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941.
Yuki Yamamoto Jun‐ya Hasegawa Yoshikatsu Ito 《Journal of Physical Organic Chemistry》2012,25(3):239-247
The kinetics of carbamate formation from the reaction of carbon dioxide with α‐amino acids in D2O was first investigated by means of nuclear magnetic resonance spectroscopy. Potassium carbonate was used as the CO2 source. For each amino acid, the maximum carbamate yield, the apparent rate constant for the carbamate formation kapp, and the rate constants for the formation k1 and the breakdown k?1 of the carbamate were estimated. Plots of log k1 or log k?1 versus pKa of amino acids indicated that the formation rate k1 increased with the basicity (pKa) of amino acid, while the decomposition rate k?1 decreased. A Br?nsted β value of 0.39 was obtained from the former plot, being in good agreement with the previously reported ones (0.26–0.43). The observed negative pKa dependence of log k?1 (Br?nsted α = 0.34) is reasonable, because the carbamate decomposition is acid‐catalyzed and the steady‐state concentration of H+ should be higher for weaker basic amines. The charge (σ) and the lone‐pair energy (EN) at the nitrogen atom of the amino group were calculated. Although log k1 correlated with σ and EN, log k?1 was unrelated with both of these parameters. Considering that the carbamate formation (k1) is not only base‐catalyzed but should also be promoted by the nucleophilicity of the amino nitrogen, its correlation with σ and EN in addition to pKa is rational. The irrelevance of log k?1 to σ and EN is not surprising, because σ and EN are not a direct measure of [H+] of the solution. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
942.
Kazuaki Yoshimura Katsuhiko Okano Rumi Ishikawa Hidetoshi Yamamoto Michinori Sumimoto Kenji Hori 《Journal of Physical Organic Chemistry》2012,25(5):394-399
Synthesis yields of organic reactions are one of the most important factors in ranking synthesis routes created by synthesis route design systems such as Transform‐Oriented Synthesis Planning and Knowledge base‐Oriented Synthesis Planning. If it is possible to predict the yields of synthesis reactions before starting experiments, one can easily determine an order of synthesis routes for experimental works. In the present study, the reaction profiles of the Curtius rearrangement with different substituents were calculated to generate an equation predicting experimental yields of this reaction. Reactions followed by the formation of isocyanates were also analyzed to consider the relationship between reaction times and experimental yields. A partial least squares (PLS) regression was used to correlate the experimental yields with the calculated activation energies, Ea(calc), together with experimental conditions such as dielectric constants of solvents, reaction times, and reaction temperatures as explanatory variables. Although the PLS regression using all the data gave very poor results, we succeeded in making a model equation with R2 = 0.887 using a modified data set. However, there is a conflict between the predictability and the interpretability on the reaction time. This discrepancy mainly comes from unnecessarily long reaction times in the experiments for azides with calculated Ea values of less than 33 kcal mol–1. To construct a good model equation for the experimental yields of the Curtius reaction, we have to use data sets obtained from within 90 min of the reaction for the PLS regression. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
943.
Optical path-length matrix method for estimating skin spectrum 总被引:2,自引:0,他引:2
Satoshi Yamamoto Izumi Fujiwara Midori Yamauchi Norimichi Tsumura Keiko Ogawa-Ochiai 《Optical Review》2012,19(6):361-365
In this article, we propose a new method??the optical path-length matrix method (OPLM)??as a faster alternative to the Monte Carlo for multi-layered media (MCML), which is often used to simulate the skin spectrum. Theoretically, peripheral oxygen saturation can be estimated by iterating MCML, but it is not a realistic strategy because it requires huge computation time. The optical path-length matrix is obtained as the probabilistic density histograms of the optical path length in skin using MCML, and once the matrix is obtained, skin spectral reflectance can be calculated by accumulating all combinations of elements in the matrix and by setting an absorption coefficient based on the Beer-Lambert law. The computational time of OPLM was approximately 26,000 times faster than that of MCML. 相似文献
944.
Uchiyama T Miyoki S Telada S Yamamoto K Ohashi M Agatsuma K Arai K Fujimoto MK Haruyama T Kawamura S Miyakawa O Ohishi N Saito T Shintomi T Suzuki T Takahashi R Tatsumi D 《Physical review letters》2012,108(14):141101
The thermal fluctuation of mirror surfaces is the fundamental limitation for interferometric gravitational wave (GW) detectors. Here, we experimentally demonstrate for the first time a reduction in a mirror's thermal fluctuation in a GW detector with sapphire mirrors from the Cryogenic Laser Interferometer Observatory at 17 and 18 K. The detector sensitivity, which was limited by the mirror's thermal fluctuation at room temperature, was improved in the frequency range of 90 to 240 Hz by cooling the mirrors. The improved sensitivity reached a maximum of 2.2×10(-19) m/√Hz at 165 Hz. 相似文献
945.
