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   1684篇
  免费   57篇
  国内免费   12篇
化学   1377篇
晶体学   23篇
力学   22篇
数学   121篇
物理学   210篇
  2023年   10篇
  2022年   16篇
  2021年   20篇
  2020年   23篇
  2019年   34篇
  2018年   24篇
  2017年   16篇
  2016年   48篇
  2015年   30篇
  2014年   44篇
  2013年   117篇
  2012年   97篇
  2011年   112篇
  2010年   77篇
  2009年   59篇
  2008年   109篇
  2007年   89篇
  2006年   89篇
  2005年   88篇
  2004年   80篇
  2003年   77篇
  2002年   57篇
  2001年   19篇
  2000年   17篇
  1999年   22篇
  1998年   16篇
  1997年   25篇
  1996年   13篇
  1995年   13篇
  1994年   20篇
  1993年   20篇
  1992年   18篇
  1991年   20篇
  1990年   9篇
  1989年   9篇
  1986年   10篇
  1985年   14篇
  1984年   21篇
  1983年   10篇
  1982年   18篇
  1981年   12篇
  1980年   11篇
  1979年   8篇
  1978年   8篇
  1976年   13篇
  1974年   13篇
  1973年   8篇
  1970年   9篇
  1969年   11篇
  1968年   7篇
排序方式: 共有1753条查询结果,搜索用时 15 毫秒
41.
42.
43.
In this note we examine the relationships between p-hyponormal operators and the operator inequality . This leads to a method for generating examples of p-hyponormal operators which are not q-hyponormal for any . Our methods are also shown to have implications for the class of Furuta type inequalities.  相似文献   
44.
Circular autocorrelation of stationary circular Markov processes   总被引:1,自引:0,他引:1  
The stationary Markov process is considered and its circular autocorrelation function is investigated. More specifically, the transition density of the stationary Markov circular process is defined by two circular distributions, and we elucidate the structure of the circular autocorrelation when one of these distributions is uniform and the other is arbitrary. The asymptotic properties of the natural estimator of the circular autocorrelation function are derived. Furthermore, we consider the bivariate process of trigonometric functions and provide the explicit form of its spectral density matrix. The validity of the model was assessed by applying it to a series of wind direction data.  相似文献   
45.
The laser-induced fluorescence spectra of jet-cooled benzo-18-crown-6 (B18C6) and dibenzo-18-crown-6 (DB18C6) exhibit a number of vibronic bands in the 35 000-37 000 cm(-1) region. We attribute these bands to monomers and hydrated clusters by fluorescence-detected IR-UV and UV-UV double resonance spectroscopy. We found four and two conformers for bare B18C6 and DB18C6, and the hydration of one water molecule reduces the number of isomers to three and one for B18C6-(H(2)O)(1) and DB18C6-(H(2)O)(1), respectively. The IR-UV spectra of B18C6-(H(2)O)(1) and DB18C6-(H(2)O)(1) suggest that all isomers of the monohydrated clusters have a double proton-donor type (bidentate) hydration. That is, the water molecule is bonded to B18C6 or DB18C6 via two O-H[dot dot dot]O hydrogen bonds. The blue shift of the electronic origin of the monohydrated clusters and the quantum chemical calculation suggest that the water molecule in B18C6-(H(2)O)(1) and DB18C6-(H(2)O)(1) prefers to be bonded to the ether oxygen atoms near the benzene ring.  相似文献   
46.
A study of the polymerization of methyl methacrylate initiated by the binary systems of some activated metals and organic halides has been made. It was found that the initiator activities of these systems were greatly dependent on the kind and the preparation or activation method of the metals (i.e., oxidation potential, surface area, and purity), and also on the kind of organic halides (i.e., bond-dissociation energy of their carbon–halogen bonds). From the kinetic studies of the polymerization at 60°C with the system reduced nickel–carbon tetrachloride, the rate of polymerization was found to be proportional to the monomer concentration and to the square root of concentration of both nickel and carbon tetrachloride at the lower concentration range of carbon tetrachloride, indicating that the system induced the radical polymerization. A similar conclusion was also obtained from the copolymerization with styrene with this system at 60°C, i.e., the resulting copolymer composition curve was in agreement with that obtained with azobisisobutyronitrile (AIBN). The apparent overall activation energy for the methyl methacrylate polymerization with this system was estimated to be 7.5 kcal/mole, which was considerably lower than that with AIBN. On the basis of the results obtained, an initiation mechanism for the polymerization with these initiator systems is presented and discussed.  相似文献   
47.
Using a highly sensitive flow‐type 27 MHz quartz crystal microbalance, we could detect a small mass change during stepwise and alternating one‐sugar transfer of glucuronic acid (GlcA) and N‐acetylgalactosamine (GalNAc) to an acceptor, catalyzed by chondroitin polymerase from Escherichia coli strain K4 (K4CP), and analyze the elongation mechanism of K4CP. K4CP was found to bind strongly to a chondroitin acceptor (Kd=0.97 μM ). Although the binding affinity and the catalytic rate constant for each monomer were considerably different, the apparent catalytic efficiency (kcat/Km) was similar (6.3×104 M ?1 s?1 for GlcA transfer and 3.4×104 M ?1 s?1 for the GalNAc transfer). This is reasonable for the smooth alternating elongation of GlcA and GalNAc on the acceptor. This is the first study to report the determination of kinetic parameters for enzymatic, alternated, sugar elongation.  相似文献   
48.
Covalently linked vancomycin dimers have attracted a great deal of attention among researchers because of their enhanced antibacterial activity against vancomycin‐resistant strains. However, the lack of a clear insight into the mechanisms of action of these dimers hampers rational optimization of their antibacterial potency. Here, we describe the synthesis and antibacterial activity of novel vancomycin dimers with a constrained molecular conformation achieved by two tethers between vancomycin units. Conformational restriction is a useful strategy for studying the relationship between the molecular topology and biological activity of compounds. In this study, two vancomycin units were linked at three distinct positions of the glycopeptide (vancosamine residue (V), C terminus (C), and N terminus (N)) to form two types of novel vancomycin cyclic dimers. Active NC‐VV‐linked dimers with a stable conformation as indicated by molecular mechanics calculations selectively suppressed the peptidoglycan polymerization reaction of vancomycin‐resistant Staphylococcus aureus in vitro. In addition, double‐disk diffusion tests indicated that the antibacterial activity of these dimers against vancomycin‐resistant enterococci might arise from the inhibition of enzymes responsible for peptidoglycan polymerization. These findings provide a new insight into the biological targets of vancomycin dimers and the conformational requirements for efficient antibacterial activity against vancomycin‐resistant strains.  相似文献   
49.
We designed bisnitroxide compounds where the radical sites are located close to each other in a molecule. Two new pincer-type bisnitroxide compounds have been synthesized, involving xanthene-4,5-diyl as a spacer and tert-butyl phenyl nitroxides as arms. From the X-ray crystal structure analysis, the shortest intramolecular interatomic N?O and O?O distances respectively are 5.074(6) and 5.258(6) Å for the m,m′-derivative and 3.624(3) and 3.771(3) Å for the p,p′-derivative. The N?O distance in the latter satisfies the empirical criterion for possible dimerization/degradation reaction accompanied by dia-/paramagnetic transition. However, the magnetic study clarified paramagnetic behavior in all the temperature range. According to a singlet-triplet model, antiferromagnetic couplings were characterized with 2J/kB = ?7.71(2) and ?8.83(4) K for the m,m′ and p,p′-derivatives, respectively. The present result suggests that a more flexible spacer is required for realization of possible dia-/paramagnetic transition.  相似文献   
50.
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