全文获取类型
收费全文 | 1169篇 |
免费 | 13篇 |
国内免费 | 120篇 |
专业分类
化学 | 1137篇 |
晶体学 | 2篇 |
数学 | 63篇 |
物理学 | 100篇 |
出版年
2023年 | 106篇 |
2022年 | 8篇 |
2021年 | 23篇 |
2020年 | 22篇 |
2019年 | 49篇 |
2018年 | 51篇 |
2017年 | 30篇 |
2016年 | 12篇 |
2015年 | 12篇 |
2014年 | 44篇 |
2013年 | 101篇 |
2012年 | 33篇 |
2011年 | 62篇 |
2010年 | 45篇 |
2009年 | 71篇 |
2008年 | 67篇 |
2007年 | 82篇 |
2006年 | 89篇 |
2005年 | 80篇 |
2004年 | 75篇 |
2003年 | 29篇 |
2002年 | 25篇 |
2001年 | 12篇 |
2000年 | 19篇 |
1999年 | 12篇 |
1998年 | 16篇 |
1997年 | 11篇 |
1996年 | 18篇 |
1995年 | 10篇 |
1994年 | 12篇 |
1993年 | 15篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 9篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 9篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 2篇 |
1968年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1302条查询结果,搜索用时 15 毫秒
1.
Hydrodynamic cavitation experiments in microfluidic systems have been performed with an aqueous solution of luminol as the working fluid. In order to identify where and how much reactive radical species are formed by the violent bubble collapse, the resulting chemiluminescent oxidation reaction of luminol was scrutinized downstream of a constriction in the microchannel. An original method was developed in order to map the intensity of chemiluminescence emitted from the micro-flow, allowing us to localize the region where radicals are produced. Time averaged void fraction measurements performed by laser induced fluorescence experiments were also used to determine the cavitation cloud position. The combination void fraction and chemiluminescence two-dimensional mapping demonstrated that the maximum chemiluminescent intensity area was found just downstream of the cavitation clouds. Furthermore, the radical yield can be obtained with our single photon counting technique. The maximum radical production rates of 1.2*107 OH/s and radical production per processed liquid volume of 2.15*1010 HO/l were observed. The proposed technique allows for two-dimensional characterisation of radical production in the microfluidic flow and could be a quick, non-intrusive way to optimise hydrodynamic cavitation reactor design and operating parameters, leading to enhancements in wastewater treatments and other process intensifications. 相似文献
2.
A novel, rational‐designed approach to access various heteroaryl‐substituted alkyl thioethers was developed via docking‐migration cascade process. By utilizing three components involving alkene, dual‐function reagent, and thioetherificating reagent, radical heteroarylalkylation of alkenes followed by thiolation of the alkyl radical intermediates proceeded smoothly, manifesting well compatibility of substrates and cascade transformations. Furthermore, this protocol also features mild conditions, broad substrate scope, and wide product diversity. 相似文献
3.
《Tetrahedron》2019,75(12):1639-1646
An efficient visible-light photocatalytic protocol for the vicinal heteroarylsulfonylation and oximinosulfonylation of unactivated olefins is described. The addition of sulfonyl radicals to alkenes triggers the intramolecular migration of remote heteroaryl and oximino groups via CC bond cleavage. The transformation features a good functional group tolerance and a broad substrate scope. A variety of valuable heteroaryl- and oximino-substituted alkyl sulfones are obtained under mild conditions in synthetically useful yields. 相似文献
4.
《Tetrahedron》2019,75(28):3856-3863
Without employing any transition metal, organic solvent and base, a facile, economical and environmentally friendly strategy has been developed for the α-hydroxylation of β-keto esters and β-keto amides with peroxides via radical cross-coupling reaction in water under open-air conditions. This protocol allows a convenient access to various α-hydroxy-β-keto esters and α-hydroxy-β-keto amides with up to 92% yield (34 examples). Moreover, the reaction was successfully scaled up to gram quantity and mechanistic studies showed the radical pathway was involved in this hydroxylation. 相似文献
5.
《Comptes Rendus Chimie》2015,18(12):1284-1288
Some aromatic 1,2-dicarbonyl compounds, i.e. 9,10-phenanthrenequinone, acenaphthenequinone and benzil, and their corresponding N-phenyl monoimines, have been reduced, using dry acetonitrile as the solvent, in the presence of sodium cyanide as a reducing agent. Comparative potentiostatic preparative-scale electrolysis is described. 相似文献
6.
