全文获取类型
收费全文 | 386篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 384篇 |
力学 | 2篇 |
数学 | 2篇 |
物理学 | 8篇 |
出版年
2023年 | 8篇 |
2022年 | 4篇 |
2021年 | 13篇 |
2020年 | 21篇 |
2019年 | 18篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 9篇 |
2015年 | 6篇 |
2014年 | 9篇 |
2013年 | 21篇 |
2012年 | 17篇 |
2011年 | 29篇 |
2010年 | 14篇 |
2009年 | 15篇 |
2008年 | 31篇 |
2007年 | 24篇 |
2006年 | 37篇 |
2005年 | 24篇 |
2004年 | 19篇 |
2003年 | 16篇 |
2002年 | 6篇 |
2001年 | 11篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1985年 | 2篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1977年 | 2篇 |
1975年 | 1篇 |
1937年 | 1篇 |
排序方式: 共有396条查询结果,搜索用时 375 毫秒
31.
Syed Rasheed Devineni Subba Rao Chennamsettty Subramanyam Shaik Thaslim Basha 《合成通讯》2014,44(20):2988-2998
An expeditious, simple, and green method was developed for the synthesis of privileged aryl/heterocyclicphosphonates, 8(a–c) to 13(a–c) through Michaelis–Arbuzov reaction of aryl/heterocyclic halides (Br), 1–6, and trialkylphosphites, 7(a–c), in room-temperature ionic liquid [bbim]Br using heterogeneous Lewis catalyst, nano-silica-supported boron trifluoride (BF3-SiO2). The advantages of this protocol are simplicity, good yield of the products, less reaction time (20–38 min), mild reaction conditions, easy workup, and reusability of the catalyst and ionic liquid. It is demonstrated that nano-BF3-SiO2 is a recoverable and easy accessible catalyst for the formation of C(sp2)-P bond in an ionic liquid. 相似文献
32.
Shaik AnwarPei-Hsun Lee Tsai-Yung ChouChihliang Chang Kwunmin Chen 《Tetrahedron》2011,67(6):1171-1177
A simple and convenient strategy was developed to synthesize a new class of pyrrolidinyl-camphor based bifunctional organocatalysts possessing varying functional linkers. Catalytic screening of these camphor-pyrrolidine linked derivatives for asymmetric Michael reaction of cyclohexanone with β-nitrostyrene was carried out. Various aryl- and heteroaryl-nitroolefins, ketones as well as aldehydes gave the corresponding Michael adducts in high chemical yields (up to 95%) and exceptionally high diastereo-(syn/anti up to 99:1) and enantioselectivity (up to 95%) using catalyst 6 under solvent-free conditions. 相似文献
33.
Schyman P Lai W Chen H Wang Y Shaik S 《Journal of the American Chemical Society》2011,133(20):7977-7984
Dopamine can be generated from tyramine via arene hydroxylation catalyzed by a cytochrome P450 enzyme (CYP2D6). Our quantum mechanical/molecular mechanical (QM/MM) results reveal the decisive impact of the protein in selecting the 'best' reaction mechanism. Instead of the traditional Meisenheimer-complex mechanism, the study reveals a mechanism involving an initial hydrogen atom transfer from the phenolic hydroxyl group of the tyramine to the iron-oxo of the compound I (Cpd I), followed by a ring-π radical rebound that eventually leads to dopamine by keto-enol rearrangement. This mechanism is not viable in the gas phase since the O-H bond activation by Cpd I is endothermic and the process does not form a stable intermediate. By contrast, the in-protein reaction has a low barrier and is exothermic. It is shown that the local electric field of the protein environment serves as a template that stabilizes the intermediate of the H-abstraction step and thereby mediates the catalysis of dopamine formation at a lower energy cost. Furthermore, it is shown that external electric fields can either catalyze or inhibit the process depending on their directionality. 相似文献
34.
Energy and hole transfer between dyes attached to titania in cosensitized dye-sensitized solar cells
Hardin BE Sellinger A Moehl T Humphry-Baker R Moser JE Wang P Zakeeruddin SM Grätzel M McGehee MD 《Journal of the American Chemical Society》2011,133(27):10662-10667
Cosensitization of broadly absorbing ruthenium metal complex dyes with highly absorptive near-infrared (NIR) organic dyes is a clear pathway to increase near-infrared light harvesting in liquid-based dye-sensitized solar cells (DSCs). In cosensitized DSCs, dyes are intimately mixed, and intermolecular charge and energy transfer processes play an important role in device performance. Here, we demonstrate that an organic NIR dye incapable of hole regeneration is able to produce photocurrent via intermolecular energy transfer with an average excitation transfer efficiency of over 25% when cosensitized with a metal complex sensitizing dye (SD). We also show that intermolecular hole transfer from the SD to NIR dye is a competitive process with dye regeneration, reducing the internal quantum efficiency and the electron lifetime of the DSC. This work demonstrates the general feasibility of using energy transfer to boost light harvesting from 700 to 800 nm and also highlights a key challenge for developing highly efficient cosensitized dye-sensitized solar cells. 相似文献
35.
The effect of the interior structure of carbon nanomaterials on their electrochemical properties is not well understood. We report here the electron transfer rate (ETR) of ferrocene (Fc) molecules covalently attached to the exposed end of carbon nanofibers (CNFs) in an embedded nanoelectrode array. The ETR in normal DC voltammetry was found to be limited by the conical graphitic stacking structure interior of CNFs. AC voltammetry, however, can cope with this intrinsic materials property and provide over 100 times higher ETR, likely by a new capacitive pathway. This provides a new method for high‐performance electroanalysis using CNF nanoelectrodes. 相似文献
36.
37.
Jennings JR Liu Y Wang Q Zakeeruddin SM Grätzel M 《Physical chemistry chemical physics : PCCP》2011,13(14):6637-6648
Replacing the nonyl groups on the solar cell dye Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-dinonyl-2,2'-bipyridine)(NCS)(2) (Z-907) with amino groups results in a marked decrease in solar cell performance. This is despite the fact that the amino derivative (Z-960) has more favourable light absorption characteristics than Z-907 when used with thick nanocrystalline TiO(2) layers. Electron transfer to the electrolyte from the exposed fluorine-doped tin oxide (FTO) substrate is particularly fast in cells employing the Z-960 dye if a compact TiO(2) blocking layer is not used. The kinetics of electron transfer from the nanocrystalline TiO(2) layer in DSCs employing Z-960 are comparable to those of bare TiO(2) and ca. 2 to 5 times faster than for cells employing Z-907. The faster charge recombination in cells employing Z-960 lowers open-circuit photovoltage and results in very significant charge collection losses that lower short-circuit photocurrent. Voltammetric measurements show that surface modification of FTO electrodes with Z-960 results in slightly more facile charge transfer to acceptor species in triiodide/iodide electrolytes in the dark. A simpler molecule, p-aminobenzoic acid, more dramatically catalyses this charge transfer reaction. Conversely, chemical modification of FTO electrodes with Z-907 or p-toluic acid retards charge transfer kinetics. Similar results are obtained for nanocrystalline TiO(2) electrodes modified with these benzoic acid derivatives. These results strongly imply that surface adsorbed molecules bearing amino groups, including dye molecules, can catalyse charge recombination in dye-sensitized solar cells. 相似文献
38.
39.
40.
Application of the configuration mixing model to the SN2 reaction illustrates that charge development in an SN2 reaction is not linearly related to the position of the transition state along the reaction coordinate. 相似文献