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991.
Joly L Antoine R Broyer M Lemoine J Dugourd P 《The journal of physical chemistry. A》2008,112(5):898-903
Electron detachment from peptide dianions is studied as a function of the laser wavelength. The first step for the detachment is a resonant electronic excitation of the dianions. Electronic excitation spectra are reported for three peptides, including gramicidin. A comparative study of the detachment yield for 13 peptides was performed at 260 nm and at 220 nm. At 260 nm, the detachment yield is mainly driven by the sum of the absorption coefficients of the aromatic amino acids that are contained in the peptide. At 220 nm, no direct relation is observed between the electron photodetachement yields and the sum of absorption efficiencies. At this wavelength, the sequence and the structure of the peptide may have an influence on the photodetachment process. 相似文献
992.
Lanfranchi DA Blanc MC Vellutini M Bradesi P Casanova J Tomi F 《Magnetic resonance in chemistry : MRC》2008,46(12):1188-1194
The (13)C NMR behaviour of 21 p-menthanic terpene bearing an oxygenated function (alcohol, ketone, acetate) was examined in the presence of a chiral lanthanide shift reagent (Yb(hfc)(3)). For each monocyclic compound, we measured the lanthanide-induced shift (LIS) on the signals of the carbons and the splitting of signals allowing the enantiomeric differentiation. Some general features were found about their LIS behaviour: experimental data establishing distinct patterns for carvomenthone-like compounds and menthone-like compounds. The enantiomeric splitting was observed for the majority of signals in the spectrum of each compound. In the case of alcohols and acetates, the influence of the relative stereochemistry (cis vs trans) of isopropyl(ene) and the binding function was discussed. 相似文献
993.
Debuigne A Champouret Y Jérôme R Poli R Detrembleur C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(13):4046-4059
Over the past few years, cobalt-mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the reason for this success and the intimate mechanism remained basically speculative. Herein, two mechanisms are shown to coexist: the reversible termination of the growing poly(vinyl acetate) chains by the Co(acac)2 complex (acac: acetylacetonato), and a degenerative chain-transfer process. The importance of one contribution over the other strongly depends on the polymerization conditions, including complexation of cobalt by ligands, such as water and pyridine. This significant progress in the CMRP mechanism relies on the isolation and characterization of the very first cobalt adducts formed in the polymerization medium and their use as CMRP initiators. The structure proposed for these adducts was supported by DFT calculations. Beyond the control of the VAc polymerization, which is the best ever achieved by CMRP, extension to other monomers and substantial progress in macromolecular engineering are now realistic forecasts. 相似文献
994.
Loison C Antoine R Broyer M Dugourd P Guthmuller J Simon D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(24):7351-7357
We present a joint experimental and theoretical study of the photoabsorption and photodissociation behavior of crystal violet, that is, the tris[p-(dimethylamino)phenyl]methyl cation. The photodissociation spectra of isolated and microsolvated crystal violet have been measured. A single band is observed for the bare cation. This is in good agreement with the calculated vibronic absorption spectrum based on time-dependent density functional theory calculations. The interaction of crystal violet with a single water molecule shifts and broadens the photodissociation spectrum, so that it approaches the spectrum obtained in solution. Theoretical calculations of the structure of the complex suggest that the shift in the absorption spectrum originates from a water molecule bonding with the central carbon atom of crystal violet. 相似文献
995.
996.
Guyon L Tabarin T Thuillier B Antoine R Broyer M Boutou V Wolf JP Dugourd P 《The Journal of chemical physics》2008,128(7):075103
Femtosecond pump-probe experiments are performed on flavin biomolecules isolated in an ion trap. Mass spectra of the photoinduced fragments show that the fragmentation pathways can be modified using two-color two-photon excitation. In particular, when an infrared probe pulse (810 nm) is added subsequent to the first excitation step (excitation of the S(1) state of flavin mononucleotide at 405 nm), branching ratios between lumichrome and lumiflavin production are inverted relative to the single excitation case. 相似文献
997.
