全文获取类型
收费全文 | 403篇 |
免费 | 31篇 |
专业分类
化学 | 340篇 |
晶体学 | 5篇 |
力学 | 20篇 |
数学 | 24篇 |
物理学 | 45篇 |
出版年
2024年 | 1篇 |
2023年 | 8篇 |
2022年 | 7篇 |
2021年 | 15篇 |
2020年 | 20篇 |
2019年 | 22篇 |
2018年 | 10篇 |
2017年 | 13篇 |
2016年 | 19篇 |
2015年 | 13篇 |
2014年 | 24篇 |
2013年 | 19篇 |
2012年 | 62篇 |
2011年 | 47篇 |
2010年 | 10篇 |
2009年 | 16篇 |
2008年 | 30篇 |
2007年 | 20篇 |
2006年 | 9篇 |
2005年 | 14篇 |
2004年 | 8篇 |
2003年 | 10篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 8篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1988年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有434条查询结果,搜索用时 78 毫秒
431.
De P Maji S Chowdhury AD Mobin SM Mondal TK Paretzki A Lahiri GK 《Dalton transactions (Cambridge, England : 2003)》2011,40(46):12527-12539
The present article describes ruthenium nitrosyl complexes with the {RuNO}(6) and {RuNO}(7) notations in the selective molecular frameworks of [Ru(II)([9]aneS(3))(bpy)(NO(+))](3+) (4(3+)), [Ru(II)([9]aneS(3))(pap) (NO(+))](3+) (8(3+)) and [Ru(II)([9]aneS(3))(bpy)(NO˙)](2+) (4(2+)), [Ru(II)([9]aneS(3))(pap)(NO˙)](2+) (8(2+)) ([9]aneS(3) = 1,4,7-trithiacyclononane, bpy = 2,2'-bipyridine, pap = 2-phenylazopyridine), respectively. The nitrosyl complexes have been synthesized by following a stepwise synthetic procedure: {Ru(II)-Cl} → {Ru(II)-CH(3)CN} → {Ru(II)-NO(2)} → {Ru(II)-NO(+)} → {Ru(II)-NO˙}. The single-crystal X-ray structure of 4(3+) and DFT optimised structures of 4(3+), 8(3+) and 4(2+), 8(2+) establish the localised linear and bent geometries for {Ru-NO(+)} and {Ru-NO˙} complexes, respectively. The crystal structures and (1)H/(13)C NMR suggest the [333] conformation of the coordinated macrocyclic ligand ([9]aneS(3)) in the complexes. The difference in π-accepting strength of the co-ligands, bpy in 4(3+) and pap in 8(3+) (bpy < pap) has been reflected in the ν(NO) frequencies of 1945 cm(-1) (DFT: 1943 cm(-1)) and 1964 cm(-1) (DFT: 1966 cm(-1)) and E°({Ru(II)-NO(+)}/{Ru(II)-NO˙}) of 0.49 and 0.67 V versus SCE, respectively. The ν(NO) frequency of the reduced {Ru-NO˙} state in 4(2+) or 8(2+) however decreases to 1632 cm(-1) (DFT: 1637 cm(-1)) or 1634 cm(-1) (DFT: 1632 cm(-1)), respectively, with the change of the linear {Ru(II)-NO(+)} geometry in 4(3+), 8(3+) to bent {Ru(II)-NO˙} geometry in 4(2+), 8(2+). The preferential stabilisation of the eclipsed conformation of the bent NO in 4(2+) and 8(2+) has been supported by the DFT calculations. The reduced {Ru(II)-NO˙} exhibits free-radical EPR with partial metal contribution revealing the resonance formulation of {Ru(II)-NO˙}(major)?{Ru(I)-NO(+)}(minor). The electronic transitions of the complexes have been assigned based on the TD-DFT calculations on their DFT optimised structures. The estimated second-order rate constant (k, M(-1) s(-1)) of the reaction of the nucleophile, OH(-) with the electrophilic {Ru(II)-NO(+)} for the bpy derivative (4(3+)) of 1.39 × 10(-1) is half of that determined for the pap derivative (8(3+)), 2.84 × 10(-1) in CH(3)CN at 298 K. The Ru-NO bond in 4(3+) or 8(3+) undergoes facile photolytic cleavage to form the corresponding solvent species {Ru(II)-CH(3)CN}, 2(2+) or 6(2+) with widely varying rate constant values, (k(NO), s(-1)) of 1.12 × 10(-1) (t(1/2) = 6.2 s) and 7.67 × 10(-3) (t(1/2) = 90.3 s), respectively. The photo-released NO can bind to the reduced myoglobin to yield the Mb-NO adduct. 相似文献
432.
Arup Ghorai Somnath Mahato Sudarshan Singh Shaona Bose Baidyanath Roy Unyong Jeong Samit Kumar Ray 《Angewandte Chemie (International ed. in English)》2023,62(22):e202302852
Although α-CsPbI3 is regarded as an attractive optical luminophore, it is readily degraded to the optically inactive δ-phase under ambient conditions. Here, we present a simple approach to revive degraded (“optically sick”) α-CsPbI3 through “medication” with thiol-containing ligands. The effect of different types of thiols is systematically studied through optical spectroscopy. The structural reconstruction of degraded α-CsPbI3 nanocrystals to cubic crystals in the presence of thiol-containing ligands is visualized through high-resolution transmission electron microscopy and supported by X-ray diffraction analysis. We found that 1-dodecanethiol (DSH) effectively revives degraded CsPbI3 and results in high immunity towards moisture and oxygen, hitherto unreported. DSH facilitates the passivation of surface defects and etching of degraded Cs4PbI6 phase, thus reverting them back to the cubic CsPbI3 phase, leading to enhanced PL and environmental stability. 相似文献
433.
We consider a modified electrokinetic model to study the electrophoresis of a hydrophobic particle by considering the finite sized ions. The mathematical model adopted in this study incorporates the ion steric repulsion, ion-solvent interactions as well as Maxwell stress on the electrolyte. The dielectric permittivity and viscosity of the electrolyte is considered to vary with the local ionic volume fraction. Based on this modified model for the electrokinetics we have analyzed the electrophoresis in a single as well as mixture of electrolytes of monovalent and non- electrolytes. The dependence of viscosity on local ionic volume fraction modifies the hydrodynamic drag as well as diffusivity of ions, which are ignored in existing studies on electrophoresis. A simplified model for electrophoresis of a hydrophobic particle incorporating the ion steric repulsion and ion-solvent interactions is developed based on the first-order perturbation on applied electric field. This simplified model is established to be efficient for a Debye layer thinner than the particle size and a smaller range of slip length. This model can be implemented for any number of ionic species as well as non- electrolytes. It is established that the ion steric interactions and dielectric decrement creates a counterion saturation in the Debye layer leading to an enhanced mobility compared to the standard model. However, experimental data for non-dilute cases often under predicts the theoretically determined mobility. The present modified model fills this lacuna and demonstrate that the consideration of finite ion size modifies the medium viscosity and hence, ionic mobility, which in combination lowers the mobility value. 相似文献
434.
Amin Owais Sinha Subhojyoti Maji Partha Sona Mukherjee Rupam 《Journal of Solid State Electrochemistry》2023,27(9):2387-2394
Journal of Solid State Electrochemistry - We report the effect of indium doping on thermal stability and ionic conductivity of beta alumina NaInxAl11-xO17 solid electrolyte which is synthesized by... 相似文献