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81.
Savarese M Aliberti A De Santo I Battista E Causa F Netti PA Rega N 《The journal of physical chemistry. A》2012,116(28):7491-7497
Although lifetimes and quantum yields of widely used fluorophores are often largely characterized, a systematic approach providing a rationale of their photophysical behavior on a quantitative basis is still a challenging goal. Here we combine methods rooted in the time-dependent density functional theory and fluorescence lifetime imaging microscopy to accurately determine and analyze fluorescence signatures (lifetime, quantum yield, and band peaks) of several commonly used rhodamine and pyronin dyes. We show that the radiative lifetime of rhodamines can be correlated to the charge transfer from the phenyl toward the xanthene moiety occurring upon the S(0) ← S(1) de-excitation, and to the xanthene/phenyl relative orientation assumed in the S(1) minimum structure, which in turn is variable upon the amino and the phenyl substituents. These findings encourage the synergy of experiment and theory as unique tool to design finely tuned fluorescent probes, such those conceived for modern optical sensors. 相似文献
82.
Ilaria Bonaduce Leslie Carlyle Maria Perla Colombini Celia Duce Carlo Ferrari Erika Ribechini Paola Selleri Maria Rosaria Tiné 《Journal of Thermal Analysis and Calorimetry》2012,107(3):1055-1066
This article presents a multi-analytical approach to investigating the drying, polymerisation and oxidative degradation of
linseed oil, which had undergone various treatments known to be undertaken during the nineteenth century in preparation for
painting. The oil was mechanically extracted from the same seed lot then processed by different methods: water washing, heat
treatments, and the addition of driers, with and without heat. The oil was prepared in 1999 within the framework of the MOLART
project. We compared thermogravimetric analysis (TG), which yields macromolecular information, with gas-chromatography mass-spectrometry
(GC/MS) and direct exposure mass spectrometry (DE-MS), which provide molecular information. This comparison enabled us to
elucidate the role of pre-treatment on the composition of the oil. TG and oxygen uptake curves registered at a constant temperature
helped us to identify the different physical behaviour of the oil samples, thus highlighting the presence of hydrolysed, oxidised
and crosslinked fractions, as a consequence of the different pre-treatments. GC/MS was used to characterise the soluble and
non-polymeric fraction of the oil, to calculate the ratios of palmitic to stearic acid (P/S), and azelaic to palmitic acid
(A/P), and to further evaluate the effects of oil pre-treatments. DE-MS using chemical ionisation with CH4, enabled us to establish the chemical composition of the oil in different stages of ageing. DE-MS proved to be a useful tool
for a simultaneous semi-quantitative characterisation of the free fatty acids, monoglycerids, diglycerides and triglycerides
present in each sample. The combination of thermal analysis with GC/MS and DE-MS enabled a model to be developed, which unravelled
how oil pre-treatments produce binders with different physical–chemical qualities. 相似文献
83.
Fabris F De Lucchi O Nardini I Crisma M Mazzanti A Mason SA Lemée-Cailleau MH Scaramuzzo FA Zonta C 《Organic & biomolecular chemistry》2012,10(12):2464-2469
(+)-syn-Benzotriborneol forms stable complexes with one molecule of water. This is due to the ability of the host to form three hydrogen bonds with water, to act simultaneously as a hydrogen-bond acceptor and donor, and to a perfect geometrical match between the pair. We report experimental (X-ray and neutron diffraction, VT NMR, DSC, TGA) and stereochemical studies carried out to elucidate and quantify the molecular and thermodynamic aspects of this supramolecular complex. 相似文献
84.
