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41.
The relative stability of the radicals that can be produced from amine–boranes and phosphine–boranes is investigated at the G3‐RAD level of theory. Aminyl ([RNH].:BH3) and phosphinyl ([RPH].:BH3) radicals are systematically more stable than the boryl analogues, [RNH2]:BH2. and [RPH2]:BH2.. Despite similar stability trends for [RNH].:BH3 and [RPH].:BH3 radicals with respect to boryl radicals, there are significant dissimilarities between amine– and phosphine–boranes. The homolytic bond dissociation energy of the N?H bond decreases upon association of the amines with BH3, whereas that of the P?H bond for phosphines increases. The stabilization of the free amine is much smaller than that of the corresponding aminyl radical, whereas for phosphines this is the other way around. The homolytic bond dissociation energy of the B?H bond of borane decreases upon complexation with both amines and phosphines. 相似文献
42.
Dr. M. Merced Montero‐Campillo Prof. Manuel Yáñez Dr. Al Mokhtar Lamsabhi Prof. Otilia Mó 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5309-5316
The most stable complexes between squaric acid and its sulfur‐ and selenium‐containing analogues (C4X4H2; X=O, S, Se) with BeY2 (Y=H, F) were studied by means of the Gaussian 04 (G4) composite ab initio theory. Squaric acid derivatives are predicted to be very strong acids in the gas phase; their acidity increases with the size of the chalcogen, with C4Se4H2 being the strongest acid of the series and stronger than sulfuric acid. The relative stability of the C4X4H2 ? BeY2 (X=O, S, Se; Y=H, F) complexes changes with the nature of the chalcogen atom; but more importantly, the formation of the C4X4H2 ? BeF2 complexes results in a substantial acidity enhancement of the squaric moiety owing to the dramatic electron‐density redistribution undergone by the system when the beryllium bond is formed. The most significant consequence of this acidity enhancement is that when BeF2 is replaced by BeH2, a spontaneous exergonic loss of H2 is observed regardless of the nature of the chalcogen atom. This is another clear piece of evidence of the important role that closed‐shell interactions play in the modulation of physicochemical properties of the Lewis acid and/or the Lewis base. 相似文献
43.
TiO2 and Pt doped TiO2 thin films were grown by pulsed laser deposition on 〈0 0 1〉 SiO2 substrates. The doped films were compared with undoped ones deposited in similar experimental conditions. An UV KrF* (λ = 248 nm, τFWHM ≅ 20 ns, ν = 2 Hz) excimer laser was used for the irradiation of the TiO2 or Pt doped TiO2 targets. The substrate temperatures were fixed during the growth of the thin films at values within the 300-500 °C range. The films’ surface morphology was investigated by atomic force microscopy and their crystalline quality by X-ray diffractometry. The corresponding transmission spectra were recorded with the aid of a double beam spectrophotometer in the spectral range of 400-1100 nm. No contaminants or Pt segregation were detected in the synthesized anatase phase TiO2 thin films composition. Titania crystallites growth inhibition was observed with the increase of the dopant concentration. The average optical transmittance in the visible-infrared spectral range of the films is higher than 85%, which makes them suitable for sensor applications. 相似文献
44.
We have performedab initio calculations to determine the structure and charge distribution of some alkynoyl cations and their parent alkynoyl fluorides. We have used Mulliken population analysis and a new technique developed by Yáñez, Stewart and Pople. Our results indicate that the mesomeric form O+C–CC–R is one of the most important contributors to the structure of these cations, in agreement with experimental conclusions. We have also found that the participation of mesomeric form O=C=C=C+
-R is not negligible and increases with -substitution. In the 3-phenylpropynoyl cation substantial delocalization of charge into the phenyl group occurs. Calculations from YSP population analysis are in good agreement with experimental evidence. 相似文献
45.
Lamsabhi AM Mó O Yáñez M Guillemin JC Haldys V Tortajada J Salpin JY 《Journal of mass spectrometry : JMS》2008,43(3):317-326
The gas-phase reactions between Ni(+) ((2)D(5/2)) and aminoacetonitrile, a molecule of prebiological interest as possible precursor of glycine, have been investigated by means of mass spectrometry techniques. The mass-analyzed ion kinetic energy (MIKE) spectrum reveals that the adduct ions [NC--CH(2)--NH(2), Ni(+)] spontaneously decompose by loosing HCN, H(2), and H(2)CNH, the loss of hydrogen cyanide being clearly dominant. The structures and bonding characteristics of the aminoacetonitrile-Ni(+) complexes as well as the different stationary points of the corresponding potential energy surface (PES) have been theoretically studied by density functional theory (DFT) calculations carried out at B3LYP/6-311G(d,p) level. A cyclic intermediate, in which Ni(+) is bisligated to the cyano and the amino group, plays an important role in the unimolecular reactivity of these ions, because it is the precursor for the observed losses of HCN and H(2)CNH. In all mechanisms associated with the loss of H(2), the metal acts as hydrogen carrier favoring the formation of the H(2) molecule. The estimated bond dissociation energy of aminoacetonitrile-Ni(+) complexes (291 kJ mol(-1)) is larger than those measured for other nitrogen bases such as pyridine or pyrimidine and only slightly smaller than that of adenine. 相似文献
46.
