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31.
Using the theory of linear group representations, we analyse the normal linear model with known sampling covariance structure invariant under a symmetry group, and sampling mean structure equivariant under the same group. In particular, assuming an invariant normal prior distribution on the parameter space, the problem of Bayesian inference is shown to decompose naturally into several independent subproblems. Within any such subproblem, if additional irreducibility conditions hold, it is shown that the posterior expectation of any parameter is a fixed scalar multiple of its unique unbiased estimator, and similarly the posterior covariance of any two parameters is a fixed scalar multiple of the prior covariance. The theoretical framework is illustrated with reference to experimental designs. 相似文献
32.
We have investigated a material made of C60Ti6H12 molecules using the classical molecular dynamic simulation. The system was studied in a wide range of temperatures, from solid to fluid. Several physical characteristics of endohedral fullerene were calculated for various temperatures: the mean square displacement, the translational and angular velocity autocorrelation function, the translational diffusion coefficient and the Lindemann index. We have observed a reduction in the rotational freedom of fullerene decorated with TiH2 functionality groups in comparison with the pure fullerene sample. 相似文献
33.
A. P. Dawid 《Journal of multivariate analysis》1978,8(4):559-566
We investigate the structure of distributions for matrices which can be embedded in arbitrarily large matrices whose distributions have properties of invariance under orthogonal rotations. 相似文献
34.
A magnetic tweezers setup is used to control both the stretching force and the relative linking number DeltaLk of a palindromic DNA molecule. We show here, in absence of divalent ions, that twisting negatively the molecule while stretching it at approximately 1 pN induces the formation of a cruciform DNA structure. Furthermore, once the cruciform DNA structure is formed, the extrusion of several kilo-base pairs of palindromic DNA sequence is directly and reversibly controlled by varying DeltaLk. Indeed the branch point behaves as a nanomechanical gear that links rotation with translation, a feature related to the helicity of DNA. We obtain experimentally a very good linear relationship between the extension of the molecule and DeltaLk. We use then this experiment to obtain a precise measurement of the pitch of B-DNA in solution: 3.61 +/- 0.03 nm/turn. 相似文献
35.
Xinghui Qi Dr. Sébastien Pillet Dr. Coen de Graaf Michał Magott Dr. El-Eulmi Bendeif Dr. Philippe Guionneau Dr. Mathieu Rouzières Dr. Valérie Marvaud Dr. Olaf Stefańczyk Dr. Dawid Pinkowicz Dr. Corine Mathonière 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(8):3141-3145
The photoinduced properties of the octacoordinated complex K4MoIV(CN)8⋅2 H2O were studied by theoretical calculations, crystallography, and optical and magnetic measurements. The crystal structure recorded at 10 K after blue light irradiation reveals an heptacoordinated Mo(CN)7 species originating from the light-induced cleavage of one Mo−CN bond, concomitant with the photoinduced formation of a paramagnetic signal. When this complex is heated to 70 K, it returns to its original diamagnetic ground state, demonstrating full reversibility. The photomagnetic properties show a partial conversion into a triplet state possessing significant magnetic anisotropy, which is in agreement with theoretical studies. Inspired by these results, we isolated the new compound [K(crypt-222)]3[MoIV(CN)7]⋅3 CH3CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution. 相似文献
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38.
Jonathan Mai Michael Morasch Dr. Dawid Jędrzkiewicz Dr. Jens Langer Dr. Bastian Rösch Prof. Dr. Sjoerd Harder 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(3):e202212463
Complex [(DIPePBDI)Ca]2(C6H6), with a C6H62− dianion bridging two Ca2+ ions, reacts with benzene to yield [(DIPePBDI)Ca]2(biphenyl) with a bridging biphenyl2− dianion (DIPePBDI=HC[C(Me)N-DIPeP]2; DIPeP=2,6-CH(Et)2-phenyl). The biphenyl complex was also prepared by reacting [(DIPePBDI)Ca]2(C6H6) with biphenyl or by reduction of [(DIPePBDI)CaI]2 with KC8 in presence of biphenyl. Benzene-benzene coupling was also observed when the deep purple product of ball-milling [(DIPPBDI)CaI(THF)]2 with K/KI was extracted with benzene (DIPP=2,6-CH(Me)2-phenyl) giving crystalline [(DIPPBDI)Ca(THF)]2(biphenyl) (52 % yield). Reduction of [(DIPePBDI)SrI]2 with KC8 gave highly labile [(DIPePBDI)Sr]2(C6H6) as a black powder (61 % yield) which reacts rapidly and selectively with benzene to [(DIPePBDI)Sr]2(biphenyl). DFT calculations show that the most likely route for biphenyl formation is a pathway in which the C6H62− dianion attacks neutral benzene. This is facilitated by metal-benzene coordination. 相似文献
39.
Stanis?aw Le?niak Anna Chrostowska Dawid Kuc Saïd Khayar ?ukasz Urbaniak 《Tetrahedron》2009,65(51):10581-6916
The synthesis of [(E)-arylimino]-acetonitriles 3 has been described. It was found that the title compounds can be obtained on the three ways, namely by: (i) dehydrogenation of arylaminoacetonitriles 1, (ii) thermal fragmentation of 1-aryl-4-cyano-β-lactams 4 and (iii) retro-ene reaction of (allyl-p-methoxyphenyl-amino)-acetonitrile (7a) under FVT conditions. 1H and 13C NMR spectra of compounds 3, 5 and 6, and all their precursors 1 and 4, were recorded and analysed in detail using chemical shifts δH and δC [from GIAO DFT B3LYP/6-31(d) calculations] and J-couplings predicted at the DFT B3LYP/IGLO-II level. Also, UV-photoelectron spectra of 4a,d and 3a,d were measured and analysed considering the theoretical evaluation of their ionisation potentials. 相似文献
40.
Richard Dawid 《Foundations of Physics》2018,48(5):492-506
It has been argued in Dawid (String theory and the scientific method, Cambridge University Press, Cambridge, [4]) that physicists at times generate substantial trust in an empirically unconfirmed theory based on observations that lie beyond the theory’s intended domain. A crucial role in the reconstruction of this argument of “non-empirical confirmation” is played by limitations to scientific underdetermination. The present paper discusses the question as to how generic the role of limitations to scientific underdetermination really is. It is argued that assessing such limitations is essential for generating trust in any theory’s predictions, be it empirically confirmed or not. The emerging view suggests that empirical and non-empirical confirmation are more closely related to each other than one may expect at first glance. 相似文献