全文获取类型
收费全文 | 248篇 |
免费 | 7篇 |
国内免费 | 2篇 |
专业分类
化学 | 132篇 |
晶体学 | 2篇 |
力学 | 2篇 |
数学 | 30篇 |
物理学 | 91篇 |
出版年
2023年 | 3篇 |
2022年 | 5篇 |
2021年 | 2篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 6篇 |
2015年 | 2篇 |
2014年 | 3篇 |
2013年 | 12篇 |
2012年 | 10篇 |
2011年 | 16篇 |
2010年 | 7篇 |
2009年 | 6篇 |
2008年 | 15篇 |
2007年 | 12篇 |
2006年 | 9篇 |
2005年 | 10篇 |
2004年 | 7篇 |
2003年 | 5篇 |
2002年 | 2篇 |
2001年 | 4篇 |
2000年 | 14篇 |
1999年 | 5篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1974年 | 5篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1966年 | 1篇 |
排序方式: 共有257条查询结果,搜索用时 31 毫秒
1.
2.
Leavitt AJ Wyrwas RB Wallace WT Serrano DS Arredondo MG Leslie LM Khan FA Whetten RL 《The journal of physical chemistry. A》2005,109(28):6218-6222
Carbon-cluster anions, CN-, are very reactive toward SO2 (sticking probability of 0.012 +/- 0.005 for C27- at 25 degrees C), in contrast to their inertness toward other common atmospheric gases and pollutants. In flow reactor experiments at ambient temperature and near atmospheric pressure, primary adsorption of SO2 by the carbon cluster anions, N = 4-60, yields CNSO2- or CN-1S-. The inferred elimination of neutral CO2 is also detected as meta-stable decay in collision-induced dissociation. At higher temperatures, the reaction of SO2 with nascent carbon clusters yields CN-1SO- as well as undetected CO. The size-dependent initial reactivity reflects the previously established structural transitions (i.e., from chain to cyclic to cage structures). Such carbon clusters are formed in sooting flames and may act as nuclei for the formation of primary soot particles and serve as models for the local structural features of active soot particle sites for black-carbon soot. The facile generation of reactive carbon-sulfide and -sulfinate units may therefore have implications for understanding the health and environmental effects attributed to the coincidence of soot and SO2. 相似文献
3.
Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献
4.
In situ observations of water production and distribution in an operating H2/O2 PEM fuel cell assembly using 1H NMR microscopy 总被引:1,自引:0,他引:1
Feindel KW LaRocque LP Starke D Bergens SH Wasylishen RE 《Journal of the American Chemical Society》2004,126(37):11436-11437
Proton NMR imaging was used to investigate in situ the distribution of water in a polymer electrolyte membrane fuel cell operating on H2 and O2. In a single experiment, water was monitored in the gas flow channels, the membrane electrode assembly, and in the membrane surrounding the catalysts. Radial gradient diffusion removes water from the catalysts into the surrounding membrane. This research demonstrates the strength of 1H NMR microscopy as an aid for designing fuel cells to optimize water management. 相似文献
5.
Fluorescence-dip infrared spectroscopy and predissociation dynamics of OH A 2Sigma+ (v = 4) radicals
Derro EL Pollack IB Dempsey LP Greenslade ME Lei Y Radenović DC Lester MI 《The Journal of chemical physics》2005,122(24):244313
Fluorescence-dip infrared spectroscopy, an UV-IR double-resonance technique, is employed to characterize the line positions, linewidths, and corresponding lifetimes of highly predissociative rovibrational levels of the excited A (2)Sigma(+) electronic state of the OH radical. Various lines of the 4 <--2 overtone transition in the excited A (2)Sigma(+) state are observed, from which the rotational, centrifugal distortion, and spin-rotation constants for the A (2)Sigma(+) (v = 4) state are determined, along with the vibrational frequency for the overtone transition. Homogeneous linewidths of 0.23-0.31 cm(-1) full width at half maximum are extracted from the line profiles, demonstrating that the N = 0 to 7 rotational levels of the OH A (2)Sigma(+) (v = 4) state undergo rapid predissociation with lifetimes of < or =23 ps. The experimental linewidths are in near quantitative agreement with first-principles theoretical predictions. 相似文献
6.
The Ramanujan Journal - For two varieties of dimension 5 constructed as double covers of $$\mathbb {P}^5$$ branched along the union of 12 hyperplanes, we prove that the number of points... 相似文献
7.
8.
9.
10.
Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献