We derive some rigorous results on the chiral phase transition in QCD and QCD-like theories with a large number of colors, N(c), based on the QCD inequalities and the large-N(c) orbifold equivalence. We show that critical phenomena and associated soft modes are forbidden in flavor-symmetric QCD at finite temperature T and finite but not so large quark chemical potential μ for any nonzero quark mass. In particular, the critical point in QCD at a finite baryon chemical potential μ(B)=N(c)μ is ruled out, if the coordinate (T, μ) is outside the pion condensed phase in the corresponding phase diagram of QCD at a finite isospin chemical potential μ(I)=2μ. 相似文献
946.
S Tonegawa K Hashimoto K Ikada YH Lin H Shishido Y Haga TD Matsuda E Yamamoto Y Onuki H Ikeda Y Matsuda T Shibauchi 《Physical review letters》2012,109(3):036401
We report the first observation of cyclotron resonance in the hidden-order phase of ultraclean URu_{2}Si_{2} crystals, which allows the full determination of angle-dependent electron-mass structure of the main Fermi-surface sheets. We find an anomalous splitting of the sharpest resonance line under in-plane magnetic-field rotation. This is most naturally explained by the domain formation, which breaks the fourfold rotational symmetry of the underlying tetragonal lattice. The results reveal the emergence of an in-plane mass anisotropy with hot spots along the [110] direction, which can account for the anisotropic in-plane magnetic susceptibility reported recently. This is consistent with the "nematic" Fermi liquid state, in which itinerant electrons have unidirectional correlations. 相似文献
947.
Velocity of ultrasound waves has proved to be a useful indicator of bone biomechanical competence. A detailed understanding of the dependence of ultrasound parameters such as velocity on bone characteristics is a key to the development of bone quantitative ultrasound (QUS). The objective of this study is to investigate the relative contributions of porosity and mineralized matrix properties to the bulk compressional wave velocity (BCV) along the long bone axis. Cross-sectional slabs from the diaphysis of four human femurs were included in the study. Seven regions of interest (ROIs) were selected in each slab. BCV was measured in through-transmission at 5 MHz. Impedance of the mineralized matrix (Zm) and porosity (Por) were obtained from 50 MHz scanning acoustic microscopy. Por and Zm had comparable effects on BCV along the bone axis (R = −0.57 and R = 0.72, respectively). 相似文献
948.
Suzuki M Kawamura N Miyagawa H Garitaonandia JS Yamamoto Y Hori H 《Physical review letters》2012,108(4):047201
We show that bulk gold (Au) exhibits temperature-independent paramagnetism in an external magnetic field by x-ray magnetic circular dichroism spectroscopy at the Au L(2) and L(3) edges. Using the sum-rule analysis, we obtained a magnetic moment of 1.3 × 10(-4) μB/atom in an external magnetic field of 10 T and a paramagnetic susceptibility of 8.9 × 10(-6) for the 5d orbit. The induced paramagnetism in bulk Au is characterized by a large (≈ 30%) orbital contribution. This orbital component was retained even when Au atoms formed nanoparticles, playing an important role in stabilizing the spontaneous spin polarization in the Au nanoparticles. 相似文献
949.
Akira Ishida Yuichi Sasaki Ginga Akimoto Taikan Suehara Toshio Namba Shoji Asai Tomio Kobayashi Haruo Saito Mitsuhiro Yoshida Kenichi Tanaka Akira Yamamoto 《Hyperfine Interactions》2012,212(1-3):133-140
Positronium is an ideal system for the research of the quantum electrodynamics (QED) in bound state. The hyperfine splitting (HFS) of positronium, ΔHFS, gives a good test of the bound state calculations and probes new physics beyond the Standard Model. A new method of QED calculations has revealed the discrepancy by 15 ppm (3.9σ) of ΔHFS between the QED prediction and the experimental average. There would be possibility of new physics or common systematic uncertainties in the previous all experiments. We describe a new experiment to reduce possible systematic uncertainties and will provide an independent check of the discrepancy. We are now taking data and the current result of ΔHFS?=?203.395 1 ±0.002 4 (stat., 12 ppm) ±0.001 9 (sys., 9.5 ppm) GHz has been obtained so far. A measurement with a precision of O(ppm) is expected within a year. 相似文献
950.
The surface deposits of the traces stained with discharges on the brass plate electrode in atmospheric pressure DC negative corona have been analyzed. The surface analysis showed that the major deposits on the traces originate from nitrogen oxide ions NOx? and neutrals NOx, or carbon clusters Cn. The relationship between the plane positions and resulting deposits obtained with the point-to-plane electrodes with arbitrary needle angle to the plane provided the information about the general behavior of negative ions NOx? and neutral species NOx occurring in stationary inhomogeneous electric fields. 相似文献