全文获取类型
收费全文 | 487篇 |
免费 | 10篇 |
国内免费 | 5篇 |
专业分类
化学 | 313篇 |
晶体学 | 2篇 |
力学 | 13篇 |
数学 | 62篇 |
物理学 | 112篇 |
出版年
2021年 | 4篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2017年 | 3篇 |
2016年 | 8篇 |
2015年 | 5篇 |
2014年 | 13篇 |
2013年 | 12篇 |
2012年 | 24篇 |
2011年 | 25篇 |
2010年 | 11篇 |
2009年 | 11篇 |
2008年 | 21篇 |
2007年 | 18篇 |
2006年 | 24篇 |
2005年 | 29篇 |
2004年 | 23篇 |
2003年 | 21篇 |
2002年 | 22篇 |
2001年 | 12篇 |
2000年 | 16篇 |
1999年 | 18篇 |
1998年 | 11篇 |
1997年 | 4篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 9篇 |
1992年 | 10篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 5篇 |
1988年 | 8篇 |
1986年 | 11篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 9篇 |
1974年 | 3篇 |
1973年 | 4篇 |
1971年 | 4篇 |
1969年 | 2篇 |
1968年 | 3篇 |
排序方式: 共有502条查询结果,搜索用时 0 毫秒
61.
The magnetic properties of synthetic goethite, precipitated from a SiO2-containing Fe(III) solution, have been studied. The Mössbauer spectra show the coexistence of a quadrupole doublet and a magnetically split component in a large temperature range. The area ratio of these two components depends strongly on temperature, indicating a normal superparamagnetic behaviour of isolated crystallites. This is in contrast to the behaviour normally exhibited by pure samples of microcrystalline goethite, in which strong magnetic interactions among the crystallites lead to a superferromagnetic behaviour. The results show that the magnetic interactions among the crystallites are drastically diminished when amorphous SiO2 separates the goethite crystallites. 相似文献
62.
Moss CL Chung TW Wyer JA Nielsen SB Hvelplund P Tureček F 《Journal of the American Society for Mass Spectrometry》2011,22(4):731-751
Electron transfer and capture mass spectra of a series of doubly charged ions that were phosphorylated pentapeptides of a
tryptic type (pS,A,A,A,R) showed conspicuous differences in dissociations of charge-reduced ions. Electron transfer from both
gaseous cesium atoms at 100 keV kinetic energies and fluoranthene anion radicals in an ion trap resulted in the loss of a
hydrogen atom, ammonia, and backbone cleavages forming complete series of sequence z ions. Elimination of phosphoric acid was negligible. In contrast, capture of low-energy electrons by doubly charged ions
in a Penning ion trap induced loss of a hydrogen atom followed by elimination of phosphoric acid as the dominant dissociation
channel. Backbone dissociations of charge-reduced ions also occurred but were accompanied by extensive fragmentation of the
primary products. z-Ions that were terminated with a deaminated phosphoserine radical competitively eliminated phosphoric acid and H2PO4 radicals. A mechanism is proposed for this novel dissociation on the basis of a computational analysis of reaction pathways
and transition states. Electronic structure theory calculations in combination with extensive molecular dynamics mapping of
the potential energy surface provided structures for the precursor phosphopeptide dications. Electron attachment produces
a multitude of low lying electronic states in charge-reduced ions that determine their reactivity in backbone dissociations
and H- atom loss. The predominant loss of H atoms in ECD is explained by a distortion of the Rydberg orbital space by the
strong dipolar field of the peptide dication framework. The dipolar field steers the incoming electron to preferentially attach
to the positively charged arginine side chain to form guanidinium radicals and trigger their dissociations. 相似文献
63.
Chemical profiling of barley (Hordeum vulgare) leaves was demonstrated using direct and indirect desorption electrospray ionization (DESI) imaging mass spectrometry. Direct DESI analysis of the untreated leaves was not possible despite a significant content of hydroxynitrile glucosides known to reside in the epidermis of the leaves. Instead, the epidermis was stripped off the leaves, thus allowing direct DESI imaging to be performed on the back of the epidermis. Furthermore, indirect DESI imaging was performed by making imprints in porous Teflon of the intact leaves as well as of the stripped epidermis. The DESI images reveal accumulation of hydroxynitrile glucosides in the leaf epidermis, homogeneously distributed throughout the surface. The indirect DESI approach enables relative quantitation, confirming variations of hydroxynitrile glucosides content in primary leaves of three different cultivars of barley seedlings. The study presents an example of how to overcome the morphological barriers from the plant surface and perform rapid and repeatable DESI imaging. In addition, a comparison is made of direct and indirect DESI imaging, contributing to the characterization of the recently developed method of indirect DESI imaging of plant material via porous Teflon imprints. 相似文献
64.
