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51.
    
The ability to locate minima on electronic excited states (ESs) potential energy surfaces both in the case of bright and dark states is crucial for a full understanding of photochemical reactions. This task has become a standard practice for small- to medium-sized organic chromophores thanks to the constant developments in the field of computational photochemistry. However, this remains a very challenging effort when it comes to the optimization of ESs of transition metal complexes (TMCs), not only due to the presence of several electronic ESs close in energy, but also due to the complex nature of the ESs involved. In this article, we present a simple yet powerful method to follow an ES of interest during a structural optimization in the case of TMCs, based on the use of a compact hole-particle representation of the electronic transition, namely the natural transition orbitals (NTOs). State tracking using NTOs is unambiguously accomplished by computing the mono-electronic wave function overlap between consecutive steps of the optimization. Here, we demonstrate that this simple but robust procedure works not only in the case of the cytosine but also in the case of the ES optimization of a ruthenium nitrosyl complex which is very problematic with standard approaches. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.  相似文献   
52.
    
The present work reports on the synthesis of a molecularly imprinted polymer (MIP) based on methacrylic acid and ethylene glycol dimethacrylate for sunitinib delivery. Sunitinib (SUT) is a tyrosine kinase inhibitor used in many cancer diseases. Like the majority of the anticancer drugs, SUT suffers of a low bioavailability, and at the same time, it is characterized by a narrow therapeutic window. In order to reduce drug systemic toxicity, we synthesized a MIP‐based drug delivery system for SUT‐controlled release. MIP was obtained by bulk polymerization through the so‐called noncovalent approach. Rebinding experiments were performed to evaluate the success of the imprinting process and the ability of MIP to bind in a specific and selective fashion the template molecule. Resulting data showed that sunitinib rebinding percentage was 70%, while nonimprinted polymer (NIP) rebinding percentage was 46%. A not significant difference was observed between MIP and NIP in semaxanib binding experiments. Moreover, the drug release profiles were studied for both MIP and NIP. A sustained release was observed from sunitinib‐loaded MIP during 24 hours, reaching 58% after 6 hours and 76% at the end‐point. NIP, on the contrary, released almost 90% of the loaded drug within 6 hours. Furthermore, the drug carrier was tested in vitro against MCF‐7 cells, in which the cytotoxic effect of sunitinib released from MIP reached the maximum after 72 hours, while NIP completed its effect within 48 hours. These results demonstrated that molecularly imprinted polymers are suitable systems for SUT release.  相似文献   
53.
    
In this work, POXC, a laccase from Pleurotus ostreatus, was immobilized on carbon nanotubes (CNTs) modified by electrografting anthraquinone and naphthoate diazonium salts. Thanks to a favorable interaction between laccase and covalently modified CNTs, this laccase exhibits high-potential/high-current oxygen reduction reaction (ORR) performances, surpassing the performances of the well-known laccase from Trametes versicolor (TvLAC) immobilized on the same nanostructured electrodes. Furthermore, immobilized POXC demonstrates high ORR activity over a wide range of pH (2 to 8), being also highly active at a gas-diffusion electrode. Finally, owing to these unique performances, this enzyme was able to operate at the interface of the microporous layer, humidified air and a polymer electrolyte, that is, Nafion®, in a conventional H2/air proton-exchange membrane fuel.  相似文献   
54.
Abstract

In this paper, the application of a multi-analytical approach for the characterisation of synthetic and natural dyes in a historical textile is presented. The work is focused on a historical dress of a Sicilian noblewoman, dating from about 1865–1870. Firstly, SERS on fibre was performed, in order to individuate the classes of dyes employed. The SERS spectra suggested the presence of two main dyes: mauveine and orcein. In order to confirm these preliminary results, two different extraction protocols were applied. The extracts obtained were analysed by ESI-MS, MALDI-ToF and UHPCL-MS analyses, confirming the SERS results. In particular, the application of the ammonia mild extraction technique allowed to selectively extract the phenoxazonic dyes, separating them already in the extraction step from the synthetic ones. Thanks to this multi-analytical approach, this dress could be considered as one of the first examples of employment of synthetic dyes in association with natural ones.  相似文献   
55.
    
This paper reports on the first phytochemical analysis ever performed on Jasminum tortuosum Willd. This analysis, mainly carried out by means of column chromatography separation, NMR spectroscopy and mass spectrometry, led to the isolation and the identification of four compounds, namely the lignans ginkgool (1) and olivil-4′-O-β-glucopyranoside (2) and the secoiridoids oleoside dimethyl ester (3) and oleoside 11-methyl ester (4). The presence of these compounds is significant from a chemotaxonomic point of view, confirming the correct botanical classification of the species and, from a phytochemical standpoint, may suggest its possible use in the ethno-medicinal field.  相似文献   
56.
    
Drawing inspiration from the structural features of some natural polyphenols, the synthesis of two different model compounds as potential inhibitors of HIV integrase (IN) has been described. The former was characterised by a diketo acid (DKA) bioisostere, such as a β-hydroxycarbonyl moiety, between two fragments containing aromatic groups, while in the latter an epoxide linked two polyoxygenated aromatic residues. The moieties present in the structures are thought to function by chelating divalent metal ions on the enzyme catalytic site. Overall, 10 compounds were prepared and some of that submitted to molecular modelling studies (to investigate their interactions with the active site of IN), to metal titration studies (to detect their chelating capability) and to biological assays.  相似文献   
57.
58.
A new system for soil respiration measurement [P. Rochette, L.B. Flanagan, E.G. Gregorich. Separating soil respiration into plant and soil components using analyses of the natural abundance of carbon-13. Soil Sci. Soc. Am. J., 63, 1207-1213 (1999).] was modified in order to collect soil-derived CO2 for stable isotope analysis. The aim of this study was to assess the suitability of this modified soil respiration system to determine the isotopic composition (delta13C) of soil CO2 efflux and to measure, at the same time, the soil CO2 efflux rate, with the further advantage of collecting only one air sample. A comparison between different methods of air collection from the soil was carried out in a laboratory experiment. Our system, as well as the other dynamic chamber approach tested, appeared to sample the soil CO2, which is enriched with respect to the soil CO2 efflux, probably because of a mass dependent fractionation during diffusion and because of the atmospheric contribution in the upper soil layer. On the contrary, the static accumulation of CO2 into the chamber headspace allows sampling of delta13C-CO2 of soil CO2 efflux.  相似文献   
59.
We report on the first experimental evidence of guided resonances (GRs) in photonic crystal slabs based on aperiodically ordered supercells. Using Ammann-Beenker (quasiperiodic, eightfold symmetric) tiling geometry, we present our study on the fabrication, experimental characterization, and full-wave numerical simulation of two representative structures (with different filling parameters) operating at near-IR wavelengths (1300-1600 nm). Our results show a fairly good agreement between measurements and numerical predictions and pave the way for the development of new strategies (based on, e.g., the lattice symmetry breaking) for GR engineering.  相似文献   
60.
Blood oxygenation level dependent (BOLD) response related to interictal activity was evaluated in a patient with post-traumatic focal epilepsy at repeated continuous electroencephalogram (EEG)-functional magnetic resonance imaging examinations. Lateralized interictal EEG activity induced a main cluster of activation co-localized with the anatomical lesion. Spreading of EEG interictal activity to both frontal lobes evoked bilateral clusters of activation indicating that topography of BOLD response might depend on the spatial distribution of epileptiform activity.  相似文献   
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