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1.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
2.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
3.
Mart Abel 《Rendiconti del Circolo Matematico di Palermo》2005,54(3):409-429
It is shown, that the category ℰ
A
(X) ofA-bundles over a topological spaceX is an additive pseudo-Abelian category for each Waelbroeck algebraA.
This research was supported by Greek State Scholarship Foundation and Estonian Science Foundation grant 6205. 相似文献
4.
Ana Luísa Daniel‐da‐Silva João Carlos Moura Bordado José Miguel Martín‐Martínez 《Journal of Polymer Science.Polymer Physics》2007,45(22):3034-3045
The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007 相似文献
5.
K.B. Welter Q. Wu Y. You K. Abel D. McCreary S.M. Bajorek J.N. Reyes Jr 《International Journal of Multiphase Flow》2004,30(12):407-1484
This article describes a comprehensive literature review of liquid entrainment in horizontal pipes with vertical-up branches. Deficiencies in the available data and correlations were identified. The Air–water Test Loop for Advanced Thermal–hydraulic Studies (ATLATS) was constructed and entrainment onset and steady-state data were collected for a wide range of flow conditions. Using new insights gained from experimental testing, the authors developed a model for predicting the onset of entrainment and steady-state entrainment rate. Previously published correlations, along with the new model, are compared against all available data. The new model shows very good agreement with the onset data, but is not very good at predicting branch quality at high liquid flow rates. 相似文献
6.
V. V. Lozhkarev S. G. Garanin R. R. Gerke V. N. Ginzburg E. V. Katin A. V. Kirsanov G. A. Luchinin A. N. Mal’shakov M. A. Mart’yanov O. V. Palashov A. K. Poteomkin N. N. Rukavishnikov A. M. Sergeev S. A. Sukharev G. I. Freidman E. A. Khazanov A. V. Charukhchev A. A. Shaikin I. V. Yakovlev 《JETP Letters》2005,82(4):178-180
In experiments on the parametrical amplification of femtosecond pulses in wide-aperture DKDP crystals, a power of more than 100 TW has been reached, which is much higher than the record level achieved in such lasers. The energy efficiency obtained for the parametric amplifier is equal to 27%. The energy of a 72-fs pulse is equal to 10 J. 相似文献
7.
The atomic structure and magnetic and electric properties of the Cr0.5TiSe2-Cr0.5TiTe2 system of intercalated phases were studied in detail by gradually replacing selenium by tellurium. It was revealed that this replacement changes the crystalline structure from monoclinic in the initial compounds to hexagonal in the compounds containing various types of chalcogen atoms; this is accompanied by disordering of chromium atoms in the van der Waals gaps. The electrical resistance and magnetic characteristics vary nonmonotonically on replacement of selenium by tellurium, which is associated with a change in the degree of atomic disordering during the transition from Cr0.5TiSe2 to Cr0.5TiTe2. 相似文献
8.
In this paper, three new direct Mutually Orthogonal Latin Squares (MOLS) constructions are presented for 7 MOLS(24), 7 MOLS(75) and 8 MOLS(36); then using recursive methods, several new constructions for 7 and 8 MOLS are obtained. These reduce the largest value for which 7 MOLS are unknown from 780 to 570, and the largest odd value for which 8 MOLS are unknown from 1935 to 419. © 2003 Wiley Periodicals, Inc. 相似文献
9.
Surface free energy of a solid surface gives a direct measure of intermolecular interactions at interfaces and has a strong influence on adsorption and adhesion behaviour. However few data are available for the surface free energies of electroless Ni–P based composition coatings. In this paper, the electroless Ni–P, Ni–P-surfactant, Ni–Cu–P, Ni–P–PTFE and Ni–Cu–P–PTFE composite coatings were prepared under various coating conditions. The chemical compositions, surface morphology and thickness of the coatings were measured using an energy dispersive X-ray microanalysis (EDX), a scanning electron microscope (SEM) and a digital micrometer respectively. The contact angles of water, diiodomethane and ethylene glycol on the coatings were measured automatically using dataphysics OCA-20 contact angle analyser. The surface free energy of the coatings and their components (e.g. dispersion, polar or acid/base portions) were calculated using various methods. The experimental results showed that the incorporation of surfactant or PTFE particles into Ni–P matrixes has a significant influence on the surface free energy of the coatings, while the incorporation of copper into Ni–P matrixes has no significant influence on the surface free energy of the coatings. 相似文献
10.
M. Abel 《Journal of Mathematical Sciences》2007,140(3):346-353
Bounded representations of bornological algebras are considered. The left and right bornological radicals in bornological
algebras are introduced. It is shown that the left (right) bornological radical of a bornological algebra A is equal to the
intersection of all bornologically closed maximal regular left (respectively, right) ideals of A, and both these radicals
of A and the Jacobson radical of A coincide if A is an advertive and simplicial bornological algebra (in particular, a bornological
Q-algebra). Bibliography: 16 titles.
Published in Zapiski Nauchnykh Seminarov POMI, Vol. 326, 2005, pp. 9–22. 相似文献