全文获取类型
收费全文 | 993篇 |
免费 | 60篇 |
国内免费 | 2篇 |
专业分类
化学 | 797篇 |
晶体学 | 2篇 |
力学 | 10篇 |
数学 | 138篇 |
物理学 | 108篇 |
出版年
2023年 | 9篇 |
2022年 | 2篇 |
2021年 | 14篇 |
2020年 | 21篇 |
2019年 | 14篇 |
2018年 | 19篇 |
2017年 | 10篇 |
2016年 | 38篇 |
2015年 | 44篇 |
2014年 | 42篇 |
2013年 | 61篇 |
2012年 | 88篇 |
2011年 | 75篇 |
2010年 | 46篇 |
2009年 | 55篇 |
2008年 | 61篇 |
2007年 | 76篇 |
2006年 | 69篇 |
2005年 | 66篇 |
2004年 | 47篇 |
2003年 | 40篇 |
2002年 | 25篇 |
2001年 | 12篇 |
2000年 | 9篇 |
1999年 | 11篇 |
1998年 | 9篇 |
1997年 | 7篇 |
1996年 | 7篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 10篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1929年 | 1篇 |
1925年 | 1篇 |
排序方式: 共有1055条查询结果,搜索用时 281 毫秒
61.
Rachel Grainger Dr. Josep Cornella Dr. David C. Blakemore Dr. Igor Larrosa Dr. Josep M. Campanera 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16680-16687
A combined experimental and computational investigation on the Ag‐catalysed decarboxylation of benzoic acids is reported herein. The present study demonstrates that a substituent at the ortho position exerts dual effects in the decarboxylation event. On one hand, ortho‐substituted benzoic acids are inherently destabilised starting materials compared to their meta‐ and para‐substituted counterparts. On the other hand, the presence of an ortho‐electron‐withdrawing group results in an additional stabilisation of the transition state. The combination of both effects results in an overall reduction of the activation energy barrier associated with the decarboxylation event. Furthermore, the Fujita–Nishioka linear free energy relationship model indicates that steric bulk of the substituent can also exert a negative effect by destabilising the transition state of decarboxylation. 相似文献
62.
Aryl‐Copper(III)‐Acetylides as Key Intermediates in CCsp Model Couplings under Mild Conditions 下载免费PDF全文
Mireia Rovira Marc Font Ferran Acuña‐Parés Dr. Teodor Parella Dr. Josep M. Luis Dr. Julio Lloret‐Fillol Dr. Xavi Ribas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):10005-10010
The mechanism of copper‐mediated Sonogashira couplings (so‐called Stephens–Castro and Miura couplings) is not well understood and lacks clear comprehension. In this work, the reactivity of a well‐defined aryl‐CuIII species ( 1 ) with p‐R‐phenylacetylenes (R=NO2, CF3, H) is reported and it is found that facile reductive elimination from a putative aryl‐CuIII‐acetylide species occurs at room temperature to afford the Caryl?Csp coupling species ( IR ), which in turn undergo an intramolecular reorganisation to afford final heterocyclic products containing 2H‐isoindole ( P , P , PHa ) or 1,2‐dihydroisoquinoline ( PHb ) substructures. Density Functional Theory (DFT) studies support the postulated reductive elimination pathway that leads to the formation of C?Csp bonds and provide the clue to understand the divergent intramolecular reorganisation when p‐H‐phenylacetylene is used. Mechanistic insights and the very mild experimental conditions to effect Caryl?Csp coupling in these model systems provide important insights for developing milder copper‐catalysed Caryl?Csp coupling reactions with standard substrates in the future. 相似文献
63.
Dr. Hua Dong Dr. Jordi Ignés‐Mullol Dr. Josep Claret Dr. Lourdes Pérez Dr. Aurora Pinazo Prof. Dr. Francesc Sagués 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7396-7401
A chiral selection process in a self‐assembled soft monolayer of an achiral amphiphile as a consequence of its interaction with chiral species dissolved in the aqueous subphase, is reported. The extent of the chiral selection is statistically measured in terms of the enantiomorphic excess of self‐assembled submillimeter domains endowed with well‐defined orientational chirality that is unambiguously resolved using optical microscopy. Our results show that the emergence of chirality is mediated by electrostatic interactions and significantly enhanced by hydrophobic effects. This chiral chemical effect can be suppressed and even reversed by opposing a macroscopic physical influence, such as vortical stirring. This result gives evidence for the crucial role of hydrodynamic effects in supramolecular aggregation. 相似文献
64.
Xavier L��pez Pere Mir�� Jorge J. Carb�� Antonio Rodr��guez-Fortea Carles Bo Josep M. Poblet 《Theoretical chemistry accounts》2011,128(4-6):393-404
Computational chemistry applied to the study of polyoxometalates has achieved its maturity in the last years. During two decades, important advances have been made using theoretical tools in the comprehension and interpretation of many relevant issues. In the present mini-review, we want to stress that different techniques have been incorporated to the routine of computation: from the very first Hartree?CFock LCAO-SCF calculation on the decavanadate anion, followed by numerous density functional theory?Cbased studies on increasingly complex systems, also applying correlated ab initio techniques for magnetism and, more recently, using molecular dynamics to analyse properties in liquid media, the information provided by computational chemistry gets more and more relevant. 相似文献
65.
