全文获取类型
收费全文 | 453篇 |
免费 | 33篇 |
国内免费 | 137篇 |
专业分类
化学 | 323篇 |
力学 | 4篇 |
综合类 | 2篇 |
数学 | 18篇 |
物理学 | 276篇 |
出版年
2023年 | 28篇 |
2022年 | 18篇 |
2021年 | 13篇 |
2020年 | 10篇 |
2019年 | 17篇 |
2018年 | 11篇 |
2017年 | 18篇 |
2016年 | 10篇 |
2015年 | 12篇 |
2014年 | 11篇 |
2013年 | 39篇 |
2012年 | 19篇 |
2011年 | 20篇 |
2010年 | 19篇 |
2009年 | 32篇 |
2008年 | 40篇 |
2007年 | 51篇 |
2006年 | 30篇 |
2005年 | 25篇 |
2004年 | 21篇 |
2003年 | 19篇 |
2002年 | 5篇 |
2001年 | 19篇 |
2000年 | 15篇 |
1999年 | 18篇 |
1998年 | 13篇 |
1997年 | 10篇 |
1996年 | 6篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 5篇 |
1992年 | 10篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1969年 | 1篇 |
排序方式: 共有623条查询结果,搜索用时 218 毫秒
21.
- Download : Download high-res image (233KB)
- Download : Download full-size image
22.
Catherine D. Clark Morton Z. Hoffman D. Paul Rillema Quinto G. Mulazzani 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):285-290
The photophysics of three complexes of the form Ru(bpy)3−(pypm)2+ (where bpy2,2′-bipyridine, pypm 2-(2′-pyridyl)pyrimidine and P=1, 2 or 3) was examined in H2O, propylene carbonate, CH3CN and 4:1 (v/v) C2H5OH---CH3OH; comparison was made with the well-known photophysical behavior of Ru(bpy)32+. The lifetimes of the luminescent metal-to-ligand charge transfer (MLCT) excited states were determined as a function of temperature (between −103 and 90 °C, depending on the solvent), from which were extracted the rate constants for radiative and non-radiative decay and ΔE, the energy gap between the MLCT and metal-centered (MC) excited states. The results indicate that *Ru(bpy)2(pypm)2+ decays via a higher lying MLCT state, whereas *Ru(pypm)32+ and *Ru(pypm)2(bpy)2+ decay predominantly via the MC state. 相似文献
23.
EFFECT OF FORESTLAND AVAILABILITY BY OWNERSHIP TYPE ON LICENSE SALES FOR HUNTING: A SPATIAL APPROACH
SEONG‐HOON CHO J.M. BOWKER ROLAND K. ROBERTS SEUNG GYU KIM DAYTON M. LAMBERT NEELAM C. POUDYAL 《Natural Resource Modeling》2012,25(4):549-573
Abstract The effect of forestland availability under different ownership types on license sales for hunting in nine Southeastern states is empirically evaluated. An equation that represents license sales for hunting is estimated assuming the sale of hunting licenses in a particular county is related to the characteristics of that county as well as the characteristics and license sales for hunting in its neighboring counties. The positive effects of the amounts of both national and private forestland on license sales reaffirm the potential benefits of maintaining forestland to stimulate hunting. The positive spillover effect of national forests on license sales for hunting suggests that availability and close access to hunting in national forests within neighboring counties are important in supporting hunting license sales in a county. This study contributes to the general understanding of the drivers affecting individuals’ decisions to use natural resources for hunting. Advances in natural resource modeling, specifically the spatial process model and geospatial data used in this research, make it possible to examine the interactions between the spatial dynamics and ownership attributes of the natural system, allowing policy makers to design natural resource management practices that respond to a system characterized by these interactions. 相似文献
24.
25.
As one of the biological endogenous pigments, biliverdin (BV) and its dimethyl ester (BVE) have extremely weak fluorescence in solution with quantum yield less than 0.01%. However, the situation reverses with the addition of zinc ions. The strength for fluorescence of BVE-Zn\begin{document}$ ^{2+} $\end{document} complex is greatly enhanced and fluorescence quantum yield can increase to \begin{document}$ \sim $\end{document} 5%. Herein, we studied ultrafast excited state dynamics of BVE-Zn\begin{document}$ ^{2+} $\end{document} complex in ethanol, \begin{document}$ n $\end{document} -propanol, and DMSO solutions in order to reveal the mechanism of fluorescence quantum yield enhancement. The results show that BVE can form a stable coordination complex with zinc with 1:1 stoichiometry in solution. BVE is structurally and energetically more stable in the complex. Using picosecond time-resolve fluorescence and femtosecond transient absorption spectroscopy, we show that smaller non-radiative rate constant of BVE-Zn\begin{document}$ ^{2+} $\end{document} complex in DMSO is the key to increasing its fluorescence quantum yield and the excited state decay mechanism is also revealed. These results provide valuable information about the fluorescence property change after BVE binding to metal ions and may provide a guidance for the study of phytochromes or other fluorescence proteins in which BV/BVE acts as chromophores. 相似文献
26.
