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Sandra Fortini Lucia Ladelli Giovanni Petris Eugenio Regazzini 《Stochastic Processes and their Applications》2002,100(1-2):147-165
Let X be a chain with discrete state space I, and V be the matrix of entries Vi,n, where Vi,n denotes the position of the process immediately after the nth visit to i. We prove that the law of X is a mixture of laws of Markov chains if and only if the distribution of V is invariant under finite permutations within rows (i.e., the Vi,n's are partially exchangeable in the sense of de Finetti). We also prove that an analogous statement holds true for mixtures of laws of Markov chains with a general state space and atomic kernels. Going back to the discrete case, we analyze the relationships between partial exchangeability of V and Markov exchangeability in the sense of Diaconis and Freedman. The main statement is that the former is stronger than the latter, but the two are equivalent under the assumption of recurrence. Combination of this equivalence with the aforesaid representation theorem gives the Diaconis and Freedman basic result for mixtures of Markov chains. 相似文献
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Cleavage of N,N-dimethylhydrazones is cleanly effected with good yield in dichloromethane using the extremely inexpensive clay-supported ferric nitrate. 相似文献
87.
James N. Pitts Eugenio Sanhueza Roger Atkinson William P. L. Carter Arthur M. Winer Geoffrey W. Harris Christopher N. Plum 《国际化学动力学杂志》1984,16(7):919-939
The formation of nitrous acid (HONO) in the dark from initial concentrations of NO2 of 0.1–20 ppm in air, and the concurrent disappearance of NO2, were monitored quantitatively by UV differential optical absorption spectroscopy in two different environmental chambers of ca.4300- and 5800-L volume (both with surface/volume ratios of 3.4 m?1). In these environmental chambers the initial HONO formation rate was first order in the NO2 concentration and increased with the water vapor concentration. However, the HONO formation rate was independent of the NO concentration and relatively insensitive to temperature. The initial pseudo-first-order consumption rate of NO2 was (2.8 ± 1.2) × 10?4 min?1 in the 5800-L Teflon-coated evacuable chamber and (1.6 ± 0.5) × 10?4 min?1 in a 4300-L all-Teflon reaction chamber at ca.300 K and ca.50% RH. The initial HONO yields were ca.40–50% of the NO2 reacted in the evacuable chamber and ca.10–30% in the all-Teflon chamber. Nitric oxide formation was observed during the later stages of the reaction in the evacuable chamber, but ca.50% of the nitrogen could not be accounted for, and gas phase HNO3 was not detected. The implications of these data concerning radical sources in environmental chamber irradiations of NOx? organic-air mixtures, and of HONO formation in polluted atmospheres, are discussed. 相似文献
88.
A terpyridine ruthenium (II) complex containing a substituted and an unsubstituted terpyridine ligand was synthesized, and its luminescence properties were studied in a solid-state single-layer light-emitting electrochemical cell. The obtained devices emitted light of a very deep red color (CIE, x = 0.717 y = 0.282) at low external applied bias. It is the first example of an electroluminescence device based on a bis-chelated ruthenium complex. Its ambient atmosphere decay is remarkably different from analogous devices using tris-chelated ruthenium complexes. 相似文献
89.
We have synthesized a new environment-sensitive fluorophore, 6-N,N-dimethylamino-2,3-naphthalimide (6DMN). This chromophore exhibits valuable fluorescent properties as a biological probe with emission in the 500-600 nm range and a marked response to changes in the environment polarity. The 6DMN fluorescence is red-shifted in polar protic environments, with the maximum emission intensity shifting more than 100 nm from 491 nm in toluene to 592 nm in water. Additionally, the fluorescence quantum yield decreases more than 100-fold from chloroform (Phi = 0.225) to water (Phi = 0.002). The scope and applications of the 6DMN probe are expanded with the synthesis of an Fmoc-protected amino acid derivative (5), which contains the fluorophore. This unnatural amino acid has been introduced into several peptides, demonstrating that it can be manipulated under standard solid-phase peptide synthesis conditions. Peptides incorporating the new residue can be implemented for monitoring protein-protein interactions as exemplified in studies with Src homology 2 (SH2) phosphotyrosine binding domains. The designed peptides exhibit a significant increase in the quantum yield of the long wavelength fluorescence emission band (596 nm) upon binding to selected SH2 domains (e.g., Crk SH2, Abl SH2, and PI3K SH2). The peptides can be used as ratiometric sensors, since the short wavelength band (460 nm) was found almost invariable throughout the titrations. 相似文献
90.
Rothman DM Petersson EJ Vázquez ME Brandt GS Dougherty DA Imperiali B 《Journal of the American Chemical Society》2005,127(3):846-847
We present the chemical and biological synthesis of caged phosphoproteins using the in vitro nonsense codon suppression methodology. Specifically, phosphoamino acid analogues of serine, threonine, and tyrosine with a single photocleavable o-nitrophenylethyl caging group were synthesized as the amino acyl tRNA adducts for insertion into full-length proteins. For this purpose, a novel phosphitylating agent was developed. The successful incorporation of these bulky and charged amino acids into the alpha-subunit of the nicotinic acetyl choline receptor (nAChR) and the vasodilator-stimulated phosphoprotein (VASP) using an in vitro translation system is reported. 相似文献