全文获取类型
收费全文 | 5562篇 |
免费 | 281篇 |
国内免费 | 68篇 |
专业分类
化学 | 3440篇 |
晶体学 | 51篇 |
力学 | 235篇 |
综合类 | 1篇 |
数学 | 1090篇 |
物理学 | 1094篇 |
出版年
2023年 | 48篇 |
2022年 | 45篇 |
2021年 | 72篇 |
2020年 | 90篇 |
2019年 | 97篇 |
2018年 | 162篇 |
2017年 | 126篇 |
2016年 | 189篇 |
2015年 | 188篇 |
2014年 | 220篇 |
2013年 | 450篇 |
2012年 | 468篇 |
2011年 | 462篇 |
2010年 | 302篇 |
2009年 | 230篇 |
2008年 | 346篇 |
2007年 | 378篇 |
2006年 | 297篇 |
2005年 | 297篇 |
2004年 | 240篇 |
2003年 | 188篇 |
2002年 | 176篇 |
2001年 | 55篇 |
2000年 | 56篇 |
1999年 | 42篇 |
1998年 | 29篇 |
1997年 | 29篇 |
1996年 | 54篇 |
1995年 | 39篇 |
1994年 | 35篇 |
1993年 | 26篇 |
1992年 | 28篇 |
1991年 | 20篇 |
1990年 | 21篇 |
1989年 | 18篇 |
1988年 | 10篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 31篇 |
1984年 | 25篇 |
1983年 | 14篇 |
1982年 | 23篇 |
1981年 | 17篇 |
1980年 | 18篇 |
1979年 | 21篇 |
1978年 | 23篇 |
1976年 | 18篇 |
1975年 | 13篇 |
1974年 | 15篇 |
1973年 | 15篇 |
排序方式: 共有5911条查询结果,搜索用时 11 毫秒
51.
Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH(2)Cl(2), PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH(2)Cl(2), but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycle. The half-wave potentials were analyzed as a function of the number of aryl substituents on the macrocycle as well as the concentration of added pyridine to PhCN solutions of the compound, and these data were combined with data from the spectroelectrochemistry experiments to determine the stoichiometry of the species actually in solution after the first oxidation or first reduction of each compound. The results of these experiments indicate that reduction of the bispyridine adduct (Cor)Co(III)(py)(2) proceeds via the monopyridine complex (Cor)Co(III)(py) to give in each case the unligated cobalt(II) corrole [(Cor)Co(II)](-). In contrast, pyridine remains coordinated after electrooxidation, and the final product was characterized as [(Cor)Co(III)(py)(2)](+). 相似文献
52.
The Ramanujan Journal - This paper provides elementary proofs for several types of congruences involving multipartitions and self-convolutions of the divisor function. Our computations use... 相似文献
53.
Nazarov Anatoly Sztrik János Kvach Anna Tóth Ádám 《Methodology and Computing in Applied Probability》2022,24(3):1503-1518
Methodology and Computing in Applied Probability - This paper deals with a retrial queuing system with a finite number of sources and collision of the customers, where the server is subject to... 相似文献
54.
Castaing Charles Godet-Thobie C. Saïdi Soumia 《Set-Valued and Variational Analysis》2022,30(2):621-656
Set-Valued and Variational Analysis - The paper deals with second-order evolution problems driven by time and state dependent maximal monotone operators with non-Lipschitz perturbations. Systems... 相似文献
55.
Frédéric Semet 《Annals of Operations Research》1995,61(1):45-65
In the partial accessibility constrained vehicle routing problem, a route can be covered by two types of vehicles, i.e. truck or truck + trailer. Some customers are accessible by both vehicle types, whereas others solely by trucks. After introducing an integer programming formulation for the problem, we describe a two-phase heuristic method which extends a classical vehicle routing algorithm. Since it is necessary to solve a combinatorial problem that has some similarities with the generalized assignment problem, we propose an enumerative procedure in which bounds are obtained from a Lagrangian relaxation. The routine provides very encouraging results on a set of test problems. 相似文献
56.
Adams MR Aïd S Anthony PL Averill DA Baker MD Baller BR Banerjee A Bhatti AA Bratzler U Braun HM Breidung H Busza W Carroll TJ Clark HL Conrad JM Davisson R Derado I Dhawan SK Dietrich FS Dougherty W Dreyer T Eckardt V Ecker U Erdmann M Faller F Fang GY Figiel J Finlay RW Gebauer HJ Geesaman DF Griffioen KA Guo RS Haas J Halliwell C Hantke D Hicks KH Hughes VW Jackson HE Jancso G Jansen DM Jin Z Kaufman S Kennedy RD Kinney ER Kirk T Kobrak HG Kotwal AV Kunori S Lancaster S Lord JJ Lubatti HJ 《Physical review letters》1995,74(9):1525-1529
57.
