全文获取类型
收费全文 | 518篇 |
免费 | 38篇 |
国内免费 | 1篇 |
专业分类
化学 | 417篇 |
晶体学 | 15篇 |
力学 | 3篇 |
数学 | 32篇 |
物理学 | 90篇 |
出版年
2024年 | 1篇 |
2023年 | 7篇 |
2022年 | 6篇 |
2021年 | 16篇 |
2020年 | 20篇 |
2019年 | 20篇 |
2018年 | 11篇 |
2017年 | 10篇 |
2016年 | 20篇 |
2015年 | 18篇 |
2014年 | 21篇 |
2013年 | 37篇 |
2012年 | 57篇 |
2011年 | 58篇 |
2010年 | 30篇 |
2009年 | 26篇 |
2008年 | 32篇 |
2007年 | 30篇 |
2006年 | 26篇 |
2005年 | 19篇 |
2004年 | 19篇 |
2003年 | 4篇 |
2002年 | 4篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1996年 | 1篇 |
1995年 | 4篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1988年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 6篇 |
1972年 | 7篇 |
1971年 | 1篇 |
1970年 | 2篇 |
1969年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有557条查询结果,搜索用时 187 毫秒
41.
42.
Shunsuke Kotani Shohei AokiMasaharu Sugiura Makoto Nakajima 《Tetrahedron letters》2011,52(22):2834-2836
Trichlorosilyl triflate, in the presence of a chiral Lewis base catalyst, provides an effective method for the enantioselective direct-type aldol reaction of aldehydes and ketones. A chiral Lewis base induces both the production and activation of trichlorosilyl enol ether, yielding an aldol product in good yield and with high diastereo- and enantioselectivities. 相似文献
43.
Kazuki OsakamaMasaharu Sugiura Makoto Nakajima Shunsuke Kotani 《Tetrahedron letters》2012,53(32):4199-4201
An efficient method was developed for the enantioselective reductive aldol reaction of α,β-unsaturated ketones with aldehydes in the presence of a Lewis base catalyst; conjugate reduction using a tertiary amine and trichlorosilyl triflate, followed by an aldol reaction with BINAP dioxide (BINAPO) as an organocatalyst, gave the corresponding product in high yield with high stereoselectivity. 相似文献
44.
45.
We have analyzed the transfer efficiency of ballistic electron emission microscopy (BEEM), taking the finite spot size of the emitted electron beam from scanning probes into account. Three-dimensional diffraction from an aperture at a surface-metal/air interface is introduced to model an effect caused by the finiteness of spot size. As a general trend, the diffraction decreases BEEM transfer efficiency. The diffraction effect increases as the spot size decreases and the air-gap distance increases. In a Au/GaAs sample, BEEM transfer efficiency markedly deteriorates down to 6% of the value derived from a conventional planar tunneling theory when a spot size of 0.2 nm, an air-gap distance of 0.6 nm, and an electron energy of 0.2 eV, measured from the bottom of the GaAs conduction band, are assumed. BEEM transfer efficiency is markedly dependent on the spot size of the emitted hot electron. This result indicates that the BEEM current depends on the spatial resolution of the scanning probe, that is, the condition of the tip apex. 相似文献
46.
Komal Garg Yasuo Matsubara Mehmed Z. Ertem Anna Lewandowska‐Andralojc Shunsuke Sato David J. Szalda James T. Muckerman Etsuko Fujita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(47):14334-14338
We prepared two geometric isomers of [Ir(tpy)(ppy)H]+, previously proposed as a key intermediate in the photochemical reduction of CO2 to CO, and characterized their notably different ground‐ and excited‐state interactions with CO2 and their hydricities using experimental and computational methods. Only one isomer, C‐trans‐[Ir(tpy)(ppy)H]+, reacts with CO2 to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH3CN/TEOA, a common reactive C‐trans‐[Ir(tpy)(ppy)]0 species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO2 and produces CO with the same catalytic efficiency. 相似文献
47.
48.
Masashi NakamuraIsao Takahashi Shunsuke YamadaYasuo Dobashi Osamu Kitagawa 《Tetrahedron letters》2011,52(1):53-55
Intramolecular Diels-Alder reactions of various N-allyl 2-furoyl amides with different substituents on the nitrogen atom were investigated. The reaction of amides having bulky substituents proceeded at a faster rate than the analogs whose substituents were of less bulkiness. From the systematic experimental survey of the substituent effects and the energetic evaluation based on the DFT calculations at the B3LYP/6-31G(d) level, the enhanced reactivity was ascribed to the relief of steric strain upon cyclization rather than the amide rotational isomerism governed by the bulky substituents. 相似文献
49.
Alexei A. Belik Pan?e Naumov Jungeun Kim Shunsuke Tsuda 《Journal of solid state chemistry》2011,184(11):3128-3133
Low-temperature structural properties of the synthetic mineral libethenite Cu2PO4OH were investigated by single-crystal X-ray diffraction, synchrotron X-ray powder diffraction, specific heat measurements, and Raman spectroscopy. A second-order structural phase transition from the Pnnm symmetry (a=8.0553(8) Å, b=8.3750(9) Å, c=5.8818(6) Å at 180 K) to the P21/n symmetry (a=8.0545(8) Å, b=8.3622(9) Å, c=5.8755(6) Å, β=90.0012(15) at 120 K) was found at 160 K during cooling. At 120 K, the monoclinic angle is 90.0012(15) from single crystal X-ray data vs 90.083(1) from powder X-ray diffraction data. The P21/n–to–Pnnm transition may be a general feature of the adamite-type compounds, M2XO4OH. 相似文献
50.
Aramburo LR Karwacki L Cubillas P Asahina S de Winter DA Drury MR Buurmans IL Stavitski E Mores D Daturi M Bazin P Dumas P Thibault-Starzyk F Post JA Anderson MW Terasaki O Weckhuysen BM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(49):13773-13781
A combination of atomic force microscopy (AFM), high‐resolution scanning electron microscopy (HR‐SEM), focused‐ion‐beam scanning electron microscopy (FIB‐SEM), X‐ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotron‐based IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM‐5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol‐to‐olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM‐5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM‐5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 5–50 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Brønsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity. 相似文献