全文获取类型
收费全文 | 993篇 |
免费 | 25篇 |
国内免费 | 3篇 |
专业分类
化学 | 619篇 |
晶体学 | 9篇 |
力学 | 15篇 |
数学 | 106篇 |
物理学 | 272篇 |
出版年
2020年 | 7篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 6篇 |
2016年 | 16篇 |
2015年 | 22篇 |
2014年 | 22篇 |
2013年 | 36篇 |
2012年 | 40篇 |
2011年 | 48篇 |
2010年 | 24篇 |
2009年 | 23篇 |
2008年 | 43篇 |
2007年 | 47篇 |
2006年 | 46篇 |
2005年 | 60篇 |
2004年 | 36篇 |
2003年 | 43篇 |
2002年 | 26篇 |
2001年 | 31篇 |
2000年 | 27篇 |
1999年 | 26篇 |
1998年 | 15篇 |
1997年 | 9篇 |
1996年 | 19篇 |
1995年 | 24篇 |
1994年 | 14篇 |
1993年 | 14篇 |
1992年 | 27篇 |
1991年 | 9篇 |
1990年 | 14篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 22篇 |
1986年 | 13篇 |
1985年 | 19篇 |
1984年 | 8篇 |
1983年 | 10篇 |
1982年 | 5篇 |
1981年 | 9篇 |
1980年 | 12篇 |
1978年 | 8篇 |
1977年 | 7篇 |
1976年 | 12篇 |
1975年 | 10篇 |
1974年 | 13篇 |
1973年 | 21篇 |
1972年 | 5篇 |
1970年 | 5篇 |
1969年 | 8篇 |
排序方式: 共有1021条查询结果,搜索用时 31 毫秒
21.
The electrochemical oxidation of various substituted chrysoidines was studied by cyclic voltammetry, to determine which have stable oxidation products. Only 4-hydroxy-chrysoidine has a stable product; the apparent oxidation potential is 0.779 V vs. NHE. 4-Methoxy- and 4-ethoxy-chrysoidine rapidly lose methanol or ethanol, respectively, so that the 4-hydroxychrysoidine wave appears on subsequent scans. All the other chrysoidines studied are irreversible. The results indicate that a hydroxy group in the 4-position is necessary for stability; the 4-alkoxychrysoidines can achieve the stable quinoidal structure by cleavage of the alkoxy group after nucleophilic attack. 相似文献
22.
Larsen DS 《The Journal of chemical physics》2004,121(11):5039-5042
A novel four-pulse photon-echo technique for exploring condensed phase dynamics at different parts of the excited-state potential energy surface is presented. In contrast to traditional three-pulse photon-echo signals, the introduction of a fourth pump pulse allows the use of photon-echo techniques to probe excited-state phenomena. Here, a "proof of principle" experiment is presented where the excited-state solvent dynamics of the coumarin 153 chromophore dissolved in methanol is explored. The fluctuations of the stimulated emission transition is probed, in contrast to the ground-state absorption transition explored in traditional echo measurements. Distinctly different excited-state dynamics, in contrast to ground-state signals, is observed and discussed. 相似文献
23.
Bond AD Derossi S Jensen F Larsen FB McKenzie CJ Nelson J 《Inorganic chemistry》2005,44(17):5987-5989
Treatment of cryptand L(1) with Cu(II) generates a H3O2(-)-bridged dicopper(II) cryptate, 2, where the guest anion has responded to steric constraint by a significant shortening of the O-O distance to 2.325(9) A; computational optimization at the B3LYP/6-31(d) level suggests that the bridging O-H...O H-bond is bent (approximately 157 degrees) but that the barrier to interchange of the bridging H atom is low (<4 kJ mol(-1)). This cryptate, rather than the [Cu2L(1)muCN]3+ species recently claimed to derive from cleavage of the C-C bond of the solvent, is the product of acetonitrile recrystallization of the initially formed reaction product, 1. 相似文献
24.
