全文获取类型
收费全文 | 9123篇 |
免费 | 332篇 |
国内免费 | 36篇 |
专业分类
化学 | 6004篇 |
晶体学 | 21篇 |
力学 | 244篇 |
数学 | 1938篇 |
物理学 | 1284篇 |
出版年
2021年 | 114篇 |
2020年 | 153篇 |
2019年 | 152篇 |
2018年 | 96篇 |
2017年 | 71篇 |
2016年 | 238篇 |
2015年 | 199篇 |
2014年 | 220篇 |
2013年 | 383篇 |
2012年 | 394篇 |
2011年 | 426篇 |
2010年 | 266篇 |
2009年 | 223篇 |
2008年 | 334篇 |
2007年 | 350篇 |
2006年 | 315篇 |
2005年 | 327篇 |
2004年 | 259篇 |
2003年 | 208篇 |
2002年 | 226篇 |
2001年 | 96篇 |
2000年 | 119篇 |
1999年 | 96篇 |
1998年 | 92篇 |
1997年 | 112篇 |
1996年 | 111篇 |
1995年 | 110篇 |
1994年 | 105篇 |
1993年 | 120篇 |
1992年 | 119篇 |
1991年 | 76篇 |
1990年 | 84篇 |
1989年 | 92篇 |
1988年 | 109篇 |
1987年 | 105篇 |
1986年 | 103篇 |
1985年 | 150篇 |
1984年 | 142篇 |
1983年 | 109篇 |
1982年 | 141篇 |
1981年 | 139篇 |
1980年 | 130篇 |
1979年 | 131篇 |
1978年 | 122篇 |
1977年 | 114篇 |
1976年 | 111篇 |
1975年 | 119篇 |
1974年 | 102篇 |
1973年 | 91篇 |
1970年 | 70篇 |
排序方式: 共有9491条查询结果,搜索用时 207 毫秒
991.
We report the vibrational and orientational dynamics of water molecules in isotopically diluted NaOH and NaOD solutions using polarization-resolved femtosecond vibrational spectroscopy and terahertz time-domain dielectric relaxation measurements. We observe a speed-up of the vibrational relaxation of the O-D stretching vibration of HDO molecules outside the first hydration shell of OH(-) from 1.7 ± 0.2 ps for neat water to 1.0 ± 0.2 ps for a solution of 5 M NaOH in HDO:H(2)O. For the O-H vibration of HDO molecules outside the first hydration shell of OD(-), we observe a similar speed-up from 750 ± 50 fs to 600 ± 50 fs for a solution of 6 M NaOD in HDO:D(2)O. The acceleration of the decay is assigned to fluctuations in the energy levels of the HDO molecules due to charge transfer events and charge fluctuations. The reorientation dynamics of water molecules outside the first hydration shell are observed to show the same time constant of 2.5 ± 0.2 ps as in bulk liquid water, indicating that there is no long range effect of the hydroxide ion on the hydrogen-bond structure of liquid water. The terahertz dielectric relaxation experiments show that the transfer of the hydroxide ion through liquid water involves the simultaneous motion of ~7 surrounding water molecules, considerably less than previously reported for the proton. 相似文献
992.
We calculate, down to low temperature and for different isotopes, the reaction rate constants for the hydrogen abstraction reaction H + H(3)COH → H(2) + CH(2)OH/CH(3)O. These explain the known abundances of deuterated forms of methanol in interstellar clouds, where CH(2)DOH can be almost as abundant as CH(3)OH. For abstraction from both the C- and the O-end of methanol, the barrier-crossing motion involves the movement of light hydrogen atoms. Consequently, tunneling plays a dominant role already at relatively high temperature. Our implementation of harmonic quantum transition state theory with on the fly calculation of forces and energies accounts for these tunneling effects. The results are in good agreement with previous semiclassical and quantum dynamics calculations (down to 200 K) and experimental studies (down to 295 K). Here we extend the rate calculations down to lower temperature: 30 K for abstraction from the C-end of methanol and 80 K for abstraction from the OH-group. At all temperatures, abstraction from the C-end is preferred over abstraction from the O-end, more strongly so at lower temperature. Furthermore, the tunneling behavior strongly affects the kinetic isotope effects (KIEs). D + H(3)COH → HD + CH(2)OH has a lower vibrationally adiabatic barrier than H + H(3)COH → H(2) + CH(2)OH, giving rise to an inverse KIE (k(H)/k(D) < 1) at high temperature, in accordance with previous experiments and calculations. However, since tunneling is more facile for the light H atom, abstraction by H is favored over abstraction by D below ~135 K, with a KIE k(H)/k(D) of 11.2 at 30 K. The H + D(3)COD → HD + CD(2)OD reaction is calculated to be much slower than the D + H(3)COH → HD + CH(2)OH, in agreement with low-temperature solid-state experiments, which suggests the preference for H (as opposed to D) abstraction from the C-end of methanol to be the mechanism by which interstellar methanol is deuterium-enriched. 相似文献
993.
Haas W Rath T Pein A Rattenberger J Trimmel G Hofer F 《Chemical communications (Cambridge, England)》2011,47(7):2050-2052
Cu(2)ZnSnSe(4) nanoparticles have high potential to be used as ink for printable solar cells. Using transmission electron microscopy we show that these nanoparticles exhibit a broad range of chemical heterogeneity. These results are contrary to the interpretation of previous experimental work and will have considerable impact on the development of these nanoparticles. 相似文献
994.
Forster J Rösner B Khusniyarov MM Streb C 《Chemical communications (Cambridge, England)》2011,47(11):3114-3116
A new mechanism for enhancing the visible light absorption of a homogeneous polyoxovanadate system is described. The photoactive pentanuclear {V(5)} isopolyoxovanadate cluster is formed in situ by a thermally-induced condensation reaction starting from a tetranuclear {V(4)} precursor. Upon irradiation with visible light, {V(5)} undergoes a light induced reduction reaction resulting in the formation of a 2-electron reduced {V(10)} cluster. Simultaneously, the oxidant methanol is selectively oxidized to formaldehyde. The {V(10)} cluster can subsequently be re-oxidized using H(2)O(2) or O(2). 相似文献
995.
Förster T Schunk SA Jentys A Lercher JA 《Chemical communications (Cambridge, England)》2011,47(11):3254-3256
Co and Mn polysiloxanes are unique catalyst/initiator systems for the liquid phase oxidation of o-xylene showing higher activity than Co naphthenates, which is related to the weak interaction of the polar products with the hydrophobic surface as well as the absence of hydroxyl groups and surrounding oxygenates limiting radical quenching. 相似文献
996.
Peptide-based molecular probes identified by bacteriophage (phage) display technology expand the peptide repertoire for in vivo diagnosis and therapy of cancer. Numerous peptides that bind cancer-associated antigens have been discovered by panning phage libraries. However, until now only few of the peptides selected by phage display have entered clinical applications. The success of phage derived peptides essentially depends on the quality of the library screened. This review summarizes the methods to achieve highly homogenous libraries that cover a maximal sequence space. Biochemical and chemical strategies for the synthesis of DNA libraries and the techniques for their integration into the viral genome are discussed in detail. A focus is set on the methods that enable the exclusion of disturbing sequences. In addition, the parameters that define the variability, the minimal numbers of copies per library and the use of alternating panning cycles to avoid the loss of selected hits are evaluated. 相似文献
997.
998.
999.
1000.