Antoine Barthélemy Dr. Harald Scherer Dr. Michael Daub Alexis Bugnet Prof. Dr. Ingo Krossing 《Angewandte Chemie (International ed. in English)》2023,62(47):e202311648
The reaction of bisdicyclohexylphosphinoethane (dcpe) and the subvalent MI sources [MI(PhF)2][pf] (M=Ga+, In+; [pf]−=[Al(ORF)4]−; RF=C(CF3)3) yielded the salts [{M(dcpe)}2][pf]2, containing the first dicationic, trans-bent digallene and diindene structures reported so far. The non-classical MI⇆MI double bonds are surprisingly short and display a ditetrylene-like structure. The bonding situation was extensively analyzed by quantum chemical calculations, QTAIM (Quantum Theory of Atoms in Molecules) and EDA-NOCV (Energy Decomposition Analysis with the combination of Natural Orbitals for Chemical Valence) analyses and is compared to that in the isoelectronic and isostructural, but neutral digermenes and distannenes. The dissolved [{Ga(dcpe)}2]2+([pf]−)2 readily reacts with 1-hexene, cyclooctyne, diphenyldisulfide, diphenylphosphine and under mild conditions at room temperature. This reactivity is analyzed and rationalized. 相似文献
998.
Thomas Luther Jackson Antoine M.D. Jost Ju Zhang Prashanth Sridharan Guilherme Amadio 《Combustion Theory and Modelling》2018,22(2):291-315
In this work we present multi-dimensional mesoscale simulations of detonation initiation in energetic materials. We solve the reactive Euler equations, with the energy equation augmented by a power deposition term. The reaction rate at the mesoscale is modelled using density-based kinetics, while the deposition term is based on simulations of void collapse at the microscale, modelled at the mesoscale as hot spots. We carry out two- and three-dimensional mesoscale simulations of random packs of HMX crystals in a binder, and show that transition between no-detonation and detonation depends on the number density of the hot spots, the packing fraction, and the post-shock pressure of an imposed shock. In particular, we show that, for a fixed post-shock pressure, there exists a critical value of the number density of hot spots, such that when the number density is below this value a detonation wave will not develop. We highlight the importance of morphology to initiation by comparing with a homogeneous counterpart, and we compare relevant length scales by examining their corresponding power spectra. We also examine the effect of packing fraction and show that at low post-shock pressures there is significant variation in the initiation times, but that this variation disappears as the post-shock pressure is increased. Finally, we compare three-dimensional simulations with the experimental data, and show that the model is capable of qualitatively reproducing the trends shown in the data. 相似文献
999.
Renaud Garrel Ronald Scherer Richard Nicollas Antoine Giovanni Maurice Ouaknine 《Journal of voice》2008,22(4):385-398
Well-known multimass models of vocal folds are useful to describe main behavior observed in human voicing but their principle of functioning, based on harmonic oscillation, may appear complex. This work is designed to show that a simple one-mass model ruled by laws of relaxation oscillation can also depict main behavior of glottis dynamic. Theory of relaxation oscillation is detailed. A relaxation oscillation model is assessed through a numerical simulation using conventional values for tissue characteristics and subglottal pressure. As expected, raising the mass decreases the fundamental frequency and increases the amplitude of vocal fold vibration: for a mass ranging from 0.01 to 0.4 g, F0 decreased from 297.5 to 42.5 Hz and vibrational amplitude increased from 1.26 to 3.25 mm (for stiffness k=10Nm(-1), damping r=0.015 N s m(-1), and subglottal pressure=1 kPa). Stiffness value has the opposite effect. The subglottal pressure controls the fundamental frequency with a rate ranging from 20 to 50 Hz/kPa. The vibrational amplitude is also controlled linearly by subglottal pressure from 0.22 to 0.26 mm/kPa. The range of phonation threshold pressure (PTP) is close to the values currently proposed, that is, 0.1 to 1 kPa and varies with the fundamental frequency. The relaxation oscillator is a simple and useful tool for modeling vocal fold vibration. 相似文献
1000.