全文获取类型
收费全文 | 10452篇 |
免费 | 364篇 |
国内免费 | 88篇 |
专业分类
化学 | 7146篇 |
晶体学 | 96篇 |
力学 | 267篇 |
综合类 | 1篇 |
数学 | 1740篇 |
物理学 | 1654篇 |
出版年
2023年 | 82篇 |
2022年 | 121篇 |
2021年 | 193篇 |
2020年 | 210篇 |
2019年 | 250篇 |
2018年 | 158篇 |
2017年 | 159篇 |
2016年 | 384篇 |
2015年 | 288篇 |
2014年 | 320篇 |
2013年 | 603篇 |
2012年 | 607篇 |
2011年 | 653篇 |
2010年 | 453篇 |
2009年 | 404篇 |
2008年 | 587篇 |
2007年 | 631篇 |
2006年 | 494篇 |
2005年 | 550篇 |
2004年 | 442篇 |
2003年 | 350篇 |
2002年 | 336篇 |
2001年 | 162篇 |
2000年 | 146篇 |
1999年 | 96篇 |
1998年 | 103篇 |
1997年 | 109篇 |
1996年 | 114篇 |
1995年 | 93篇 |
1994年 | 84篇 |
1993年 | 101篇 |
1992年 | 79篇 |
1991年 | 80篇 |
1990年 | 75篇 |
1989年 | 65篇 |
1988年 | 52篇 |
1987年 | 57篇 |
1986年 | 69篇 |
1985年 | 103篇 |
1984年 | 102篇 |
1983年 | 80篇 |
1982年 | 69篇 |
1981年 | 72篇 |
1980年 | 69篇 |
1979年 | 64篇 |
1978年 | 69篇 |
1977年 | 41篇 |
1976年 | 41篇 |
1975年 | 50篇 |
1974年 | 54篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
972.
Jan van Calker 《Analytical and bioanalytical chemistry》1936,105(11-12):396-406
973.
974.
975.
Micha Glesk Marta K. Dudek Peter Kinkade Evelyn C. S. Santos Vitold B. Glinski Daneel Ferreira Ewa Seweryn Sawomir Ka
mierski Joao B. Calixto Jan A. Glinski 《Molecules (Basel, Switzerland)》2022,27(9)
Echimidine is the main pyrrolizidine alkaloid of Echium plantagineum L., a plant domesticated in many countries. Because of echimidine’s toxicity, this alkaloid has become a target of the European Food Safety Authority regulations, especially in regard to honey contamination. In this study, we determined by NMR spectroscopy that the main HPLC peak purified from zinc reduced plant extract with an MS [M + H]+ signal at m/z 398 corresponding to echimidine (1), and in fact also represents an isomeric echihumiline (2). A third isomer present in the smallest amount and barely resolved by HPLC from co-eluting (1) and (2) was identified as hydroxymyoscorpine (3). Before the zinc reduction, alkaloids (1) and (2) were present mostly (90%) in the form of an N-oxide, which formed a single peak in HPLC. This is the first report of finding echihumiline and hydroxymyoscorpine in E. plantagineum. Retroanalysis of our samples of E. plantagineum collected in New Zealand, Argentina and the USA confirmed similar co-occurrence of the three isomeric alkaloids. In rat hepatocyte primary culture cells, the alkaloids at 3 to 300 µg/mL caused concentration-dependent inhibition of hepatocyte viability with mean IC50 values ranging from 9.26 to 14.14 µg/mL. Our discovery revealed that under standard HPLC acidic conditions, echimidine co-elutes with its isomers, echihumiline and to a lesser degree with hydroxymyoscorpine, obscuring real alkaloidal composition, which may have implications for human toxicity. 相似文献
976.
Huang S Yee WA Tjiu WC Liu Y Kotaki M Boey YC Ma J Liu T Lu X 《Langmuir : the ACS journal of surfaces and colloids》2008,24(23):13621-13626
Polyvinylidene difluoride (PVDF) solutions containing a very low concentration of single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs) of similar surface chemistry, respectively, were electrospun, and the nanofibers formed were collected using a modified rotating disk collector. The polymorphic behavior and crystal orientation of the nanofibers were studied using wide-angle X-ray diffraction and infrared spectroscopy, while the nanotube alignment and interfacial interactions in the nanofibers were probed by transmission electron microscopy and Raman spectroscopy. It is shown that the interfacial interaction between the SWCNTs and PVDF and the extensional force experienced by the nanofibers in the electrospinning and collection processes can work synergistically to induce highly oriented beta-form crystallites extensively. In contrast, the MWCNTs could not be well aligned along the nanofiber axis, which leads to a lower degree of crystal orientation. 相似文献
977.
Well‐Defined Palladium Nanoparticles Supported on Siliceous Mesocellular Foam as Heterogeneous Catalysts for the Oxidation of Water 下载免费PDF全文
Dr. Oscar Verho Dr. Torbjörn Åkermark Dr. Eric V. Johnston Karl P. J. Gustafson Dr. Cheuk‐W. Tai Henrik Svengren Dr. Markus D. Kärkäs Prof. Jan‐E. Bäckvall Prof. Björn Åkermark 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5909-5915
Herein, we describe the use of Pd nanoparticles immobilized on an amino‐functionalized siliceous mesocellular foam for the catalytic oxidation of H2O. The Pd nanocatalyst proved to be capable of mediating the four‐electron oxidation of H2O to O2, both chemically and photochemically. The Pd nanocatalyst is easy to prepare and shows high chemical stability, low leaching, and recyclability. Together with its promising catalytic activity, these features make the Pd nanocatalyst of potential interest for future sustainable solar‐fuel production. 相似文献
978.
