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81.
Lerma-García MJ Ramis-Ramos G Herrero-Martínez JM Simó-Alfonso EF 《Rapid communications in mass spectrometry : RCM》2007,21(22):3751-3755
Amino acid profiles, established by direct infusion mass spectrometry, have been used to classify vegetable oils according to their botanical origin. The proteins present in hazelnut, sunflower, corn, soybean, olive, avocado, peanut and grapeseed oils were precipitated with acetone, and the residue was hydrolyzed in acid medium, diluted in a hydrochloric acid/ethanol mixture, and infused into the mass spectrometer. The spectra of the hydrolyzed protein extracts showed [M+H]+ ions of the following amino acids: glycine, alanine, serine, proline, valine, threonine, cysteine, isoleucine + leucine, aspartic acid, lysine, glutamic acid, methionine, histidine, phenylalanine, arginine and tyrosine. These ions were used to construct linear discriminant analysis (LDA) models. The ratios of the ion signal intensities selected by pairs were used as predictors. With the sequential application of three LDA models, the eight botanical origin categories of the samples were well resolved. 相似文献
82.
Woo HY Korystov D Mikhailovsky A Nguyen TQ Bazan GC 《Journal of the American Chemical Society》2005,127(40):13794-13795
Addition of the surfactant sodium dodecyl sulfate at concentrations above the critical micelle concentration increases the fluorescence quantum yield and the two-photon absorption cross-section of charged [2.2]paracyclophane chromophores containing pairs of D-pi-D chromophores. The resulting spectra in the micellar solutions are very similar to those obtained for neutral isostructural analogues in toluene. The measured etadelta values are 1300 GM for 1C and 1920 GM for 2C, which are comparable or larger to those in toluene. These results highlight possible misleading interpretation of two-photon-induced emission for evaluating the concentration of labeled substrates used in two-photon microscopy and provide guidelines for designing molecular structures with optimized two-photon action cross-sections in water. 相似文献
83.
Patricia W. Stege Germán A. Messina Guillermo Bianchi Roberto A. Olsina Julio Raba 《Analytical and bioanalytical chemistry》2010,397(3):1347-1353
Soil microorganisms and enzymes are the primary mediators of soil biological processes, including organic matter degradation,
mineralization, and nutrient recycling. They play an important role in maintaining soil ecosystem quality and functional diversity.
Moreover, enzyme activities can provide an indication of quantitative changes in soil organic matter. β-Glucosidase (β-Glu)
activity has been found to be sensitive to soil management and has been proposed as a soil quality indicator because it provides
an early indication of changes in organic matter status and its turnover. The aims of the present study were to test and use
a simple and convenient procedure for the assay of β-Glu activity in agricultural soil. The method described here is based
on the enzymatic degradation of cellobiose by β-Glu present in the soil sample and the subsequent determination of glucose
produced by the enzymatic reaction using screen-printed carbon electrodes modified with multiwalled carbon nanotubes (SPCE-CNT)
equipped with coimmobilized glucose oxidase and horseradish peroxidase enzymes. The potential applied to the SPCE-CNT detection
was −0.15 V versus a Ag/AgCl pseudo-reference electrode. A linear calibration curve was obtained in the range 2.7–11.3 mM
with a correlation coefficient. In the present study, an easy and effective SPCE-CNT-modified electrode allowed an improved
amperometric response to be achieved and this is attributed to the increased surface area upon electrode modification. 相似文献
84.
A Theoretical and Computational Framework for Isometry Invariant Recognition of Point Cloud Data 总被引:1,自引:0,他引:1
Point clouds are one of the most primitive and fundamental manifold
representations. Popular sources of point clouds are three-dimensional
shape acquisition devices such as laser range scanners. Another
important field where point clouds are found is in the representation
of high-dimensional manifolds by samples. With the increasing
popularity and very broad applications of this source
of data, it is natural and important to work directly with this
representation, without having to go through the intermediate and
sometimes impossible and distorting steps of surface reconstruction.
A geometric framework for comparing manifolds given by point clouds
is presented in this paper. The underlying theory is based on
Gromov-Hausdorff distances, leading to isometry invariant and
completely geometric comparisons. This theory is embedded in a
probabilistic setting as derived from random sampling of manifolds,
and then combined with results on matrices of pairwise geodesic distances
to lead to a computational implementation of the framework. The theoretical and
computational results presented here are complemented with
experiments for real three-dimensional shapes. 相似文献
85.
