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831.
The short-time photodynamics (1 ps) of formamide in its low-lying singlet excited n(O)-pi(*) and pi-pi(*) states have been investigated by the direct trajectory surface-hopping method based on multiconfigurational ab initio calculations. The simulations showed that in both states, the primary deactivation process is C-N bond dissociation. In the ground state, the energy is transferred to (a) translational motion of the HCO and NH(2) fragments, (b) additional C-H dissociation from the vibrationally hot HCO fragment, or (c) formation of NH(3) and CO. In addition to the C-N dissociation pathway, C-O bond fission is found to be an additional primary deactivation path in the pi-pi(*) dynamics. From fractional occupations of trajectories, lifetimes of formamide were estimated: tau(S(1))=441 fs and tau(S(2))=66 fs. 相似文献
832.
HEMA, the copolymer of 2-hydroxyethyl methacrylate and ethylene dimethacrylate, has proven to be a suitable stationary phase for the size-exclusion chromatographic (SEC) characterization of humic substances in a wide pH range. The SEC measurements were performed typically with alkaline borate-based mobile phase: 0.025 mol/l Na2B4O7, 0.025 mol/l NaCl, 0.001 mol/l Na4P2O7, pH 9.1. After calibrating with globular protein standards, apparent molecular weights of typical peat- and coal-derived humic acids were estimated. The average molecular weights determined with the aid of the HEMA column were quite comparable with the values obtained previously by the method of low-pressure gel-permeation chromatography on the Sephadex column. 相似文献
833.
Dijana Pešić Ivana Ozimec Landek Ana Čikoš Biserka Metelko Vesna Gabelica Barbara Stanić Mladen Merćep Milan Mesić 《Journal of heterocyclic chemistry》2007,44(5):1129-1133
834.
Pace A Pibiri I Piccionello AP Buscemi S Vivona N Barone G 《The Journal of organic chemistry》2007,72(20):7656-7666
The experimental investigation of the base-catalyzed rearrangements of 3-acylamino-1,2,4-oxadiazoles evidenced a new reaction pathway which competes with the well-known ring-degenerate Boulton-Katritzky rearrangement (BKR). The new reaction consists of a one-atom side-chain rearrangement that is base-activated, occurs at a higher temperature than the BKR, and irreversibly leads to the corresponding 2-acylamino-1,3,4-oxadiazoles. An extensive DFT study is reported to elucidate the proposed reaction mechanism and to compare the three possible inherent routes: (i) the reversible three-atom side-chain ring-degenerate BKR, (ii) the ring contraction-ring expansion route (RCRE), and (iii) the one-atom side-chain rearrangement. The results of the computational investigation point out that the latter route is kinetically preferred over the RCRE and can be considered as the ground-state analogue of a previously proposed C(3)-N(2) migration-nucleophilic attack-cyclization (MNAC) photochemically activated pathway. The MNAC consists of the formation of a diazirine intermediate, involving the exocyclic nitrogen, that eventually evolves into a carbodiimide intermediate (migration); the latter undergoes a single intramolecular nucleophilic attack-cyclization step leading to the final 2-acylamino-1,3,4-oxadiazole. 相似文献
835.
Ivana Slamić 《Journal of Fourier Analysis and Applications》2014,20(4):766-783
Various properties of the system \({\mathcal {B}}_{\psi }\) of integer translates of a square integrable function \(\psi \in L^2({\mathbb {R}})\) can be completely described in terms of the periodization function \(p_{\psi }(\xi )=\sum _{k\in {\mathbb {Z}}}|\widehat{\psi }(\xi +k)|^2\) . In this paper, we consider the problem of \(\ell ^p\) -linear independence, where \(p>2\) . The results we present include the method of construction for one type of counterexamples to several naturally taken conjectures, a new sufficient condition for \(\ell ^p\) -linear independence and a characterization theorem having an additional assumption on \({\mathcal {B}}_{\psi }\) . In the latter, we obtain the characterization in terms of the sets of multiplicity of Lebesgue measure zero. 相似文献
836.
837.
