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21.
A study is presented of the localisation of excitonic states on extended molecular aggregates composed of identical monomers arising, not from disorder due to statistical energy shifts of the monomers, induced by environmental interactions (Anderson localisation), but rather simply due to changes in the orientation and geometrical arrangement of the transition dipoles. It is shown further that such small changes nevertheless can have a drastic effect on the shape of the vibronic spectrum of the aggregate. The vibronic spectra are calculated using the ‘coherent exciton scattering’ (CES) approximation whose derivation we generalise to be applicable to aggregates of arbitrary size and geometry. 相似文献
22.
Stephanie Greed Edward L. Briggs Dr. Fahima I. M. Idiris Dr. Andrew J. P. White Dr. Ulrich Lücking Dr. James A. Bull 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12533-12538
Sulfonimidamides present exciting opportunities as chiral isosteres of sulfonamides, with potential for additional directional interactions. Here, we present the first modular enantioselective synthesis of sulfonimidamides, including the first stereoselective synthesis of enantioenriched sulfonimidoyl fluorides, and studies on their reactivity. A new route to sulfonimidoyl fluorides is presented from solid bench-stable, N-Boc-sulfinamide (Boc=tert-butyloxycarbonyl) salt building blocks. Enantioenriched arylsulfonimidoyl fluorides are shown to be readily racemised by fluoride ions. Conditions are developed, which trap fluoride and enable the stereospecific reaction of sulfonimidoyl fluorides with primary and secondary amines (100 % es, es=enantiospecificity) generating sulfonimidamides with up to 99 % ee. Aryl and alkyl sulfonimidoyl fluoride reagents are suitable for mild late stage functionalisation reactions, exemplified by coupling with a selection of complex amines in marketed drugs. 相似文献
23.
Benjamin D. Egleston Konstantin V. Luzyanin Michael C. Brand Rob Clowes Michael E. Briggs Rebecca L. Greenaway Andrew I. Cooper 《Angewandte Chemie (International ed. in English)》2020,59(19):7362-7366
Control of pore window size is the standard approach for tuning gas selectivity in porous solids. Here, we present the first example where this is translated into a molecular porous liquid formed from organic cage molecules. Reduction of the cage window size by chemical synthesis switches the selectivity from Xe‐selective to CH4‐selective, which is understood using 129Xe, 1H, and pulsed‐field gradient NMR spectroscopy. 相似文献
24.
Hydrogen/deuterium exchange rates in amide-functionalized monolayer protected gold clusters (MPCs) are controlled by the radial nature of the surface, with inhibition and catalysis observed at different chain lengths. 相似文献
25.
The appearance of body-frame singularities in gauge potentials when three collective angles are separated by means of Wigner D-functions is a fundamental difficulty in the quantum N-body problem. We show that the use of the overcomplete basis of minimal multipolar harmonics allows these singularities to be avoided at the expense of increasing the dimension of the resulting system of coupled equations describing the internal motion of the system. 相似文献
26.
Thermal degradation of 1,2-bis(dichloroboryl)ethane gives low yields of a white solid (BCl)6(CH)4 which has a hexaboro-adamantane structure. Substitution of the chlorine atoms by bromine or methyl occurs on treatment with BBr3 and Sn(CH3)4, respectively. 相似文献
27.
Biancardo M Quinn AJ Floyd L Mendes PM Briggs SS Preece JA Bignozzi CA Redmond G 《The journal of physical chemistry. B》2005,109(18):8718-8722
We report on charge transport measurements through laterally contacted assemblies of Au nanoparticles capped with 11-mercaptoundecanoic acid ligands. Both alternating- and direct-current data indicate that although the nanoparticles behave as electrically isolated metallic islands, there is a significant influence from the nanoparticle environment, indicating the existence of a slow reorganization process linked to charge transport. On the basis of the observation of temperature-dependent hysteresis of charge tunneling, we propose that this process is due to proton transfer between the carboxylic acid tails of the ligands. 相似文献
28.
Morton JJ Tyryshkin AM Ardavan A Porfyrakis K Lyon SA Briggs GA 《Physical review letters》2005,95(20):200501
Systematic errors in spin rotation operations using simple rf pulses place severe limitations on the usefulness of the pulsed magnetic resonance methods in quantum computing applications. In particular, the fidelity of quantum logic operations performed on electron spin qubits falls well below the threshold for the application of quantum algorithms. Using three independent techniques, we demonstrate the use of composite pulses to improve this fidelity by several orders of magnitude. The observed high-fidelity operations are limited by pulse phase errors, but nevertheless fall within the limits required for the application of quantum error correction. 相似文献
29.
A random network model containing defects has been developed and applied to the deposition of amorphous SiOx films on a flat substrate. A new Monte Carlo procedure enables dangling bonds to migrate and annihilate. The degree of porosity in the films is found to increase with oxygen content. As the oxygen content increases a larger fraction of pore surfaces is covered with oxygen, and the density of dangling bonds on pore surfaces decreases. Oxygen plays the role of a surfactant, lowering the energies of pore surfaces and enhancing the porosity of amorphous SiO2 compared to amorphous Si. 相似文献
30.
15N n.m.r. spectra have been recorded from salts of 15N enriched ammonium ions in aqueous solution. Shifts of the resonance frequency have been attributed to direct interaction between the ammonium and its counter ion in solution. 相似文献