We describe the photoisomerization of hetero Diels-Alder adducts of tetramethylpurpurogallin bearing β,γ-unsaturated ketone chromophores and endocyclic -N-O- or -N-N- groups. Based on spectroscopic and crystallographic data, our results indicate that the outcome of the reaction for the two types of substrates can be correlated with the difference in the stabilities of the radical intermediates generated in each case. For oxazines, the photoisomerization involves both the β,γ-unsaturated ketone and -N-O- moieties, and proceeds through the formation of allyl, benzoyl, phenyl, and α-carbonyl radical intermediates. While the same allylic and benzoyl radicals are formed in adducts with an -N-N- group, the hydrazine does not participate in the reaction and the product is a simple rearrangement of the initial intermediate. 相似文献
86.
Lianet Contreras Rodríguez Evaristo Jos Madarro-Cap
Carlos Miguel Legn-Prez
Omar Rojas Guillermo Sosa-Gmez 《Entropy (Basel, Switzerland)》2021,23(5)
Entropy makes it possible to measure the uncertainty about an information source from the distribution of its output symbols. It is known that the maximum Shannon’s entropy of a discrete source of information is reached when its symbols follow a Uniform distribution. In cryptography, these sources have great applications since they allow for the highest security standards to be reached. In this work, the most effective estimator is selected to estimate entropy in short samples of bytes and bits with maximum entropy. For this, 18 estimators were compared. Results concerning the comparisons published in the literature between these estimators are discussed. The most suitable estimator is determined experimentally, based on its bias, the mean square error short samples of bytes and bits. 相似文献
87.
Matteo Villani Guillermo Albareda Carlos Destefani Xavier Cartoix Xavier Oriols 《Entropy (Basel, Switzerland)》2021,23(4)
Without access to the full quantum state, modeling quantum transport in mesoscopic systems requires dealing with a limited number of degrees of freedom. In this work, we analyze the possibility of modeling the perturbation induced by non-simulated degrees of freedom on the simulated ones as a transition between single-particle pure states. First, we show that Bohmian conditional wave functions (BCWFs) allow for a rigorous discussion of the dynamics of electrons inside open quantum systems in terms of single-particle time-dependent pure states, either under Markovian or non-Markovian conditions. Second, we discuss the practical application of the method for modeling light–matter interaction phenomena in a resonant tunneling device, where a single photon interacts with a single electron. Third, we emphasize the importance of interpreting such a scattering mechanism as a transition between initial and final single-particle BCWF with well-defined central energies (rather than with well-defined central momenta). 相似文献
88.
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
89.
Literature published in the last decade concerning the use of mid-infrared spectrometry as a detection system in separation techniques employing a liquid mobile phase is reviewed. In addition to the continued use of isocratic liquid chromatographic (LC) techniques, advances in chemometric data evaluation techniques now allow the use of gradient techniques on a routine basis, thus significantly broadening the range of possible applications of LC-IR. The general trend towards miniaturized separation systems was also followed for mid-IR detection where two key developments are of special importance. Firstly, concerning on-line detection the advent of micro-fabricated flow-cells with inner volumes of only a few nL for transmission as well as attenuated total reflection measurements enabled on-line mid-IR detection in capillary LC and opened the path for the first successful realization of on-line mid-IR detection in capillary zone electrophoresis as well as micellar electrokinetic chromatography. Secondly, concerning off-line detection the use of micro-flow through dispensers now enables to concentrate eluting analytes on dried spots sized a few tens of micrometers, thus matching the dimensions for sensitive detection by mid-IR microscopy. Finally in an attempt to increase detection sensitivity of on-line mid-IR detection, mid-IR quantum cascade lasers have been used. Applications cover the field of food analysis, environmental analysis and the characterization of explosives among others. Best detection sensitivities for on-line and off-line detection have been achieved in miniaturized systems and are in the order of 50 ng and 2 ng on column, respectively. 相似文献
90.
Guillermo A. Ludueña Martin Wegner Lars Bjålie Daniel Sebastiani Priv.‐Doz. Dr. 《Chemphyschem》2010,11(11):2353-2360
Amides and imides of alkali metals are a very promising class of materials for use as a hydrogen‐storage system, as they are able to store and release hydrogen via a chemical route at controllable temperatures and pressures. We critically revise the present picture of the atomic structure of the lightest member (LiNH2/Li2NH) by using a combined computational and experimental approach. Specifically, ab initio path integral molecular dynamics simulations and solid‐state 1H NMR techniques are combined. The results show that the presently assumed local structure might be inconsistent or at least incomplete and needs considerable revision. In particular, the Li atoms turn out to be more mobile and more disordered than suggested by structural data obtained from X‐ray scattering. Also, the configuration of the hydrogen atoms, which is accessible via the NMR experiment and the corresponding first‐principles calculations, is different from the previously assumed data. The computed and experimentally observed 1H NMR parameters are in very good mutual agreement and illustrate the unusual chemical environment of the hydrogen atoms in this system. Incorporating our results on the new lithium data, we show that the effect of nuclear quantum delocalization for the hydrogen atoms is considerably reduced compared to the perfect crystal structure. 相似文献