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   536篇
  免费   16篇
  国内免费   4篇
化学   378篇
晶体学   11篇
力学   6篇
数学   91篇
物理学   70篇
  2023年   6篇
  2022年   3篇
  2021年   9篇
  2020年   10篇
  2019年   8篇
  2018年   5篇
  2017年   2篇
  2016年   16篇
  2015年   6篇
  2014年   17篇
  2013年   36篇
  2012年   36篇
  2011年   49篇
  2010年   22篇
  2009年   18篇
  2008年   32篇
  2007年   23篇
  2006年   24篇
  2005年   26篇
  2004年   25篇
  2003年   18篇
  2002年   27篇
  2001年   8篇
  2000年   10篇
  1999年   10篇
  1998年   2篇
  1997年   10篇
  1996年   10篇
  1995年   5篇
  1994年   10篇
  1993年   4篇
  1991年   5篇
  1990年   3篇
  1989年   4篇
  1988年   6篇
  1985年   6篇
  1984年   8篇
  1982年   3篇
  1981年   4篇
  1979年   3篇
  1978年   5篇
  1977年   2篇
  1976年   3篇
  1975年   3篇
  1974年   3篇
  1967年   1篇
  1966年   1篇
  1942年   1篇
  1938年   1篇
  1922年   1篇
排序方式: 共有556条查询结果,搜索用时 15 毫秒
41.
A C60+ cluster ion projectile is employed for sputter cleaning biological surfaces to reveal spatio-chemical information obscured by contamination overlayers. This protocol is used as a supplemental sample preparation method for time of flight secondary ion mass spectrometry (ToF-SIMS) imaging of frozen and freeze-dried biological materials. Following the removal of nanometers of material from the surface using sputter cleaning, a frozen-patterned cholesterol film and a freeze-dried tissue sample were analyzed using ToF-SIMS imaging. In both experiments, the chemical information was maintained after the sputter dose, due to the minimal chemical damage caused by C60+ bombardment. The damage to the surface produced by freeze-drying the tissue sample was found to have a greater effect on the loss of cholesterol signal than the sputter-induced damage. In addition to maintaining the chemical information, sputtering is not found to alter the spatial distribution of molecules on the surface. This approach removes artifacts that might obscure the surface chemistry of the sample and are common to many biological sample preparation schemes for ToF-SIMS imaging.  相似文献   
42.
An ion chromatography method with non-suppressed conductivity detection was developed for the simultaneous determination of methylamines (methylamine, dimethylamine, trimethylamine) and trimethylamine-N-oxide in particulate matter air samples. The analytes were well separated by means of cation-exchange chromatography using a 3 mM nitric acid/3.5% acetonitrile (v/v) eluent solution and a Metrosep C 2 250 (250 mm × 4 mm i.d.) separation column. The effects of the different chromatographic parameters on the separation were also investigated. Detection limits of methylamine, dimethylamine, trimethylamine, and trimethylamine-N-oxide were 43, 46, 76 and 72 μg/L, respectively. The relative standard deviations of the retention times were between 0.42% and 1.14% while the recoveries were between 78.8% and 88.3%. The method is suitable for determining if methylamines and trimethylamine-N-oxide are a significant component of organic nitrogen aerosol in areas with high concentration of these species.  相似文献   
43.
Both English and Japanese have two voiceless sibilant fricatives, an anterior fricative /s/ contrasting with a more posterior fricative /∫/. When children acquire sibilant fricatives, English children typically substitute [s] for /∫/, whereas Japanese children typically substitute [∫] for /s/. This study examined English- and Japanese-speaking adults' perception of children's productions of voiceless sibilant fricatives to investigate whether the apparent asymmetry in the acquisition of voiceless sibilant fricatives reported previously in the two languages was due in part to how adults perceive children's speech. The results of this study show that adult speakers of English and Japanese weighed acoustic parameters differently when identifying fricatives produced by children and that these differences explain, in part, the apparent cross-language asymmetry in fricative acquisition. This study shows that generalizations about universal and language-specific patterns in speech-sound development cannot be determined without considering all sources of variation including speech perception.  相似文献   
44.
45.

