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101.
Maria A. Lebedeva Dr. Thomas W. Chamberlain Dr. E. Stephen Davies Dr. Dorothée Mancel Bradley E. Thomas Dr. Mikhail Suyetin Dr. Elena Bichoutskaia Prof. Dr. Martin Schröder Prof. Dr. Andrei N. Khlobystov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):11999-12008
A covalently‐linked salen–C60 (H2L) assembly binds a range of transition metal cations in close proximity to the fullerene cage to give complexes [M(L)] (M=Mn, Co, Ni, Cu, Zn, Pd), [MCl(L)] (M=Cr, Fe) and [V(O)L]. Attaching salen covalently to the C60 cage only marginally slows down metal binding at the salen functionality compared to metal binding to free salen. Coordination of metal cations to salen–C60 introduces to these fullerene derivatives strong absorption bands across the visible spectrum from 400 to 630 nm, the optical features of which are controlled by the nature of the transition metal. The redox properties of the metal–salen–C60 complexes are determined both by the fullerene and by the nature of the transition metal, enabling the generation of a wide range of fullerene‐containing charged species, some of which possess two or more unpaired electrons. The presence of the fullerene cage enhances the affinity of these complexes for carbon nanostructures, such as single‐, double‐ and multiwalled carbon nanotubes and graphitised carbon nanofibres, without detrimental effects on the catalytic activity of the metal centre, as demonstrated in styrene oxidation catalysed by [Cu(L)]. This approach shows promise for applications of salen–C60 complexes in heterogeneous catalysis. 相似文献
102.
Hybrid density functional theory has been applied for investigations of the electronic and atomic structure of bulk phases, nanolayers, and nanotubes based on titanium and zirconium disulfides. Calculations have been performed on the basis of the localized atomic functions by means of the CRYSTAL‐2009 computer code. The full optimization of all atomic positions in the regarded systems has been made to study the atomic relaxation and to determine the most favorable structures. The different layered and isotropic bulk phases have been considered as the possible precursors of the nanotubes. Calculations on single‐walled TiS2 and ZrS2 nanotubes confirmed that the nanotubes obtained by rolling up the hexagonal crystalline layers with octahedral 1T morphology are the most stable. The strain energy of TiS2 and ZrS2 nanotubes is small, does not depend on the tube chirality, and approximately obeys to D–2 law (D is nanotube diameter) of the classical elasticity theory. It is greater than the strain energy of the similar TiO2 and ZrO2 nanotubes; however, the formation energy of the disulfide nanotubes is considerably less than the formation energy of the dioxide nanotubes. The distance and interaction energy between the single‐wall components of the double‐wall nanotubes is proved to be close to the distance and interaction energy between layers in the layered crystals. Analysis of the relaxed nanotube shape using radial coordinate of the metal atoms demonstrates a small but noticeable deviation from completely cylindrical cross‐section of the external walls in the armchair‐like double‐wall nanotubes. © 2013 Wiley Periodicals, Inc. 相似文献
103.
Victor P. Arkhipov Ruslan V. Arkhipov Andrei Filippov 《Magnetic resonance in chemistry : MRC》2022,60(3):359-368
We examined a series of amino acid-based surfactants with two carboxylic groups separated by a spacer of one, two, or three carbon atoms with sodium and calcium counterions in the premicellar concentration region near the CMC. 1H nuclear magnetic resonance (NMR) spectroscopy and NMR diffusometry techniques were used to study the local environment, association, and translational dynamics of the surfactant's molecules. We measured the self-diffusion coefficients of the micelles, calculated the effective hydrodynamic radii, and determined the temperature region in which the premicelles exist. With an increase in temperature from 295 to 335 K, the premicellar state of the surfactant is replaced by the monomeric state. 相似文献
104.
