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941.
We show that a poset P contains a subset isomorphic to if and only if the poset J(P) consisting of ideals of P contains a subset isomorphic to the power set of κ. If P is a join-semilattice this amounts to the fact that P contains an independent set of size κ. We show that if κ := ω and P is a distributive lattice, then this amounts to the fact that P contains either or as sublattices, where Γ and Δ are two special meet-semilattices already considered by J. D. Lawson, M. Mislove and H. A. Priestley.Dedicated to the memory of Ivan RivalReceived April 22, 2003; accepted in final form July 11, 2004.This revised version was published online in August 2005 with a corrected cover date.  相似文献   
942.
A new method of measuring the resonance properties of a vocal fold using electromagnetic excitation and laser optoreflectometry for response monitoring is described. Two resonance peaks were experimentally identified with one magnet stuck on the vocal fold at frequencies F0(1m)=54.7 Hz and F0'(1m)=35.8 Hz. The addition of a second magnet allowed calculation of the actual viscoelastic properties of the vocal fold: F0=71.8 Hz; quality factor Q=8.03; mass m=0.057 g; stiffness k=11.6 Nm; and damping zeta=0.0032 Nm(-1). A numerical simulation of a two-layered model verified the experimental data.  相似文献   
943.
    
A series of olefin metathesis catalysts bearing cyclic (alkyl)(amino)carbene (CAAC) ligands of varying size and steric demand has been synthesized and evaluated in ring-closing-, self-, and cross-metathesis reactions at room temperature. The catalysts were also probed for potential applications in dynamic covalent chemistry. The majority of the catalysts showed high stability, and remained active in the reaction mixtures for several days, including in methanol-based solutions. Higher temperatures could be used to control the reactivity towards sterically challenging substrates, enabling formation of tetrasubstituted olefins. The CAAC complexes exhibited remarkable functional group tolerance towards heteroaromatic and nucleophilic additives, making them potentially useful in the screening of biologically active compounds.  相似文献   
944.
945.
    
Development of cost-effective and increasingly efficient sustainable materials for energy-storage devices, such Li-ion batteries, is of crucial future importance. Herein, the preparation of carbon nanofibres from biopolymer blends of lignin (byproduct from the paper and pulp industry) and polylactic acid (PLA) or a thermoplastic elastomeric polyurethane (TPU) is described. SEM analysis shows the evolving microstructural morphology after each processing step (electrospinning, stabilisation and carbonisation). Importantly, it is possible to tailor the nanofibre porosity by utilising miscibility/immiscibility rules between lignin and the polymer additive (PLA/TPU). PLA blends (immiscible) generate porous structures whereas miscible lignin/TPU blends are solid when carbonised. Electrodes produced from 50 % PLA blends have capacity values of 611 mAh g−1 after 500 charge/discharge cycles, the highest reported to date for sustainable electrodes for Li-ion batteries. Thus, this work will promote the development of lignocellulose waste materials as high-performance energy-storage materials.  相似文献   
946.
Thermodynamics and kinetics of hydrophilic ion transfers across water|n-octanol (W|OCT) interface have been electrochemically studied by means of novel three-phase and thin-film electrodes. Three-phase electrodes used for thermodynamics measurements comprise edge plane pyrolytic graphite, the surface of which was partly modified with an ultrathin film of OCT, containing hydrophobic lutetium bis(tetra-tert-butylphthalocyaninato) (Lu[tBu4Pc]2) as a redox probe. The transfers of anions and cations from W to OCT were electrochemically driven by reversible redox transformations of Lu[tBu4Pc]2 to chemically stable lipophilic monovalent cation and anion , respectively. Upon reduction of Lu[tBu4Pc]2, the transfers of alkali metal cations from W to OCT have been studied for the first time, enabling estimation of their Gibbs transfer energies. For kinetic measurements, a thin-film electrode configuration has been used, consisting of the same electrode covered completely with a thin layer of OCT that contained the redox probe and a suitable electrolyte. Combining the fast and sensitive square-wave voltammetry with thin-film electrodes, the kinetics of , , and Cl transfers have been estimated. Dedicated to Professor Dr. Yakov I. Tur’yan on the occasion of his 85th birthday.  相似文献   
947.
