全文获取类型
收费全文 | 1989篇 |
免费 | 43篇 |
国内免费 | 6篇 |
专业分类
化学 | 1202篇 |
晶体学 | 10篇 |
力学 | 36篇 |
数学 | 196篇 |
物理学 | 594篇 |
出版年
2022年 | 13篇 |
2021年 | 21篇 |
2020年 | 24篇 |
2019年 | 12篇 |
2018年 | 19篇 |
2016年 | 28篇 |
2015年 | 27篇 |
2014年 | 36篇 |
2013年 | 73篇 |
2012年 | 91篇 |
2011年 | 132篇 |
2010年 | 49篇 |
2009年 | 46篇 |
2008年 | 95篇 |
2007年 | 95篇 |
2006年 | 105篇 |
2005年 | 105篇 |
2004年 | 99篇 |
2003年 | 90篇 |
2002年 | 85篇 |
2001年 | 56篇 |
2000年 | 59篇 |
1999年 | 16篇 |
1998年 | 19篇 |
1997年 | 20篇 |
1996年 | 36篇 |
1995年 | 17篇 |
1994年 | 41篇 |
1993年 | 41篇 |
1992年 | 40篇 |
1991年 | 38篇 |
1990年 | 26篇 |
1989年 | 23篇 |
1988年 | 14篇 |
1987年 | 11篇 |
1986年 | 20篇 |
1985年 | 23篇 |
1984年 | 18篇 |
1983年 | 20篇 |
1982年 | 10篇 |
1981年 | 11篇 |
1980年 | 14篇 |
1979年 | 13篇 |
1978年 | 12篇 |
1977年 | 9篇 |
1976年 | 10篇 |
1975年 | 14篇 |
1974年 | 11篇 |
1973年 | 23篇 |
1967年 | 10篇 |
排序方式: 共有2038条查询结果,搜索用时 0 毫秒
81.
Dr. A. Pernille Tofteng Dr. Søren L. Pedersen Prof. Dan Staerk Prof. Knud J. Jensen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(29):9024-9031
Precise microwave heating has changed the way many small molecules are being synthesized and, currently, the field of solid‐phase peptide synthesis is undergoing dramatic changes owing to the use of microwave heating. To fully reap the benefits of precise microwave heating for the formation of amide bonds in peptide synthesis, it is important to understand the kinetics of formation and break‐down of activated esters and their N‐acylation of the nascent peptide chain at elevated temperatures. Herein, we present systematic studies of, first, the rate of formation of activated esters by NMR spectroscopy and, second, their N‐acylation during peptide synthesis. A study of the amount of residual water in the solvents revealed a significant effect on electrophilic reagents and intermediates. This observation was expanded into a general study of microwave heating in peptide synthesis. 相似文献
82.
C. R.H. Bahl J. Garde K. Lefmann T. B.S. Jensen P.-A. Lindgård D. E. Madsen S. Mørup 《The European Physical Journal B - Condensed Matter and Complex Systems》2008,62(1):53-57
In magnetic nanoparticles the uniform precession
(q = 0 spin wave) mode gives the predominant contribution
to the magnetic excitations. We have calculated the energy of the
uniform mode in antiferromagnetic nanoparticles with uncompensated
magnetic moments, using the coherent potential approximation. In
the presence of uncompensated moments, an antiferromagnetic
nanoparticle must be considered as a kind of a ferrimagnet. Two
magnetic anisotropy terms are considered, a planar term confining
the spins to the basal plane, and an axial term determining an
easy axis in this plane. Excitation energies are calculated for
various combinations of these two anisotropy terms, ranging from
the simple uniaxial case to the planar case with a strong
out-of-plane anisotropy. In the simple uniaxial case, the
uncompensated moment has a large influence on the excitation
energy, but in the planar case it is much less important. The
calculations explain recent neutron scattering measurements on
nanoparticles of antiferromagnetic α-Fe2O3 and NiO. 相似文献
83.
Renz M Blasco T Corma A Fornés V Jensen R Nemeth L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4708-4717
Sn-Beta is used as a heterogeneous catalyst for the Baeyer-Villiger reaction with hydrogen peroxide. Cyclic ketones are transformed into the corresponding lactones, while unsaturated ketones are oxidized to the corresponding unsaturated lactones with very high chemoselectivity. The catalyst is also selective for the oxidation of aromatic aldehydes with H2O2, producing the formate ester or the corresponding hydrolyzed product, that is the alcohol. Shape-selective oxidations are observed for isomeric reactants with different molecular shapes. The catalytic Sn sites have been characterized by 119Sn MAS-NMR spectroscopy, and tetrahedral incorporation into the zeolite framework has been demonstrated. In situ IR spectroscopy and 18O labeling experiments have shown that the oxidation mechanism involves an intermediate of the Criegee type. 相似文献
84.
Li W Nelson DP Jensen MS Hoerrner RS Cai D Larsen RD Reider PJ 《The Journal of organic chemistry》2002,67(15):5394-5397
3-Pyridylboronic acid was prepared in high yield and bulk quantity from 3-bromopyridine via a protocol of lithium-halogen exchange and "in situ quench". This technique was further studied and evaluated on other aryl halides in the preparation of arylboronic acids. 相似文献
85.