Kirketerp MB Ryhding T Støchkel K Brøndsted Nielsen M Brøndsted Nielsen S 《The journal of physical chemistry. A》2011,115(7):1222-1227
Oligo(p-phenyleneethynylene)s (OPEs) are conjugated oligomers of great interest within materials science and molecular electronics on account of their highly applicable electronic and optical properties. Here we use gas-phase action spectroscopy to elucidate how the intrinsic electronic properties of these chromophores are affected by nearby charges. An OPE3 chromophore with two nearby ammonium groups was synthesized. This molecule and a related OPE3 with only one amine protonation site were transferred to the gas phase by electrospray ionization and subjected to action spectroscopy. Ions were bunched in a 14-pole ion trap, accelerated to 50-keV kinetic energies, mass-to-charge selected by a magnet, and photoexcited in a crossed-beam configuration. Fragment ions were finally mass-analyzed by an electrostatic analyzer. The setup enables photodissociation mass spectrometry and action spectroscopy on the microsecond time scale. The gas-phase absorption of the mono- and dication was measured and compared to that of neutral chromophores in solution. Similar absorption was found for neutral chromophores (in solution) and the dication (in gas phase or solution), whereas the monocation absorbs at lower energies in the gas phase. Simple electrostatic considerations lead to an energy difference like the one found from the experiment. The work presented here addresses how the electronic properties of a π-conjugated system are affected by nearby charges, a question of fundamental interest in, for example, molecular electronics. 相似文献
65.
On the Exciton Coupling between Two Chlorophyll Pigments in the Absence of a Protein Environment: Intrinsic Effects Revealed by Theory and Experiment 下载免费PDF全文
Dr. Bruce F. Milne Christina Kjær Jørgen Houmøller Dr. Mark H. Stockett Dr. Yoni Toker Prof. Angel Rubio Prof. Steen Brøndsted Nielsen 《Angewandte Chemie (International ed. in English)》2016,55(21):6248-6251
Exciton coupling between two or more chlorophyll (Chl) pigments is a key mechanism associated with the color tuning of photosynthetic proteins but it is difficult to disentangle this effect from shifts that are due to the protein microenvironment. Herein, we report the formation of the simplest coupled system, the Chl a dimer, tagged with a quaternary ammonium ion by electrospray ionization. Based on action spectroscopic studies in vacuo, the dimer complexes were found to absorb 50–70 meV to the red of the monomers under the same conditions. First‐principles calculations predict shifts that somewhat depend on the relative orientation of the two Chl units, namely 50 and 30 meV for structures where the Chl rings are stacked and unstacked, respectively. Our work demonstrates that Chl association alone can produce a large portion of the color shift observed in photosynthetic macromolecular assemblies. 相似文献
66.
Jens Martin Knudsen Steen Mørup Jolanta Galazka-Friedman 《Hyperfine Interactions》1990,57(1-4):2231-2235
Both the USSR and US have plans of performing rover missions and sample return missions to the planet Mars in the coming decade. There may be possibilities of performingin situ Mössbauer spectroscopy on Mars or on fresh samples returned to a space station. 相似文献
67.
Electrical model of a liquid crystal pixel with dynamic, voltage history-dependent capacitance value
The voltage history-dependent nature of a liquid crystal pixel capacitance becomes an important issue in active matrix addressing as large storage capacitors are replaced with more intelligent circuitry such as in-pixel frame buffers. In this paper, a simple but flexible Spice macro model is introduced that allows accurate simulations of the electrical behaviour of a nematic liquid crystal pixel capacitance. The model correctly predicts voltage drops caused by the increasing dielectric constant when liquid crystal molecules align themselves to the electric field. An internal node of the macro model represents the average director orientation and can also be used to predict the optical response. In its basic embodiment, the model uses a first-order, low pass RMS filter to implement the dynamic behaviour of the pixel, which suffices to predict response delays and asymmetric rise and fall times. However, the model also supports more elaborated filters that offer more control over the simulated dynamic behaviour. A number of simulations are performed that illustrate the usefulness of the new model during the design of novel 'smart' pixel architectures. 相似文献
68.
69.
MØrup Steen Frandsen Cathrine BØdker Franz Klausen Stine Nyborg Lefmann Kim LindgÅrd Per-Anker Hansen Mikkel Fougt 《Hyperfine Interactions》2002,144(1-4):347-357
Hyperfine Interactions - The magnetic properties of antiferromagnetic nanoparticles have been studied by Mössbauer spectroscopy and neutron scattering. Temperature series of Mössbauer... 相似文献
70.
J.R. Owen W.C. Maskell B.C.H. Steele T.Steen Nielsen O.Toft Sørensen 《Solid State Ionics》1984,13(4):329-334
LiAl thin film electrodes were formed by cathodic conversion of the surface of a 50 micron Al foil in a propylene carbonate based electrolyte. The films were cycled both in Li-doped poly(ethylene oxide) and propylene carbonate. On charging, an overpotential of 40 mV was required to sustain growth of the LiAl phase, but the diffusional overpotential was minimal. A simple diffusional model for the discharge predicted serious rate limitation due to slow diffusion in the α phase. However, measurements of the diffusion coefficient gave values many orders higher than previously reported and even greater values were required to explain the discharge rates. Cycling behaviour showed that the electrode degradation was less severe in the polymeric electrolyte than in propylene carbonate. 相似文献