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31.
32.
In this contribution, a pulse sequence is described for recording accordion-optimized DEPT experiments. The proposed ACCORDEPT experiment detects a wide range of one-bond coupling constants using accordion optimization. As a proof of concept, this strategy has been applied to a mesogen containing a large range of one-bond (1)J(CH) coupling constants associated with the various structural elements. The ACCORDEPT experiment afforded significant enhancements for the resonances with the larger (1)J(CH) couplings, similar SNR for aliphatic resonances, but reduced SNR for aliphatic resonances as compared with the standard DEPT experiment. In addition, the ACCORDEPT is straightforward to implement, does not require any supplementary calibration procedures and can be used under automated conditions without difficulty by inexperienced users. 相似文献
33.
34.
Santoni MP Hanan GS Hasenknopf B Proust A Nastasi F Serroni S Campagna S 《Chemical communications (Cambridge, England)》2011,47(12):3586-3588
A planar bis-dipyrid-2'-yltriazine (bis-dpt) bridging ligand forms dinuclear Ru(II) complexes able to store up to eight electrons upon electrochemical reduction. 相似文献
35.
Cooke MW Hanan GS Loiseau F Campagna S Watanabe M Tanaka Y 《Journal of the American Chemical Society》2007,129(34):10479-10488
Ru(II) polypyridine species have been assembled about dirhodium(II, II) tetracarboxylate cores. The complexes prepared have general formulas [{(terpy)Ru(La)}n{Rh2(CH3COO)4-n(CH3CN)2}]2n+ (a-type compounds: terpy = 2,2':6',2' '-terpyridine; La = 4'-(p-carboxyphenyl)-2,2':6',2' '-terpyridine; n = 1, 1a; n = 2, cis-2a and trans-2a-cis and trans refer to the arrangement of the Ru(II) species around the dirhodium core; n = 3, 3a), [{(Lb)Ru(La)}n{Rh2(CH3COO)4-n(CH3CN)2}]2n+ (b-type compounds: Lb = 6-phenyl-2,4-di(2-pyridyl)-s-triazine; n = 1, 1b; n = 2, an inseparable mixture of cis-2b and trans-2b; n = 3, 3b; n = 4, 4b), and [{(terpy)Ru(Lc)}{Rh2(CH3COO)3(CH3CN)2}]2+ (1c; Lc = 6-(p-carboxyphenyl)-2,4-di(2-pyridyl)-s-triazine). As model species, also the mononuclear [(terpy)Ru(La)]2+ (5a), [(La)Ru(Lb)]2+ (5b), and [(terpy)Ru(Lc)]2+ (5c) have been prepared. All of the complexes have been characterized by several techniques, including NMR and mass spectra, and the stability of the various species is discussed. The absorption spectra of all of the compounds are dominated by the Ru(II) polypyridine moieties, showing intense ligand-centered (LC) bands in the UV region and intense metal-to-ligand charge-transfer (MLCT) bands in the visible. The compounds exhibit several metal-centered oxidation and ligand-centered reduction processes, which have been assigned to specific subunits. Both absorption and redox data indicate a supramolecular nature of the assembled systems. Efficient energy transfer from the MLCT triplet state of the Ru-based components to the lowest-energy excited state of the dirhodium core takes place for the a-type compounds at 298 K in acetonitrile solution, whereas such a process is inefficient for the b-type and c-type species, which exhibit the typical MLCT emission. At 77 K in butyronitrile matrix, Ru-to-Rh2 energy transfer is partly efficient for both the a-type and the b-type compounds and is inefficient for 1c. The reasons for such behavior are discussed by taking into account arguments concerning the driving force and reorganization energy of the complexes. 相似文献
36.
Mineo P Vitalini D Scamporrino E Bazzano S Alicata R 《Rapid communications in mass spectrometry : RCM》2005,19(19):2773-2779
The dependence of the calculated average molecular mass of a polyethylene glycol with a large polydispersity on the instrumental parameters adopted in the acquisition of mass spectra using delayed extraction matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (DE MALDI-TOFMS) was investigated. It has been shown that a combined effect of delay times and potential gradients can act on the ion cloud in the source chamber affecting both mass resolution and average molecular mass value of the analyzed polymeric sample. Also examined was a blend of two different polymers (a PEG and a PMMA commercial sample having a similar average molecular mass), which presents an additional problem concerning the discrimination among the different polymer species as a function of the experimental conditions. In this work, the best instrumental conditions to obtain both good resolution and a correct average molecular mass for the examined polydisperse sample are reported. 相似文献
37.
We address the problem of observables in generally invariant spacetime theories such as Einstein’s general relativity. Using
the refined notion of an event as a “point-coincidence” between scalar fields that completely characterise a spacetime model,
we propose a generalisation of the relational local observables that does not require the existence of four everywhere invertible
scalar fields. The collection of all point-coincidences forms in generic situations a four-dimensional manifold, that is naturally
identified with the physical spacetime. 相似文献
38.
Let ℱ be a local net of von Neumann algebras in four spacetime dimensions satisfying certain natural structural assumptions.
We prove that if ℱ has trivial superselection structure then every covariant, Haag-dual subsystem ℬ is of the form ℱ1
G
⊗I for a suitable decomposition ℱ=ℱ1⊗ℱ2 and a compact group action. Then we discuss some application of our result, including free field models and certain theories
with at most countably many sectors.
Received: 26 January 2000 / Accepted: 28 September 2000 相似文献
39.
In this work we introduce a spatio-temporal bounded noise derived by the sine-Wiener noise and by the spatially colored unbounded noise proposed by García-Ojalvo, Sancho, and Ramírez-Piscina (GSR noise). We characterize the behavior of the equilibrium distribution of this novel noise by showing its dependence on both the temporal and the spatial autocorrelation lengths. In particular, we show that the distribution experiences a stochastic transition from bimodality to trimodality. Then, we employ the noise here defined to study the emergence of phase transitions in the real Ginzburg–Landau model. Various phenomena are evidenced by means of numerical simulations, among which reentrant transitions, as well as differences in the response of the system to “equivalent” GSR additive noise perturbations. 相似文献