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   4120篇
  免费   177篇
  国内免费   36篇
化学   2795篇
晶体学   38篇
力学   156篇
综合类   3篇
数学   404篇
物理学   937篇
  2024年   16篇
  2023年   28篇
  2022年   186篇
  2021年   194篇
  2020年   144篇
  2019年   134篇
  2018年   162篇
  2017年   116篇
  2016年   160篇
  2015年   158篇
  2014年   161篇
  2013年   314篇
  2012年   256篇
  2011年   281篇
  2010年   162篇
  2009年   145篇
  2008年   150篇
  2007年   170篇
  2006年   131篇
  2005年   134篇
  2004年   85篇
  2003年   78篇
  2002年   70篇
  2001年   71篇
  2000年   55篇
  1999年   58篇
  1998年   27篇
  1997年   27篇
  1996年   44篇
  1995年   41篇
  1994年   28篇
  1993年   32篇
  1992年   35篇
  1991年   40篇
  1990年   22篇
  1989年   24篇
  1988年   31篇
  1987年   27篇
  1986年   26篇
  1985年   38篇
  1984年   23篇
  1983年   23篇
  1982年   22篇
  1981年   12篇
  1980年   28篇
  1979年   21篇
  1978年   27篇
  1977年   27篇
  1976年   18篇
  1968年   10篇
排序方式: 共有4333条查询结果,搜索用时 31 毫秒
991.
Direct interaction force measurements using atomic force microscopy (AFM) were carried out between a silicon nitride tip and renal epithelial cells (Madin-Darby Canine Kidney-MDCK and proximal tubular epithelial cells derived from pig kidneys, LLC-PK1). The approaching (extending) portion of the force/distance curves is considered, and repulsive forces in the long range of 2-3 microm were seen in both MDCK as well as LLC-PK1 cells growing under normal conditions. The repulsive force in the shorter distance range of 50-200 nm was also observed, when cells were damaged exposing the underlying basal membrane. LLC-PK1 cells were more prone to damage than the MDCK cells, hence short-range forces were common in the former and long-range forces in the latter cells. The functional dependence of repulsive force on the indentation depth changes, at small indentation depth the force increases linearly, while at larger indentations the force is a quadratic function of the distance, which is attributed to the elasticity of the membrane and the solid-like response of cells, respectively. The oxalate treatment of cells for 2-4 h gives rise to an increase in the elastic modulus of the cells.  相似文献   
992.
993.
Room temperature reaction of 2-aminooxazole 1 and its 4- and 4,5-substituted derivatives, with dimethyl acetylenedicarboxylate gave good yields of Diels-Alder adducts 2 , isolated as stable crystalline compounds. A competing process produced oxazole[3,2-a]pyrimidines 3 , also in good yield. Minor products were also identified. 2-Amino-4-methylthiazole ( 6 ) reacted in a similar manner and gave the Diels-Alder adduct 7 and a thia-zolo[3,2-a]pyrimidine 8 as main products with a lesser amount of a thiazole [3,2-d][1:3]diazepine ( 9 ). The aminooxazoles reacted with olefinic dienophiles to give pyridine derivative, formed by breakdown of the original unstable adducts.  相似文献   
994.
The surface-enhanced resonance Raman scattering (SERRS) activity of a statistically significant number of silver nanoparticles has been studied using a correlated SERRS mapping and transmission electron microscopy (TEM) method. TEM allowed the nature of each entity to be directly identified, and the SERRS activity was obtained from the corresponding SERRS map. Particles in various states of aggregation were analyzed to establish relative activities. It was established that SERRS activity is dependent on the specific batch of colloid tested. By averaging different colloid batches, it was shown that increasing SERRS activity is observed with increasing numbers of particles in the aggregates. By reducing the surface coverage of the particles to the extent that single moieties could be examined optically, the ratio of the relative activities of single particles, dimers, trimers, and larger aggregates was estimated. High-resolution TEM images of a number of active and inactive particles are reported. However, no clear correlation between microstructure and SERRS activity was observed.  相似文献   
995.
Reaction of Pt(PnBu3)2Cl2 (1) or Pt(AsnBu32Cl2 (2) with stoichiometric amounts of 1,3,5-triethynylbenzene, [1,3,5-(H? C?C? )3C6H3] (3)yields monomeric, [1,3,5-Cl(PnBu3)2(Pt? C? C? )3C6H3] (4), [1,3,5-(C1)(AsnBu3)2Pt? C? C? 3C6H3] (5) or polymeric, {1,3,5-[(PnBu3)2Pt? C?C? ]3C6H3? )n (6), {1,3,5-[(AsnBu3)2Pt? C? C? ]3C6H3? }n (7) complexes. Treatment of (1) with (3) and 2,5-diethynyl-p-xylene,H? C? C? C6H2(CH3)2? C? C? H (8) in varying molar ratios yields a series of high molecular weight cross linked platinum metal containing polyyne copolymers.  相似文献   
996.