Medina A Claessens CG Rahman GM Lamsabhi AM Mó O Yáñez M Guldi DM Torres T 《Chemical communications (Cambridge, England)》2008,(15):1759-1761
We have designed, synthesized and probed a dodecafluoro-subphthalocyaninato boron(III) unit, which bears a triphenylamine moiety in its axial position, as a novel electron donor-acceptor system. 相似文献
47.
48.
Andreea Iosageanu Daniela Ilie Oana Craciunescu Ana-Maria Seciu-Grama Anca Oancea Otilia Zarnescu Ionut Moraru Florin Oancea 《Molecules (Basel, Switzerland)》2021,26(9)
In the present study, we evaluated for the first time the photoprotective effect of fish bone bioactive peptides (FBBP) preparation isolated from silver carp (Hypophthalmichthys molitrix) discarded tissue using in vitro experimental models of skin cells exposed to ultraviolet B (UVB) irradiation and stressing agents. FBBP preparation was obtained by papain treatment of minced bones and centrifugal ultrafiltration, and the molecular weight (MW) distribution was characterized by size exclusion and reversed-phase high performance liquid chromatography (RP-HPLC). In vitro assessment of the effect of FBBP pretreatment in UVB-irradiated L929 fibroblasts and HaCaT keratinocytes revealed their cytoprotective activity. Their capacity to efficiently reduce reactive oxygen species (ROS) production and lipid peroxidation varied in a dose-dependent manner, and it was greater in fibroblasts. A decrease of proinflammatory cytokines secretion, in particular of tumor necrosis factor alpha (TNF-α), was found after FBBP pretreatment of THP-1-derived inflamed macrophages. Melanin production and tyrosinase activity investigated in UVB-irradiated Mel-Juso cells were lowered in direct relation to FBBP concentrations. FBBP fractions with high radical scavenging activity were separated by ion exchange chromatography, and two collagenic sequences were identified. All these results offer new scientific data on aquaculture fish bone-derived peptides confirming their ability to control the antioxidant, anti-inflammatory and pigmentation processes developed during UV irradiation of skin cells and recommend their use as valuable natural ingredients of photoprotective cosmeceutical products. 相似文献
49.
The prototropic tautomerism of 2-, 4-selenouracil and 2,4-diselenouracil has been studied using density functional theory (DFT) methods, at the B3LYP/6-311 + G(3df,2p)//B3LYP/6-31G(d,p) level. The relative stability order of selenouracil tautomers does not resemble that of uracil tautomers, but it is similar to that of thiouracils, even though the energy gaps between the different tautomers of selenouracils are smaller than for thiouracils. The tautomerism activation barriers are high enough as to conclude that only the oxo-selenone or the diselenone structures should be found in the gas phase. The specific interaction with one water molecule reduces these barriers by a half, but still the oxo-selenone form is always the most stable tautomer. The addition of a second water molecule has a relatively small effect, as well as bulk effects, evaluated by means of a continuum-polarized model. For isolated 2- and 4-selenouracils, the more favorable tautomerization process corresponds to a hydrogen transfer towards the selenium atom, the activation barriers for transfer towards the oxygen atom being much higher. This situation changes when specific and bulk effects are included, and the latter process becomes the more favorable one. For 2,4-diselenouracil the more favorable tautomerization, in the gas phase, corresponds to the H shift from N1 to the Se atom at C2, while solvation effects favor the transfer from N3 to the Se atom at C4. 相似文献
50.
Ane Eizaguirre Al Mokhtar Lamsabhi Otilia M�� Manuel Y��?ez 《Theoretical chemistry accounts》2011,128(4-6):457-464
The structure and relative stability of the complexes between uracil dimers and Ca2+, as well as the proton transfer (PT) processes within these dimers, have been investigated by the density functional theory methods. Although in uracil dimers PT occurs as an almost synchronous double PT processes that connect the diketo dimer with a keto-enol dimer, the process within the most stable (uracil)2Ca2+ complexes is much more complicated, and the product of the reaction looks like the result of an intramolecular PT from one of the NH groups of one monomer to one of the carbonyl groups of the same monomer. An analysis of the force profile along the reaction coordinate shows that the intimate mechanism implies three elementary steps, two intermolecular PTs, and an in-plane displacement of one monomer with respect to the other. The result of this so-called assisted intramolecular proton transfer is the formation of a dimer in which only one monomer is a keto-enol derivative, the other monomer being apparently unchanged, although it suffers significant structural rearrangements along the reaction coordinate. Quite importantly, this dimer is significantly stabilized upon Ca2+ association; therefore, while the most stable uracil dimers correspond systematically to associations involving only the diketo forms, in (uracil)2Ca2+ complexes the most stable structures correspond to those in which one of the monomers is a keto-enol uracil isomer. 相似文献