全文获取类型
收费全文 | 1468篇 |
免费 | 75篇 |
国内免费 | 5篇 |
专业分类
化学 | 1172篇 |
晶体学 | 7篇 |
力学 | 17篇 |
数学 | 166篇 |
物理学 | 186篇 |
出版年
2024年 | 2篇 |
2023年 | 18篇 |
2022年 | 39篇 |
2021年 | 42篇 |
2020年 | 49篇 |
2019年 | 34篇 |
2018年 | 17篇 |
2017年 | 25篇 |
2016年 | 51篇 |
2015年 | 54篇 |
2014年 | 47篇 |
2013年 | 74篇 |
2012年 | 94篇 |
2011年 | 121篇 |
2010年 | 57篇 |
2009年 | 49篇 |
2008年 | 96篇 |
2007年 | 108篇 |
2006年 | 86篇 |
2005年 | 91篇 |
2004年 | 60篇 |
2003年 | 66篇 |
2002年 | 68篇 |
2001年 | 13篇 |
2000年 | 13篇 |
1999年 | 5篇 |
1998年 | 10篇 |
1997年 | 7篇 |
1996年 | 34篇 |
1995年 | 22篇 |
1994年 | 17篇 |
1993年 | 11篇 |
1992年 | 16篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 5篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有1548条查询结果,搜索用时 31 毫秒
161.
We investigate the decomposition of ammonia on bimetallic surfaces prepared by the deposition of a monolayer of Fe, Co, or Cu on a Pt(111) surface computationally and experimentally. We explore the correlation between predicted activities based on the nitrogen binding energies with experimental decomposition activity on these bimetallic and corresponding monometallic surfaces. Through density functional theory calculations and microkinetic modeling, it is predicted that the Fe-Pt-Pt(111) and Co-Pt-Pt(111) surfaces, with a monolayer of Fe or Co on top of Pt(111), are active toward decomposing ammonia. In contrast, the corresponding subsurface configurations, Pt-Fe-Pt(111) and Pt-Co-Pt(111) are inactive. These predictions were confirmed experimentally through temperature programmed desorption experiments. Decomposition was seen at temperatures below 350 K for the Fe-Pt-Pt(111) and Co-Pt-Pt(111) surfaces. For the Cu∕Pt(111) system, the surface, subsurface and parent metals were each predicted to be inactive, consistent with experiments, further validating the model predictions. The stability of these bimetallic surfaces in the presence of adsorbed nitrogen is also discussed. 相似文献
162.
Tomohiro Ohta Takeru Ito Masahiro Shimizu Lisa Tauchi Huy‐Danh Nguyen‐Tran Jong‐Chul Park Byoung‐Suhk Kim Ick‐Soo Kim Kazuchika Ohta 《先进技术聚合物》2011,22(12):2653-2658
We have developed a novel synthetic method that enables us to easily synthesize metal‐capsulated carbon nanotubes (CNTs) in a laboratory by using a combined technology of electrospinning‐metallization and microwave heating. These techniques greatly shorten the time for the synthesis of the CNTs in comparison with the conventional methods. TEM analysis confirmed a successful formation of the CNTs, and the resulting CNTs were multi‐walled and found to be about 25–100 nm in diameters. The products prepared by heating at 600 and 900°C exhibited less‐developed and strongly curved CNTs, whereas the products prepared by heating at 700 and 800°C relatively well‐developed long CNTs. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
163.
NHC catalysed rearrangement of α,β-unsaturated enol esters derived from formyl acetates and cyclopentyl annulated α,β-unsaturated acids provides the cyclopentapyranone core of (-)-7-deoxyloganin (1) with diastereo- and chemoselectivity in 6 steps starting from (-)-citronellal. The elaboration to the natural product has been investigated using two new approaches. The most successful intercepts our previous work on (-)-7-deoxyloganin (1) allowing completion of a formal total synthesis in 10-steps. 相似文献
164.
Chien CC Zhang G Hwu Y Liu P Yue W Sun J Li Y Xu H Xue H Xu LX Wang CH Chen N Lu CH Lee TK Yang YC Lu YT Ching YT Shih TF Yang PC Je JH Margaritondo G 《Analytical and bioanalytical chemistry》2011,401(3):827-835
Refractive-index (phase-contrast) radiology was able to detect lung tumors less than 1 mm in live mice. Significant micromorphology differences were observed in the microradiographs between normal, inflamed, and lung cancer tissues. This was made possible by the high phase contrast and by the fast image taking that reduces the motion blur. The detection of cancer and inflammation areas by phase contrast microradiology and microtomography was validated by bioluminescence and histopathological analysis. The smallest tumor detected is less than 1 mm(3) with accuracy better than 1 × 10(-3) mm(3). This level of performance is currently suitable for animal studies, while further developments are required for clinical application. 相似文献
165.
Lisa Beck 《Annali di Matematica Pura ed Applicata》2011,190(4):553-588
We consider weak solutions ${u \in u_0 + W^{1,2}_0(\Omega,\mathbb{R}^N) \cap L^{\infty}(\Omega,\mathbb{R}^N)}$ of second-order nonlinear elliptic systems of the type $$- {\rm div} \,a (\, \cdot \,, u, Du ) = b(\, \cdot \,,u,Du)\qquad \text{ in }\Omega$$ with an inhomogeneity satisfying a natural growth condition. In dimensions ${n \in \{2,3,4\}}$ , we show that ${\mathcal{H}^{n-1}}$ -almost every boundary point is a regular point for Du, provided that the boundary data and the coefficients are sufficiently smooth. 相似文献
166.