Mondal A  Li Y  Khan MA  Ross JH  Houser RP 《Inorganic chemistry》2004,43(22):7075-7082
The self-assembly of supramolecular copper "tennis balls" that possess unusual magnetic properties using a small pyridyl amide ligand is described. Copper(II) complexes of N-(2-pyridylmethyl)acetamide (HL) were synthesized in methanol. In the absence of base, the mononuclear complex [Cu(HL)(2)](ClO(4))(2) (1) was prepared. The structure of 1, determined by X-ray crystallography, contains a copper(II) ion surrounded by bidentate HL ligands coordinated via the pyridyl N atom and the carbonyl O atom in a trans, square planar arrangement. Reactions carried out in the presence of triethylamine resulted in cluster complexes [Cu(8)L(8)(OH)(4)](ClO(4))(4) and [Cu(8)L(8)(OH)(4)](CF(3)SO(3))(4) [2(ClO(4))(4) and 2(OTf)(4), respectively]. The cationic portions of 2(ClO(4))(4) and 2(OTf)(4) are isostructural, containing eight copper(II) ions, eight deprotonated ligands (L(-)), and four mu(3)-hydroxide ligands. The top and bottom halves of the cluster are related by a pseudo-S(4) symmetry operation and are held together by bridging L(-) ligands. Solutions of 2(ClO(4))(4) and 2(OTf)(4), which were shown to contain the full [Cu(8)L(8)(OH)(4)](4+) fragment by electrospray mass spectrometry and conductance experiments, are EPR silent. Magnetic susceptibility measurements for 2(ClO(4))(4) as a function of temperature and magnetic field showed the Cu ions all to exhibit magnetic moments in the range expected for the d(9) configuration. At low temperatures, the magnetization was reduced due to predominantly antiferromagnetic interactions between ions. Analysis showed that partially frustrated interactions among the four Cu ions making up each half of the cluster gave good agreement with the data once a large molecular anisotropy was taken into account, with J(c) = 106 cm(-1), D = 27 cm(-1), and g = 2.17.  相似文献   
997.
In present studies a new series of twenty four complexes of seven and ten coordinated compounds derived from 4[Ncinnamalidene) amino]antipyrine semicarbazone (CAAPS) as primary ligand and diphenyl sulfoxide (DPSO) as secondary ligand has been reported. All the complexes have the general composition LnX3.n(CAAPS).DPSO (Ln = La, Pr, Nd, Sm, Gd, Tb, Dy or Ho, X = NCS or ClO4, n = 2, X = NO3, n = 1). The compounds have been characterized by elemental analysis, molar conductance, magnetic susceptibility, infrared and electronic spectra. Thermal characteristics were also reported. Based on the data appropriate structures are assigned for these complexes.  相似文献   
998.
A windowless Si(Li) electron detector has been used in conjunction with the gas filled fission product separator JOSEF to study totally converted transitions in Zr and Mo isotopes. The existence of twoβ-decay modes in96Y,98Y and100Nb is confirmed. The half-lives of theβ-decaying levels feeding O 2 + states in96Zr and98Zr are 6.0 ± 0.4 sec and 0.60±0.05 sec respectively. A search for other first excited O 2 + states shows that no such states are apparent in100Zr and104Mo.  相似文献   
999.
Asymmetric catalytic epoxidation of alkenes such as styrenes, chromenes and indene using transition metal complexes both inhomogeneous and heterogeneous phase has been discussed in this review. The various strategies to make the catalysts recyclable by introducing in-built phase transfer ability, converting these to dimeric form, exchanging into clays and supporting on polymeric or inorganic supports are discussed at length.  相似文献   
1000.
The kinetics of the aqueous cleavage of N‐ethoxycarbonylphthalimide (NCPH) in CH3NHOH buffers of different pH reveals that the cleavage follows the general irreversible consecutive reaction path NCPH ENMBC A B , where ENMBC, A , and B represent ethyl N‐[o‐(N‐methyl‐N‐hydroxycarbamoyl)benzoyl]carbamate, N‐hydroxyl group cyclized product of ENMBC, and o ‐(N‐methyl‐N‐hydroxycarbamoyl)benzoic acid, respectively. The rate constant k1 obs at a constant pH, obeys the relationship k1 obs = kw + knapp [Am]T + kb[Am]T2, where [Am]T is the total concentration of CH3NHOH buffer and kw is first‐order rate constant for pH‐independent hydrolysis of NCPH. Buffer‐dependent rate constant kb shows the presence of both general base and general acid catalysis. Both the rate constants k2 obs and k3 obs are independent of [Am]T (within the [Am]T range of present study) at a constant pH and increase linearly with the increase in aOH with definite intercepts. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 95–103, 2002  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