全文获取类型
收费全文 | 189篇 |
免费 | 9篇 |
国内免费 | 4篇 |
专业分类
化学 | 146篇 |
数学 | 26篇 |
物理学 | 30篇 |
出版年
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 7篇 |
2019年 | 4篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 5篇 |
2014年 | 5篇 |
2013年 | 12篇 |
2012年 | 12篇 |
2011年 | 13篇 |
2010年 | 3篇 |
2009年 | 1篇 |
2008年 | 8篇 |
2007年 | 15篇 |
2006年 | 10篇 |
2005年 | 16篇 |
2004年 | 5篇 |
2003年 | 6篇 |
2002年 | 7篇 |
2001年 | 5篇 |
2000年 | 12篇 |
1999年 | 3篇 |
1997年 | 5篇 |
1996年 | 11篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1978年 | 1篇 |
排序方式: 共有202条查询结果,搜索用时 15 毫秒
41.
Mello R Martínez-Ferrer J Asensio G Gonzalez-Núñez ME 《The Journal of organic chemistry》2007,72(24):9376-9378
1,1,1-Trifluoroacetone (2a) reacts as a hydride-acceptor in the Oppenauer oxidation of secondary alcohols (1) in the presence of diethylethoxyaluminum. The oxidant allows for selective oxidation of secondary alcohols in the presence of primary alcohols. 相似文献
42.
Corzana F Busto JH Jiménez-Osés G Asensio JL Jiménez-Barbero J Peregrina JM Avenoza A 《Journal of the American Chemical Society》2006,128(45):14640-14648
The structural features of the mucin-type simplest model, namely, the glycopeptide alpha-O-GalNAc-l-Ser diamide, have been investigated by combining NMR spectroscopy, molecular dynamics simulations, and DFT calculations. In contrast to previous reports, the study reveals that intramolecular hydrogen bonds between sugar and peptide residues are very weak and, as a consequence, not strong enough to maintain the well-defined conformation of this type of molecule. In fact, the observed conformation of this model glycopeptide can be satisfactorily explained by the presence of water pockets/bridges between the sugar and the peptide moieties. Additionally, DFT calculations reveal that not only the bridging water molecules but also the surrounding water molecules in the first hydration shell are essential to keep the existing conformation. 相似文献
43.
Sandra Díaz Asensio Gonzlez Sandra Gonzlez de Riancho Ana Rodríguez 《Journal of organometallic chemistry》2000,610(1-2)
S-Trityl-
-cysteine and S-tritylglutathione have been converted to 1,3,2-oxazaborolidine-5-ones by reaction with B-methoxydialkylborane derivatives. The synthesis of dicyclohexyl[S-trityl-(R)-cysteinato-O,N]boron (2), diisopinocampheyl[S-trityl-(R)-cysteinato-O,N]boron (3) and 9-borabicyclo[3.3.1]non-9-yl[S-tritylglutathionato-O,N]boron (5), dicyclohexyl[S-tritylglutathionato-O,N]boron (6) and diisopinocampheyl[S-tritylglutathionato-O,N]boron (7) from S-trityl-
-cysteine and S-tritylglutathione, respectively, with potential application in boron neutron capture therapy is reported. The structure of 9-borabicyclo[3.3.1]non-9-yl[S-trityl-(R)-cysteinato-O,N]boron 1 has been determined by X-ray diffraction. 相似文献
44.
45.
S.L. Molodtsov Th. Gantz C. Laubschat A.G. Viatkine J. Avila C. Casado M.C. Asensio 《Zeitschrift für Physik B Condensed Matter》1997,100(3):381-385
A graphite-intercalation compound (GIC) of La was prepared by a thermally induced surface reaction of a metallic La film on a graphite (0001) substrate. The LEED pattern shows a characteristic (√3 × √3) R30° reconstruction pointing to the formation of LaC6. Angleresolved photoemission combined with Fermi-surfaces mapping reveals a strongly anisotropic electronic bandstructure of La-GIC. The unfolded π-symmetry graphitederived bands in the La intercalation compound may be described in good approximation within a simple rigidband model by charge transfer from La to graphite. Despite the presence of filled La-5d states large photoemission intensities close to the Fermi level around the K-points of the nonreconstructed Brillouin zone are related to carbon-derived pπ*-bands, which become partly occupied in the GIC. 相似文献
46.
N.L. Saini J. Avila M.C. Asensio S. Tajima G.D. Gu N. Koshizuka A. Valletta A. Lanzara A. Bianconi 《Zeitschrift für Physik B Condensed Matter》1997,104(4):703-706
A complete Fermi surface in the normal state of superconducting Bi2Sr2CaCu2O8+δ at the optimum doping (T c = 91K) has been measured by angle scanning photoemission spectroscopy using synchrotron radiation. The Fermi surface reveals broken segments and hot spots of high photointensity along lines of k y = n:0:23Å?1 in the (π; π) direction. The pseudogap observed at (π,0) in underdoped materials is one of this missing segments. The results indicate the presence of characteristic subbands of a superlattice of quantum stripes. This is formed by an ordered array of ~ 14Å large stripes. 相似文献
47.
