational spectroscopy (FTIR), and 13C CP-MAS NMR spectroscopy. The results obtained enabled us to structurally characterize the -CD inclusion complex with p-HB.  相似文献   
308.
Metal tellurolates (M = B3+; BuTeTeBu/NaBH4/EtOH; Li3+, Te0/BuLi/THF; In3+, BuTeTeBu/InI/EtOH) react with aminoalkynes to produce vinylic tellurides containing amino groups; the regio-, and stereo-chemistry of the hydrotelluration reaction depend on the metallic counter ion and on the nature of the amino group substituent.  相似文献   
309.
Vinylic selenides were prepared in good yields by hydroselenation of alkynes with lithium butylselenolate generated by reaction of n-butyllithium with elemental selenium. The regio- and stereochemistry of the hydroselenation depend on the nature of the substituents bonded to the alkyne.  相似文献   
310.
Variable-pressure 1H-NMR Spectroscopy has been used to study the fluxionality of some five-coordinated Fe complexes in solution. For [Fe(CO)2 1,3-cyclooctadiene (PPh3)], the CO site exchange is known (by analogy with [Fe(CO)3(1,3-cyclooctadiene)]) to be a non-dissociative process, and an activation volume of ca. 0 cm3.mol?1 was indeed obtained. However, for [Fe(CO2){2,3-η:O-σ-(7,7-dimethoxybicyclo[2.2.1]hept-2-ene)}(PPh3)], the activation volume of +5 cm3 mol?1 suggests that an unprecedented dissociation process is responsible for the CO site exchange. The molecular structure of [Fe(CO)2(1,3-cyclooctadiene)(PPh3)] was ascertained by single-crystal X-ray diffractometry. The crystals are triclinic, space group P1 , a = 9.606(3), b = 16.795(2), c = 7.743(8) Å, α = 97.83(4), β = 109.63(4), γ = 83.37(2)°. The structure determination has shown that the complex possesses a tetragonal pyramidal coordination, with the endocyclic C?C bond and PPh3 occupying basal sites.  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