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101.
Kondo M Mates TE Fischer DA Wudl F Kramer EJ 《Langmuir : the ACS journal of surfaces and colloids》2010,26(22):17000-17012
Interfaces between phenylacetylene (PA) monolayers and two silicon surfaces, Si(111) and Si(100), are probed by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and the results are analyzed using ab initio molecular orbital calculations. The monolayer systems are prepared via the surface hydrosilylation reaction between PA and hydrogen-terminated silicon surfaces. The following spectral features are obtained for both of the PA-Si(111) and PA-Si(100) systems: a broad π-π* shakeup peak at 292 eV (XPS), a broad first ionization peak at 3.8 eV (UPS), and a low-energy C 1s → π* resonance peak at 284.3 eV (NEXAFS). These findings are ascribed to a styrene-like π-conjugated molecular structure at the PA-Si interface by comparing the experimental data with theoretical analysis results. A conclusion is drawn that the vinyl group can keep its π-conjugation character on the hydrogen-terminated Si(100) [H:Si(100)] surface composed of the dihydride (SiH(2)) groups as well as on hydrogen-terminated Si(111) having the monohydride (SiH) group. The formation mechanism of the PA-Si(100) interface is investigated within cluster ab initio calculations, and the possible structure of the H:Si(100) surface is discussed based on available data. 相似文献
102.
Leibfarth FA Schneider Y Lynd NA Schultz A Moon B Kramer EJ Bazan GC Hawker CJ 《Journal of the American Chemical Society》2010,132(42):14706-14709
The functionalization and cross-linking of polyethylene is synthetically challenging, commonly relying on highly optimized radical based postpolymerization strategies. To address these difficulties, a norbornene monomer containing Meldrum's acid is shown to be effectively copolymerized with polyethylene using a nickel α-iminocarbaxamidato complex, providing high-melting, semicrystalline polymers with a tunable incorporation of the functional comonomer. Upon heating the copolymer to common polyethylene processing temperatures, the thermolysis of Meldrum's acid to ketene provides the desired reactive group. This simple and versatile methodology does not require small molecule radical sources or catalysts, and the dimerization of the in situ generated ketenes is shown to provide tunable cross-linking densities in polyethylene. Subsequent rheological and tensile experiments illustrate the ability to tune cross-linked polyethylene properties by comonomer incorporation and elucidate valuable structure/property relationships in these materials. This study illustrates the power of well-defined and synthetically accessible functional groups in polyolefin synthesis and functionalization. 相似文献
103.
Yang Luo Tuo Li Fang Yu Tal Kramer Ileana M. Cristea 《Journal of the American Society for Mass Spectrometry》2010,21(1):34-46
Current biological studies have been advanced by the continuous development of robust, accurate, and sensitive mass spectrometric
technologies. The MALDI LTQ Orbitrap is a new addition to the Orbitrap configurations, known for their high resolving power
and accuracy. This configuration provides features inherent to the MALDI source, such as reduced spectra complexity, forgiveness
to contaminants, and sample retention for follow-up analyses with targeted or hypothesis-driven questions. Here we investigate
its performance for characterizing the composition of isolated protein complexes. To facilitate the assessment, we selected
two well characterized complexes from Saccharomyces cerevisiae, Apl1 and Nup84. Manual and automatic MS and MS/MS analyses readily resolved their compositions, with increased confidence
of protein identification compared with our previous reports using MALDI QqTOF and MALDI IT. CID fragmentation of singly-charged
peptides provided sufficient information for conclusive identification of the isolated proteins. We then assessed the resolution,
accuracy, and sensitivity provided by this instrument in the context of analyzing the isolated protein assemblies. Our analysis
of complex mixtures of singly-charged ions up to m/z 4000 showed that (1) the resolving power, inversely proportional to the square root of m/z, had over four orders of magnitude dynamic range; (2) internal calibration led to improved accuracy, with an average absolute
mass error of 0. 5 ppm and a distribution centered at 0 ppm; and (3) subfemtomole sensitivity was achieved using both CHCA
and DHB matrices. Additionally, our analyses of a synthetic phosphorylated peptide in mixtures showed subfemtomole level of
detection using neutral loss scanning. 相似文献
104.
