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51.
Baptiste Joalland Nuwandi M. Ariyasingha Sren Lehmkuhl Thomas Theis Stephan Appelt Eduard Y. Chekmenev 《Angewandte Chemie (International ed. in English)》2020,59(22):8654-8660
Radio amplification by stimulated emission of radiation (RASER) was recently discovered in a low‐field NMR spectrometer incorporating a highly specialized radio‐frequency resonator, where a high degree of proton‐spin polarization was achieved by reversible parahydrogen exchange. RASER activity, which results from the coherent coupling between the nuclear spins and the inductive detector, can overcome the limits of frequency resolution in NMR. Here we show that this phenomenon is not limited to low magnetic fields or the use of resonators with high‐quality factors. We use a commercial bench‐top 1.4 T NMR spectrometer in conjunction with pairwise parahydrogen addition producing proton‐hyperpolarized molecules in the Earth's magnetic field (ALTADENA condition) or in a high magnetic field (PASADENA condition) to induce RASER without any radio‐frequency excitation pulses. The results demonstrate that RASER activity can be observed on virtually any NMR spectrometer and measures most of the important NMR parameters with high precision. 相似文献
52.
Peptide synthesis in aqueous environments: the role of extreme conditions and pyrite mineral surfaces on formation and hydrolysis of peptides 总被引:1,自引:0,他引:1
Schreiner E Nair NN Wittekindt C Marx D 《Journal of the American Chemical Society》2011,133(21):8216-8226
A comprehensive study of free energy landscapes and mechanisms of COS-mediated polymerization of glycine via N-carboxy anhydrides (NCAs, "Leuchs anhydrides") and peptide hydrolysis at the water-pyrite interface at extreme thermodynamic conditions is presented. Particular emphasis is set on the catalytic effects of the mineral surface including the putative role of the ubiquitous sulfur vacancy defects. It is found that the mere presence of a surface is able to change the free energetics of the elementary reaction steps. This effect can be understood in terms of a reduction of entropic contributions to the reactant state by immobilizing the reactants and/or screening them from bulk water in a purely geometric ("steric") sense. Additionally, the pyrite directly participates chemically in some of the reaction steps, thus changing the reaction mechanism qualitatively compared to the situation in bulk water. First, the adsorption of reactants on the surface can preform a product-like structure due to immobilizing and scaffolding them appropriately. Second, pyrite can act as a proton acceptor, thus replacing water in this role. Third, sulfur vacancies are found to increase the reactivity of the surface. The finding that the presence of pyrite speeds up the rate-determining step in the formation of peptides with respect to the situation in bulk solvent while stabilizing the produced peptide against hydrolysis is of particular interest to the hypothesis of prebiotic peptide formation at hydrothermal aqueous conditions. Apart from these implications, the generality of the studied organic reactions are of immediate relevance to many fields such as (bio)geochemistry, biomineralization, and environmental chemistry. 相似文献
53.
Czechoslovak Mathematical Journal - The goal of this paper is to present a different approach to the homogenization of the Dirichlet boundary value problem in porous medium. Unlike the standard... 相似文献
54.
Eduard Looijenga 《Geometriae Dedicata》1997,64(1):69-83
Let S be a closed orientable surface of genus at least 2 and let
to S be a connected finite abelian covering with covering group $G$. The lifts of liftable mapping classes of S determine a central extension (by G) of a subgroup of finite index of the mapping class group of S. This extension acts on H1(
). With a few exceptions for genus 2, we determine the Zariski closure of the image of this representation, and prove that the image is an arithmetic group. 相似文献
55.
We show that any solution of the scalar conservation law (u+k*u)t+σ(u)x=0 starting from spatially periodic initial datum stabilizes to its integral mean as time goes to infinity. No convexity or ‘genuinely non-linear’ like conditions are assumed concerning σ. © 1997 by B. C. Teubner stuttgart–John Wiley & Sons Ltd. 相似文献
56.
57.
Mykhaylychenko Sergiy S. Markitanov Yuriy N. Rudenko Timofii V. Rusanov Eduard B. Shermolovich Yuriy G. 《Chemistry of Heterocyclic Compounds》2019,55(2):189-192
Chemistry of Heterocyclic Compounds - New 4-polyfluoroalkyl-1,3-dithiolanes were synthesized by reaction of polyfluoroalkanethioamides with thiocarbonyl ylide that was generated in situ by... 相似文献
58.
Swathi K. Manchili Johan Wendel Yu Cao Eduard Hryha Lars Nyborg 《Surface and interface analysis : SIA》2020,52(12):1045-1049
Demand for high-density press and sinter components is increasing day by day. Of the different ways to improve the sinter density, the addition of nanopowder to the conventional micrometer-sized metal powder is an effective solution. The present investigation is aimed at studying the surface chemistry of iron nanopowder coated with graphitic carbon, which is intended to be mixed with the conventional iron powder. For this purpose, iron nanopowder in the size range of 30 nm to submicron (less than 1 micron) was investigated using thermogravimetry at different temperatures: 400°C, 600°C, 800°C, 1000°C, and 1350°C. The X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and high-resolution scanning electron microscopy (HR-SEM) were used for characterizing the powder as well as samples sintered at different temperatures. The presence of iron, oxygen, carbon, chromium, and zinc were observed on the surface of the nanopowder. Iron was present in oxide state, although a small metallic iron peak at 707 eV was also observed in the XPS spectra obtained from the surface indicating the oxide scale to be maximum of about 5 nm in thickness. For the sample treated at 600°C, presence of manganese was observed on the surface. Thermogravimetry results showed a two-step mass loss with a total mass loss of 4 wt.% when heated to 1350°C where the first step corresponds to the surface oxide reduction. 相似文献
59.
Gomes João Pedro Agra Mourão Eduard David Simões dos Anjos Janaina Versiani de Alencar Filho Edilson Beserra 《Structural chemistry》2020,31(6):2501-2512
Structural Chemistry - In this paper, we present a quantitative structure–activity relationships modelling for two series of heterocyclic synthetic compounds with larvicidal activity against... 相似文献
60.
Kirill F. Sheberstov Eduard Sistaré Guardiola Damien Jeannerat 《Magnetic resonance in chemistry : MRC》2020,58(5):376-389
The fundamental concept of phase discussed in this tutorial aimed at providing students with an explanation of the delays and processing parameters they may find in nuclear magnetic resonance (NMR) pulse programs. We consider the phase of radio-frequency pulses, receiver, and magnetization and how all these parameters are related to phases and offsets of signals in spectra. The impact of the off-resonance effect on the phase of the magnetization is discussed before presenting an overview of how adjustment of the time reference of the free induction decay avoids first-order correction of the phase of spectra. The main objective of this tutorial is to show how the relative phase of a pulse and the receiver can be used to change the reference frequency along direct and indirect dimensions of NMR experiments. Unusual of phase incrementation with non-90° angles will be illustrated on one- and two-dimensional NMR spectra. 相似文献