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41.
Li M Bonnet D Bill E Neese F Weyhermüller T Blum N Sellmann D Wieghardt K 《Inorganic chemistry》2002,41(13):3444-3456
Two new pentadentate, pendent arm macrocyclic ligands of the type 1-alkyl-4,7-bis(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane where alkyl represents an isopropyl, (L(Pr))(2-), or an ethyl group, (L(Et))(2-), have been synthesized. It is shown that they bind strongly to ferric ions generating six-coordinate species of the type [Fe(L(alk))X]. The ground state of these complexes is governed by the nature of the sixth ligand, X: [Fe(III)(L(Et))Cl] (2) possesses an S = 5/2 ground state as do [Fe(III)(L(Et))(OCH(3))] (3) and [Fe(III)(L(Pr))(OCH(3))] (4). In contrast, the cyano complexes [Fe(III)(L(Et))(CN)] (5) and [Fe(III)(L(Pr))(CN)] (6) are low spin ferric species (S = 1/2). The octahedral [FeNO](7) nitrosyl complex [Fe(L(Pr))(NO)] (7) displays spin equilibrium behavior S = 1/2<==>S = (3)/(2) in the solid state. Complexes [Zn(L(Pr))] (1), 4.CH(3)OH, 5.0.5toluene.CH(2)Cl(2), and 7.2.5CH(2)Cl(2) have been structurally characterized by low-temperature (100 K) X-ray crystallography. All iron complexes have been carefully studied by zero- and applied-field M?ssbauer spectroscopy. In addition, Sellmann's complexes [Fe(pyS(4))(NO)](0/1+) and [Fe(pyS(4))X] (X = PR(3), CO, SR(2)) have been studied by EPR and M?ssbauer spectroscopies and DFT calculations (pyS(4) = 2,6-bis(2-mercaptophenylthiomethyl)pyridine(2-)). It is concluded that the electronic structure of 7 with an S = 1/2 ground state is low spin ferrous (S(Fe) = 0) with a coordinated neutral NO radical (Fe(II)-NO) whereas the S = 3/2 state corresponds to a high spin ferric (S(Fe) = 5/2) antiferromagnetically coupled to an NO(-) anion (S = 1). The S = 1/2<==>S = 3/2 equilibrium is then that of valence tautomers rather than that of a simple high spin<==>low spin crossover. 相似文献
42.
43.
We report six-dimensional quantum dynamics calculations of the dissociative scattering of molecular hydrogen from the copper111 surface. Two potential energy surfaces are investigated and the results are compared with experiment. Our study completes the preliminary work of Somers et al. [Chem. Phys. Lett. 360, 390 (2002)] and focuses on the role of initial vibrational excitation and on isotopic effects. None of the two investigated potential energy surfaces is found satisfactory: the use of neither potential yields reaction and vibrational excitation probabilities and vibrational efficacies that are in close agreement with experiment. In addition to showing the shortcomings of existing potential energy surfaces we point out an inconsistency in the experimental fits for D2. 相似文献
44.
A general approach to information correction and fusion for belief functions is proposed, where not only may the information items be irrelevant, but sources may lie as well. We introduce a new correction scheme, which takes into account uncertain metaknowledge on the source’s relevance and truthfulness and that generalizes Shafer’s discounting operation. We then show how to reinterpret all connectives of Boolean logic in terms of source behavior assumptions with respect to relevance and truthfulness. We are led to generalize the unnormalized Dempster’s rule to all Boolean connectives, while taking into account the uncertainties pertaining to assumptions concerning the behavior of sources. Eventually, we further extend this approach to an even more general setting, where source behavior assumptions do not have to be restricted to relevance and truthfulness. We also establish the commutativity property between correction and fusion processes, when the behaviors of the sources are independent. 相似文献
45.
Maillard Christophe Maloubier Didier Boulay Olivier Savigny Victor Quemet Alexandre 《Journal of Radioanalytical and Nuclear Chemistry》2021,330(3):579-587
Journal of Radioanalytical and Nuclear Chemistry - Due to unexpected Pu behavior using the U/TEVA resin and the most-recognized reagents, some key separation stages need to be studied for the... 相似文献
46.
Didier Lesesvre Paul Pegon Filippo Santambrogio 《Set-Valued and Variational Analysis》2013,21(3):541-556
The main result of this paper is the existence of an optimal transport map T between two given measures μ and ν, for a cost which considers the maximal oscillation of T at scale δ, given by ω δ (T) :?=??sup|x???y|?<?δ |T(x)???T(y)|. The minimization of this criterion finds applications in the field of privacy-respectful data transmission. The existence proof unfortunately only works in dimension one and is based on some monotonicity considerations. 相似文献
47.
48.
Taratra André Fenoradosoa Céline Laroche Cedric Delattre Virginie Dulong Didier Le Cerf Luc Picton Philippe Michaud 《Applied biochemistry and biotechnology》2012,167(5):1303-1313
The rheological behavior of a sulfated galactan extracted from Halymenia durvillei, a red seaweed collected in the coastal waters of a small island of Madagascar (Nosy-be in Indian Ocean), was investigated in dilute and semi-dilute solutions. In dilute solution with NaCl at 0.3?M, the polysaccharide adopted a coil conformation whereas, at higher concentrations, the polymer had the behavior of shear-thinning fluid, typical of polymer with high molar mass or semi-rigid conformation. Degradations of this lambda carrageenan-like, using radical depolymerization, and high-pressure homogenization led to several samples of various and controlled molar masses. The measure of their intrinsic viscosities permitted the determination of the relationship of Mark?CHouwink?CSakurada. 相似文献
49.
Xanthates were easily prepared by adsorption of alcohol on KF-Al2O3 followed by treatment of carbon disulfide and iodomethane at room temperature. Pyrolysis of benzyl xanthate affords to a complex mixture of products. A radical process was proposed to explain the nature of products obtained. 相似文献
50.
Hang Yin Qian Cheng Roselyne Rosas Prof. Stéphane Viel Dr. Valérie Monnier Prof. Laurence Charles Prof. Didier Siri Dr. Didier Gigmes Dr. Olivier Ouari Prof. Ruibing Wang Dr. Anthony Kermagoret Dr. David Bardelang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(54):12552-12559
A viologen derivative carrying a benzimidazole group ( V-P-I 2+; viologen–phenylene–imidazole V-P-I ) can be dimerized in water using cucurbit[8]uril (CB[8]) in the form of a 2:2 complex resulting in a negative shift of the guest pKa, by more than 1 pH unit, contrasting with the positive pKa shift usually observed for CB-based complexes. Whereas 2:2 complex protonation is unclear by NMR, silver cations have been used for probing the accessibility of the imidazole groups of the 2:2 complexes. The protonation capacity of the buried imidazole groups is reduced, suggesting that CB[8] could trigger proton release upon 2:2 complex formation. The addition of CB[8] to a solution containing V-P- I 3+ indeed released protons as monitored by pH-metry and visualized by a coloured indicator. This property was used to induce a host/guest swapping, accompanied by a proton transfer, between V-P-I 3+ ⋅ CB[7] and a CB[8] complex of 1-methyl-4-(4-pyridyl)pyridinium. The origin of this negative pKa shift is proposed to stand in an ideal charge state, and in the position of the two pH-responsive fragments inside the two CB[8] which, alike residues engulfed in proteins, favour the deprotonated form of the guest molecules. Such proton release triggered by a recognition event is reminiscent of several biological processes and may open new avenues toward bioinspired enzyme mimics catalyzing proton transfer or chemical reactions. 相似文献