全文获取类型
收费全文 | 3905篇 |
免费 | 938篇 |
国内免费 | 318篇 |
专业分类
化学 | 1613篇 |
晶体学 | 33篇 |
力学 | 30篇 |
综合类 | 16篇 |
数学 | 125篇 |
物理学 | 3026篇 |
无线电 | 318篇 |
出版年
2024年 | 11篇 |
2023年 | 62篇 |
2022年 | 100篇 |
2021年 | 144篇 |
2020年 | 165篇 |
2019年 | 139篇 |
2018年 | 124篇 |
2017年 | 116篇 |
2016年 | 150篇 |
2015年 | 162篇 |
2014年 | 207篇 |
2013年 | 292篇 |
2012年 | 252篇 |
2011年 | 281篇 |
2010年 | 230篇 |
2009年 | 293篇 |
2008年 | 234篇 |
2007年 | 254篇 |
2006年 | 233篇 |
2005年 | 187篇 |
2004年 | 167篇 |
2003年 | 169篇 |
2002年 | 184篇 |
2001年 | 152篇 |
2000年 | 162篇 |
1999年 | 117篇 |
1998年 | 124篇 |
1997年 | 44篇 |
1996年 | 40篇 |
1995年 | 43篇 |
1994年 | 38篇 |
1993年 | 37篇 |
1992年 | 35篇 |
1991年 | 27篇 |
1990年 | 23篇 |
1989年 | 15篇 |
1988年 | 23篇 |
1987年 | 12篇 |
1986年 | 21篇 |
1985年 | 12篇 |
1984年 | 15篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 9篇 |
1980年 | 10篇 |
1979年 | 9篇 |
1978年 | 9篇 |
1977年 | 9篇 |
1974年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有5161条查询结果,搜索用时 106 毫秒
71.
The partition of the spin label TEMPO in the hydrophobic region of di-palmitoyl-phosphatidylcholine unilamellar vesicles has been used to investigate the influence of high concentration (up 3M) of Li+, Na+, K+, and Cs+ on the phase transitions at 20–60°C. All of the above salts increase the permeation of TEMPO. The efficiency of monovalent cations in inducing the partition of the spin label in the hydrophobic environment of the bilayer increases in the order: Cs++++. The disappearing of the pretransition and the downward shift of the main phase transition temperature from 37°C to 33.5°C is related to the increased permeation of TEMPO into the bilayer. The presence of salts in the bulk solution disturbs the hydration of the zwitterionic polar head of the DPPC molecules and changes the electrical interaction between the polar groups of the bilayer. This reduces the packing density of the lipid molecules and promotes the permeation of TEMPO. 相似文献
72.
Omar Deeb Prof. Monika Leibscher Dr. Jörn Manz Prof. Wulf von Muellern Tamar Seideman Prof. 《Chemphyschem》2007,8(2):322-328
We propose an approach for separating nuclear spin isomers with coherent light and illustrate it by numerical calculations using fulvene as a model system. The scheme employs the equivalence of torsion and interchange of equivalent H-atoms in a class of molecules of which fulvene is a simple example. The exchange symmetry couples with the rotational symmetry to produce a spatial distinction between the two photo-excited nuclear spin isomers, and wavepacket interferometry is applied to separate the species. 相似文献
73.
The unrestricted Hartree-Fock (UHF) method of Snyder and Amos is used to calculate, in the -electron approximation, the spin density distributions in radical anions of heterocyclic amine N-oxides. The computed spin densities are observed to be in good agreement with the experimental values. The computed spin density distribution of the radical anion of pyridine N-oxide is consistent with the greater susceptibility of pyridine N-oxide relative to pyridine to electrophilic nitration. Also, the calculations are consistent with the lower basicity of the N-oxides relative to the parent bases. 相似文献
74.
In NMR spectroscopy, homonuclear scalar couplings normally lead to modulations of spin echoes that tend to interfere with the accurate determination of transverse relaxation rates by Carr-Purcell-Meiboom-Gill (CPMG) multiple refocusing experiments. Surprisingly, the echo modulations are largely cancelled when the refocusing pulses applied to the coupling partner deviate slightly from ideal pi rotations due to tilted effective radio-frequency (RF) fields, even at offsets that are much smaller than the radio-frequency amplitude. Experiments and simulations illustrate these effects for two-spin IS systems containing donor and acceptor (15)N nuclei I=N (D) and S=N(A) in RNA Watson-Crick base pairs with homonuclear scalar couplings J(IS)=(2h)J(N(D), N(A)) across the hydrogen bonds. 相似文献
75.