We implement a dynamic model that describes the polarization behavior in vertical-cavity surface-emitting lasers that contain an absorbing region surrounding the active zone. We find four regions of qualitatively different behavior: stable linearly polarized operation, intensity pulsations of a linearly polarized component, pulsations of both total-intensity and polarization components, and polarization self-pulsation with constant total intensity. We characterize the four regions by computing the polarization-resolved optical and power spectra. The predicted behavior agrees with recent experimental results. 相似文献
66.
Martínez-Teipel B Teixidó J Pascual R Mora M Pujolà J Fujimoto T Borrell JI Michelotti EL 《Journal of combinatorial chemistry》2005,7(3):436-448
Heterocyclic demonstration libraries for agrochemical screening were prepared from the common intermediates 2-methoxy-6-oxo-1,4,5,6-tetrahydropyridine-3-carbonitriles (1), using standard solution-phase techniques. A total of 18 screening libraries were prepared in good to excellent yields. Several members of these libraries were active in the first level of agrochemical screening, especially in the fungicide screen. 相似文献
67.
Camarero J Sort J Hoffmann A García-Martín JM Dieny B Miranda R Nogués J 《Physical review letters》2005,95(5):057204
The magnetization reversal in exchange-biased ferromagnetic-antiferromagnetic (FM-AFM) bilayers is investigated. Different reversal pathways on each branch of the hysteresis loop, i.e., asymmetry, are obtained both experimentally and theoretically when the magnetic field is applied at certain angles from the anisotropy direction. The range of angles and the magnitude of this asymmetry are determined by the ratio between the FM anisotropy and the interfacial FM-AFM exchange anisotropy. The occurrence of asymmetry is linked with the appearance of irreversibility, i.e., finite coercivity, as well as with the maximum of exchange bias, increasing for larger anisotropy ratios. Our results indicate that asymmetric hysteresis loops are intrinsic to exchange-biased systems and the competition between anisotropies determines the asymmetric behavior of the magnetization reversal. 相似文献
68.
In this paper we compute the line integral of a complex function on a rectifiable cycle homologous to zero obtaining a Green’s
formula with multiplicities that involves the
of the function and the index of the cycle. We consider this formula in several settings and we obtain a sharp version in
terms of the Lebesgue integrability properties of the partial derivatives of the function. This result depends on the proven
fact that the index of a rectifiable cycle is square integrable with respect to the planar Lebesgue measure.
The work of both authors is partially supported by grants 2000SGR-00059, 2001SGR 00172 of Generalitat de Catalunya and BFM
2002-04072-C02-02 of Ministerio de Ciencia y Tecnologia 相似文献
69.
Ventura-Gayete JF Rodenas-Torralba E Morales-Rubio A Garrigues S de la Guardia M 《Journal of AOAC International》2004,87(5):1252-1259
A highly sensitive method was developed for determination of bismuth in milk shakes by multicommutation hydride generation atomic fluorescence spectrometry (HG-AFS) based on off-line sonication for 10 min with aqua regia 8% (v/v) and on-line waste treatment. The instrumentation and chemistry variables were studied in order to provide the best performance. The limit of detection in the original samples, established for a probability level of 99.6% (k = 3), was 1.67 ng/g Bi. The method provides a fast alternative in control analysis with a sampling throughput of 72 h as compared with 31 h obtained by the classical continuous measurement. Additionally, multicommutation reduces waste generation by a factor of 2.6. The consumption of sample, reductant, and blank, as compared with continuous mode HG-AFS, was reduced 9.6, 4.5, and 13.3 times, respectively. To confirm the accuracy of the method, recovery studies were performed, and excellent agreement between multicommutation and continuous measurement-based values was obtained. Application of the developed methodology for bismuth determination in milk shake samples from the Spanish market provided concentrations ranging from 4.2 to 15.0 ng/mL, and good comparability with data obtained by continuous measurements after microwave-assisted total digestion of samples for a 95% probability level and 12 degrees of freedom was found. 相似文献
70.
The present study describes an extensive conformational search of substance P using two different computational methods. On the one hand, the peptide was studied using the iterative simulated annealing, and on the other, molecular dynamics simulations at 300 and 400 K. With the former method, the peptide was studied in vacuo with a dielectric constant of 80, whereas using the latter study the peptide was studied in a box of TIP3P water molecules. Analysis of the results obtained using both methodologies was carried out using an in-house methodology using a cluster analysis method based on information theory. Comparison of the two sampling methodologies and the different environment used in the calculations is also analyzed. Finally, the conformational motifs that are characteristic of substance P in a hydrophilic environment are presented and compared with the experimental results available in the literature. 相似文献