全文获取类型
收费全文 | 1673篇 |
免费 | 20篇 |
国内免费 | 7篇 |
专业分类
化学 | 1263篇 |
晶体学 | 11篇 |
力学 | 54篇 |
数学 | 156篇 |
物理学 | 216篇 |
出版年
2023年 | 11篇 |
2022年 | 19篇 |
2021年 | 24篇 |
2020年 | 22篇 |
2019年 | 26篇 |
2018年 | 21篇 |
2017年 | 13篇 |
2016年 | 18篇 |
2015年 | 17篇 |
2014年 | 27篇 |
2013年 | 87篇 |
2012年 | 67篇 |
2011年 | 73篇 |
2010年 | 46篇 |
2009年 | 46篇 |
2008年 | 106篇 |
2007年 | 89篇 |
2006年 | 88篇 |
2005年 | 87篇 |
2004年 | 91篇 |
2003年 | 74篇 |
2002年 | 49篇 |
2001年 | 17篇 |
1999年 | 16篇 |
1998年 | 16篇 |
1997年 | 15篇 |
1996年 | 27篇 |
1995年 | 15篇 |
1994年 | 18篇 |
1993年 | 26篇 |
1992年 | 22篇 |
1991年 | 12篇 |
1990年 | 11篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 15篇 |
1986年 | 14篇 |
1985年 | 40篇 |
1984年 | 29篇 |
1983年 | 20篇 |
1982年 | 29篇 |
1981年 | 17篇 |
1980年 | 30篇 |
1979年 | 18篇 |
1978年 | 23篇 |
1977年 | 15篇 |
1976年 | 18篇 |
1975年 | 21篇 |
1974年 | 27篇 |
1973年 | 14篇 |
排序方式: 共有1700条查询结果,搜索用时 537 毫秒
1.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
2.
Tuomas Aitasalo Jorma Hls Hgne Jungner Jean-Claude Krupa Mika Lastusaari Janina Legendziewicz Janne Niittykoski 《Radiation measurements》2004,38(4-6):727-730
The UV excited and persistent luminescence properties as well as thermoluminescence (TL) of Eu2+ doped strontium aluminates, SrAl2O4:Eu2+ were studied at different temperatures. Two luminescence bands peaking at 445 and 520 nm were observed at 20 K but only the latter at 295 K. Both Sr-sites in the lattice are thus occupied by Eu2+ but at room temperature efficient energy transfer occurs between the two sites. The UV excited and persistent luminescence spectra were similar at 295 K but the excitation spectra were different. Thus the luminescent centre is the same in both phenomena but excitation processes are different. Two TL peaks were observed between 50 and 250 °C in the glow curve. Multiple traps were, however, observed by preheating and initial rise methods. With longer delay times only the high temperature TL peak was observed. The persistent luminescence is mainly due to slow fading of the low temperature TL peak but the step-wise feeding process from high temperature traps is also probable. 相似文献
3.
The time delay experiment proposed by I.I. Shapiro in 1964 and conducted in the seventies was the most precise experiment
of general relativity until that time. Further experimentation has improved the accuracy level of both the time delay and
the light deflection experiments. A simulation model is proposed that involves only a simple mass and time transformation
factor involving velocity of light. The light deflection and the time delay experiments are numerically simulated using this
model that does not use the general relativistic equations. The computed values presented in this paper compare well with
recent levels of accuracy of their respective experimental results. 相似文献
4.
5.
S. D. Borkute U. H. Nagvekar S. A. Balakrishnan R. S. Mani 《Journal of Radioanalytical and Nuclear Chemistry》1987,119(4):297-302
A novel method to eliminate T3 from gross sera/plasma based on prior treatment with 8-anilino-1-naphthalene sulphonic acid has been standardized. This method is rapid with a minimum loss of protein and uses only small quantities of charcoal. The treated sera have been tested for acceptance in the RIA system for routine assays. 相似文献
6.
Raj Gandhi Kamales Kar S. Uma Sankar Abhijit Bandyopadhyay Rahul Basu Pijushpani Bhattacharjee Biswajoy Brahmachari Debrupa Chakraborti M. Chaudhury J. Chaudhury Sandhya Choubey E. J. Chun Atri Desmukhya Anindya Datta Gautam Dutta Sukanta Dutta Anjan Giri Sourendu Gupta Srubabati Goswami Namit Mahajan H. S. Mani A. Mukherjee Biswarup Mukhopadhyaya S. N. Nayak M. Randhawa Subhendu Rakshit Asim K. Ray Amitava Raychaudhuri D. P. Roy Probir Roy Suryadeep Roy Shiv Sethi G. Sigl Arunansu Sil N. Nimai Singh Mark Vagins Urjit Yagnik 《Pramana》2003,60(2):405-409
This is the report of neutrino and astroparticle physics working group at WHEPP-7. Discussions and work on CP violation in
long baseline neutrino experiments, ultra high energy neutrinos, supernova neutrinos and water Cerenkov detectors are discussed. 相似文献
7.
