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41.
Novák V Olejník K Wunderlich J Cukr M Výborný K Rushforth AW Edmonds KW Campion RP Gallagher BL Sinova J Jungwirth T 《Physical review letters》2008,101(7):077201
We observe a singularity in the temperature derivative drho/dT of resistivity at the Curie point of high-quality (Ga,Mn)As ferromagnetic semiconductors with Tc's ranging from approximately 80 to 185 K. The character of the anomaly is sharply distinct from the critical contribution to transport in conventional dense-moment magnetic semiconductors and is reminiscent of the drho/dT singularity in transition metal ferromagnets. Within the critical region accessible in our experiments, the temperature dependence on the ferromagnetic side can be explained by dominant scattering from uncorrelated spin fluctuations. The singular behavior of drho/dT on the paramagnetic side points to the important role of short-range correlated spin fluctuations. 相似文献
42.
Lucía Aristizabal Mariana Ángel Camila Orozco Pablo Ruiz Jairo Quijano Rafael Notario 《Structural chemistry》2018,29(3):897-907
In spite of the several experimental and computational studies on the thermal decomposition of allyl ethers and allyl sulfides, there are still disagreements on aspects of the reaction mechanism, such as the true nature of the transition states and the grade of synchronicity of the reactions. This work presents a computational study of the gas-phase thermolysis reaction of allyl ethers and allyl sulfides substituted at α-carbon, at the M05-2X/6-31+G(d,p) level of theory and a temperature range from 586.15 to 673.15 K. The substituent groups were methyl, ethyl, n-propyl, i-propyl, allyl, benzyl and acetonyl. It was found that the sulfides react faster than the homologous ethers and that the substituent groups with the capacity of delocalize charge increase the reaction rate. Through natural bond orbital calculations, the transition states were characterized. The synchronicities and atomic charges of the studied reactions were determined. A computational study at the G3 level of theory on the thermochemistry of allyl ethers and sulfides was also carried out. 相似文献
43.
Jairo Villalona Peyton M. Higgins Prof. Andrew R. Buller 《Angewandte Chemie (International ed. in English)》2023,62(43):e202311189
Non-canonical amino acids (ncAAs) are useful synthons for the development of new medicines, materials, and probes for bioactivity. Recently, enzyme engineering has been leveraged to produce a suite of highly active enzymes for the synthesis of β-substituted amino acids. However, there are few examples of biocatalytic N-substitution reactions to make α,β-diamino acids. In this study, we used directed evolution to engineer the β-subunit of tryptophan synthase, TrpB, for improved activity with diverse amine nucleophiles. Mechanistic analysis shows that high yields are hindered by product re-entry into the catalytic cycle and subsequent decomposition. Additional equivalents of l -serine can inhibit product reentry through kinetic competition, facilitating preparative scale synthesis. We show β-substitution with a dozen aryl amine nucleophiles, including demonstration on a gram scale. These transformations yield an underexplored class of amino acids that can serve as unique building blocks for chemical biology and medicinal chemistry. 相似文献
44.
Design and performance of BOREAS,the beamline for resonant X‐ray absorption and scattering experiments at the ALBA synchrotron light source 下载免费PDF全文
Alessandro Barla Josep Nicolás Daniele Cocco Secundino Manuel Valvidares Javier Herrero-Martín Pierluigi Gargiani Jairo Moldes Claude Ruget Eric Pellegrin Salvador Ferrer 《Journal of synchrotron radiation》2016,23(6):1507-1517
The optical design of the BOREAS beamline operating at the ALBA synchrotron radiation facility is described. BOREAS is dedicated to resonant X‐ray absorption and scattering experiments using soft X‐rays, in an unusually extended photon energy range from 80 to above 4000 eV, and with full polarization control. Its optical scheme includes a fixed‐included‐angle, variable‐line‐spacing grating monochromator and a pair of refocusing mirrors, equipped with benders, in a Kirkpatrick–Baez arrangement. It is equipped with two end‐stations, one for X‐ray magnetic circular dichroism and the other for resonant magnetic scattering. The commissioning results show that the expected beamline performance is achieved both in terms of energy resolution and of photon flux at the sample position. 相似文献
45.
