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21.
A new method for measuring hydrogen chemisorption on polymer‐stabilized metal colloids, in conjunction with variable coverage infrared spectroscopy of adsorbed CO, is applied to analyse the surface of Pt/polyvinylpyrrolidone colloids. The results correlate well with the measured activity of Pt/PVP as a hydrogenation catalyst. 相似文献
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First and second-order necessary and sufficient optimality conditions for infinite-dimensional programming problems 总被引:2,自引:0,他引:2
First-order and second-order necessary and sufficient optimality conditions are given for infinite-dimensional programming problems with constraints defined by arbitrary closed convex cones. The necessary conditions are immediate generalizations of those known for the finite-dimensional case. However, this does not hold for the sufficient conditions as illustrated by a counterexample. Here, to go from finite to infinite dimensions, causes an essential change in the proof-techniques and the results. We present modified sufficient conditions of first-order and of second-order which are based on a strengthening of the usual assumptions on the derivative of the objective function and on the second derivative of the Lagrangian. 相似文献
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Abstract Contrary to statements in the literature the PhP/Se system does contain a compound with a PhP/Se ratio lower than 1. The reaction of pentaphenyl-cyclopentaphosphane and elemental selenium yields depending on the molar ratio the heterocyclic compounds (PhP)4Se (1), (PhP)3Se3 (2), or (PhP)2Se4 (3). 1, 2, and 3 are yellow to orange-red crystalline stable compounds. Their molecular structures, as shown by the 31P- and 77Se-NMR data as well as by the X-ray crystal structure determination of 2, parallel those of the corresponding sulfur derivatives. Nucleophiles add easily to the phosphorus in 3 splitting the P2Se2-ring. 相似文献
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Jochem H. J. Wijten Dr. Iván Garcia-Torregrosa Eva A. Dijkman Prof. Dr. Bert M. Weckhuysen 《Chemphyschem》2020,21(6):518-524
Non-noble metal electro-catalysts for water splitting are highly desired when we are moving towards a society where green electrons are becoming abundantly available, offering clear prospects to make our society more sustainable. In this work, Ni−Fe−S is reported as a high performing anode material for the water splitting reaction, operating at low overpotentials and showing high apparent stability. Furthermore, Ni−Mo electrodes are developed on metallic foam substrates and optimized in terms of their performance. The Ni−Fe−S material as anode, combined and integrated with Ni−Mo as cathode in a cell configuration, splits water at 10 mA cm−2 and a potential of 1.55 V. Similar to previous reports, we confirm that Mo leaches from Ni−Mo/Ni foam electrodes. Cycling tests and ICP-AES measurements show that the stability of Ni−Fe−S is apparent, and that in reality S is leaching from the material as was already suggested in literature. We expand on this knowledge and show that the leaching of S is dependent on both pH and the cation used during electrocatalysis. Furthermore, we find that applying an oxidative potential is in truth stabilizing towards S and that the alkalinity causes leaching. S was furthermore mobile and found to segregate towards the surface. Finally, using too low pH values (11 and lower) result in the passivating hydroxide metal layers being destroyed and the Ni−Fe−S dissolving completely. 相似文献
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Wang SJ Wu ST Gokemeijer J Fura A Krishna M Morin P Chen G Price K Wang-Iverson D Olah T Weiner R Tymiak A Jemal M 《Analytical and bioanalytical chemistry》2012,402(3):1229-1239
High-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) and enzyme-linked immunosorbent assay (ELISA) methods were developed for the quantification of a PEGylated scaffold protein drug in monkey plasma samples. The LC-MS/MS method was based on the extraction of the therapeutic protein with a water-miscible organic solvent and the subsequent trypsin digestion of the extract followed by the detection of a surrogate peptide. The assay was linear over a range of 10-3,000 ng/mL. The ELISA method utilized a therapeutic target-binding format in which the recombinant target antigen was used to capture the drug in the sample, followed by detection with an anti-PEG monoclonal antibody. The assay range was 30-2,000 ng/mL. A correlation study between the two methods was performed by measuring the drug concentrations in plasma samples from a single-dose pharmacokinetic (PK) study in cynomolgus monkeys following a 5-mg/kg subcutaneous administration (n = 4). In the early time points of the PK profile, the drug concentrations obtained by the LC-MS/MS method agreed very well with those obtained by the ELISA method. However, at later time points, the drug concentrations measured by the LC-MS/MS method were consistently higher than those measured by the ELISA method. The PK parameters calculated based on the concentration data showed that the two methods gave equivalent peak exposure (C(max)) at 24-48 h. However, the LC-MS/MS results exhibited about 1.53-fold higher total exposure (AUC(tot)) than the ELISA results. The discrepancy between the LC-MS/MS and ELISA results was investigated by conducting immunogenicity testing, anti-drug antibody (ADA) epitope mapping, and Western blot analysis of the drug concentrations coupled with Protein G separation. The results demonstrated the presence of ADA specific to the engineered antigen-binding region of the scaffold protein drug that interfered with the ability of the drug to bind to the target antigen used in the ELISA method. In the presence of the ADAs, the ELISA method measured only the active circulating drug (target-binding), while the LC-MS/MS method measured the total circulating drug. The work presented here indicates that the bioanalysis of protein drugs may be complicated owing to the presence of drug-binding endogenous components or ADAs in the post-dose (incurred) samples. The clear understanding of the behavior of different bioanalytical techniques vis-à-vis the potentially interfering components found in incurred samples is critical in selecting bioanalytical strategies for measuring protein drugs. 相似文献
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