全文获取类型
收费全文 | 1050篇 |
免费 | 37篇 |
国内免费 | 3篇 |
专业分类
化学 | 744篇 |
晶体学 | 6篇 |
力学 | 33篇 |
数学 | 177篇 |
物理学 | 130篇 |
出版年
2024年 | 5篇 |
2023年 | 11篇 |
2022年 | 19篇 |
2021年 | 19篇 |
2020年 | 17篇 |
2019年 | 20篇 |
2018年 | 16篇 |
2017年 | 13篇 |
2016年 | 31篇 |
2015年 | 22篇 |
2014年 | 35篇 |
2013年 | 48篇 |
2012年 | 88篇 |
2011年 | 116篇 |
2010年 | 74篇 |
2009年 | 51篇 |
2008年 | 82篇 |
2007年 | 55篇 |
2006年 | 69篇 |
2005年 | 50篇 |
2004年 | 51篇 |
2003年 | 48篇 |
2002年 | 41篇 |
2001年 | 9篇 |
2000年 | 8篇 |
1999年 | 10篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 14篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1976年 | 5篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有1090条查询结果,搜索用时 15 毫秒
91.
Sylvain Celanire Frederic Marlin Jack E. Baldwin Robert M. Adlington 《Tetrahedron》2005,61(12):3025-3032
The synthesis of 3,11-dioxatricyclo[5.3.1.01,5]undeca-5,9-dien-8-ones is reported from suitable 5-substituted furfuryl alcohols bearing an acetylenic side-chain. Successive peracid-mediated oxidative rearrangement of furan carbinols and base-assisted intramolecular 1,3-dipolar cycloaddition afforded oxygen-bridged tricyclo-undecane derivatives. Stereoselective transformations of cycloadducts are also discussed. 相似文献
92.
Direct synthesis of new arylanthranilic acids via a Suzuki cross-coupling reaction with iodoisatins as key intermediates is described. A ‘one pot’ procedure is proposed. 相似文献
93.
Broussy S Coppel Y Nguyen M Bernadou J Meunier B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(9):2034-2038
Isoniazid (INH) is easily oxidized with manganese(III) pyrophosphate, a chemical model of the KatG protein involved in activation of INH inside the bacteria Mycobacterium tuberculosis. Performed in the presence of NAD(+), this oxidation generates a family of isomeric INH-NAD(H) adducts, which have been shown to be effective inhibitors of InhA, an enzyme essential in mycolic acid biosynthesis. In this work, we fully characterized by (1)H and (13)C NMR spectroscopy four main species of INH-NAD(H) adducts that coexist in solution. Two of them are open diastereoisomers consisting of the covalent attachment of the isonicotinoyl radical at position four of the nicotinamide coenzyme. The other two result from a cyclization involving the amide group from the nicotinamide and the carbonyl group from the isonicotinoyl radical to give diastereoisomeric hemiamidals. Although an INH-NAD(H) adduct with a 4S configuration has been characterized within the active site of InhA from Xray crystallography and this bound adduct interpreted as an open form (Rozwarski et al., Science 1998, 279, 98-102), it is legitimate to raise the question about the effective active form(s), open or cyclic, of INH-NAD(H) adduct(s). Is there a single active form or are several forms able to inhibit the InhA activity with different levels of inhibitory potency? 相似文献
94.
95.
96.
Clède S Lambert F Sandt C Gueroui Z Réfrégiers M Plamont MA Dumas P Vessières A Policar C 《Chemical communications (Cambridge, England)》2012,48(62):7729-7731
A rhenium tris-carbonyl derivative has been designed to couple infrared and luminescent detection in cells. Both spectroscopies are consistent with one another; they point out the reliability of the present SCoMPI (for Single Core Multimodal Probe for Imaging) for bimodal imaging and unambiguously indicate a localization at the Golgi apparatus in MDA-MB-231 breast cancer cells. 相似文献
97.