Pablo Ruiz Manuela Castro Steffanía López Ángela Zapata Jairo Quijano Rafael Notario 《Structural chemistry》2016,27(5):1373-1381
In this work, a theoretical study at the MP2/6-31G(d) level of the thermal decomposition retro-ene reaction of 2-methylbutyraldehyde was carried out at a pressure of 1.5 atm. and temperatures ranging from 1110 to 1190 K. The progress of the reaction has been followed by means of the Wiberg bond indices which in turn allowed the calculation of the reaction synchronicity. Transition state theory was used to calculate the theoretical rate constant at 1150 K which was compared with the previously reported experimental value at the same conditions. We found that both values show a close agreement. The obtained computational evidence allowed us to support a reaction mechanism which proceeds in two steps: the first one with the formation of ethylene and 1-propenol via a six-membered cyclic transition state and the second one involving keto-enol equilibrium of 1-propenol to propionaldehyde via a four-membered cyclic transition state. It was found that the reaction is a highly synchronous and concerted process. The results obtained for the thermolysis of 2-methylbutyraldehyde were compared with those obtained for the thermolysis of 2-pentanone. A comparison of our results with those reported for their corresponding β-hydroxy counterparts, 3-hydroxy-2-methylpropionaldehyde and 4-hydroxy-2-butanone has also been made. A study of the thermochemistry of the compounds involved in the reactions studied has been carried out at the G3 level. 相似文献
46.
A series of 2-(pyrazolo[1,5-a]pyrimidin-5-yl)benzoic acids 5 has been prepared by a novel protocol that uses the fusion method between 5-amino-1H-pyrazoles 4 and 3-(3-oxo-2-benzofuran-1(3H)-ylidene)pentane-2,4-dione 3. The use of this novel protocol renders good to excellent yields along with short reaction times. In addition, this solvent-free cyclocondensation proceeds in a regiospecific fashion by intramolecular ring opening of the furane ring in a Michael-type reaction. 相似文献
47.
Jairo Quiroga Mario Alvarado Braulio Insuasty Manuel Nogueras Adolfo Snchez M. Dolores Lpez 《Journal of heterocyclic chemistry》1999,36(1):113-115
The title compounds 4 and 5 have been prepared in one-step reaction from 6-amino-4-pyrimidinones 1 , the corresponding 4-substituted benzaldehyde 2 and ethyl cyanoacetate 3 in very good yields. The structure of the final compounds was determined on the basis of nmr measurements, especially by 1H, 1H-, 1H,13C COSY, and DEPT. 相似文献
48.
Jairo Quiroga Mario Alvarado Braulio Insuasty Rodolfo Moreno Enrique Ravia Isabel Estevez Regina H. De Almeida S. 《Journal of heterocyclic chemistry》1999,36(5):1311-1316
This paper describes the synthesis of a new series of 6-amino-4-aryl-5-cyanopyrazolo[3,4-b]pyridines 4 and 4-aryl-5-cyano-6H-pyrazolo[3,4-b]pyridin-6-ones 5 from the reaction of 5-amino-3-methyl-1-phenylpyrazole 1 with arylidene derivatives of malonodinitrile 2 and ethyl cyanoacetate 3 . The structure of the final compounds was determined on the basis of nmr measurements, especially by 1H, 1H-, 1H, 13C-COSY, DEPT and X-ray diffraction. 相似文献
49.
John N. Low Justo Cobo Manuel Nogueras Adolfo Snchez Jairo Quiroga Carlos Cisneros 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(1):o38-o39
The supramolecular structure of the title compound, C18H17ClN2O2, is determined by the intersection of two chains formed by N—H⋯O and N—H⋯N hydrogen bonds, forming a two‐dimensional sheet. 相似文献
50.
Paola Acosta Braulio Insuasty Rodrigo Abonia Margarita Gutierrez Jairo Quiroga 《Molecular diversity》2017,21(4):943-955
An efficient route for the synthesis of novel 7-aryl and 7-spiropyrazolo[4\(^{\prime }\),3\(^{\prime }\):5,6]pyrido[2,3-d]pyrimidine derivatives is described. These compounds were obtained by a cyclocondensation reaction between pyrazolopyridinediamines 4 and aldehydes 5 or cyclic ketones 6 in the presence of acetic acid as catalyst. This procedure provides the desired compounds in good yields under a simple two-step methodology. The obtained compounds were evaluated as AChE inhibitors and showed weak AChe inhibition with \(\hbox {IC}_{50} = 115{-}470 \, \upmu \hbox {M}\). 相似文献