Davies IW Marcoux JF Wu J Palucki M Corley EG Robbins MA Tsou N Ball RG Dormer P Larsen RD Reider PJ 《The Journal of organic chemistry》2000,65(15):4571-4574
Substituted acetic acids or acetyl chlorides react with phosphorus oxychloride in DMF to yield the vinamidinium salts 3a-j in moderate to excellent recrystallized yields (28-90%). The cations are conveniently isolated as their hexafluorophosphate salts, which are easily handled nonhygroscopic solids. The nitro compound 3l is prepared in 91% yield by nitration of the parent vinamidinium 3k. The X-ray crystal structure is reported for the 2-phenyl isomer 3e and displays minimal overlap of the two pi-systems. 相似文献
25.
The simultaneous analysis of α-HCH, β-HCH, γ-HCH, HCB, p,p′-DDD, p,p′-DDT, p,p′-DDE, o,p′-DDT, mirex, dieldrin and 62 chlorobiphenyl congeners on two parallel capillary GC columns of different polarity is described for nine Mediterranean fish species. Ten commercially available columns with stationary phases completely characterized in respect of their PCB elution patterns were considered for dual-column GC-ECD analysis. The combination of a 60 m × 0.25 mm i.d. column coated with a 0.25 μm film of 50% diphenyl dimethylsiloxane and a series combination of a 25 m × 0.25 mm i.d. column coated with a 0.25 μm film of 5% diphenyl dimethylsiloxane with a 25 m × 0.22 mm i.d. column coated with a 0.10 μm film of 1, 10-dicarba-closo-dodecarborane dimethylpolysiloxane furnished the highest number of separated chlorobiphenyl congeners (104). The dual-column GC system performed with high stability and reproducibility over a broad concentration range (1–3000 ng/g lipid) of the organochlorine compounds in the investigated fish. 相似文献
26.
We have used the oscillating peroxidase-oxidase (PO) reaction as a model system to study how oscillatory dynamics may affect the influence of toxic reaction intermediates on enzyme stability. In the peroxidase-oxidase reaction reactive intermediates, such as hydrogen peroxide, superoxide, and hydroxyl radical are formed. Such intermediates inactivate many cellular macromolecules such as proteins and nucleic acids. These reaction intermediates also react with peroxidase itself to form an inactive enzyme. The fact that the PO reaction shows bistability between an oscillatory and a steady state gives us a unique possibility to compare such inactivation when the system is in one of these two states. We show that inactivation of peroxidase is slower when the system is in an oscillatory state, and using numerical simulations we provide evidence that oscillatory dynamics lower the average concentration of the reactive intermediates. 相似文献
27.
28.
29.
A. R. Hutter R. J. Larsen H. Maring J. T. Merrill 《Journal of Radioanalytical and Nuclear Chemistry》1995,193(2):309-318
Continuous measurements of atmospheric222Rn were made for the past three years by the Environmental Measurements Laboratory (EML) at the Atmosphere/Ocean Chemistry Experiment site located at Tudor Hill, Bermuda and at the National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostics Laboratory Mauna Loa Observatory. The222Rn analyzer is based on the two-filter tube method. At the Bermuda site, monthly median222Rn concentration range from 50 to 700 mBq m–3, and the concentrations vary seasonally, with a maximum in the winter and a minimum in the summer. The concentrations are significantly elevated when local winds traverse the island. At MLO, monthly median222Rn concentrations range from 100 mBq m–3 during the fall months to 400 mBq m–3 during the spring months. The springtime maximum values correspond to periods of rapid transport in the free troposphere from the Asian continent, corroborated by backward air mass trajectories. The222Rn data are also used to help decipher local daily upslope/downslope conditions present at MLO. This study illustrates the value of atmospheric222Rn monitoring, when screened through the filter of local meteorology, in studying the transport of continental air to the oceans, as well as the dynamics of local meteorological effects. 相似文献
30.