Carmen van der Linde Monica Barone Silvia Turroni Patrizia Brigidi Enver Keleszade Jonathan R. Swann Adele Costabile 《Molecules (Basel, Switzerland)》2021,26(8)
The response of a coeliac and a healthy gut microbiota to the green algae Chlorella pyrenoidosa was evaluated using an in vitro continuous, pH controlled, gut model system, which simulated the human colon. The effect of C. pyrenoidosa on the microbial structure was determined by 16S rRNA gene sequencing and inferred metagenomics, whereas the metabolic activitywas determined by1H-nuclear magnetic resonancespectroscopic analysis. The addition of C. pyrenoidosa significantly increased the abundance of the genera Prevotella, Ruminococcus and Faecalibacterium in the healthy donor, while an increase in Faecalibacterium, Bifidobacterium and Megasphaera and a decrease in Enterobacteriaceae were observed in the coeliac donor. C. pyrenoidosa also altered several microbial pathways including those involved in short-chain fatty acid (SCFA) production. At the metabolic level, a significant increase from baseline was seen in butyrate and propionate (p < 0.0001) in the healthy donor, especially in vessels 2 and 3. While acetate was significantly higher in the healthy donor at baseline in vessel 3 (p < 0.001) compared to the coeliac donor, this was markedly decreased after in vitro fermentation with C. pyrenoidosa. This is the first in vitro fermentation study of C. pyrenoidosa and human gut microbiota, however, further in vivo studies are needed to prove its efficacy. 相似文献
105.
We present an option of the experiment with a correlated pair of particles in the entangled state, which provides the effect of a change in the polarization for entangled photons, and demonstrate the reality of all different superposition states and the corresponding vector of the quantum system state; also we analyze possible consequences of this fact. We propose a quantum realism paradigm within the relational paradigm instead of the local realism concept disproved by the experiments on verifying the Bell inequalities. We analyze the results of experimental research of the Leggett inequality violation with respect to the verification of the adequacy of different kinds of nonlocal hidden variable theories and suggest a new way of their evaluation based on the study of the photon cross-correlation suppression after a beam splitter and preparation of quantum squeezed states. We show that the interpretation based on the nonlocal hidden variable theory is inconsistent. 相似文献
106.
Weber CP Orenstein J Bernevig BA Zhang SC Stephens J Awschalom DD 《Physical review letters》2007,98(7):076604
We describe measurements of spin dynamics in the two-dimensional electron gas in GaAs/GaAlAs quantum wells. Optical techniques, including transient spin-grating spectroscopy, are used to probe the relaxation rates of spin polarization waves in the wave vector range from zero to 6x10(4) cm-1. We find that the spin polarization lifetime is maximal at a nonzero wave vector, in contrast with expectations based on ordinary spin diffusion, but in quantitative agreement with recent theories that treat diffusion in the presence of spin-orbit coupling. 相似文献
107.
108.
Jakob Heller Tobias F. Pascher Dr. Christian van der Linde Dr. Milan Ončák Prof. Dr. Martin K. Beyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16367-16376
Hydrated aluminium cations have been investigated as a photochemical model system with up to ten water molecules by UV action spectroscopy in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Intense photodissociation was observed starting at 4.5 eV for two to eight water molecules with loss of atomic hydrogen, molecular hydrogen and water molecules. Quantum chemical calculations for n=2 reveal that solvation shifts the intense 3s–3p excitations of Al+ into the investigated photon energy range below 5.5 eV. During the photochemical relaxation, internal conversion from S1 to T2 takes place, and photochemical hydrogen formation starts on the T2 surface, which passes through a conical intersection, changing to T1. On this triplet surface, the electron that was excited to the Al 3p orbital is transferred to a coordinated water molecule, which dissociates into a hydroxide ion and a hydrogen atom. If the system remains in the triplet state, this hydrogen radical is lost directly. If the system returns to singlet multiplicity, the reaction may be reversed, with recombination with the hydroxide moiety and electron transfer back to aluminium, resulting in water evaporation. Alternatively, the hydrogen radical can attack the intact water molecule, forming molecular hydrogen and aluminium dihydroxide. Photodissociation is observed for up to n=8. Clusters with n=9 or 10 occur exclusively as HAlOH+(H2O)n-1 and are transparent in the investigated energy range. For n=4–8, a mixture of Al+(H2O)n and HAlOH+(H2O)n-1 is present in the experiment. 相似文献
109.
110.