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   697篇
  免费   9篇
  国内免费   1篇
化学   514篇
晶体学   10篇
力学   8篇
数学   69篇
物理学   106篇
  2023年   5篇
  2022年   6篇
  2021年   13篇
  2020年   15篇
  2019年   22篇
  2018年   7篇
  2017年   7篇
  2016年   18篇
  2015年   20篇
  2014年   18篇
  2013年   28篇
  2012年   42篇
  2011年   48篇
  2010年   31篇
  2009年   35篇
  2008年   36篇
  2007年   29篇
  2006年   42篇
  2005年   41篇
  2004年   28篇
  2003年   31篇
  2002年   20篇
  2001年   10篇
  2000年   13篇
  1999年   13篇
  1998年   9篇
  1997年   4篇
  1996年   9篇
  1995年   9篇
  1994年   6篇
  1993年   6篇
  1992年   4篇
  1990年   4篇
  1989年   4篇
  1987年   4篇
  1985年   3篇
  1984年   7篇
  1981年   5篇
  1979年   3篇
  1978年   4篇
  1975年   3篇
  1974年   3篇
  1973年   3篇
  1971年   2篇
  1965年   3篇
  1959年   2篇
  1958年   2篇
  1955年   2篇
  1909年   2篇
  1887年   2篇
排序方式: 共有707条查询结果,搜索用时 0 毫秒
81.
82.
    
We report a study on diol cleavage of cyclic 1,2-dihydroxysilanes for the preparation of functionalized acylsilanes. Sodium periodate turned out to be an efficient reagent for this transformation, resulting in good to excellent yields. The method is characterized by mild reaction conditions, and sometimes simple aqueous workup of the reaction mixture was sufficient to obtain the acylsilanes in high purity. An acyclic 1,2-dihydroxysilane was readily cleaved as well.  相似文献   
83.
    
An important biomolecule found in plant seeds and tissues, and in eukaryotic cells is myo-inositol-1,2,3,4,5,6-hexakisphosphate (phytate, IP6). Phytate has many roles, including phosphate, myo-inositol, and mineral storage and retrieval in plants, and a number of metabolic roles, not all of which are known. Despite the importance of phytate in biology, structural information is limited. Aside from this report of the potassium phytate structure, K3[H9IP6]·2H2O, only the structures of the sodium and zinc salts have appeared. The potassium structure reveals the importance of metal ion chelation in stabilizing the conformation, and the two previously reported structures support this finding. Potassium ion and hydrogen bond bridges link the interwoven phytate networks throughout the lattice. 1H NMR (800 MHz) titrations show the conformation crossover from the 1a5e to the 5a1e conformation between pH 9 and 10, and detailed 1H deconvolution studies at low pH reveal the underlying pattern assignments for individual protons.  相似文献   
84.
85.
86.
    
Femtosecond time‐resolved spectroscopy in the visible and IR range was utilized to study the primary reaction dynamics of the proteorhodopsin (PR) D97N mutant in comparison with wild type PR at different pH values. The analysis of the data obtained in the mid‐IR closely resembles the results for wild type PR. The observation of the first ground state intermediate K is initially obscured by a complex reaction scheme of vibrational relaxation and heating effects, but its spectral signature clearly emerges at long delay times. In the visible range, a biexponential decay of the excited state within 30 ps and the formation of the K photoproduct is observed. The decay time constants derived for the D97N mutant in D2O are slightly larger than in H2O due to H/D exchange. This kinetic isotope effect is even less pronounced than for wild type PR at pH 6. These results support the current notion of a pH dependent hydrogen bonding network in the retinal binding pocket of PR and a weaker interaction between the retinal Schiff base and the counter ion complex compared to bacteriorhodopsin.  相似文献   
87.
88.
    
Nuclear magnetic resonance (NMR) analysis of the 13C‐labeled chain ends of polystyrene, polyMMA, and styrene‐MMA copolymers prepared by polymerizations initiated using 13C‐labeled‐phenacyl radicals were investigated. The phenacyl radicals were generated by anaerobic oxidation of acetophenone‐methyl‐13C using a Cu(II) octanoate‐pyridine complex in the presence of triethylamine and triphenylphosphine. NMR analysis of the 13C‐labeled chain ends of these polymers afforded insight into the initiation mechanism. In copolymerization experiments using 13C‐labeled acetophenone initiator, the NMR spectra provided evidence that the phenacyl radical reacts 2.7 times faster with styrene than with MMA. The resonances of the labeled phenacyl carbons also showed that the sequence and stereosequence distributions of monomer units at the chain ends are nearly the same as those that prevail along the polymer chains. Styrene–styrene, styrene–MMA, and MMA–styrene enchainments at the chain ends are equally likely to have meso (erythro) or racemic(threo) configurations but the ratio of meso to racemic MMA‐MMA enchainments is ~ 3/7. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2347–2356, 2008  相似文献   
89.
    
Ovarian cancer is the fifth leading cause of cancer death for women in the US, yet survival rates are over 90% when it is diagnosed at an early stage, highlighting the need for biomarkers for early detection. To enhance the discovery of tumor‐specific proteins that could represent novel serum biomarkers for ovarian cancer, we depleted serum of highly abundant proteins which can mask the detection of proteins present in serum at low concentrations. Three commercial immunoaffinity columns were used in parallel to deplete the highly abundant proteins in serum from 60 patients with serous ovarian carcinoma and 60 non‐cancer controls. Medium and low abundance serum proteins from each serum pool were then evaluated by the quantitative proteomic technique of differential in‐gel electrophoresis. The number of protein spots that were elevated in ovarian cancer sera by at least twofold ranged from 36 to 248, depending upon the depletion and separation methods. From the 33 spots picked for MS analysis, nine different proteins were identified, including the novel candidate ovarian cancer biomarkers leucine‐rich α2 glycoprotein‐1 and ficolin 3. Western blotting validated the relative increases in serum protein levels for three of the proteins identified, demonstrating the utility of this approach for the identification of novel serum biomarkers for ovarian cancer.  相似文献   
90.
    
A novel mode of reaction towards arylethynes is shown by the β-trimethylsilyl-substituted α,β-unsaturated Fischer carbene complexes 1 . A mixture of the isomeric, highly substituted spiro[4.4]nonatrienes 2 and 3 is formed by the formal insertion of three alkyne molecules and subsequent cyclization (see scheme). Such selective triple insertions of alkynes into ethenylcarbene complexes have not been previously observed.  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