全文获取类型
收费全文 | 478篇 |
免费 | 14篇 |
国内免费 | 1篇 |
专业分类
化学 | 279篇 |
晶体学 | 2篇 |
力学 | 1篇 |
数学 | 62篇 |
物理学 | 149篇 |
出版年
2022年 | 5篇 |
2021年 | 11篇 |
2020年 | 5篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 9篇 |
2016年 | 10篇 |
2015年 | 10篇 |
2014年 | 13篇 |
2013年 | 32篇 |
2012年 | 26篇 |
2011年 | 31篇 |
2010年 | 26篇 |
2009年 | 19篇 |
2008年 | 20篇 |
2007年 | 34篇 |
2006年 | 28篇 |
2005年 | 31篇 |
2004年 | 25篇 |
2003年 | 14篇 |
2002年 | 18篇 |
2001年 | 8篇 |
2000年 | 18篇 |
1999年 | 12篇 |
1998年 | 6篇 |
1997年 | 7篇 |
1996年 | 2篇 |
1995年 | 9篇 |
1994年 | 3篇 |
1993年 | 9篇 |
1992年 | 2篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1983年 | 3篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1973年 | 2篇 |
1934年 | 2篇 |
1933年 | 2篇 |
排序方式: 共有493条查询结果,搜索用时 15 毫秒
41.
42.
Quéméner B Cabrera Pino JC Ralet MC Bonnin E Thibault JF 《Journal of mass spectrometry : JMS》2003,38(6):641-648
Partially acetylated and methylated oligogalacturonides produced by enzymatic hydrolysis of sugar beet pectin were analysed by negative electrospray ionization ion trap mass spectrometry (ESI-ITMS). The (18)O labelling of the oligomer reducing end allowed the precise assignment of the fragments resulting from glycosidic bond and cross-ring cleavages. The collisional-induced dissociation of the C(i) and Z(j) fragment ions through sequential MS(n) experiments always displayed (0, 2)A-type cross-ring cleavage ions which were related to C(2)H(4)O(2) losses. These (0, 2)A ions appeared to be highly diagnostic ions allowing the precise location of the acetyl groups to the O-2 and/or O-3 of the acetylated galacturonic acid residues. 相似文献
43.
R. Cabrera‐Trujillo J. R. Sabin Y.
hrn E. Deumens 《International journal of quantum chemistry》2003,94(4):215-221
Under certain collision conditions, a swift ion projectile colliding with a target will gain rather than lose kinetic energy, contrary to the standard conception of stopping power. In this work, we consider the conditions for such a collision such that the energy loss is negative, that is, that there will be projectile kinetic energy gain. In particular, for a target initially in the ground state we find that the projectile gains kinetic energy only when charge exchange and de‐excitation processes are involved. This occurs when the electron affinity of the projectile is larger than the ionization potential of the target. Consequences of this effect are analyzed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 215–221, 2003 相似文献
44.
Gerd Schfer Wilder Carrillo‐Cabrera Stefano Leoni Horst Borrmann Rüdiger Kniep 《无机化学与普通化学杂志》2002,628(1):67-76
A novel borophosphate, Zn3(C6H14N2)3[B6P12O39(OH)12] · (C6H14N2)[HPO4] has been synthesised under mild hydrothermal conditions at T = 165 °C. The chiral crystal structure was determined by single crystal X‐ray diffraction data (trigonal, R3 (no. 146), Z = 3, a = 2089.55(4) pm, c = 1237.03(4) pm, V = 4677.5(2) · 106 pm3, R1 = 0.066, wR2 = 0.164 for 5100 observed reflections). The title compound can be considered as an ordered composite of the two different and neutral structures which fit into each other: An open framework of composition Zn3(C6H14N2)3[B6P12O39(OH)12] and columns of composition (C6H14N2)[HPO4]. The framework structure is formed by mixed octahedral‐tetrahedral secondary building units, in a three‐dimensional arrangement reflecting a hierarchical derivative of the NbO structure type. The underlying NbO topology is illustrated with the help of Periodic Nodal Surfaces. The composite nature of the compound is resolved in the spatial segregation of two frameworks with a separating surface. 相似文献
45.
46.
José L. Arias Pankaj Sharma Armando Cabrera Fernando Beristain Rafael Sampere Cesar Arizmendi 《Transition Metal Chemistry》2013,38(7):787-792
In the cobalt-catalysed hydroformylation of 3,4-dihydro[2H]pyran, the influence of different reaction parameters such as time, pressure, triphenylphosphine addition, catalyst and substrate concentration has been investigated. 2-formyl-tetrahydropyran, tetrahydropyran and a hydroalkylcarbonylation product were the main reaction products. The selectivity towards 2-formyl-tetrahydropyran formation is favoured at constant catalyst and substrate concentration. The coordination of the pyran’s oxygen to the cobalt atom seems to be an important intermediate for the formation of 2-formyl-tetrahydropyran. Different substrate or catalyst concentrations promote the formation of other reduced products. The addition of triphenylphosphine to the catalyst leads to a less active species, which decreases the yield and promotes the hydroalkylcarbonylation reaction. 相似文献
47.