S. Kalavathi J. Janaki Awadhesh Mani V. Sankara Sastry 《Solid State Communications》2006,139(7):334-338
Some new members of a ruthenocuprate(2212) series have been synthesized by Mn substitution for Ru in Gd1.4Ce0.6Sr2RuCu2O10. Characterization by x-ray diffraction (XRD) phase analysis has been carried out. Changes in structural features on substitution, including a significant change in lattice parameter for a very low substitution level, have been observed. Four-probe resistivity studies indicate the coexistence of superconductivity and magnetism for the pristine compound and a semiconductor-like upturn in resistivity and the absence of superconductivity even for very low levels of Mn substitution. AC susceptibility measurements show a progressive suppression of the magnetic transition temperature as well as a smearing of the magnetic transition as a function of Mn substitution. Possible reasons for the absence of superconductivity have been discussed. 相似文献
8.
Ghandi K Addison-Jones B Brodovitch JC McCollum BM McKenzie I Percival PW 《Journal of the American Chemical Society》2003,125(32):9594-9595
Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 degrees C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto-enol equilibrium have been studied. 相似文献
9.
Jean-Claude Grenier Grard Schiffmacher Paul Caro Michel Pouchard Paul Hagenmuller 《Journal of solid state chemistry》1977,20(4):365-379
In order to check the extended defect model previously proposed for the nonstoichiometric perovskite AnMnO3n−1 (n 2), the Ca2Ti2−2xFe2xO6−x solid solution has been studied by means of X-ray diffraction and electron microscope investigations. The results show the existence of a continuous evolution (0 x 1) with two different regions. Close to the CaTiO3 composition (0 x 0.40) the oxygen vacancies seem to be randomly distributed and the symmetry remains pseudocubic. In the composition range 0.55 x 1, the electron microscope patterns show an ordering of the defects: the oxygen vacancies are ordered in the (0k0) planes in strings parallel to the [101] direction. It is concluded from these observations that perpendicular to the Oy direction isolated planes of tetrahedra arranged in rows separate planes of corner-linked octahedra. The n = 2; 2.5; 3, et 4 terms of the AnMnO3n−1 series have been identified. C.S. planes characteristic of classical nonstoichiometric oxides with small cations do not appear: instead, tetrahedra planes succeed to the previous octahedra planes as the degree of nonstoichiometry increases.
Résumé
Afin de vérifier le modèle de non-stoechiométrie proposé dans un travail précédent pour les perovskites lacunaires AnMnO3n−1 (n 2), la solution solide Ca2Ti2−2xFe2xO6−x a été, étudiée par diffraction X et microscopie électronique. Les résultats montrent l'existence d'une évolution continue (0 x 1) avec deux domaines différents. Pour les compositions proches de CaTiO3 (0 x 0.40), les lacunes oxygénées semblent être distribuées statistiquement et la symétrie demeure pseudocubique. Dans le domaine de compositions 0.55 x 1, les images de microscopie électronique montrent un ordre des défauts: les lacunes d'oxygène sont ordonnées dans les plans (0k0) en rangées parallèles à la direction [101]. Ces observations ont permis de conclure que perpendiculairement à la direction Oy des plans isolés de files de tétraèdres séparent des plans d'octaèdres liés par leurs sommets. Les termes n = 2; 2.5; 3 et 4 des séries AnMnO3n−1 ont été identifiés. Des plans de cisaillement rencontrés dans les oxydes non-stoechiométriques classiques de petits cations n'ont pas été mis en évidence: par contre, des plans de tétraèdres se substituent aux plans d'octaèdres initiaux lorsque le degré de non-stoechiométrie augmente. 相似文献10.
A straightforward preparation of various sulfoforms of the trisaccharide 4-methoxyphenyl O-(sodium beta-d-glucopyranosyluronate)-(1-->3)-( beta-d-galactopyranosyl)-(1-->3)-beta-d-galactopyranoside (1), namely its 6a- and 4a-monosulfate, 6b- and 4b-monosulfate and 6a,6b-disulfate derivatives, is reported for the first time. These compounds, which are partial structures of the linkage region of proteoglycans, will serve as probes for the study of the biosynthesis and sorting of these macromolecules. A key trisaccharide derivative, in which the two similar d-Gal units were differentiated at C-4,6 with 4,6-benzylidene and 4,6-di-tert-butylsilylene acetals, respectively, was used as a common intermediate. Both acetal groups showed excellent orthogonality, and allowed the preparation of all target compounds in high yield. Noteworthy is the possibility to prepare the 6a- and 6b-monosulfated and the 6a,6b-disulfated species through a one-pot regioselective procedure starting from a tetrol precursor. 相似文献