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   1425篇
  免费   58篇
  国内免费   2篇
化学   1062篇
晶体学   11篇
力学   34篇
数学   49篇
物理学   329篇
  2023年   13篇
  2022年   21篇
  2021年   23篇
  2020年   40篇
  2019年   26篇
  2018年   17篇
  2017年   24篇
  2016年   36篇
  2015年   26篇
  2014年   30篇
  2013年   69篇
  2012年   74篇
  2011年   86篇
  2010年   51篇
  2009年   37篇
  2008年   74篇
  2007年   78篇
  2006年   71篇
  2005年   73篇
  2004年   74篇
  2003年   46篇
  2002年   44篇
  2001年   44篇
  2000年   27篇
  1999年   22篇
  1998年   12篇
  1997年   16篇
  1996年   22篇
  1995年   17篇
  1994年   22篇
  1993年   16篇
  1992年   13篇
  1990年   12篇
  1989年   16篇
  1988年   12篇
  1987年   12篇
  1986年   7篇
  1985年   18篇
  1984年   15篇
  1983年   9篇
  1982年   8篇
  1980年   16篇
  1979年   12篇
  1978年   11篇
  1976年   12篇
  1975年   10篇
  1974年   8篇
  1973年   11篇
  1969年   7篇
  1967年   7篇
排序方式: 共有1485条查询结果,搜索用时 15 毫秒
81.
The aim of this study is to clarify the effect of doped metal type on CO2 reduction characteristics of TiO2 with NH3 and H2O. Cu and Pd have been selected as dopants for TiO2. In addition, the impact of molar ratio of CO2 to reductants NH3 and H2O has been investigated. A TiO2 photocatalyst was prepared by a sol-gel and dip-coating process, and then doped with Cu or Pd fine particles by using the pulse arc plasma gun method. The prepared Cu/TiO2 film and Pd/TiO2 film were characterized by SEM, EPMA, TEM, STEM, EDX, EDS and EELS. This study also has investigated the performance of CO2 reduction under the illumination condition of Xe lamp with or without ultraviolet (UV) light. As a result, it is revealed that the CO2 reduction performance with Cu/TiO2 under the illumination condition of Xe lamp with UV light is the highest when the molar ratio of CO2/NH3/H2O = 1:1:1 while that without UV light is the highest when the molar ratio of CO2/NH3/H2O = 1:0.5:0.5. It is revealed that the CO2 reduction performance of Pd/TiO2 is the highest for the molar ratio of CO2/NH3/H2O = 1:1:1 no matter the used Xe lamp was with or without UV light. The molar quantity of CO per unit weight of photocatalyst for Cu/TiO2 produced under the illumination condition of Xe lamp with UV light was 10.2 μmol/g, while that for Pd/TiO2 was 5.5 μmol/g. Meanwhile, the molar quantity of CO per unit weight of photocatalyst for Cu/TiO2 produced under the illumination condition of Xe lamp without UV light was 2.5 μmol/g, while that for Pd/TiO2 was 3.5 μmol/g. This study has concluded that Cu/TiO2 is superior to Pd/TiO2 from the viewpoint of the molar quantity of CO per unit weight of photocatalyst as well as the quantum efficiency.  相似文献   
82.
83.
The functionalization of fullerene has been extensively studied and various fullerene derivatives have been synthesized. We have succeeded in the functionalization of [60]fullerene by using α‐aminoalkyl radicals generated by visible‐light‐mediated single‐electron oxidation of α‐silylamines as synthetic intermediates. In these reactions, the introduction of diarylamino groups, which are useful electron donors, has been easily achieved.  相似文献   
84.
A catalytic variant of the direct thiolation of arenes, bearing directing groups, with disulfides or thiols has been developed under palladium and copper co‐catalysis. Both sulfenyl moieties of the disulfide could be incorporated into the thiolated products, therefore, the reactions reached completion with only half an equivalent of disulfide, with respect to the starting arene. Experimental evidence suggested that the reaction proceeds through a PdII/PdIV mechanism.  相似文献   
85.
Anti‐MUC1 monoclonal antibodies (mAbs) are powerful tools that can be used to recognize cancer‐related MUC1 molecules, the O‐glycosylation status of which is believed to affect binding affinity. We demonstrate the feasibility of using a rapid screening methodology to elucidate those effects. The approach involves i) “one‐bead‐one‐compound”‐based preparation of bilayer resins carrying glycopeptides on the shell and mass‐tag tripeptides coding O‐glycan patterns in the core, ii) on‐resin screening with an anti‐MUC1 mAb, iii) separating positive resins by utilizing secondary antibody conjugation with magnetic beads, and (iv) decoding the mass‐tag that is detached from the positive resins pool by using mass spectrometric analysis. We tested a small library consisting of 27 MUC1 glycopeptides with different O‐glycosylations against anti‐MUC1 mAb clone VU‐3C6. Qualitative mass‐tag analysis showed that increasing the number of glycans leads to an increase in the binding affinity. Six glycopeptides selected from the library were validated by using a microarray‐based assay. Our screening provides valuable information on O‐glycosylations of epitopes leading to high affinity with mAb.  相似文献   
86.