Hydrogen bonding to the photoaccumulated secondary acceptor radical anion A1√− in photosystem (PS) I has been studied using pulsed Q-band ENDOR spectroscopy. With deuterated quinone in protonated PS I particles it is demonstrated that the observed radical anion has only one hydrogen-bond hyperfine coupling (hfc) tensor with tensor components above the 2 MHz range. Below 2 MHz the protein matrix protons dominate and a second weak H-bond could not be detected. The spectral resolution of pulsed Q-band ENDOR is critically required to separate the signals of the H-bond proton from those of the primary chlorophyll acceptor, A0√−, which cannot be avoided to be formed to some extent in the photoaccumulation procedure. The determined H-bond hfc tensor of A1√− is found to be close to axial symmetry with a small isotropic component, as expected from a predominantly dipolar electron–proton spin interaction in a hydrogen-bond. The principal tensor components are A=(+)7.7, MHz A=(−)4.9 MHz, Aiso=(−)0.7 MHz. The magnitude of the dipolar tensor corresponds to an unusually short H-bond which can be estimated from the point-dipole approximation (1.5±0.1 Å). Based on previous studies with A- and B-branch specific site-directed mutants of the A1 site of PS I and the chosen photoaccumulation protocol, the observed A1√− radical anion can be assigned to the QK–A site of the A-branch. The observed H-bond hfc tensor is compared to those determined for related quinone radical anions observed in frozen protic solution as well as in the QA site of type II bacterial reaction centers.  相似文献   
948.
The syntheses of three original trifluoromethylated enaminones L1H-L3H, an unexplored type of ligand with possible multiple coordination centres, their redox properties and explorative coordination chemistry with copper(II) are presented. The ability of these ligands to coordinate copper(II) and then to form new mono- and dinuclear complexes is presented and discussed. The consequences of this metal coordination on redox properties are also explored.  相似文献   
949.
950.
The multiphoton multichannel photodynamics of NO(2) has been studied using femtosecond time-resolved coincidence imaging. A novel photoelectron-photoion coincidence imaging machine was developed at the laboratory in Amsterdam employing velocity map imaging and "slow" charged particle extraction using additional electron and ion optics. The NO(2) photodynamics was studied using a two color pump-probe scheme with femtosecond pulses at 400 and 266 nm. The multiphoton excitation produces both NO(2) (+) parent ions and NO(+) fragment ions. Here we mainly present the time dependent photoelectron images in coincidence with NO(2) (+) or NO(+) and the (NO(+),e) photoelectron versus fragment ion kinetic energy correlations. The coincidence photoelectron spectra and the correlated energy distributions make it possible to assign the different dissociation pathways involved. Nonadiabatic dynamics between the ground state and the A (2)B(2) state after absorption of a 400 nm photon is reflected in the transient photoelectron spectrum of the NO(2) (+) parent ion. Furthermore, Rydberg states are believed to be used as "stepping" states responsible for the rather narrow and well-separated photoelectron spectra in the NO(2) (+) parent ion. Slow statistical and fast direct fragmentation of NO(2) (+) after prompt photoelectron ejection is observed leading to formation of NO(+)+O. Fragmentation from both the ground state and the electronically excited a (3)B(2) and b (3)A(2) states of NO(2) (+) is observed. At short pump probe delay times, the dominant multiphoton pathway for NO(+) formation is a 3x400 nm+1x266 nm excitation. At long delay times (>500 fs) two multiphoton pathways are observed. The dominant pathway is a 1x400 nm+2x266 nm photon excitation giving rise to very slow electrons and ions. A second pathway is a 3x400 nm photon absorption to NO(2) Rydberg states followed by dissociation toward neutral electronically and vibrationally excited NO(A (2)Sigma,v=1) fragments, ionized by one 266 nm photon absorption. As is shown in the present study, even though the pump-probe transients are rather featureless the photoelectron-photoion coincidence images show a complex time varying dynamics in NO(2). We present the potential of our novel coincidence imaging machine to unravel in unprecedented detail the various competing pathways in femtosecond time-resolved multichannel multiphoton dynamics of molecules.  相似文献   
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