José L. Gó mez Pardo Pedro A. Guil Asensio 《Proceedings of the American Mathematical Society》1996,124(8):2301-2309
Let be a ring, its injective envelope, and the Jacobson radical of . It is shown that if every finitely generated submodule of embeds in a finitely presented module of projective dimension , then every finitley generated right -module is canonically isomorphic to . This fact, together with a well-known theorem of Osofsky, allows us to prove that if, moreover, is completely pure-injective (a property that holds, for example, when the right pure global dimension of is and hence when is a countable ring), then is semiperfect and is finite-dimensional. We obtain several applications and a characterization of right hereditary right noetherian rings.
48.
Cecilia Sáenz Barrio Elena Romero Melgosa Jesús Sanz Asensio Javier Galbán Bernal 《Mikrochimica acta》1996,122(3-4):267-277
Three different extraction procedures for eight pesticides (chlorfenvinphos, diazinon, ethyl parathion, ethiofencarb, fenitrothion, malathion, metalaxyl, pirimicarb) in water samples are compared. The extraction procedures are: liquid-liquid extraction (LLE), solid-phase extraction (SPE) and microextraction (ME). For each procedure the most suitable conditions were obtained experimentally, with special remarks on ME, in which the effects of different mixtures of Kaltron with other solvents were tested. A preconcentration factor (PF) was used to rank the methods; the best results were observed for ME, (PF 15–45, whereas PF < 10 for SPE, and PF 13 for LLE). In all cases, the determination was performed by gas chromatography, using a nitrogen phosphorus detector and the internal standard method (methyl parathion) as the quantification procedure. 相似文献
49.
Pisano L Farriol M Asensio X Gallardo I González-Lafont A Lluch JM Marquet J 《Journal of the American Chemical Society》2002,124(17):4708-4715
Fragmentation reactions of radical anions (mesolytic cleavages) of cyanobenzyl alkyl ethers (intramolecular dissociative electron transfer, heterolytic cleavages) have been studied electrochemically. The intrinsic barriers for the processes have been established from the experimental thermodynamic and kinetic parameters. These values are more than 3 kcal/mol lower as an average than the related homolytic mesolytic fragmentations of radical anions of 4-cyanophenyl ethers. In the particular case of isomers 4-cyanobenzyl phenyl ether and 4-cyanophenyl benzyl ether, the difference in intrinsic barriers amounts to 5.5 kcal/mol, and this produces an energetic crossing where the thermodynamically more favorable process (homolytic) is the kinetically slower one. The fundamental reasons for this behavior have been established by means of theoretical calculations within the density functional theory framework, showing that, in this case, the factors that determine the kinetics are clearly different (mainly present in the transition state) from those that determine the thermodynamics and they are not related to the regioconservation of the spin density ("spin regioconservation principle"). Our theoretical results reproduce quite well the experimental energetic difference of barriers and demonstrate the main structural origin of the difference. 相似文献
50.
Gorb L Asensio A Tuñón I Ruiz-López MF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6743-6753
The neutral hydrolysis of formamide in water is a suitable reference to quantify the efficiency of proteolytic enzymes. However, experimental data for this reaction has only very recently been obtained and the kinetic constant determined experimentally is significantly higher than that predicted by previous theoretical estimations. In this work, we have investigated in detail the possible mechanisms of this reaction. Several solvent models have been considered that represent a considerable improvement on those used in previous studies. Density functional and ab initio calculations have been carried out on a system which explicitly includes the first solvation shell of the formamide molecule. Its interaction with the bulk has been treated with the aid of a dielectric continuum model. Molecular dynamics simulations at the combined density functional/molecular mechanics level have been carried out in parallel to better understand the structure of the reaction intermediates in aqueous solution. Overall, the most favored mechanism predicted by our study involves two reaction steps. In the first step, the carbonyl group of the formamide molecule is hydrated to form a diol intermediate. The corresponding transition structure involves two water molecules. From this intermediate, a water-assisted proton transfer occurs from one of the hydroxy groups to the amino group. This reaction step may lead either to the formation of a new reaction intermediate with a marked zwitterionic character or to dissociation of the system into ammonia and formic acid. The zwitterionic intermediate dissociates quite easily but its lifetime is not negligible and it could play a role in the hydrolysis of substituted amides or peptides. The predicted pseudo-first-order kinetic constant for the rate-limiting step (the first step) of the hydrolysis reaction at 25 degrees C (3.9x10(-10) s(-1)) is in excellent agreement with experimental data (1.1x10(-10) s(-1)). 相似文献