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   6086篇
  免费   713篇
  国内免费   685篇
化学   4167篇
晶体学   73篇
力学   462篇
综合类   67篇
数学   564篇
物理学   2151篇
  2025年   6篇
  2024年   85篇
  2023年   138篇
  2022年   231篇
  2021年   277篇
  2020年   342篇
  2019年   307篇
  2018年   204篇
  2017年   217篇
  2016年   272篇
  2015年   306篇
  2014年   365篇
  2013年   423篇
  2012年   508篇
  2011年   529篇
  2010年   359篇
  2009年   356篇
  2008年   331篇
  2007年   268篇
  2006年   241篇
  2005年   230篇
  2004年   198篇
  2003年   166篇
  2002年   171篇
  2001年   173篇
  2000年   109篇
  1999年   116篇
  1998年   97篇
  1997年   69篇
  1996年   87篇
  1995年   50篇
  1994年   66篇
  1993年   34篇
  1992年   28篇
  1991年   27篇
  1990年   20篇
  1989年   12篇
  1988年   15篇
  1987年   10篇
  1986年   14篇
  1985年   7篇
  1984年   2篇
  1983年   4篇
  1982年   8篇
  1981年   2篇
  1980年   3篇
  1975年   1篇
排序方式: 共有7484条查询结果,搜索用时 31 毫秒
61.
    
The aromatic nitrogen atoms of heteroarylaldehydes are activated by carbene catalysts to react with ketone electrophiles. Multi-functionalized cyclic N,O-acetal products are afforded in good to excellent yields and optical purities. Our reaction involves the formation of an unprecedented aza-fulvene-type acylazolium intermediate. A broad range of N-heteroaromatic aldehydes and electron-deficient ketone substrates works effectively in this transformation. Several of the chiral N,O-acetal products afforded through this protocol exhibit excellent antibacterial activities against Ralstonia solanacearum (Rs) and are valuable in the development of novel agrichemicals for plant protection.  相似文献   
62.
    
Journal of Solid State Electrochemistry - This work presents the development and characterization of an electrochemical sensor of tin hexacyanoferrate (SnHCF), produced from the modification by...  相似文献   
63.
    
The ATP-binding cassette (ABC) transporter P-glycoprotein (P-gp) is a physiologically essential membrane protein that protects many tissues against xenobiotic molecules, but limits the access of chemotherapeutics into tumor cells, thus contributing to multidrug resistance. The atomic-level mechanism of how substrates and inhibitors differentially affect the ATP hydrolysis by P-gp remains to be elucidated. In this work, atomistic molecular dynamics simulations in an explicit membrane/water environment were performed to explore the effects of substrate and inhibitor binding on the conformational dynamics of P-gp. Distinct differences in conformational changes that mainly occurred in the nucleotide-binding domains (NBDs) were observed from the substrate- and inhibitor-bound simulations. The binding of rhodamine-123 can increase the probability of the formation of an intermediate conformation, in which the NBDs were closer and better aligned, suggesting that substrate binding may prime the transporter for ATP hydrolysis. By contrast, the inhibitor QZ-Leu stabilized NBDs in a much more separated and misaligned conformation, which may result in the deficiency of ATP hydrolysis. The significant differences in conformational modulation of P-gp by substrate and inhibitor binding provided a molecular explanation of how these small molecules exert opposite effects on the ATPase activity. A further structural analysis suggested that the allosteric communication between transmembrane domains (TMDs) and NBDs was primarily mediated by two intracellular coupling helices. Our computational simulations provide not only valuable insights into the transport mechanism of P-gp substrates, but also for the molecular design of P-gp inhibitors.  相似文献   
64.
    
Optimizing interfacial contacts and thus electron transfer phenomena in heterogeneous electrocatalysts is an effective approach for enhancing electrocatalytic performance. Herein, we successfully synthesized ultrafine β-Mo2C nanoparticles confined within hollow capsules of nitrogen-doped porous carbon (β-Mo2C@NPCC) and found that the surface layer of molybdenum atoms was further oxidized to a single Mo–O surface layer, thus producing intimate O–Mo–C interfaces. An arsenal of complementary technologies, including XPS, atomic-resolution HAADF-STEM, and XAS analysis clearly reveals the existence of O–Mo–C interfaces for these surface-engineered ultrafine nanostructures. The β-Mo2C@NPCC electrocatalyst exhibited excellent electrocatalytic activity for the hydrogen evolution reaction (HER) in water. Theoretical studies indicate that the highly accessible ultrathin O–Mo–C interfaces serving as the active sites are crucial to the HER performance and underpinned the outstanding electrocatalytic performance of β-Mo2C@NPCC. This proof-of-concept study opens a new avenue for the fabrication of highly efficient catalysts for HER and other applications, whilst further demonstrating the importance of exposed interfaces and interfacial contacts in efficient electrocatalysis.