Abstract  

The single-crystal X-ray structures and in vivo activities of three aryl acetylenic inhibitors of cytochromes P450 1A1, 1A2, 2A6, and 2B1 have been determined and are reported herein. These are 1-ethynylpyrene, 1-propynylpyrene, and 4-propynylpyrene. To investigate electronic influences on the mechanism of enzyme inhibition, the experimental electron density distribution of 1-ethynylpyrene has been determined using low-temperature X-ray diffraction measurements, and the resulting net atomic charges compared with various theoretical calculations. A total of 82,390 reflections were measured with Mo Kα radiation to a (sinθ/λ)max = 0.985 Å−1. Averaging symmetry equivalent reflections yielded 8,889 unique reflections. A least squares refinement procedure was used in which multipole parameters were added to describe the distortions of the atomic electron distributions from spherical symmetry. A map of the model electron density distribution of 1-ethynylpyrene was obtained. Net atomic charges calculated from refined monopole population parameters yielded charges that showed that the terminal acetylenic carbon atom (C18) is more negative than the internal carbon (C17). Net atomic charges calculated by ab initio, density functional theory, and semi-empirical methods are consistent with this trend suggesting that the terminal acetylenic carbon atom is more likely to be the site of oxidation. This is consistent with the inhibition mechanism pathway that results in the formation of a reactive ketene intermediate. This is also consistent with assay results that determined that 1-ethynylpyrene acts as a mechanism-based inhibitor of P450s 1A1 and 1A2 and as a reversible inhibitor of P450 2B1. Crystallographic data: 1-ethynylpyrene, C18H10, P21/c, a = 14.571(2) Å, b = 3.9094(5) Å, c = 20.242(3) Å, β = 105.042(2)°, V = 1,113.5(2) Å3; 1-propynylpyrene, C19H12, P21/n, a = 8.970(2) Å, b = 10.136(1) Å, c = 14.080(3) Å, β = 99.77(2)°, V = 1,261.5(4) Å3; 4-propynylpyrene, C19H12, Pbca, a = 9.904(1) Å, b = 13.174(2) Å, c = 19.401(1) Å, V = 2,531.4(5) Å3.  相似文献   
46.
The structure consists of two acetyl-substituted PCU cages linked by a diyne fragment. The conformation about the linker is midway between staggered and eclipsed, and the acetyl groups are somewhat distorted due to the proximity to the bulky cage units.  相似文献   
47.
A divergent synthesis of (-)-4-epi-shikimic acid was developed. This route features a one-pot zinc-mediated reductive ring opening of an arabinofuranose followed by a Barbier reaction and culminates in a ring-closing metathesis. Functionalization of (-)-4-epi-shikimic acid via conjugate addition of a thiol occurs in high diastereoselectivity to afford a product with the features of fucosylated glycans.  相似文献   
48.
Continuous flow enzyme-catalyzed polymerization in a microreactor   总被引:1,自引:0,他引:1  
Enzymes immobilized on solid supports are increasingly used for greener, more sustainable chemical transformation processes. Here, we used microreactors to study enzyme-catalyzed ring-opening polymerization of ε-caprolactone to polycaprolactone. A novel microreactor design enabled us to perform these heterogeneous reactions in continuous mode, in organic media, and at elevated temperatures. Using microreactors, we achieved faster polymerization and higher molecular mass compared to using batch reactors. While this study focused on polymerization reactions, it is evident that similar microreactor based platforms can readily be extended to other enzyme-based systems, for example, high-throughput screening of new enzymes and to precision measurements of new processes where continuous flow mode is preferred. This is the first reported demonstration of a solid supported enzyme-catalyzed polymerization reaction in continuous mode.  相似文献   
49.
50.
Previous research has investigated the representational translation practices of high school students, high school teachers, and college preservice teachers in various mathematical contexts including linear functions. Findings from qualitative research has frequently led to new notions about participant work and understanding. Many quantitative research has investigated the degree to which some in these populations correctly perform these translations. However, it seems that only infrequently have empirical research investigated findings from qualitative studies and vice versa, and findings regarding one population are rarely compared with findings of another population. This study (a) empirically explores the frequency of success of preservice teachers (N = 80) regarding representational translations in the context of linear functions, (b) quantifies results from previous qualitative, literature‐based research regarding high school students and teachers, and (c) quantitatively compares the results. This study demonstrates that some mathematical representational translations are more difficult than others.  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