《Comptes Rendus Chimie》2017,20(3):261-271
A review of recent advancements in metal-free arylations via photogenerated triplet aryl cations and decatungstate anion ([W10O32]4−) photocatalyzed C–C bond formation is reported herein. These approaches are two examples of the great potentialities of photons as green activants in organic synthesis, allowing the functionalization of different chemical substrates under mild conditions (room temperature, aqueous solvents, absence of aggressive and unstable reactants and of expensive transition metal-based catalysts, and chance to use solar light as the energy source). 相似文献
7.
《Comptes Rendus Chimie》2017,20(1):87-95
This study focuses on the heterogeneous Fenton-like reaction performed over a novel hybrid Cu–Mn–O catalyst for the degradation of a model compound benzophenone-3 (BP-3) in aqueous media. The hybrid Cu–Mn–O catalysts with different Cu/Mn molar ratios were synthesized using co-precipitation and hydrothermal methods, and their composition and morphology were characterized using XRD and SEM analyses. Key parameters including the Cu/Mn ratio in the synthesis, pH and titration of H2O2 were shown to significantly influence the degradation of BP-3. A hybrid catalyst with a chemical composition of Cu1.4Mn1.6O4, Mn3O4, and Mn2O3 exhibiting a morphology of nanofibers and nanoparticles demonstrated the highest catalytic activity in the degradation of BP-3. After 240 min of degradation, 81.5% of BP-3 was removed, which could be mostly related to the presence of hydroxyl radicals (˙OH). Unlike the conventional Fenton reaction that performs well under highly acidic conditions, BP-3 can be degraded in a wider pH range (2.6–7.1) in the Fenton-like reaction presented herein. Considering the mild conditions used for this Fenton-like system, this novel hybrid catalyst remains promising for wastewater treatment. 相似文献
8.
Dr. Peng Zhang Qian-Cheng Luo Dr. Zhenhua Zhu Wanrong He Nan Song Junting Lv Xuning Wang Prof. Quan-Guo Zhai Prof. Yan-Zhen Zheng Prof. Jinkui Tang 《Angewandte Chemie (International ed. in English)》2023,62(12):e202218540
The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)6]{CoI[(μ3-HAN)RE2Cp*4]2} ( 1-RE ) and [K(Crypt)]2{CoI[(μ3-HAN)RE2Cp*4]2} ( 2-RE ) containing hexaazatrinaphthylene radicals (HAN⋅3−) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy . Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs. 相似文献
9.
Dr. Wenqing Wang Xiao-Hui Ma Min Liu Shuxuan Tang Xuguang Ding Yue Zhao Prof. Yuan-Zhi Tan Prof. Miklos Kertesz Prof. Xinping Wang 《Angewandte Chemie (International ed. in English)》2023,62(8):e202217788
We report on the largest open-shell graphenic bilayer and also the first example of triply negatively charged radical π-dimer. Upon three-electron reduction, bilayer nanographene fragment molecule (C96H24Ar6)2 (Ar=2,6-dimethylphenyl) ( 1 2) was transformed to a triply negatively charged species 1 23.−, which has been characterized by single-crystal X-ray diffraction, electron paramagnetic resonance (EPR) spectroscopy and magnetic properties on a superconducting quantum interference device (SQUID). 1 23.− features a 96-center-3-electron (96c/3e) pancake bond with a doublet ground state, which can be thermally excited to a quartet state. It consists of 34 π-fused rings with 96 conjugated sp2 carbon atoms. Spin frustration is observed with the frustration parameter f>31.8 at low temperatures in 1 23.−, which indicates graphene upon reduction doping may behave as a quantum spin liquid. 相似文献
10.
Dr. Shubham Dutta Dr. Rajendra K. Mallick Prof. Dr. Akhila K. Sahoo 《Angewandte Chemie (International ed. in English)》2023,62(30):e202300816
The use of ynamides in organic synthesis has gained significant attention due to their ability to provide access to complex molecular structures through transformations such as 1,2-difunctionalization and annulation reactions. These reactions enable the formation of highly functionalized N-bearing olefins and unusual N-bearing heterocycles. In this minireview, we present a systematic overview of the regioselective difunctionalization and annulation reactions of ynamides. We discuss the multi-component reactions, and radical-triggered functionalizations across the ynamides carbon–carbon multiple bonds and the use of bifunctional reagents in annulation of ynamides, highlighting their potential in expanding the substrate scope. Furthermore, we provide insights into the mechanistic breakthroughs that have been achieved in recent years in the development of these reactions. Finally, we emphasize the promising future prospects of ynamides as versatile building blocks for the synthesis of complex molecular architectures. 相似文献