J. P. Girardeau-Montaut M. Afif C. Girardeau-Montaut S. D. Moustaïzis N. Papadogiannis 《Applied Physics A: Materials Science & Processing》1996,62(1):3-6
The sensitivity of photoelectric emission of polycrystalline aluminium, produced by 248 nm laser pulses with p-polarization and 450 fs duration, under incidence angles = 74–86°, has been measured. A nonlinear increase of photoemission efficiency, as a function of the incident laser peak intensity in the range of 1–50 GW/cm2, was displayed, which confirms earlier observations with gold and tungsten. This nonlinearity is consecutive to the non-thermal distribution of electron gas of laser-heated metal on the time scale of the electron-phonon relaxation time. Analysis of experimental data, using the model previously developed by us [1], gives a value of electron-phonon relaxation time 0.55 ± 0.11 ps. 相似文献
58.
Two pyrene-labeled hydroxylamines, 5-Bn and 5-Bz, O-protected with the benzyl and the benzoyl group, respectively, have been prepared for the generation of siderophore-based new chelators incorporating both the pyrene chromophore and the hydroxamic acid functionality. 5-Bz formed the starting point toward the synthesis of the tripod-shaped trishydroxamate, 1. That trichromophoric ligand displays remarkable fluorescence emission properties (dual emission: "monomer" and excimer type) which are markedly and selectively modified by binding Fe(NO(3))(3) and Ga(NO(3))(3). Ferric ions induce a quasi total quenching of the pyrene fluorescence, whereas the nonquenching Ga(III) cations are observed to affect the value of the excimer-to-monomer fluorescence intensity ratio. Ethylenediaminetetraacetic acid (EDTA) competition reactions yielded an estimated value of 3.8 for log K of the complex LFe in methanol/water (80/20 v/v), where K = ([LFe][H(+)](3))/([LH(3)][Fe(3+)]) and L is the ligand in its totally deprotonated form. Compound 1 is the prototype of a new class of photoresponsive molecular systems which could act as sensitive probes for metal cation detection and recognition. 相似文献
59.
Giant unilamellar vesicles (diameter of a few tens of micrometers) are commonly produced by hydration of a dried lipidic film. After addition of the aqueous solution, two major protocols are used: (i) the gentle hydration method where the vesicles spontaneously form and (ii) the electroformation method where an ac electric field is applied. Electroformation is known to improve the rate of unilamellarity of the vesicles though it imposes more restricting conditions for the lipidic composition of the vesicles. Here we further characterize these methods by using fluorescence microscopy. It enables not only a sensitive detection of the defects but also an evaluation of the quantity of lipids in these defects. A classification of the defects is proposed and statistics of their relative importance in regard to both methods and lipid composition are presented: it shows for example that 80% of the vesicles obtained by electroformation from 98% 1,2-dioleoyl-sn-glycero-3-phosphocholine are devoid of significant defects against only 40% of the vesicles with the gentle hydration method. It is also shown that the presence of too many negatively charged lipids does not favor the formation of unilamellar vesicles with both methods. For the gentle hydration, we checked if the negatively charged lipids were inserted in the vesicles membrane in the same proportion as that of the lipid mixture from which they are formed. The constant incorporation of a negatively charged labeled lipid despite an increasing presence of negatively charged 1,2-dioleoyl-sn-glycero-3-[phospho-l-serine] tends to confirm that the composition of vesicles is indeed close to that of the initial mixture. 相似文献
60.
Trifluoromethoxy-substituted anilines undergo hydrogen/lithium permutation ("metalation") with optional site selectivity depending on the N-protective group employed. N-tert-Butoxycarbonyl-2- and -4-(trifluoromethoxy)aniline react with tert-butyllithium at the nitrogen-adjacent 6- and 2-position affording, after electrophilic trapping, products 1-6. In contrast, deprotonation of the para isomer occurs at the oxygen-neighboring 3-position, giving rise to the acid 12, when the amino group is carrying two trimethylsilyl groups. sec-Butyllithium attacks 3-trifluoromethoxy-N-mono(trimethylsilyl)aniline at the 2-position, but 3-trifluoromethoxy-N,N-bis(trimethylsilyl)aniline at the 4-position to provide respectively the acids 10 and 11 after carboxylation. The synthesis of two new benzodiazepines illustrates (19 and 22) the preparative potential of the aniline functionalization mediated by organometallic reagents. 相似文献