Ultrafine β-Mo2C nanostructures encapsulated in N-doped carbon capsules featuring O–Mo–C interfaces as the active sites for HER have been unveiled.  相似文献   
65.
    
Tunneled metal oxides such as α-Mn8O16 (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K+ ions (which act as structure-stabilizing dopants) and H2O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K+-doped α-Mn8O16 (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H2O displaces K+ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K2+ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li+/Na+ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K2+) in the tunnels of hollandite.  相似文献   
66.
67.
张洁辉  郑邦乾 《合成化学》1997,5(3):311-316
以二乙烯苯和双丙烯酸多缩乙二醇酯为交联剂、聚醋酸乙烯酯(PVAc)或它与醋酸丁酯(BAC)的混合物为致孔剂、BPO为引发剂,用悬浮聚合随后水解的方法制得了部分水解聚(丙烯酸甲酯-醋酸乙烯酯-甲基丙烯酸甲酯)[HP(MA-VAc-MMA)]多孔载体,研究了PVAc及(PVAc+BAC)用量、分子量及混合比对HP(MA-VAc-MMA)孔结构的影响。结果表明,当PVAc的M>2.5×105,PVAc/BAC为2.3,用量为10~20%时,可制得孔隙率较高,孔径分布较窄,孔表面积较大的多孔载体。这种载体适用于微生物固定化。  相似文献   
68.
Xing WL  He XW 《Talanta》1997,44(6):959-965
A single piezoelectric quartz crystal coated with one kind of crown ether was applied to the simultaneous determination of binary acid and amine vapor mixtures. From the adsorption and desorption curves of analytes, which were somewhat different in shape, frequency shifts from ten time windows were taken as inputs for artificial neural networks (ANN). Prediction results were satisfactory for ANN in both sample sets. The average relative errors, for formic acid and acrylic acid were 5%, for n-butylamine and aniline, they were 3% with ANN respectively. The effects of number of neurons in the hidden layer of ANN on the performance of the network are also discussed.  相似文献   
69.
介绍了化学测量仪器的分类、特点、检定/校准的必要性及化学计量检定/校准的现状,分析了化学计量标准的特点,探讨了化学计量最高标准的划定和考核的有关问题。  相似文献   
70.
Xing Chen  He Tian  Ze Zhang 《物理化学学报》2020,36(11):1906019-0
It is important to determine the effects of misfit dislocations and other defects on the domain structure, ferroelectricity, conductivity, and other physical properties of ferroelectric thin films to understand their ferroelectric and piezoelectric behaviors. Much attention has been given to ferroelectric PbTiO3/SrTiO3 or PbZr0.2Ti0.8O3/SrTiO3 heterointerfaces, at which improper ferroelectricity, a spin-polarized two-dimensional electron gas, and other physical phenomena have been found. However, those heterointerfaces were all (001) planes, and there has been no experimental studies on the growth of (010) PbTiO3/SrTiO3 heterointerface due to the 6.4% misfit between two materials. In this study, we selected an atomically flat (010) PbTiO3/SrTiO3 heterointerface grown using a two-step hydrothermal method as the research subject, and this is the first experimental report on that interface. Interfacial dislocations can play a significant role in causing dramatic changes in the Curie temperature and polarization distribution near the dislocation cores, especially when the size of a ferroelectric thin film is scaled down to the nanoscale. The results of previous studies on the effects of interfacial dislocations on the physical properties of ferroelectric thin films have been contradictory. Thus, this issue needs to be explored more deeply in the future. This study used aberration corrected scanning transmission electron microscopy (STEM) to study the atomic structure of a (010) PbTiO3/SrTiO3 heterointerface and found periodic misfit dislocations with a Burgers vector of a[001]. The extra planes at the dislocation cores could relieve the misfit strain between the two materials in the [001] direction and thus allowed the growth of such an atomically sharp heterointerface. Moreover, monochromated electron energy-loss spectroscopy with an atomic scale spatial resolution and high energy resolution was used to explore the charge distribution near the periodic misfit dislocation cores. The fine structure of the Ti L edge was quantitatively analyzed by linearly fitting the experimental spectra recorded at various locations near and at the misfit dislocation cores with the Ti3+ and Ti4+ reference spectra. Therefore, the accurate valence change of Ti could be determined, which corresponded to the charge distribution. The probable existence of an aggregation of electrons was found near the a[001] dislocation cores, and the density of the electrons calculated from the valence change was 0.26 electrons per unit cell. Based on an analysis of the fine structure of the oxygen K edge, it could be argued that the electrons aggregating at the dislocation cores came from the oxygen vacancies in the interior regions of the PbTiO3. This aggregation of electrons will probably increase the electron conductivity along the dislocation line. The physics of two-dimensional charge distributions at oxide interfaces have been intensively studied, however, little attention had been given to the one-dimensional charge distribution. Therefore, the results of this study can stimulate research interest in exploring the influence of the interfacial dislocations on the physics of ferroelectric heterointerfaces.  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