Comini LR Montoya SC Páez PL Argüello GA Albesa I Cabrera JL 《Journal of photochemistry and photobiology. B, Biology》2011,102(2):108-114
Photosensitizing anthraquinones isolated from Heterophyllaea pustulata Hook f. (Rubiaceae), namely soranjidiol, rubiadin, damnacanthal and 5,5'-bisoranjidiol, showed antibacterial activity (bacteriostatic/bactericide) on Staphylococcus aureus. The mechanism of action seems to involve an increase in the levels of superoxide anion (O(2)(·-)) and/or singlet molecular oxygen ((1)O(2)). Moreover, the effect of actinic irradiation as a boosting agent for the production of both reactive species of oxygen as well as its influence on antibacterial activity was assessed. The routine susceptibility assay (minimum inhibitory concentration determination) was carried out by means of the broth macrodilution method. Bactericide activity was determined counting the colony-forming units per milliliter (cfu/mL) in plate. The O(2)(·-) production was determined by means of an indirect photobiological assay (Nitroblue Tetrazolium test), and the production of (1)O(2) was followed using an indirect steady-state method, with methionine as the (1)O(2) chemical quencher. 相似文献
48.
A. Narros Sierra J. S. Durand Alegría A. Cabrera Martín 《Fresenius' Journal of Analytical Chemistry》1993,345(6):437-440
Summary A chemiluminescent method for the determination of vanadium in steel with cinchomeronic hydrazide as analytical reagent is proposed. The optimum conditions are pH 11.75 (phosphate buffer), 1.0×10–3 mol/l cinchomeronic hydrazide, 6.6×10–3 mol/l hydrogen peroxide and 2.8×10–3 mol/l V(IV). The maximum chemiluminescent emission is obtained at 420 nm. A linear relationship exists in the range of 0.04–1.00 g/ml of V(IV) with a 3.6% variation coefficient at 0.50 g/ml of V(IV) level for ten replicates. Cobalt(II), copper(II) and chromium(VI) show strong interference and a chloroform extraction procedure with -benzo-inoxime is recommended to avoid these interferences. This method has been applied to determine vanadium in a certified steel with excellent results.Presented at Euroanalysis VII 相似文献
49.
María Pérez-SánchezÁlvaro Cortés Cabrera Héctor García-MartínJ. Vicent Sinisterra José I. GarcíaMaría J. Hernáiz 《Tetrahedron》2011,67(40):7708-7712
A noticeably increase in activity, keeping total regioselectivity was found in the synthetic behaviour of Escherichia coli β-galactosidase in glycerol-based solvents using a 1:7 molar ratio of donor (pNP-β-Gal): acceptor (GlcNAc). Yields of up to 97% of β(1→6) with different solvents were found. These reactions take place without noticeable hydrolytic activity and with total regioselectivity, representing a considerable improvement over the use of aqueous buffer or conventional organic solvents. There is a clear dependence of the catalytic results on the solvent structure, which is analysed in terms of polarity and hydrophobicity. 相似文献
50.
Cabrera S Reyes E Alemán J Milelli A Kobbelgaard S Jørgensen KA 《Journal of the American Chemical Society》2008,130(36):12031-12037
It is shown that racemic oxazolones are excellent reagents for the synthesis of chiral quaternary amino acids and its derivatives by the diastereo- and enantioselective nucleophilic addition to alpha,beta-unsaturated aldehydes catalyzed by diarylprolinol silyl ethers. The scope of this new organocatalytic reaction is demonstrated for different oxazolones having aromatic and alkyl groups at the reactive carbon atom and different aromatic and aliphatic substituted alpha,beta-unsaturated aldehydes, for which the stereoselective reaction proceeds with good yield, moderate to good to very high diastereoselectivity, and very high enantioselectivity. The potential of the reaction is shown for the synthesis of optically active alpha,alpha-disubstituted alpha-amino acids, alpha-quaternary proline derivatives, amino alcohols, lactams, and tetrahydropyranes. Furthermore, we have calculated by DFT-methods the transition-state structures that account for both the diastereo- and enantioselectivity observed for the addition of oxazolones to the alpha,beta-unsaturated aldehydes. For one class of compounds, the stereoselectivity is controlled by a hydrogen-bonding interaction of the enolate-form of the oxazolone with an ortho-hydroxy-phenyl substituent of the alpha,beta-unsaturated aldehyde, whereas the benzhydryl-protecting group in the oxazolone determines the diastereo- and enantioselectivity in a more general manner for both aromatic and aliphatic alpha,beta-unsaturated aldehydes. 相似文献