Fluorescence has recently been applied to the analysis of the molecular organization state of the polyene antibiotic amphotericin
B (AmB) in solution or in lipid membranes. The polyene chain of AmB monomer gives rise to two fluorescence emissions; S1(21Ag) → S0(11Ag) between 500 and 700 nm, S2(11Bu) → S0(11Ag) between 400 and 500 nm. However, Raman scattering might interfere with the S2 → S0 emission fluorescence due to the weak fluorescence quantum yield and close proximity to the exciting lines. In fact, we show
here that a change in the excitation wavelength results in a shift of three emission bands, an effect which excludes their
assignment to fluorescence. These bands originate from the water Raman at 3382 cm-1and AmB resonance Raman at 1556 and 1153 cm-1. As a consequence, some former conclusions on the molecular organization state of AmB should be reconsidered. 相似文献
105.
The conformational analyses of six non-rigid N-acetyl glucosamine (NAG) derivatives employing residual dipolar couplings (RDCs) and NOEs together with molecular dynamics (MD) simulations are presented. Due to internal dynamics we had to consider different conformer ratios existing in solution. The good quality of the correlation between theoretically and experimentally obtained RDCs show the correctness of the calculated conformers even if the ratios derived from the MD simulations do not exactly meet the experimental data. If possible, the results were compared to former published data and commented. 相似文献
106.
We prove the following rigidity results. Coarse equivalences between metrically complete Euclidean buildings preserve spherical buildings at infinity. If all irreducible factors have dimension at least two, then coarsely equivalent Euclidean buildings are isometric (up to scaling factors); if in addition none of the irreducible factors is a Euclidean cone, then the isometry is unique and has finite distance from the coarse equivalence. 相似文献
107.
S. Caroli M. Spagnoli G. Forte M. Alessandrelli R. Cresti S. D'Ilio J. Pauwels G. N. Kramer Gy. Zray 《Microchemical Journal》2000,67(1-3)
In the framework of the activities of the Community Reference Laboratory (CRL) for residues at the Istituto Superiore di Sanità (ISS) of Rome, a number of proficiency tests were performed in order to assess and improve, wherever necessary, the quality of regulatory residue analysis within the EU. In this context, a pilot study was undertaken with the purpose of ascertaining the feasibility of a project for the certification of a new reference material for trace elements in bovine muscle. On behalf of the ISS, approximately 70 kg of bovine muscle, collected at a slaughterhouse in Geel (Belgium), were freeze-dried, homogenized, stabilized and bottled under argon atmosphere by the Institute for Reference Materials and Measurements, Joint Research Centre, European Commission (IRMM-JRC-EC). Preliminary analyses were carried out with Quadrupole (Q) and High Resolution (HR) Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to evaluate the content of As, Cd, Cu and Pb, whereas the Flow Injection Mercury System (FIMS) was used to quantify Hg. Digestion of the matrix was achieved by acid-assisted microwave irradiation. The mean values of experimentally obtained data were the following (in nanograms per gram): As, 24.2±1.2; Cd, 5.48±0.29; Cu, 4765±95; Hg, 3.37±0.73; and Pb, 184±7. Subsequently, 16 National Reference Laboratories (NRLs) for residues in the Member States plus the Norwegian one and eight Italian public laboratories were accepted to participate in the project and received one bottle of the freeze-dried bovine muscle. The laboratories were requested to perform three different analytical runs (in three different days), each consisting of three individual measurements. Preliminary results showed good agreement and fair evidence for homogeneity of the entire mass, thus setting the stage for the future certification of this candidate CRM. 相似文献
108.
A synthetic route towards surface modified, monodisperse, spherical particles is presented. The precursor particles exhibit epoxy‐functionalities which can be opened afterwards with an appropriate nucleophile. Via this route, dye labeled particles are obtained. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
109.
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