Multifrequency EPR and redox reactivity investigations of a bis(mu-thiolato)-dicopper(II,II) complex
Rammal W Belle C Béguin C Duboc C Philouze C Pierre JL Le Pape L Bertaina S Saint-Aman E Torelli S 《Inorganic chemistry》2006,45(25):10355-10362
From a new tripodal ligand [N2SS'H] with mixed N, S(thioether), and S(thiolate) donor set, the corresponding bis(mu-thiolato)dicopper(II) complex has been prepared and characterized. X-ray crystallographic analysis of the complex [Cu2(N2SS')2](ClO4)2.C4H10O (1) demonstrates that the two five-coordinated Cu atoms are bridged by two thiolates leading to a nearly planar Cu2S2 core with a Cu1...Cu1* distance of 3.418(8) A and a large bridging angle Cu1S1Cu1* of 94.92 degrees. X-band (10 GHz), Q-band (34 GHz), and F-Band (115 GHz) EPR spectra of 1 are consistent with a weakly coupled dicopper(II,II) center attributed to an S = 1 state. Simulations for the three frequencies are obtained with a unique set of electronic parameters. The mean values of the spin Hamiltonian parameters for 1 are D = 0.210(3) cm(-1), E = 0.0295(5) cm(-1), |E/D| = 0.140, gx = 2.030(2), gy = 2.032(2), gz = 2.128(2). The electrochemical one-electron reduction of 1 generates the mixed-valent CuIICuI species. EPR and UV-vis spectra are consistent with a type I localized mixed-valent species, while dinuclear CuA centers of native cytochrome c oxidase (CcO)1-3 or nitrous oxide reductase (N2OR)4 have a delocalized CuIICuI mixed-valent state. After reoxidation of the CuIICuI species, the initial complex 1 is regenerated through a reversible interconversion process. 相似文献
98.
Dr. Julian J. Holstein Priv.‐Doz. Dr. Birger Dittrich Miriam Simon Dr. Sylvain Prévost Prof. Dr. Michael Gradzielski Prof. Dr. Guido H. Clever 《Angewandte Chemie (International ed. in English)》2018,57(41):13652-13656
A series of metal‐mediated cages, having multiple cavities, was synthesized from PdII cations and tris‐ or tetrakis‐monodentate bridging ligands and characterized by NMR spectroscopy, mass spectrometry, and X‐ray methods. The peanut‐shaped [Pd3L14] cage deriving from the tris‐monodentate ligand L1 could be quantitatively converted into its interpenetrated [5Cl@Pd6L18] dimer featuring a linear {[Pd‐Cl‐]5Pd} stack as an unprecedented structural motif upon addition of chloride anions. Small‐angle neutron scattering (SANS) experiments showed that the cigar‐shaped assembly with a length of 3.7 nm aggregates into mono‐layered discs of 14 nm diameter via solvophobic interactions between the hexyl sidechains. The hepta‐cationic [5Cl@Pd6L18] cage was found to interact with polyanionic oligonucleotide double‐strands under dissolution of the aggregates in water, rendering the compound class interesting for applications based on non‐covalent DNA binding. 相似文献
99.
d'Alessandro C Rilliard A Le Beux S 《The Journal of the Acoustical Society of America》2011,129(3):1594-1604
Intonation stylization is studied using "chironomy," i.e., the analogy between hand gestures and prosodic movements. An intonation mimicking paradigm is used. The task of the ten subjects is to copy the intonation pattern of sentences with the help of a stylus on a graphic tablet, using a system for real-time manual intonation modification. Gestural imitation is compared to vocal imitation of the same sentences (seven for a male speaker, seven for a female speaker). Distance measures between gestural copies, vocal imitations, and original sentences are computed for performance assessment. Perceptual testing is also used for assessing the quality of gestural copies. The perceptual difference between natural and stylized contours is measured using a mean opinion score paradigm for 15 subjects. The results indicate that intonation contours can be stylized with accuracy by chironomic imitation. The results of vocal imitation and chironomic imitation are comparable, but subjects show better imitation results in vocal imitation. The best stylized contours using chironomy seems perceptually indistinguishable or almost indistinguishable from natural contours, particularly for female speech. This indicates that chironomic stylization is effective, and that hand movements can be analogous to intonation movements. 相似文献
100.
Sylvain Rodriguez Jean-Luc Wolfender Kurt Hostettmann Gendaramyn Odontuya Ondognii Purev 《Helvetica chimica acta》1996,79(2):363-370
Chemical screening of the secondary metabolites from Halenia corniculata L. (CORNAZ ), by LC/UV,LC/TSP-MS (thermospray), and LC/ES-MS (electrospray) was used for the targeted isolation of corniculoside ( 1 ), a new biosidic ester secoiridoid. The structure was established as 7-β-[(E)-4′-O-(β-D -glucopyranosyl)caffeoyloxy]-sweroside by 1D- and 2D-NMR, LC/UV, LC/MS, and FAB-MS data, in combination with chemical reactions. 相似文献