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排序方式: 共有116条查询结果,搜索用时 11 毫秒
1.
2.
The bimolecular hydrogen-deuterium exchange behavior of protonated alkyl dipeptides in the gas phase
Erez H. Gur Leo J. de Koning Nico M. M. Nibbering 《Journal of the American Society for Mass Spectrometry》1995,6(6):466-477
As part of an ongoing characterization of the intrinsic chemical properties of peptides, thermal hydrogen-deuterium exchange has been studied for a series of fast-atom-bombardment-generated protonated alkyldipeptides and related model compounds in the reaction with D2O, CH3OD, and ND3 in a Fourier transform ion cyclotron resonance mass spectrometer. Despite the very large basicity difference between the dipeptides and the D2O and CH3OD exchange reagents, efficient exchange of all active hydrogen atoms occurs. From the kinetic data it appears that exchange of the amino, amide, and hydroxyl hydrogens proceeds with different efficiencies, which implies that the proton in thermal protonated dipeptides is immobile. The selectivity of the exchange at the different basic sites is governed by the nature of both the dipeptide and the exchange reagent. The results indicate that reversible proton transfer in the reaction complexes, which effectuates the deuterium incorporation, is assisted by formation of multiple hydrogen bonds between the reagents. Exchange is considered to proceed via the intermediacy of different competing intermediate complexes, each of which specifically leads to deuterium incorporation at different basic sites. The relative stabilization of the competing intermediate complexes can be related to the relative efficiencies of deuterium incorporation at different basic sites in the dipeptide. For all protonated dipeptides studied, the exchange in the reaction with ND3 proceeds with unit efficiency, whereas all active hydrogen atoms are exchanged equally efficiently. Evidently specific multiple hydrogen bond formations are far less important in the reversible proton transfers with the relatively basic ammonia, which allows effective randomization of all active hydrogen atoms in the reaction complexes. 相似文献
3.
This paper presents methods for designing and recording optimal computer-generated diffractive optical elements. The design method is based on an analytic ray-tracing procedure for minimizing aberrations. The recording involves computer-generated masks and multiple lithographic processes in order to form reflective and transmissive multilevel, surface relief-phase, diffractive elements. As a result, the elements can have high diffraction efficiencies over a broad range of incidence angles. Even generalized diffractive elements that operate with highly uniform diffraction efficiency and polychromatic radiation can be designed and recorded by optimizing the shape and height of the relief gratings. To illustrate the effectiveness of the diffractive optical elements, they have been incorporated into a number of applications, involving visible as well as infra-red radiation. Some that deal with coordinate transformation, beam shaping, and polarization control are briefly reviewed. 相似文献
4.
Spiral phase elements with topological charges based on space-variant Pancharatnam-Berry phase optical elements are presented. Such elements can be achieved by use of continuous computer-generated space-variant subwavelength dielectric gratings. We present a theoretical analysis and experimentally demonstrate spiral geometrical phases for infrared radiation at a wavelength of 10.6microm . 相似文献
5.
Real-time analysis of partially polarized light with a space-variant subwavelength dielectric grating 总被引:1,自引:0,他引:1
A novel method for real-time polarization measurement is presented. The method is based on a space-variant wave plate that we realized as a computer-generated space-variant subwavelength dielectric grating. The Stokes parameters of the incident beam are determined by Fourier analysis of the space-variant intensity transmitted through the grating and an analyzer. We discuss the design and realization of such wave plates and demonstrate our technique with polarization measurements of both polarized and partially polarized CO(2)-laser radiation at a wavelength of 10.6 mum. 相似文献
6.
We report the appearance of a geometrical phase in space-variant polarization-state manipulations. This phase is related to the classic Pancharatnam-Berry phase. We show a method with which to calculate it and experimentally demonstrate its effect, using subwavelength metal stripe space-variant gratings. The experiment is based on a unique grating for converting circularly polarized light at a wavelength of 10.6 mum into an azimuthally polarized beam. Our experimental evidence relies on analysis of far-field images of the resultant polarization. 相似文献
7.
The effect of the thin membrane on the time evolution of the shock wave induced turbulent mixing between the two gases initially
separated by it is investigated using two different sets of experiments. In the first set, in which a single-mode large-amplitude
initial perturbation was studied, two gas combinations (air/SF
and air/air) and two membrane thicknesses were used. The main conclusion of these experiments was that the tested membrane has a negligible
effect on the evolution of the mixing zone, which evolves as predicted theoretically. In the second set, in which similar
gas combinations and membrane thicknesses were used, small amplitude random-mode initial perturbation, caused by the membrane
rupture, rather than the large amplitude single-mode initial perturbation used in the first set, was studied. The conclusions
of these experiments were: (1) The membrane has a significant effect on the mixing zone during the initial stages of its growth.
This has also been observed in the air/air experiment where theoretically no growth should exist. (2) The membrane effect on the late time evolution, where the mixing
zone width has reached a relatively large-amplitude, was relatively small and in good agreement with full numerical simulations.
The main conclusion from the present experiments is that the effect of the membrane is important only during the initial stages
of the evolution (before the re-shock), when the perturbations have very small amplitudes, and is negligible when the perturbations
reach relatively large amplitudes.
Received 29 August 1998 / Accepted 25 December 1998 相似文献
8.
9.
Steady-state and time-resolved techniques were employed to study the excited-state proton transfer (ESPT) from d-luciferin, the natural substrate of the firefly luciferase, to the mild acetate base in aqueous solutions. We found that in 1 M aqueous solutions of acetate or higher, a proton transfer (PT) process to the acetate takes place within 30 ps in both H(2)O and D(2)O solutions. The time-resolved emission signal is composed of three components. We found that the short-time component decay time is 300 and 600 fs in H(2)O and D(2)O, respectively. This component is attributed either to a PT process via the shortest water bridged complex available, ROH··H(2)O··Ac(-), or to PT taking place within a contact ion pair. The second time component of 2000 and 3000 fs for H(2)O and D(2)O, respectively, is attributed to ROH* acetate complex, whose proton wire is longer by one water molecule. The decay rate of the third, long-time component is proportional to the acetate concentration. We attribute it to the diffusion-assisted reaction as well as to PT process to the solvent. 相似文献
10.
Michal Maymon Erez Michal Yerushalmy 《International Journal of Computers for Mathematical Learning》2006,11(3):271-299
This paper describes a study of the cognitive complexity of young students, in the pre-formal stage, experiencing the dragging
tool. Our goal was to study how various conditions of geometric knowledge and various mental models of dragging interact and
influence the learning of central concepts of quadrilaterals. We present three situations that reflect this interaction. Each
situation is characterized by a specific interaction between the students’ knowledge of quadrilaterals and their understanding
of the dragging tool. The analyses of these cases offer a prism for viewing the challenge involved in changing concept images
of quadrilaterals while lacking understanding of the geometrical logic that underlies dragging. Understanding dragging as
a manipulation that preserves the critical attributes of the shape is necessary for constructing the concept images of the
shapes. 相似文献