Herein we report the first all-carbon N-heterocyclic carbene-catalyzed (4 + 2) cycloaddition. The reaction proceeds with α,β-unsaturated acid fluorides and silyl dienol ethers and produces 1,3-cyclohexadienes with complete diastereocontrol (dr >20:1) while demonstrating a new type of reaction cascade exploiting α,β-unsaturated acyl azoliums. 相似文献
167.
We demonstrate a simple method to tune and pattern the wettability of polydimethylsiloxane (PDMS) to generate microfluidic mimics of heterogeneous porous media. This technique allows one to tailor the capillary forces at different regions within the PDMS channel to mimic multi-phase flow in oil reservoirs. In this method, UV-ozone treatment is utilized to oxidize and hydrophilize the surface of PDMS. To maintain a stable surface wettability, the oxidized surfaces are immersed in water. Additionally, the use of a photomask makes it convenient to pattern the wettability in the porous media. A one-dimensional diffusive reaction model is established to understand the UV-ozone oxidation as well as hydrophobic recovery of oxidized PDMS surfaces. The modeling results show that during UV-ozone, surface oxidation dominates over diffusion of low-molecular-weight (LMW) species. However, the diffusivity of LMW species plays an important role in wettability control of PDMS surfaces. 相似文献
168.
Berreau LM Borowski T Grubel K Allpress CJ Wikstrom JP Germain ME Rybak-Akimova EV Tierney DL 《Inorganic chemistry》2011,50(3):1047-1057
The mononuclear nickel(II) enolate complex [(6-Ph(2)TPA)Ni(PhC(O)C(OH)C(O)Ph]ClO(4) (I) was the first reactive model complex for the enzyme/substrate (ES) adduct in nickel(II)-containing acireductone dioxygenases (ARDs) to be reported. In this contribution, the mechanism of its O(2)-dependent aliphatic carbon-carbon bond cleavage reactivity was further investigated. Stopped-flow kinetic studies revealed that the reaction of I with O(2) is second-order overall and is ~80 times slower at 25 °C than the reaction involving the enolate salt [Me(4)N][PhC(O)C(OH)C(O)Ph]. Computational studies of the reaction of the anion [PhC(O)C(OH)C(O)Ph](-) with O(2) support a hydroperoxide mechanism wherein the first step is a redox process that results in the formation of 1,3-diphenylpropanetrione and HOO(-). Independent experiments indicate that the reaction between 1,3-diphenylpropanetrione and HOO(-) results in oxidative aliphatic carbon-carbon bond cleavage and the formation of benzoic acid, benzoate, and CO:CO(2) (~12:1). Experiments in the presence of a nickel(II) complex gave a similar product distribution, albeit benzil [PhC(O)C(O)Ph] is also formed, and the CO:CO(2) ratio is ~1.5:1. The results for the nickel(II)-containing reaction match those found for the reaction of I with O(2) and provide support for a trione/HOO(-) pathway for aliphatic carbon-carbon bond cleavage. Overall, I is a reasonable structural model for the ES adduct formed in the active site of Ni(II)ARD. However, the presence of phenyl appendages at both C(1) and C(3) in the [PhC(O)C(OH)C(O)Ph](-) anion results in a reaction pathway for O(2)-dependent aliphatic carbon-carbon bond cleavage (via a trione intermediate) that differs from that accessible to C(1)-H acireductone species. This study, as the first detailed investigation of the O(2) reactivity of a nickel(II) enolate complex of relevance to Ni(II)ARD, provides insight toward understanding the chemical factors involved in the O(2) reactivity of metal acireductone species. 相似文献
169.
The M(CO)(4) fragment can be assigned to be isolobal with both CH(3)(+) and CH(2). In order to investigate this ambiguous isolobal assignment, we report calculations on compounds of the type M(CO)(4)L(n), where M is Fe (n = 0), Mn (n = -1), and Co (n = +1) and L is an η(2) ligand with a π bond, generally an alkene. The L's are varied in electron-withdrawing ability, and patterns in computed structural parameters are investigated. We report that the equatorial OC-M-CO angle is sensitive to the electron-withdrawing ability of the alkene just as the isolobal prediction suggests. Other structural parameters that vary monotonically with electron-withdrawing ability of the alkene are the "bending back" of the alkene, the metal-ligand bond distances, and carbon-oxygen bond distances. Changing the metal from neutral Fe to a negatively charged Mn or positively charged Co has the result of increasing and decreasing, respectively, the OC-M-CO angle. Several compounds of Ni(CO)(3)L are also investigated as a further example of the ability of the isolobal concept to yield chemically useful information. 相似文献
170.
A set of N-substituted benzoperylene monoimide (BPI) fluorophores was synthesized and characterized structurally and photophysically. Condensation of benzo[ghi]perylene-1,2-dicarboxylic anhydride in the presence of "swallow tail" alkyl amines produced fluorophores that are soluble in a range of organic solvents, highly absorbing in the near-UV (ε(334) = 79,000 M(-1) cm(-1)), and fluorescent in the visible range. Photophysical behavior of the compounds was studied with steady-state and time-correlated single photon counting. The synthesized BPIs exhibit positive solvachromatic emission (λ(em) (hexane) = 469 nm; λ(em) (ethanol) = 550 nm) as a function of solvent polarity with little change in their excited-state lifetime (9.6-6.5 ns) and fluorescence quantum yield (0.27-0.44) over the polarity range studied. Solvachromatic shifts were analyzed using the Lippert-Mataga approach. In nonpolar hydrocarbon solvents evidence of dual emission from closely spaced (562 cm(-1)) S(1) and S(2) excited states is observed. Preliminary peak assignments for the anomalous S(2) emission are made. 相似文献