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311.
Mallik BS Kuo IF Fried LE Siepmann JI 《Physical chemistry chemical physics : PCCP》2012,14(14):4884-4890
With the aim to understand the relatively high solubility of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), an important energetic material with a high degree of inter- and intra-molecular hydrogen bonding, in fluoride anion containing ionic liquids (ILs), first principles molecular dynamics simulations in the isobaric-isothermal ensemble were carried out for a system using hydrous tetramethylammonium fluoride as the prototypical solvent. Simulations initiated from both molecular TATB and its Meisenheimer complex (i.e., a σ-complex of the fluoride and the electrophilic ring of TATB) yield a Zundel-type complex where a proton is shared between an amino group and an F(-) ion, whereas the Meisenheimer complex is found to be only transiently stable. An analysis of the electronic structure probing the Wannier function centers supports the finding of a proton-sharing complex with a three-center four-electron like bond. The Zundel-type complex also yields an electronic absorption spectrum consistent with the experimentally observed color change. This study provides evidence that the remarkable solubility of otherwise hard-to-dissolve molecular crystals in ILs can be aided by chemical modification of the solute. 相似文献
312.
313.
Fowler JN Saito T Gao R Fried ES Long TE Green DL 《Langmuir : the ACS journal of surfaces and colloids》2012,28(5):2347-2356
Using rheo-optical techniques, we investigated the impact of interfacial wetting of symmetric diblock copolymers (BCPs) on the coalescence and aggregation of polydimethylsiloxane (PDMS) droplets in immiscible polyethylene-propylene (PEP) homopolymers. Anionic polymerization was used to synthesize well-defined matrix homopolymers and symmetric 16 kg/mol-to-16 kg/mol PDMS-b-PEP diblock copolymers with low polydispersity (PDI ≈ 1.02) as characterized with size exclusion chromatography and nuclear magnetic resonance spectroscopy. Blends were formulated to match the viscosities between the droplets and the matrix. Moreover, molecular weights of these components were varied to ensure that the inner block of the copolymer inside the droplet was collapsed and dry, whereas the outer block of the copolymer outside of the droplet was stretched and wet. Droplet breakup and coalescence as well as interfacial tensions were measured using rheo-optical experiments with Linkam shearing stage and an optical microscope. Subsequent to droplet breakup at high shear rates, we found that the BCPs mitigated shear-induced coalescence at lower shear rates. Based on surface tension measurements, the stretching of the BCP increased in lower molecular weight matrices, causing the droplet surface to saturate at lower coverage in line with theoretical predictions. Droplet aggregation was detected with further reductions in shear rate, which was attributed to the dewetting or the expulsion of the matrix from a saturated brush. Ultimately, the regions of droplet coalescence and aggregation were scaled by balancing the forces of shear with those due to the attraction between BCP-coated droplets. 相似文献
314.
An all-atom force field for 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is presented. The classical intermolecular interaction potential for TATB is based on single-point energies determined from high-level ab initio calculations of TATB dimers. The newly developed potential function is used to examine bulk crystalline TATB via molecular dynamics simulations. The isobaric thermal expansion and isothermal compression under hydrostatic pressures obtained from the molecular dynamics simulations are in good agreement with experiment. The calculated volume-temperature expansion is almost one dimensional along the c crystallographic axis, whereas under compression, all three unit cell axes participate, albeit unequally. 相似文献
315.
Mundy CJ Curioni A Goldman N Will Kuo IF Reed EJ Fried LE Ianuzzi M 《The Journal of chemical physics》2008,128(18):184701
We report herein ab initio molecular dynamics simulations of graphite under shock compression in conjunction with the multiscale shock technique. Our simulations reveal that a novel short-lived layered diamond intermediate is formed within a few hundred of femtoseconds upon shock loading at a shock velocity of 12 kms (longitudinal stress>130 GPa), followed by formation of cubic diamond. The layered diamond state differs from the experimentally observed hexagonal diamond intermediate found at lower pressures and previous hydrostatic calculations in that a rapid buckling of the graphitic planes produces a mixture of hexagonal and cubic diamond (layered diamond). Direct calculation of the x-ray absorption spectra in our simulations reveals that the electronic structure of the final state closely resembles that of compressed cubic diamond. 相似文献
316.
Summary A capillary zone electrophoresis method has been developed for the determination of dextromethorphan and its metabolite, dextrorphan, in urine. A linear relationship was observed between the peak area and the concentration of both dextromethorphan and dextrorphan within the range of 490 ng mL–1 to 500 g mL–1 with a correlation coefficient of greater than 0.9999. The limit of detection was 80 ng mL–1 for both compounds. The inter-day coefficients of variation for the concentrations of 2.5 g mL–1 and 50 g mL–1 were 6.2% and 4.1% for dextromethorphan, and 5.6% and 2.8% for dextrorphan (n=15). The method could be applied directly to the determination of dextromethorphan and dextrorphan in human urine without any sample pretreatment for the elimination of interfering compounds as is required in published highperformance liquid chromatography and gas chromatography methods. Using dextromethorphan as a probe of the debrisoquin-oxidation metabolic phenotype, the 44 healthy volunteers were phenotyped after oral administration of a 15 mg dose using both this capillary electrophoresis method and a high-performance liquid chromatography assay from the literature. Good agreement was found between the two methods. 相似文献
317.
The constitutive equations for liquid crystalline polymers recently proposed by one of us [1] are applied here to interpret the behaviour of the shear viscosity η and the first normal stress difference N1() measured for liquid crystalline (LC) solutions of hydroxypropylcellulose in acetic acid. N1( ) is observed to change from positive to negative and again to positive, as the shear rate increases, at lower concentrations, in the LC phase. The -values at which N1 changes sign depend on the molecular mass (degree of polymerization) and on the concentration. η shows a small Newtonian plateau at low shear rates and a strong shear-thinning at higher values of . The rate of decrease of η in this region shows an “hesitation” similar to one previously observed in LC solutions of poly-γ-benzyl-L-glutamate PBLG. All these observations can be rationalized within the frame-work of Martins' theory. The expressions for N1() and η derived from this theory fit very well (quantitatively) to the experimental data and some fundamental viscoelastic parameters of the system under study are thereby obtained for the first time. 相似文献
318.
Motivated by the Debye theory of rotary diffusion in a dipolar fluid, we systematically develop a continuum mechanical theory
of rotary diffusion. This theory generalizes classical kinematics to include continuous rotary degrees of freedom and introduces
an additional balance law associated with the rotary degrees of freedom. Various constitutive relations are proposed in accordance
with standard procedures of nonlinear continuum mechanics. The resulting set of equations provides a properly invariant and
thermodynamically consistent theory that allows for constitutive nonlinearities. In particular, the classical Debye theory
along with the Nernst-Einstein relations are shown to follow from a special case of linear constitutive relations and an assumption
of ideality in which the free energy consists only of a classical entropic contribution. Within our theory, the notion of
osmotic pressure arises naturally as a consequence of accounting for
forces that act conjugate to the rotary degrees of freedom and serves as the driving force for rotary diffusion.
Accepted November 18, 2000?Published online April 23, 2001 相似文献