76.
John A. Rogers Zhenan Bao 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3327-3334
Plastic electronic materials and high‐resolution printing methods may be important technologies for new classes of consumer electronic devices that are lightweight, mechanically flexible and bendable, and that can cover large areas at low cost. This article summarizes some of our recent work in this area. It focuses on the materials and patterning techniques that we used to produce plastic active‐matrix backplane circuits for a type of paperlike display. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3327–3334, 2002 相似文献
77.
We implemented ab initio self‐consistent field (SCF) fractional occupation numbers (FON) calculation with Dunlap's interpolation scheme for the twisted ethylene, which is a prototype molecule of a σ–π biradical system. The calculational results are compared with those of complete‐active‐space (CAS) SCF and spin‐unrestricted Kohn–Sham (UKS) calculations on potential surfaces, occupation numbers of natural orbitals, and correlation entropies. It was found that the UKS methods gave similar results to CASSCF, while the FON solutions appeared in only the nearly complete degenerate region. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 317–323, 2003 相似文献
78.
Sadafumi NishiharaTomoyuki Akutagawa Tatsuo Hasegawa Shigeki FujiyamaToshikazu Nakamura Takayoshi Nakamura 《Journal of solid state chemistry》2002,168(2):661-667
Two polymorphs of monovalent [Ni(dmit)2]− (dmit2−=2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dmit)2], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)2]− molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dmit)2], whose magnetism had been well fitted by spin ladder equation with the spin gap of Δ=190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dmit)2]− dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dmit)2]− arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K. 相似文献
79.
L. A. Errede E. B. Aus R. W. Duerst 《Journal of polymer science. Part A, Polymer chemistry》1992,30(6):1145-1153
The electron paramagnetic resonance (EPR) signal and the residual number (αt) of volatile molecules per phenyl group of poly(styrene-co-divinylbenzene) in samples that had been swelled to saturation in a dilute solution of a nitroxide spin-probe (TEMPO or 4-oxo-TEMPO), dissolved in a volatile liquid, were monitored simultaneously as the system containing excess liquid was allowed to evaporate to dryness. The results showed that the characteristic motionally narrowed three-line EPR spectrum began to change when αt became equal to αg (the number of sorbed molecules per phenyl group of polymer at liquid-saturation). The ratio of the intensity of the low-field and high-field hyperfine peaks relative to the middle peak decreased monotonically to an asymptotic limit that was attained when αt became equal to αg (the number of residual adsorbed molecules per phenyl group of polymer at completion of the transition from the rubbery state to the glassy state). The EPR hyperfine pattern, from which the rotational correlation times were estimated, changed most significantly as αt decreased from αG to αg while exhibiting inflections at about α′s and α′g the compositions that mark, respectively, incipient desorption of adsorbed molecules and incipient transition from the rubbery state to the glassy state. The pattern between these inflections points, however, varied with the affinity of the solvent for the polymer. 相似文献
80.
Cataldo L Dutan C Misra SK Loss S Grützmacher H Geoffroy M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3463-3468
The EPR spectrum of the novel radical Mes*(CH3)P--PMes* (Mes*=2,4,6-(tBu)3C6H2) was measured in the temperature range 100-300 K, and was found to be drastically temperature dependent as a result of the large anisotropy of the 31P hyperfine tensors. Below 180 K, a spectrum of the liquid solution is accurately simulated by calculating the spectral modifications due to slow tumbling of the radical. To achieve this simulation, an algorithm was developed by extending the well-known nitroxide slow-motion simulation technique for the coupling of one electron spin to two nuclear spins. An additional dynamic process responsible for the observed line broadening was found to occur between 180 K and room temperature; this broadening is consistent with an exchange between two conformations. The differences between the isotropic 31P couplings associated with the two conformers are shown to be probably due to an internal rotation about the P--P bond. 相似文献