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41.
We study the quenched complexity in spin-glass mean-field models satisfying the Becchi-Rouet-Stora-Tyutin supersymmetry. The outcome of such study, consistent with recent numerical results, allows, in principle, to conjecture the absence of any supersymmetric contribution to the complexity in the Sherrington-Kirkpatrick model. The same analysis can be applied to any model with a full replica symmetry breaking phase, e.g., the Ising p-spin model below the Gardner temperature. The existence of different solutions, breaking the supersymmetry, is also discussed. 相似文献
42.
We prove the existence of chaos in temperature in the Sherrington-Kirkpatrick model. The effect is exceedingly small, namely, of the ninth order in perturbation theory. The equations describing two systems at different temperatures constrained to have a fixed overlap are studied analytically and numerically, yielding information about the behavior of the overlap distribution function PT1(,T2)(q) in finite-size systems. 相似文献
43.
Birarda Giovanni Delneri Ambra Lagatolla Cristina Parisse Pietro Cescutti Paola Vaccari Lisa Rizzo Roberto 《Analytical and bioanalytical chemistry》2019,411(27):7315-7325
Analytical and Bioanalytical Chemistry - Biofilms are communities of bacteria living embedded in a highly hydrated matrix composed of polysaccharides, proteins, and extracellular DNA. This life... 相似文献
44.
Gaetano Guerra Christophe Daniel Paola Rizzo Oreste Tarallo 《Journal of Polymer Science.Polymer Physics》2012,50(5):305-322
Polymeric “cocrystalline forms,” that is, structures were a polymeric host and a low‐molecular‐mass guest are cocrystallized, were early recognized, and in many cases also well characterized by X‐ray diffraction studies. However, only in the last two decades cocrystalline forms have received attention in material science, due to the ability (of few of them) to maintain an ordered polymer host structure even after guest removal, thus leading to the formation of “nanoporous‐crystalline forms,” for which many applications in the fields of molecular separation and sensors have been proposed. Moreover, in the last decade, an accurate control of the orientation of the polymer cocrystalline phases has been achieved, thus leading to a control of the orientation of the guest molecules, not only in the crystalline phase but also in macroscopic films. In addition, on the basis of this orientation control, in the last few years, cocrystalline films where active molecules are present as guests of polymer cocrystalline phases have been proposed for optical, magnetic and electric applications. In the last few years, it has been also discovered that polymer cocrystallization, when induced by nonracemic guest molecules, can produce stable chiral optical films. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
45.
[structures: see text] A regio- and stereoselective glycosylation of ribose tetraester with persilylated alloxazine to give either beta-N1 or beta-N3 nucleosides is described. The N3 product is potentially of interest as a fluorescent nucleoside and is predicted to have the hydrogen-bonding characteristics of thymidine. 相似文献
46.
The origin dependence of the expression of two-photon circular dichroism in the length formulation employed by the authors in a recent computational study [B. Jansik et al., Chem. Phys. Lett. 414, 461 (2005)] is discussed in detail, and some inherently origin invariant alternative formulations are introduced. Extensive computational tests on a small reference chiral system, namely, a chiral form of H(2)O(2), are performed at the density functional theory (DFT)/B3LYP level of theory with large diffuse correlation consistent basis sets. The results indicate that the velocity formulation originally proposed by Tinoco, Jr. [J. Chem. Phys. 62, 1006 (1975)] provides the most convenient approach for an origin invariant calculation of two-photon circular dichroism. 相似文献
47.
Dr. Valérie Alain‐Rizzo Delphine Drouin‐Kucma Cédric Rouxel Dr. Issa Samb Jérémy Bell Dr. Patrick Y. Toullec Dr. Véronique Michelet Dr. Isabelle Leray Dr. Mireille Blanchard‐Desce 《化学:亚洲杂志》2011,6(4):1080-1091
A series of rod‐shaped and related three‐branched push–pull derivatives containing phosphane oxide or phosphane sulfide (PO or PS)—as an electron‐withdrawing group conjugated to electron‐donating groups, such as amino or ether groups, with a conjugated rod consisting of arylene–vinylene or arylene–ethynylene building blocks—were prepared. These compounds were efficiently synthesized by a Grignard reaction followed by Sonogashira coupling. Their photophysical properties including absorption, emission, time‐resolved fluorescence, and two‐photon absorption (TPA) were investigated with special attention to structure–property relationships. These fluorophores show high fluorescence quantum yields and solvent‐dependent experiments reveal that efficient intramolecular charge transfer occurs upon excitation, thereby leading to highly polar excited states, the polarity of which can be significantly enhanced by playing on the end groups and conjugated linker. Rod‐shaped and related three‐branched systems show similar fluorescence properties in agreement with excitation localization on one of the push–pull branches. By using stronger electron donors or replacing the arylene–ethynylene linkers with an arylene–vinylene one induces significant redshifts of both the low‐energy one‐photon absorption and TPA bands. Interestingly, a major enhancement in TPA responses is observed, whereas OPA intensities are only weakly affected. Similarly, phosphane oxide derivatives show similar OPA responses than the corresponding sulfides but their TPA responses are significantly larger. Finally, the electronic coupling between dipolar branches promoted by common PO or PS acceptor moieties induces either slight enhancement of the TPA responses or broadening of the TPA band in the near infrared (NIR) region. Such behavior markedly contrasts with triphenylamine‐core‐mediated coupling, which gives evidence for the different types of interactions between branches. 相似文献
48.
