全文获取类型
收费全文 | 800篇 |
免费 | 21篇 |
国内免费 | 3篇 |
专业分类
化学 | 680篇 |
晶体学 | 1篇 |
力学 | 8篇 |
综合类 | 1篇 |
数学 | 52篇 |
物理学 | 82篇 |
出版年
2023年 | 5篇 |
2022年 | 6篇 |
2021年 | 11篇 |
2020年 | 20篇 |
2019年 | 7篇 |
2018年 | 19篇 |
2017年 | 9篇 |
2016年 | 23篇 |
2015年 | 29篇 |
2014年 | 20篇 |
2013年 | 40篇 |
2012年 | 55篇 |
2011年 | 62篇 |
2010年 | 28篇 |
2009年 | 32篇 |
2008年 | 37篇 |
2007年 | 51篇 |
2006年 | 48篇 |
2005年 | 49篇 |
2004年 | 40篇 |
2003年 | 42篇 |
2002年 | 24篇 |
2001年 | 13篇 |
2000年 | 5篇 |
1999年 | 7篇 |
1998年 | 6篇 |
1997年 | 7篇 |
1996年 | 5篇 |
1995年 | 6篇 |
1993年 | 6篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1985年 | 3篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1979年 | 4篇 |
1973年 | 7篇 |
1968年 | 3篇 |
1967年 | 5篇 |
1966年 | 3篇 |
1962年 | 2篇 |
1959年 | 2篇 |
1930年 | 2篇 |
1891年 | 2篇 |
排序方式: 共有824条查询结果,搜索用时 15 毫秒
1.
2.
Marilena Vasilescu Titus Constantinescu Mariana Voicescu Helge Lemmetyinen Elina Vuorimaa 《Journal of fluorescence》2003,13(4):315-322
The spectrophotometric study of luminol (LH2) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH2 absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L2–) formation at 3 × 10–4 – 2.4 × 10–3
M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH2-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH2-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH+
3 cation formation. In LH2-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH2-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed. 相似文献
3.
4.
Lu XX Tang HS Ko CC Wong JK Zhu N Yam VW 《Chemical communications (Cambridge, England)》2005,(12):1572-1574
The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies. 相似文献
5.
Erwin Gtschi Christian-Johannes Jenny Peter Reindl Fabienne Ricklin 《Helvetica chimica acta》1996,79(8):2219-2234
A total synthesis of cyclothialidine ( 1 ), a new DNA gyrase inhibitor isolated from Streptomyces filipinensis, is described. The synthetic concept was tested by preparing the lactone 13 (Scheme 2) which contains the characteristic bicyclic core entity of 1 . Key features of the synthesis of 1 are: preparation of 3,5-dihydroxy-2,6-dimethylbenzoic acid ( 23 ) from 3,5-dihydroxybenzoic acid ( 19 ) by two consecutive Mannich aminomethylation/hydrogenation sequences; benzylic N-bromosuccinimide bromination of an ester derivative 25 thereof and its subsequent coupling with Boc-Ser-Cys-OMe ( 11 ); cyclization of the ω-hydroxy acid 29 29 to the 12-membered lactone 30 using preferably Mitsunobu conditions; completion of the peptidic side chains of 1 using Boc strategy (Scheme 4). Optically pure cis-N-(tert-butoxycarbonyl)-3-hydroxy-L -proline ((–)- 14 ) was obtained by resolution of the racemate via an efficient reaction sequence containing a lipase-catalyzed enantiospecific acetate hydrolysis (Scheme 3). The structure of natural 1 was confirmed by comparison with the synthetic material. The synthetic route described provides also easy access to analogues of 1 , e.g., via the intermediate 30 . 相似文献
6.
4,4-Dimethyl-2-phenyl-2-thiazolin-5-thione () reacts with 2,3-diphenylcyclopropenone () at 145°C and with benzonitrilio-2-propanide () at room temperature to yield the 1,6-dithia-spiro[4.4]nonadienes and , respectively. 相似文献
7.
Thomas F. Jenny Jennifer Horlacher Nicoletta Previsani Steven A. Benner 《Helvetica chimica acta》1992,75(6):1944-1954
A set of derivatives of cyclopentaneacetic acid cis-substituted at position 3 by nucleoside bases (both purines and pyrimidines) were prepared and characterized (see 11, 14 , and 23a, b; Schemes 2–4). These molecules are carbocyclic analogs of 2′,3′-dideoxy-5′-homonucleosides. In this synthesis, the skeleton was constructed from norbornanone and a novel method based on Mitsunobu chemistry used for the introduction of nucleoside-base substituents. The scope of this method was further explored via the preparation of a cyclobutyl analog of dideoxyguanosine (see 17 , Scheme 3). 相似文献
8.
Title compound 1 was synthesized by a published route which had to be modified (seven steps from readily obtainable starting materials). Characterization of 1 was achieved by spectroscopic means (FAB-MS, 1H-NMR, including 2D-COSY). Furthermore, commercially available reference material purchased for comparison, was unequivocally established to be 10 , i.e. incompletely deprotected 1 . 相似文献
9.
Erlanson DA McDowell RS He MM Randal M Simmons RL Kung J Waight A Hansen SK 《Journal of the American Chemical Society》2003,125(19):5602-5603
Protein tyrosine phosphatases play important roles in many signaling cascades involved in human disease. The identification of druglike inhibitors for these targets is a major challenge, and the discovery of suitable phosphotyrosine (pY) mimetics remains one of the key difficulties. Here we describe an extension of tethering technology, "breakaway tethering", which is ideally suited for discovering such new chemical entities. The approach involves first irreversibly modifying a protein with an extender that contains both a masked thiol and a known pY mimetic. The extender is then cleaved to release the pY mimetic, unmasking the thiol. The resulting protein is screened against a library of disulfide-containing small molecule fragments; any molecules with inherent affinity for the pY binding site will preferentially form disulfides with the extender, allowing for their identification by mass spectrometry. The ability to start from a known substrate mimimizes perturbation of protein structure and increases the opportunity to probe the active site using tethering. We applied this approach to the anti-diabetic protein PTP1B to discover a pY mimetic which belongs to a new molecular class and which binds in a novel fashion. 相似文献
10.
Myron S. Huzan Manuel Fix Matteo Aramini Peter Bencok J. Frederick W. Mosselmans Shusaku Hayama Franziska A. Breitner Leland B. Gee Charles J. Titus Marie-Anne Arrio Anton Jesche Michael L. Baker 《Chemical science》2020,11(43):11801
Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L2,3-edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine FeI dopant ions to be linearly coordinated, occupying a D6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L2,3-edge XAS from which the energy reduction of 3dz2 due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L3-edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (∼280 cm−1), that corresponds with Orbach relaxation via the first excited, MJ = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.Taking advantage of synchrotron light source methods, we present the geometric and electronic structure of iron doped in lithium nitride. 相似文献