全文获取类型
收费全文 | 4149篇 |
免费 | 717篇 |
国内免费 | 350篇 |
专业分类
化学 | 2740篇 |
晶体学 | 56篇 |
力学 | 298篇 |
综合类 | 18篇 |
数学 | 422篇 |
物理学 | 1682篇 |
出版年
2024年 | 16篇 |
2023年 | 114篇 |
2022年 | 158篇 |
2021年 | 171篇 |
2020年 | 181篇 |
2019年 | 166篇 |
2018年 | 169篇 |
2017年 | 124篇 |
2016年 | 228篇 |
2015年 | 205篇 |
2014年 | 240篇 |
2013年 | 321篇 |
2012年 | 397篇 |
2011年 | 388篇 |
2010年 | 254篇 |
2009年 | 222篇 |
2008年 | 247篇 |
2007年 | 230篇 |
2006年 | 220篇 |
2005年 | 178篇 |
2004年 | 130篇 |
2003年 | 105篇 |
2002年 | 83篇 |
2001年 | 73篇 |
2000年 | 83篇 |
1999年 | 71篇 |
1998年 | 65篇 |
1997年 | 52篇 |
1996年 | 55篇 |
1995年 | 52篇 |
1994年 | 28篇 |
1993年 | 40篇 |
1992年 | 41篇 |
1991年 | 23篇 |
1990年 | 22篇 |
1989年 | 15篇 |
1988年 | 11篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 1篇 |
1983年 | 6篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有5216条查询结果,搜索用时 359 毫秒
1.
2.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献
3.
Pu Duan Bo Zhi Luke Coburn Christy L. Haynes Klaus Schmidt-Rohr 《Magnetic resonance in chemistry : MRC》2020,58(11):1130-1138
The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by 13C, 13C{1H}, 1H─13C, 13C{14N}, and 15N solid-state nuclear magnetic resonance (NMR) experiments. 13C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. 15N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved 13C NMR peaks, including an unusual ═CH signal at 84 ppm (1H chemical shift of 5.8 ppm) and ═CN2 at 155 ppm, and two distinctive 15N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a 1H─13C HETCOR spectrum with brief 1H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative 13C and 15N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in 13C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation. 相似文献
4.
Shi-Tao Han Hong-Ying Duan Lan-Yun Chen Dr. Tian-Guang Zhan Dr. Li-Juan Liu Li-Chun Kong Prof. Kang-Da Zhang 《化学:亚洲杂志》2021,16(23):3886-3889
A photo-switchable hetero-complementary quadruple H-bonding array, which consists of an azobenzene-derived ureidopyrimidinone (UPy) module ( Azo-UPy ) and a nonphotoactive diamidonaphthyridine (DAN) derivative ( Napy-1 ), is constructed based on a reversible photo-locking approach. Upon UV (390 nm)/Vis (460 nm) light irradiations, photo-switchable quadruple H-bonded dimerization between Azo-UPy and Napy-1 can be achieved with exhibiting 4.8×104-fold differences in binding strength (ON/OFF ratios). Furthermore, smart polymeric gels with unique photo-controlled macroscopic self-assembly behavior can be fabricated by introducing such quadruple H-bonding array as photo-regulable noncovalent interfacial connections. 相似文献
5.
Based on the vectorial Rayleigh–Sommerfeld diffraction integrals, analytical expressions for the transversal and axial field distribution of plane waves propagating through a thin lens followed by a small circular aperture are derived and used to study the focusing and diffraction properties of plane waves. Some special cases of our general result are discussed, and illustrative numerical calculation results are given. It is found that the vectorial nonparaxial approach should be applied if the aperture dimension is comparable with the wavelength or the focusing is strong. 相似文献
6.
C.-G. Duan L.-H. Song L.-J. Huo G.-L. Li 《The European Physical Journal C - Particles and Fields》2003,29(4):557-561
The energy loss effect in nuclear matter, which is a nuclear effect apart from the nuclear effect on the parton distribution as in deep-inelastic scattering process, can be measured best by the nuclear dependence of the high energy nuclear Drell-Yan process. By means of the nuclear parton distribution studied only with lepton deep-inelastic scattering experimental data, the measured Drell-Yan production cross sections for 800 GeV proton incident on a variety of nuclear targets are analyzed within the Glauber framework which takes into account the energy loss of the beam proton. It is shown that the theoretical results with considering the energy loss effect are in good agreement with the FNAL E866 data.Arrival of the final proofs: 24 June 2003 相似文献
7.
The microstructure of CosoNi22Ga28 ribbon with the L10 structure is examined. The band-like morphology is observed. These bands with the width in a range of 40-200 nm appear along the transverse direction of the ribbon. The giant magnetoimpedance (GMI) effect in this alloy is measured. The results show that Co5oNi22Ga28 exhibits a sharp peak of the GAI effect. The maximum GAH ratio up to 360% is detected. The GMI effect measured versus temperature shows large jumps of the magnetoimpedance amplitude at the reversal martensitic transformation temperature 240℃ and Curie temperature 375℃C respectively. The jump ratios of the magnetoimpedance amplitude examined at these temperatures are about 5 and 10, respectively. 相似文献
8.
9.
A simple model has been developed to describe the Zeeman patterns of far-infrared laser magnetic resonance spectra of the monobromomethyl radical CH2Br observed at 447.3 and 671.1μm. A satisfactory agreement between the experimental spectra of the radical and their simulation with this simple model has been achieved. This approach can be used to gain further information about the structure and the spectrum of this interesting radical. 相似文献
10.