全文获取类型
收费全文 | 444篇 |
免费 | 15篇 |
国内免费 | 1篇 |
专业分类
化学 | 337篇 |
晶体学 | 10篇 |
力学 | 3篇 |
数学 | 41篇 |
物理学 | 69篇 |
出版年
2023年 | 6篇 |
2022年 | 7篇 |
2021年 | 24篇 |
2020年 | 16篇 |
2019年 | 9篇 |
2018年 | 5篇 |
2017年 | 6篇 |
2016年 | 20篇 |
2015年 | 12篇 |
2014年 | 14篇 |
2013年 | 42篇 |
2012年 | 36篇 |
2011年 | 25篇 |
2010年 | 29篇 |
2009年 | 13篇 |
2008年 | 31篇 |
2007年 | 10篇 |
2006年 | 24篇 |
2005年 | 25篇 |
2004年 | 21篇 |
2003年 | 19篇 |
2002年 | 12篇 |
2001年 | 12篇 |
2000年 | 5篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 8篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1969年 | 1篇 |
1964年 | 1篇 |
1961年 | 1篇 |
1957年 | 2篇 |
1956年 | 1篇 |
1948年 | 1篇 |
排序方式: 共有460条查询结果,搜索用时 31 毫秒
1.
We investigate the possibility of phantom crossing in the dark energy sector and the solution for the Hubble tension between early and late universe observations. We use robust combinations of different cosmological observations, namely the Cosmic Microwave Background (CMB), local measurement of Hubble constant (), Baryon Acoustic Oscillation (BAO) and SnIa for this purpose. For a combination of CMB+BAO data that is related to early universe physics, phantom crossing in the dark energy sector was confirmed at a 95% confidence level and we obtained the constraint km/s/Mpc at a 68% confidence level, which is in perfect agreement with the local measurement by Riess et al. We show that constraints from different combinations of data are consistent with each other and all of them are consistent with phantom crossing in the dark energy sector. For the combination of all data considered, we obtained the constraint km/s/Mpc at a 68% confidence level and the phantom crossing happening at the scale factor at a 68% confidence level. 相似文献
2.
Dr. Carla Carrera Dr. Eleonora Cavallari Dr. Giuseppe Digilio Dr. Oksana Bondar Prof. Silvio Aime Dr. Francesca Reineri 《Chemphyschem》2021,22(11):1042-1048
An efficient synthesis of vinyl-[1-13C]pyruvate has been reported, from which 13C hyperpolarized (HP) ethyl-[1-13C]pyruvate has been obtained by means of ParaHydrogen Induced Polarization (PHIP). Due to the intrinsic lability of pyruvate, which leads quickly to degradation of the reaction mixture even under mild reaction conditions, the vinyl-ester has been synthesized through the intermediacy of a more stable ketal derivative. 13C and 1H hyperpolarizations of ethyl-[1-13C]pyruvate, hydrogenated using ParaHydrogen, have been compared to those observed on the more widely used allyl-derivative. It has been demonstrated that the spin order transfer from ParaHydrogen protons to 13C, is more efficient on the ethyl than on the allyl-esterdue to the larger J-couplings involved. The main requirements needed for the biological application of this HP product have been met, i. e. an aqueous solution of the product at high concentration (40 mM) with a good 13C polarization level (4.8 %) has been obtained. The in vitro metabolic transformation of the HP ethyl-[1-13C]pyruvate, catalyzed by an esterase, has been observed. This substrate appears to be a good candidate for in vivo metabolic investigations using PHIP hyperpolarized probes. 相似文献
3.
Eleonora Catsigeras Jean-Marc Gambaudo Fernando Moreira 《Proceedings of the American Mathematical Society》1998,126(1):297-304
We show that, among area contracting embeddings of the 2-disk, infinitely renormalizable maps with a bounded geometry either have positive topological entropy or correspond to a cascade of period doubling.
4.
Following recent studies which showed that the most stable structures for (ZnS)(n) clusters (n= 10-47) are the so-called "bubble clusters", in which all the atoms are three-coordinated, we have used simulated annealing techniques to find the most stable structure for a larger cluster, (ZnS)(60). We find an onion-like structure, with one small cluster enclosed inside a bigger one. The inner cluster has the structure of a sodalite cage. Bonding between the inner and the outer clusters creates a network of four-coordinated atoms. 相似文献
5.
Carlo Bruno Eleonora Ussano Gianni Barucca Davide Vanossi Giovanni Valenti Edward A. Jackson Andrea Goldoni Lucio Litti Simona Fermani Luca Pasquali Moreno Meneghetti Claudio Fontanesi Lawrence T. Scott Francesco Paolucci Massimo Marcaccio 《Chemical science》2021,12(23):8048
The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.A bottom-up synthesis of wavy graphene structures obtained through an anodic polymerization process, combined with an electrochemically triggered oxidative cyclodehydrogenation, of the bowl-shaped polyaromatic hydrocarbon corannulene. 相似文献
6.
In a recent paper we have solved several well-known combinatorial problems treating them as special cases of our generalization of Shannon's notion of graph capacity. We present a new simple formalism to deal with all such problems in a unified manner, considering graphs or families of graphs as special formulæ the variables of which are pairs of vertices of their common vertex sets. In all of these problems, the maximum size of a set ofn-length sequences from a fixed alphabet is to be determined under various restrictions on the element pairs present in the same coordinate of any two sequences from the set. For sufficiently homogeneous formulæ capacity becomes computable.New applications include generalizations of our result on the maximum number of pairwise qualitatively independentk-partitions of ann-set from independence to various forms of qualitative dependence.Work partially supported by the Italian Ministry of the University and Scientific Research, Project: Algoritmi, Modelli di Calcolo e Strutture Informative. 相似文献
7.