A simple desalting procedure for the coupling of a polymer microchip injector to mass spectrometry is proposed. The overall process is based on the adsorption of proteins on a poly(vinylidene difluoride) (PVDF) membrane, which are then directly eluted in the spraying solution. This microchip-based approach has been successfully applied to small drugs, peptides and proteins originally diluted in phosphate-buffered saline (PBS). Moreover, when eluting the retained proteins in small volumes, a preconcentration is obtained. The combination of single-use, mass-produceable, low-sample-consumption, easy-to-automate, miniaturized polymer injectors with easy-to-handle solution-exchange membranes makes this system particularly amenable to screening applications. 相似文献
86.
EXAFS investigations of the mechanism of facilitated ion transfer into a room-temperature ionic liquid 总被引:1,自引:0,他引:1
Jensen MP Dzielawa JA Rickert P Dietz ML 《Journal of the American Chemical Society》2002,124(36):10664-10665
The Sr(II)-crown ether complexes formed in a room-temperature ionic liquid (RTIL), 1-methyl-3-pentylimidazolium bis[(trifluoromethyl)sulfonyl]amide, have been studied by X-ray absorption fine structure measurements at the Sr K-edge. When a Sr(NO(3))(2)-crown ether complex is directly dissolved in a water-saturated RTIL, both nitrate ligands and the crown ether coordinate the Sr, as observed in a conventional two-phase water-octanol system. When the cationic Sr-crown ether complex is created in a two-phase water-RTIL system, however, only cationic Sr-crown ether complexes are observed in the RTIL phase. This difference in the coordination complexes arises from differences in the mechanism of cation extraction between the RTIL and conventional molecular organic solvents, a finding with important implications for synthesis, catalysis, and ion separations using two-phase water-RTIL systems. 相似文献
87.
We show that the fractal growth described by the dielectric breakdown model exhibits a phase transition in the multifractal spectrum of the growth measure. The transition takes place because the tip splitting of branches forms a fixed angle. This angle is eta dependent but it can be rescaled onto an "effectively" universal angle of the diffusion-limited aggregation branching process. We derive an analytic rescaling relation which is in agreement with numerical simulations. The dimension of the clusters decreases linearly with the angle and the growth becomes non-ractal at an angle close to 74 degrees (which corresponds to eta = 4.0+/-0.3). 相似文献
88.
Frame rate in ultrasound imaging can be dramatically increased by using sparse synthetic transmit aperture (STA) beamforming techniques. The two main drawbacks of the method are the low signal-to-noise ratio (SNR) and the motion artifacts, that degrade the image quality. In this paper we propose a spatio-temporal encoding for STA imaging based on simultaneous transmission of two quasi-orthogonal tapered linear FM signals. The excitation signals are an up- and a down-chirp with frequency division and a cross-talk of -55 dB. The received signals are first cross-correlated with the appropriate code, then spatially decoded and finally beamformed for each code, yielding two images per emission. The spatial encoding is a Hadamard encoding previously suggested by Chiao et al. [in: Proceedings of the IEEE Ultrasonics Symposium, 1997, p. 1679]. The Hadamard matrix has half the size of the transmit element groups, due to the orthogonality of the temporal encoded wavefronts. Thus, with this method, the frame rate is doubled compared to previous systems. Another advantage is the utilization of temporal codes which are more robust to attenuation. With the proposed technique it is possible to obtain images dynamically focused in both transmit and receive with only two firings. This reduces the problem of motion artifacts. The method has been tested with extensive simulations using Field II. Resolution and SNR are compared with uncoded STA imaging and conventional phased-array imaging. The range resolution remains the same for coded STA imaging with four emissions and is slightly degraded for STA imaging with two emissions due to the -55 dB cross-talk between the signals. The additional proposed temporal encoding adds more than 15 dB on the SNR gain, yielding a SNR at the same order as in phased-array imaging. 相似文献
89.
A high-performance liquid chromatography system for the determination of aldehydes in food was developed incorporating an Cation MicroMembrane Suppressor (CMMS) and enzyme reactors packed with VA-Epoxy on which aldehyde dehydrogenase from bakers yeast and NADH oxidase from Bacillus licheniformis were immobilized. The method was based on the principle that the separation efficiency of HPLC is combined with the sensitivity of electrochemical detection and the specificity of enzymes. Main attention was directed to the determination of 5-hydroxymethyl-2-furaldehyde and 2-furaldehyde, the occurence of which is an indication of quality deterioration in several food products. The efficiency of the method has been shown by the analysis of honey, coffee and related beverages, refreshments, sherry, port, dry fruits and breakfast cereals. 相似文献
90.
Michael K. Jensen Modjtaba Pourdashti Henry P. Bensler 《International Journal of Multiphase Flow》1985,11(2):201-211
An experimental study has been conducted to determine the effect of twisted-tape swirl generators on adiabatic and diabatic two-phase flow pressure drops in vertical straight tubes. Tape-twist ratios (length for 180° twist/inside tube diameter) of 3.94, 8.94, and 13.92 were tested with R-113 over a range of pressures, mass velocities, qualities, and heat fluxes. Empty tube refcrence data were successfully predicted with a correlation from the literature. The twisted tape data were successfully correlated by using the hydraulic diameter and a single-phase swirl flow friction factor in the empty tube correlation. Data from the literature also were predicted well with this correlation. 相似文献