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   873篇
  免费   35篇
  国内免费   5篇
化学   560篇
晶体学   11篇
力学   29篇
数学   109篇
物理学   204篇
  2023年   11篇
  2022年   12篇
  2021年   50篇
  2020年   22篇
  2019年   31篇
  2018年   52篇
  2017年   33篇
  2016年   41篇
  2015年   37篇
  2014年   33篇
  2013年   64篇
  2012年   71篇
  2011年   71篇
  2010年   45篇
  2009年   30篇
  2008年   59篇
  2007年   59篇
  2006年   39篇
  2005年   39篇
  2004年   37篇
  2003年   29篇
  2002年   15篇
  2001年   4篇
  2000年   2篇
  1999年   3篇
  1998年   3篇
  1996年   1篇
  1995年   4篇
  1994年   3篇
  1992年   1篇
  1991年   1篇
  1990年   2篇
  1989年   1篇
  1984年   1篇
  1981年   1篇
  1980年   1篇
  1978年   1篇
  1977年   4篇
排序方式: 共有913条查询结果,搜索用时 15 毫秒
71.
72.
The present article investigates the influence of dispersion medium on the aggregate stability of cross-linked poly-(methyl methacrylate) particles on the surface layer of which aliphatic amino groups are localized. It is shown that particle size depends on the ionic strength of dispersion medium. The research determines the optimal content of cross-linked agent, ethylene glycol dimetharylate that results in the formation of cationic particles being stable in saline. Particle modification is performed by bovine serum albumin and luminophore fluorescein 5(6)-isothiocyanate. Protein sorption is observed not to influence luminescent properties of the particles. It is also determined that due to the aggregate stability of particles obtained from 5?wt% of ethylene glycol dimethacrylate in saline, the monodispersity and the absence of inversion of zeta potential in wide pH range is retained, such particles may be considered as perspective carriers of biologically active substances.  相似文献   
73.
Metal atom clusters constitute very promising candidates as luminophores for applications in biotechnology because they are nanosized entities offering robust luminescence in the near-infrared field (NIR). However, they cannot be used as prepared for biological applications because of potential toxic effects and quenching of the clusters' luminescence in aqueous media, and they therefore need to be dispersed in a biocompatible matrix. We describe herein the encapsulation of octahedral rhenium clusters, denoted as A(4)[Re(6)Q(8)L(6)] (A = Cs or K, Q = S or Se, and L = OH or CN), in silica nanoparticles by a water-in-oil microemulsion process, paying particular attention to the clusters' stability. The obtained A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles are 30 nm in size with good monodispersity and a perfectly spherical shape, as shown by scanning electron microscopy (SEM). The presence of cluster units inside the silica matrix was evidenced by scanning transmission electron microscopy in annular dark-field mode (ADF-STEM). From the point of view of their optical properties, the A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles show red and NIR emission under UV excitation, even when dispersed in water. The evolution of the structural and luminescence properties of clusters before and after encapsulation was followed by Raman and photoluminescence spectroscopy.  相似文献   
74.
75.
76.
The complex phosphate tricaesium calcium iron bis(diphosphate), Cs3CaFe(P2O7)2, has been prepared by the flux method. Isolated [FeO5] and [CaO6] polyhedra are linked by two types of P2O7 groups into a three‐dimensional framework. The latter is penetrated by hexagonal channels along the a axis where three Cs atoms are located. Calculations of caesium Voronoi–Dirichlet polyhedra give coordination schemes for the three Cs atoms as [8 + 3], [9 + 1] and [9 + 4]. The structure includes features of both two‐ and three‐dimensional frameworks of caesium double pyrophosphates.  相似文献   
77.
The present study reports the evidence for the multiple carbon–carbon bond insertion into the metal–heteroatom bond via a five‐coordinate metal complex. Detailed analysis of the model catalytic reaction of the carbon–sulfur (C? S) bond formation unveiled the mechanism of metal‐mediated alkyne insertion: a new pathway of C? S bond formation without preliminary ligand dissociation was revealed based on experimental and theoretical investigations. According to this pathway alkyne insertion into the metal–sulfur bond led to the formation of intermediate metal complex capable of direct C? S reductive elimination. In contrast, an intermediate metal complex formed through alkyne insertion through the traditional pathway involving preliminary ligand dissociation suffered from “improper” geometry configuration, which may block the whole catalytic cycle. A new catalytic system was developed to solve the problem of stereoselective S? S bond addition to internal alkynes and a cost‐efficient Ni‐catalyzed synthetic procedure is reported to furnish formation of target vinyl sulfides with high yields (up to 99 %) and excellent Z/E selectivity (>99:1).  相似文献   
78.
Understanding the radiation background at the north crossing point (NCP) in the tunnel of BEPCII is crucial for the performance safety of the High Purity Germanium (HPGe) detector, and in turn of great significance for long-term stable running of the energy measurement system. Therefore, as the first step, a NaI(Tl) detector is constructed to continuously measure the radiation level of photons as background for future experiments. Furthermore, gamma and neutron dosimeters are utilized to explore the radiation distribution in the vicinity of the NCP where the HPGe detector will be located. Synthesizing all obtained information, the shielding for neutron irradiation is studied based on model-dependent theoretical analysis.  相似文献   
79.
The origin of the anomalously large value of the heat capacity of liquid water is discussed. Comparing the temperature dependence of the heat capacities for water with those for argon and hydrogen sulfide, we separate contributions of the translational and rotational degrees of freedom. The residual part is considered as being caused by the specific contributions of the transversal vibrations of H-bonds. The estimate for the number of H-bonds per molecule is obtained from the analysis of this contribution. This estimate is in quite good agreement with the estimates which follow from the analysis of the specific volume, heat of evaporation, and kinematic shear viscosity.  相似文献   
80.
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