全文获取类型
收费全文 | 536篇 |
免费 | 16篇 |
国内免费 | 4篇 |
专业分类
化学 | 378篇 |
晶体学 | 11篇 |
力学 | 6篇 |
数学 | 91篇 |
物理学 | 70篇 |
出版年
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.
Michael E. Kurczy Paul D. Piehowsky David Willingham Kathleen A. Molyneaux Michael L. Heien Nicholas Winograd Andrew G. Ewing 《Journal of the American Society for Mass Spectrometry》2010,21(5):833-836
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.
Mark E. Erupe Allegra Liberman-Martin Philip J. Silva Quentin G.J. Malloy Naomi Yonis David R. Cocker III Kathleen L. Purvis-Roberts 《Journal of chromatography. A》2010,1217(13):2070-2073
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.
Li F Munson B Edwards J Yoneyama K Hall K 《The Journal of the Acoustical Society of America》2011,129(2):999-1011
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.
Naijue Zhu Danielle Lightsey Jiawang Liu Maryam Foroozesh Kathleen M. Morgan Edwin D. Stevens Cheryl L. Klein Stevens 《Journal of chemical crystallography》2010,40(4):343-352
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.
Simon G. Bott Alan P. Marchand L. Kathleen Talafuse D. Rajagopal 《Journal of chemical crystallography》1995,25(9):543-547
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.
Kundu S Bhangale AS Wallace WE Flynn KM Guttman CM Gross RA Beers KL 《Journal of the American Chemical Society》2011,133(15):6006-6011
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.
Kwaku Adu‐Gyamfi Michael J. Boss Kathleen Lynch‐Davis 《School science and mathematics》2019,119(7):396-404
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