Alasdair A. MacDonald Sheila H. Dewitt Shomir Ghosh Eleonora M. Hogan Laura Kieras Anthony W. Czarnik Robert Ramage 《Molecular diversity》1996,1(3):183-186
Summary A major objective of the DIVERSOMER® technology is to provide pure and characterized compounds for biological testing in order to prevent false negatives in our libraries. On several occasions, analysis of the final products by1H-NMR and MS, has revealed by-products from the polystyrene solid support. Subsequently, three alternative methods were studied to remove polystyrene by-products; (i) prewashing of the resin prior to execution of the synthesis; (ii) pretreatment of the resin with the cleavage conditions consistent with the solid-phase synthesis reaction scheme; and (iii) parallel purification. 相似文献
8.
Shtykova EV Svergun DI Chernyshov DM Khotina IA Valetsky PM Spontak RJ Bronstein LM 《The journal of physical chemistry. B》2004,108(20):6175-6185
Functionality-enhanced nanostructured matrices generated by intercalating polyoctadecylsiloxane (PODS) with octadecene (ODC) or octadecylamine (ODA) are employed as reaction media in which to grow Pt nanoparticles. Small-angle X-ray scattering (SAXS) signatures confirm that the amphiphilic PODS matrix orders into lamellae with a periodicity (d) of 5.24 nm, which corresponds to the siloxy bilayer and a double layer of alkyl tails. The regular packing of the hydrophobic tails becomes distorted upon introduction of ODC or ODA. Incorporation of K[(C2H4)PtCl3].H2O (a Zeise salt) into the PODS/ODC matrix, followed by reduction of the Pt ions by NaBH4 or H2, results in the localization of Pt compounds and nanoparticles along the siloxy bilayers, which remain dimensionally unchanged. Electron density profiles deduced from PODS/ODA, however, provide evidence for considerable structural reorganization upon metalation with H2PtCl6.6H2O. In this case, the siloxy bilayers broaden due to the presence of PtCl62- ions, and the hydrophobic layers become distorted due to the formation of (PtCl62-)(ODAH+)2 complexes. Subsequent reduction by NaBH4 restores the inherent PODS organization, while H2 reduction partially preserves the distorted matrix, indicating that some Pt nanoparticles form in close proximity to the siloxy bilayer. Transmission electron microscopy reveals that relatively monodisperse Pt nanoparticles measuring approximately 1 nm in diameter are located along the siloxy bilayers, whereas anomalous SAXS further indicates that nanoparticles form aggregates of comparable size to d within the PODS double layers. 相似文献
9.
Eleonora Freire Sergio Baggio Juan Carlos Muoz Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(8):m455-m458
The structure of bis(1,10‐phenanthroline‐κ2N,N′)(thiosulfato‐κ2O:S)manganese(II) methanol solvate, [Mn(S2O3)(C12H8N2)2]·CH3OH, is made up of Mn2+ centers coordinated to two bidentate phenanthroline (phen) groups and an S,O‐chelating thiosulfate anion, forming monomeric entities. The structure of catena‐poly[[diaqua(2,9‐dimethyl‐1,10‐phenanthroline‐κ2N,N′)manganese(II)]‐μ‐thiosulfato‐κ2O:S], [Mn(S2O3)(C14H12N2)(H2O)2]n, is polymeric, consisting of Mn(dmph)(H2O)2 units (dmph is 2,9‐dimethyl‐1,10‐phenanthroline) linked by thiosulfate anions acting in an S,O‐chelating manner. 相似文献
10.
Amantini D Fringuelli F Piermatti O Pizzo F Vaccaro L 《The Journal of organic chemistry》2003,68(24):9263-9268
The [4 + 2] cycloadditions of 3-nitrocoumarin (1a), 6-chloro-3-nitrocoumarin (1b), and 6-, 7-, and 8-hydroxy-3-nitrocoumarins (1c, 5, and 6) with (E)-piperylene (7), isoprene (8), 2,3-dimethyl-1,3-butadiene (9), 2-methoxy-1,3-butadiene (10), 2,3-dimethoxy-1,3-butadiene (11), and cyclopentadiene (12) were investigated in aqueous medium, in organic solvent and under solventless conditions. The reactions performed in water occurred in heterogeneous phase but were faster than those executed in toluene or dichloroethane (DCE). 1a-c, 5, and 6 behaved as 2pi components in the Diels-Alder cycloadditions with 7-10 and 12, and exo adducts were preferentially or exclusively produced. Surprisingly 1a, behaved as a 4pi component in the cycloaddition in water with 11 and 4-substituted 3-nitrochromanones 20 and 21 were isolated. The cycloadditions of hydroxy-3-nitrocoumarins 1c, 5, and 6 with 1,3-diene 9 did not work in water or in organic solvent, but did work under solventless conditions. Nitrotetrahydrobenzo[c]chromenones 13-16, 24, and 25, originating from the normal electron-demand Diels-Alder reactions, were converted into dihydrodibenzo[b,d]furans 27-31 in water, via one-pot Nef-cyclodehydration reactions. 相似文献