UV and IR spectroscopic studies of cold alkali metal ion-crown ether complexes in the gas phase 总被引:1,自引:0,他引:1
Inokuchi Y Boyarkin OV Kusaka R Haino T Ebata T Rizzo TR 《Journal of the American Chemical Society》2011,133(31):12256-12263
We report UV photodissociation (UVPD) and IR-UV double-resonance spectra of dibenzo-18-crown-6 (DB18C6) complexes with alkali metal ions (Li(+), Na(+), K(+), Rb(+), and Cs(+)) in a cold, 22-pole ion trap. All the complexes show a number of vibronically resolved UV bands in the 36,000-38,000 cm(-1) region. The Li(+) and Na(+) complexes each exhibit two stable conformations in the cold ion trap (as verified by IR-UV double resonance), whereas the K(+), Rb(+), and Cs(+) complexes exist in a single conformation. We analyze the structure of the conformers with the aid of density functional theory (DFT) calculations. In the Li(+) and Na(+) complexes, DB18C6 distorts the ether ring to fit the cavity size to the small diameter of Li(+) and Na(+). In the complexes with K(+), Rb(+), and Cs(+), DB18C6 adopts a boat-type (C(2v)) open conformation. The K(+) ion is captured in the cavity of the open conformer thanks to the optimum matching between the cavity size and the ion diameter. The Rb(+) and Cs(+) ions sit on top of the ether ring because they are too large to enter the cavity of the open conformer. According to time-dependent DFT calculations, complexes that are highly distorted to hold metal ions open the ether ring upon S(1)-S(0) excitation, and this is confirmed by extensive low-frequency progressions in the UVPD spectra. 相似文献
49.
Aloe plants have been widely documented in artists’ treatises dating from the sixteenth to the nineteenth century as a source
of colorant to achieve lustrous golden glazes on tin- and silver-foiled objects and warm-toned finishes on musical instruments,
such as violins. Aloe extracts contain characteristic anthraquinone and phenolic components which impart a distinctive orange
tone and fluorescence to mixtures containing them. Because of the low concentration of colorant in the coatings and its probable
degradation by high temperature during manufacture, the identification of aloe in heated oil–resin mixtures represents an
analytical challenge. For this reason, the possible presence of aloe in glazes and coatings has been largely overlooked. This
paper describes various analytical approaches to the identification of aloe in historic samples, from comparison with results
obtained from reference standards and mock-up samples. Complementary analytical techniques including thermally assisted hydrolysis
and methylation–gas chromatography–mass spectrometry, high-performance liquid chromatography, laser desorption–mass spectrometry,
matrix-assisted laser desorption-ionization-mass spectrometry and surface-enhanced Raman scattering were used. Different chemical
markers were identified by the individual methods and the advantages and limitations of each technique for the identification
of aloe in oil–resin varnishes are discussed. 相似文献
50.
Inherently Chiral Macrocyclic Oligothiophenes: Easily Accessible Electrosensitive Cavities with Outstanding Enantioselection Performances 下载免费PDF全文
Prof. Francesco Sannicolò Prof. Patrizia R. Mussini Prof. Tiziana Benincori Dr. Roberto Cirilli Prof. Sergio Abbate Serena Arnaboldi Simone Casolo Dr. Ettore Castiglioni Prof. Giovanna Longhi Dr. Rocco Martinazzo Dr. Monica Panigati Dr. Marco Pappini Dr. Elsa Quartapelle Procopio Dr. Simona Rizzo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15298-15302
Linear conjugated oligothiophenes of variable length and different substitution pattern are ubiquitous in technologically advanced optoelectronic devices, though limitations in application derive from insolubility, scarce processability and chain‐end effects. This study describes an easy access to chiral cyclic oligothiophenes constituted by 12 and 18 fully conjugated thiophene units. Chemical oxidation of an “inherently chiral” sexithiophene monomer, synthesized in two steps from commercially available materials, induces the formation of an elliptical dimer and a triangular trimer endowed with electrosensitive cavities of different tunable sizes. Combination of chirality with electroactivity makes these molecules unique in the current oligothiophenes literature. These macrocycles, which are stable and soluble in most organic solvents, show outstanding chiroptical properties, high circularly polarized luminescence effects and an exceptional enantiorecognition ability. 相似文献