The intermolecular hydrogen bonds of mono‐ and dihydrated complexes of 7‐(3′‐Pyridyl)indole (7‐3′PI) have been investigated using the time‐dependent density functional theory (TD‐DFT) method. The electrostatic potential analysis of monomer 7‐3′PI and 7‐(3′‐Pyridyl)indole‐water (7‐3′PI‐W) indicates that an intermolecular hydrogen bond between two waters can be formed for 7‐(3′‐Pyridyl)indole‐2water (7‐3′PI‐2W) complex. The calculated bond lengths of the intermolecular hydrogen bonds of 7‐3′PI‐W and 7‐3′PI‐2W in the S1 state (the first excited singlet state) are all shortened compared to the ground state. By the analysis of bond length, charge population and infrared spectra, it is demonstrated that the intermolecular hydrogen bonds of 7‐3′PI‐W and 7‐3′PI‐2W are all strengthened upon electronic excitation to the S1 state. Moreover, the fluorescence of 7‐3′PI‐W and 7‐3′PI‐2W are all red‐shifted to larger wavelength compared to monomer 7‐3′PI. The red‐shift of fluorescence peak of 7‐3′PI‐W and 7‐3′PI‐2W should be attributed to the change of hydrogen bond interaction before and after photoexcitation. Therefore, it can be concluded that the intermolecular hydrogen bonding strengthening in the excited S1 state induces the fluorescence weakening of 7‐3′PI. 相似文献
27.
《Arabian Journal of Chemistry》2014,7(3):261-266
Effect of the micelles of anionic, cationic and non-ionic surfactants on the fluorescence quenching of 1- and 2-naphthols has been studied in the presence of copper ion. The excited state lifetime, dynamic and static quenching constants for these systems have been determined. Fluorescence quenching in water and SDS micelle is due to the collision of the fluorophore with the quencher with a small static component. The negatively charged naphtholate ions in the excited state are quenched with significantly higher rates than the neutral naphthol molecules, which are located further inside the mesophase. CTAB micelle is less effective than the SDS micelle for fluorescence quenching. The effect of CTAB on water-assisted excited-state deprotonation has been investigated in the presence of ZnSO4. For TX-100 micelle there is negligible quenching even at higher concentration of the quencher. 相似文献
28.
采用DFT/TDDFF计算和极化率的态求和方法研究了四氧杂卟啉二价正离子(TOP2+)B态(S2态)激发的共振拉曼(RR)光谱, 计算模型同时处理了A项和B项对拉曼极化率的贡献.用PBE1PBE、B3LYP、Cam-B3LYP、B3LYP-D3四种交换-相关泛函计算得到的RR光谱总体上相似,其中PBE1PBE和B3LYP 给出的RR 强度与实验吻合得更好一些. 对于全对称振动(A1g),其拉曼谱带相对强度的理论计算结果与实验一致;TDDFF计算表明: 相对于基态,TOP2+的B态沿υ2、υ6、υ7、υ8简正模式有较大的无量纲位移, 导致相应的RR带有较大的强度. 非全对称的B1g和B2g 模式通过B项机理增强,其强度比A1g模式小1~2个量级,与实验结果定性符合. 与实验相比,υ10模式(B1g)RR强度的理论值过小,而υ11模式(B1g)的理论值偏大;这可能是由于TOP2+的B-态(S2态)具有Jahn-Teller效应. 相似文献
29.
2000年以来,中国出境旅游高增长、高消费,影响力不断增大,成为国家外交战略的重要内容,外交效应逐渐显现。通过辨析中国出境旅游外交效应的概念、表现形式和结果,基于10个中国主要出境目的国的旅游互动数据,采用DIF-GMM计量经济模型,实证检验了中国出境旅游外交效应。结果表明,中国通过有序推进ADS协议、加强经济援助、举办“旅游年”活动、实施旅游“制裁”,并积极参与国际制度建设等旅游外交行为,促进了与世界各国的友好交往,维护了自身核心利益,提升了外交软实力和国际影响力。国际旅游反作用于国际关系,对国际关系具有显著的正向促进作用,不仅是国际关系的结果,而且是其重要动因之一。中国出境旅游与政治、经济、社会、文化等联动,多方面提升了中国的国际影响力。 相似文献
30.
ZHAO Xue CHEN De-Zhan WANG Zhen HAO Zhao-Ling 《结构化学》2007,26(8):980-987
5,8-Hihydroxyl-1,4-naphthazarin was taken as a model compound to explore the effect of halogen substitution on intramolecular proton transfer process. Calculations indicate that the substitution in the R2- and R4-positions far away from the active region has much weaker influence on the IPT process than that in the R1-and R3-positions. IPT barriers for substitution in the R1-position are higher than that of parent molecule. However, it is quite reverse for substitution in the R3-position. The IPT process is a proton transfer process coupled with charge separation and coulombic interaction would be dominant during this process. As for naphthazarin, halogen substitution would decrease the quantum yields of O2 but increase those of 1O2. 相似文献