Vector potentials are known to have a direct significance to quantum particles moving in the magnetic field. This is called
the Aharonov–Bohm effect and is known as one of the most remarkable quantum phenomena. Here we study this quantum effect through
the resonance problem. We consider the scattering system consisting of two scalar potentials and one magnetic field with supports
at large separation in two dimensions. The system has trajectories oscillating between these supports. We give a sharp lower
bound on the resonance widths as the distances between the three supports go to infinity. The bound is described in terms
of the backward amplitude for scattering by each of the scalar potentials and by the magnetic field, and it also depends heavily
on the magnetic flux of the field. 相似文献
838.
Aleksandra Č. Mišan Neda M. Mimica-Dukić Anamarija I. Mandić Marijana B. Sakač Ivan Lj. Milovanović Ivana J. Sedej 《Central European Journal of Chemistry》2011,9(1):133-142
Rapid Resolution HPLC/DAD method, on a 1.8 μm, 4.6×50 mm column, was developed to enable a rapid separation of a mixture of
17 compounds, which consisted of hydroxybenzoic acids, hydroxycinnamic acids, flavones, flavonols, flavanone, flavonol-glycoside
and antraquinone, in a single run, within 22 minutes. The developed method is precise, accurate and sensitive enough for simultaneous
quantitative evaluation of major compounds in crude and hydrolyzed extracts of parsley, buckthorn, mint, caraway and birch.
In order to overcome the inability to quantify all the phenolic compounds present in the samples caused by lack of external
standards, HPLC approaches for the total phenolic content estimation based on sum of all integrated peak areas were made.
These results were compared with the total phenolic content determined by Folin-Cioacalteu method. Although the correlation
between the series of data was not significant (p<0.05), the difference between the results of total phenolic content obtained spectrophotometrically and by HPLC was not high
in the case of parsley, buckthorn and mint extract. Regarding the obtained results, the HPLC approach could serve as an excellent
tool for total phenolic content estimation, without the need for complete identification of the individual compounds.
相似文献
839.
1-D and 2-D comprehensive (LC×LC) liquid chromatography methods have been developed and compared for the separation and quantification of flavanones in various Citrus juices. 1-D analyses were carried out on a superficially porous C18 column, whereas the 2-D LC approach was composed of a polyethylene glycol silica narrow-bore column packed with totally porous particles in the first dimension (D1) and a superficially porous C18 column in the second dimension (D2). Low-selectivity correlations were ensured by the complementary separation mechanisms offered by the D1 and D2 columns. Quantification was carried out both manually and by means of a software capable of detecting and quantifying each peak from the 2-D plot. Limit of detection (LOD) values as low as 0.023 μg/mL were obtained for hesperidin used as reference material for 1-D LC analyses, whereas values as high as 0.432 μg/mL were obtained by comprehensive LC. This discrepancy can be traced back to the minor sensitivity experienced in comprehensive LC due to both sample dilution in D1 and the high flow rates employed in D2. On the other hand, the separation capabilities of the LC×LC approach allowed to reduce the interferences coming from the matrix and to achieve the separation of some critical pairs, e.g. hesperidin/naringin difficult to accomplish in 1-D LC. 相似文献
840.
Two flavonoids, rutin and hesperidin, were investigated in vitro for anticoagulant activity through coagulation tests: activated partial thromboplastin time (aPTT), prothrombin time (PT) and thrombin time (TT). Only an ethanolic solution of rutin at the concentration of 830 μM prolonged aPTT, while TT and PT were unaffected. In order to evaluate whether the prolongation of aPTT was due to the decrease of coagulation factors, the experiment with deficient plasma was performed, showing the effects on factors VIII and IX. Since pharmacological activity of flavonoids is believed to increase when they are coordinated with metal ions, complexes of these flavonoids with Al(III) and Cu(II) ions were also tested. The results showed that complexes significantly prolonged aPTT and had no effects on PT and TT. Assay with deficient plasma (plasma having the investigated factor at less then 1%) revealed that complexes could bind to the coagulation factors, what may lead to a non-specific inhibition and aPTT prolongation. An effort was made to correlate stability of complexes with their anticoagulant properties. 相似文献