Jan Kopecký 《Tetrahedron letters》1984,25(24):2613-2616
Irradiation of the title compound brings about consecutive photoisomerizations via derivatives of 1,2,3-triazolyl-2H-azirine, 1,2,3-triazolo[1,2-a]-1,2,4-triazole and 1,2,4-triazolyl-2H-azirine, leading finally to a dihydrotetraazabenz [e] azulene. 相似文献
979.
Bould J Macháček J Londesborough MG Macías R Kennedy JD Bastl Z Rupper P Baše T 《Inorganic chemistry》2012,51(3):1685-1694
Three nido-decaborane thiol cluster compounds, [1-(HS)-nido-B(10)H(13)] 1, [2-(HS)-nido-B(10)H(13)] 2, and [1,2-(HS)(2)-nido-B(10)H(12)] 3 have been characterized using NMR spectroscopy, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. In the solid state, 1, 2, and 3 feature weak intermolecular hydrogen bonding between the sulfur atom and the relatively positive bridging hydrogen atoms on the open face of an adjacent cluster. Density functional theory (DFT) calculations show that the value of the interaction energy is approximately proportional to the number of hydrogen atoms involved in the interaction and that these values are consistent with a related bridging-hydrogen atom interaction calculated for a B(18)H(22)·C(6)H(6) solvate. Self-assembled monolayers (SAMs) of 1, 2, and 3 on gold and silver surfaces have been prepared and characterized using X-ray photoelectron spectroscopy. The variations in the measured sulfur binding energies, as thiolates on the surface, correlate with the (CC2) calculated atomic charge for the relevant boron vertices and for the associated sulfur substituents for the parent B(10)H(13)(SH) compounds. The calculated charges also correlate with the measured and DFT-calculated thiol (1)H chemical shifts. Wetting-angle measurements indicate that the hydrophilic open face of the cluster is directed upward from the substrate surface, allowing the bridging hydrogen atoms to exhibit a similar reactivity to that of the bulk compound. Thus, [PtMe(2)(PMe(2)Ph)(2)] reacts with the exposed and acidic B-H-B bridging hydrogen atoms of a SAM of 1 on a gold substrate, affording the addition of the metal moiety to the cluster. The XPS-derived stoichiometry is very similar to that for a SAM produced directly from the adsorption of [1-(HS)-7,7-(PMe(2)Ph)(2)-nido-7-PtB(10)H(11)] 4. The use of reactive boron hydride SAMs as templates on which further chemistry may be carried out is unprecedented, and the principle may be extended to other binary boron hydride clusters. 相似文献
980.
Marco Felici Pablo Contreras‐Carballada Dr. Yolanda Vida Dr. Jan M. M. Smits Roeland J. M. Nolte Prof. Dr. Luisa De Cola Prof. Dr. René M. Williams Dr. Martin C. Feiters Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(47):13124-13134
Novel 2‐(1‐substituted‐1H‐1,2,3‐triazol‐4‐yl)pyridine (pytl) ligands have been prepared by “click chemistry” and used in the preparation of heteroleptic complexes of Ru and Ir with bipyridine (bpy) and phenylpyridine (ppy) ligands, respectively, resulting in [Ru(bpy)2(pytl‐R)]Cl2 and [Ir(ppy)2(pytl‐R)]Cl (R=methyl, adamantane (ada), β‐cyclodextrin (βCD)). The two diastereoisomers of the Ir complex with the appended β‐cyclodextrin, [Ir(ppy)2(pytl‐βCD)]Cl, were separated. The [Ru(bpy)2(pytl‐R)]Cl2 (R=Me, ada or βCD) complexes have lower lifetimes and quantum yields than other polypyridine complexes. In contrast, the cyclometalated Ir complexes display rather long lifetimes and very high emission quantum yields. The emission quantum yield and lifetime (Φ=0.23, τ=1000 ns) of [Ir(ppy)2(pytl‐ada)]Cl are surprisingly enhanced in [Ir(ppy)2(pytl‐βCD)]Cl (Φ=0.54, τ=2800 ns). This behavior is unprecedented for a metal complex and is most likely due to its increased rigidity and protection from water molecules as well as from dioxygen quenching, because of the hydrophobic cavity of the βCD covalently attached to pytl. The emissive excited state is localized on these cyclometalating ligands, as underlined by the shift to the blue (450 nm) upon substitution with two electron‐withdrawing fluorine substituents on the phenyl unit. The significant differences between the quantum yields of the two separate diastereoisomers of [Ir(ppy)2(pytl‐βCD)]Cl (0.49 vs. 0.70) are attributed to different interactions of the chiral cyclodextrin substituent with the Δ and Λ isomers of the metal complex. 相似文献