Fortage J Puntoriero F Tuyèras F Dupeyre G Arrigo A Ciofini I Lainé PP Campagna S 《Inorganic chemistry》2012,51(9):5342-5352
A series of linearly arranged donor-spacer-acceptor (D-S-A) systems 1-3, has been prepared and characterized. These dyads combine an Os(II)bis(terpyridine) unit as the photoactivable electron donor (D), a biphenylene (2) or phenylene-xylylene (3) fragment as the spacer (S), and a N-aryl-2,6-diphenylpyridinium electrophore (with aryl = 4-pyridyl or 4-pyridylium in 1 or 2/3, respectively) as the acceptor (A). Their absorption spectra, redox behavior, and luminescence properties (both at 77 K in rigid matrix and at 298 K in fluid solution) have been studied. The electronic structure and spectroscopic properties of a representative compound of the series (i.e., 2) have also been investigated at the theoretical level, performing Density Functional Theory (DFT)-based calculations. Time-dependent transient absorption spectra of 1-3 have also been recorded at room temperature. The results indicate that efficient photoinduced oxidative electron transfer takes place in the D-S-A systems at room temperature in fluid solution, for which rate constants (in the range 4 × 10(8)-2 × 10(10) s(-1)) depend on the driving force of the process and the spacer nature. In all the D-S-A systems, charge recombination is faster than photoinduced charge separation, in spite of the relatively large energy of the D(+)-S-A(-) charge-separated states (between 1.47 and 1.78 eV for the various species), which would suggest that the charge recombination occurs in the Marcus inverted region. Considerations based on superexchange mechanism suggest that the reason for the fast charge recombination is the presence of a virtual D-S(+)-A(-) state at low energy--because of the involvement of the easily oxidizable biphenylene spacer--which is beneficial for charge recombination via superexchange but unsuitable for photoinduced charge separation. To further support the above statement, we prepared a fourth D-S-A species, 4, analogous to 2 but with a (hardly oxidizable) single phenylene fragment serving as the spacer. For such a species, charge recombination (about 3 × 10(10) s(-1)) is slower than photoinduced charge separation (about 1 × 10(11) s(-1)), thereby confirming our suggestions. 相似文献
85.
86.
Deemed as poorly represented in nature, aurones have been often overlooked by researchers compared to other members of the flavonoid superfamily. However, over the past two decades, they have been reassessed by the scientific community, who are increasingly appreciating their ability to modulate several biological pathways. This review summarizes the recent literature on this class of compounds, which has been analyzed from both a chemical and a functional point of view. Original articles, reviews and editorials featured in Pubmed and Scifinder over the last twenty years have been taken into account to provide the readers with a view of the chemical strategies to obtain them, their functional properties, and their potential of technological use. The resulting comprehensive picture aims at raising the awareness of these natural derivatives as effective drug candidates, fostering the development of novel synthetic analogues. 相似文献
87.
Tarek Benameur Giulia Giacomucci Maria Antonietta Panaro Melania Ruggiero Teresa Trotta Vincenzo Monda Ilaria Pizzolorusso Dario Domenico Lofrumento Chiara Porro Giovanni Messina 《Molecules (Basel, Switzerland)》2022,27(1)
Curcumin, the dietary polyphenol isolated from Curcuma longa (turmeric), is commonly used as an herb and spice worldwide. Because of its bio-pharmacological effects curcumin is also called “spice of life”, in fact it is recognized that curcumin possesses important proprieties such as anti-oxidant, anti-inflammatory, anti-microbial, antiproliferative, anti-tumoral, and anti-aging. Neurodegenerative diseases such as Alzheimer’s Diseases, Parkinson’s Diseases, and Multiple Sclerosis are a group of diseases characterized by a progressive loss of brain structure and function due to neuronal death; at present there is no effective treatment to cure these diseases. The protective effect of curcumin against some neurodegenerative diseases has been proven by in vivo and in vitro studies. The current review highlights the latest findings on the neuroprotective effects of curcumin, its bioavailability, its mechanism of action and its possible application for the prevention or treatment of neurodegenerative disorders. 相似文献
88.
Claudio Frezza Alessandro Venditti Giorgia Matrone Ilaria Serafini Sebastiano Foddai Armandodoriano Bianco 《Natural product research》2018,32(13):1583-1589
In this work, the phytochemical analysis of Teucrium chamaedrys L. collected in Italy was reported. Eight compounds were isolated and identified by means of classical column chromatography and spectroscopic techniques, such as NMR and MS. In detail, these compounds were: verbascoside (1), forsythoside b (2), samioside (3), alyssonoside (4), harpagide (5), 8-O-acetyl-harpagide (6), cirsiliol (7) and β-arbutin (8). The presence of these compounds, in particular iridoids and phenyl-ethanoid glycosides, has a chemotaxonomic relevance and results to be in perfect accordance with the current botanical classification of the species. In addition, it provides a phytochemical rationale for the use of this particular plant in the ethno-pharmacological field. Conversely, it is worth of mention the absence of potentially toxic components, unlike to what observed in other species of the genus which can no longer be used for ethno-medicinal purposes. 相似文献
89.
First-principles [density-functional theory (DFT)] molecular-dynamic simulations of the Berry pseudorotation mechanism in SF4 were performed using the atom-centered density-matrix propagation method. The reaction was monitored by following the chemical shieldings of the fluorine atoms, computed on snapshots along the trajectories. In particular we compared the results obtained using a standard functional based on the generalized gradient approximation with those issuing from its hybrid Hartree-Fock-DFT counterpart using a number of basis sets. Our results show that both the basis set and the functional choice rule the quality of the molecular properties monitored as well as the trajectory over the potential-energy surface. 相似文献