Back electron transfer (BET) is one of the important processes that govern the decay of generated ion pairs in intermolecular photoinduced electron transfer reactions. Unfortunately, a detailed mechanism of BET reactions remains largely unknown in spite of their importance for the development of molecular photovoltaic structures. Here, we examine the BET reaction of pyrene (Py) and 1,4‐dicyanobenzene (DCB) in acetonitrile (ACN) by using time‐resolved near‐ and mid‐IR spectroscopy. The Py dimer radical cation (Py2.+) and DCB radical anion (DCB.?) generated after photoexcitation of Py show asynchronous decay kinetics. To account for this observation, we propose a reaction mechanism that involves electron transfer from DCB.? to the solvent and charge recombination between the resulting ACN dimer anion and Py2.+. The unique role of ACN as a charge mediator revealed herein could have implications for strategies that retard charge recombination in dye‐sensitized solar cells.  相似文献   
87.
We investigated the optical response of a huge number of silver nanoparticles (AgNPs) densely assembled on an organic microsphere, i.e., AgNP-fixed bead, under the collective phenomena of localized surface plasmons. For this purpose, various optical properties of such a AgNP-fixed bead were analyzed in aqueous solution by dark-field optical microscopy and laser Raman microscopy. In particular, in comparison with the optical spectrum of single AgNPs, significant spectral broadening and redshift were observed due to plasmonic superradiance with decreasing interparticle distance to the subnanoscale when using small binder molecules in the AgNP-fixed bead. Furthermore, we observed surface-enhanced Raman scattering and clarified the sensitivity of the signal intensity to the size of the binder molecules between the AgNPs, which can be explained based on optical response theory using a discrete integral with spherical cells. These results and discussion provide a guiding principle for broadband plasmonic light absorbers and for highly sensitive detection of small molecules and nanoscale biomaterials based on vast numbers of nanogaps produced by a bottom-up self-assembly process.  相似文献   
88.
We investigated the fluorescent properties, including the excited-state intermolecular proton transfer, of urea derivatives comprising a coumarin ring, which is a widely used fluorophore. We prepared two different coumarin–urea derivatives, 6CU and 7CU, which bear a urea-based substituent at the 6 and 7 positions of a coumarin ring, respectively. In the presence of the acetate ion, 7CU showed additional tautomer fluorescence emission with respect to 6CU, indicating that tautomer formation depends on the positions of the urea-based substituent on the coumarin ring. Thus, the resonance structures of urea derivatives might play an important role in the behavior of dual fluorescence, which is an important phenomenon applicable to photochemical anion sensing. Moreover, in order to further improve the fluorescence properties of the mentioned derivatives, a CF3 group was introduced in a phenyl ring opposite to a coumarin ring. The fluorescence quantum yield of 7CUCF3 thus synthesized was 65 times as large as that of 7CU, an observation that renders 7CUCF3 a suitable anion sensor candidate. The results of this study will contribute to the development of new molecular designs for highly fluorescent sensing.  相似文献   
89.
An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism.  相似文献   
90.
Linear polybiurets have been synthesized by polyaddition of benzyloxyamine and diisocyanates, and properties of the novel polymeric materials have been elucidated. Prior to polymerization, model reactions between benzyloxyamine and phenyl isocyanate were examined in detail and proved to be controlled by the molar ratio of reagents and by catalysts to give the urea (1:1 adduct) and/or biuret (1:2 adduct). Under appropriate conditions, the biuret was synthesized in a quantitative yield. Polymerization of equimolar amounts of benzyloxyamine and diphenylmethane or hexamethylene diisocyanate proceeded smoothly to give polybiurets with inherent viscosities up to 0.52 dL/g. The benzyl group of the model biuret and polybiuret could be removed by catalytic hydrogenation. Both the N-benzyloxy-type and N-hydroxy-type polybiurets showed excellent solubility in common organic solvents. The two kinds of polybiurets as well as model biurets adsorbed metal cations efficiently. The N-hydroxybiuret structure exhibited particularly high affinity for iron(III) and was useful for selective removal of iron from metal cation mixtures. © 1996 John Wiley & Sons, Inc.  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