全文获取类型
收费全文 | 1000篇 |
免费 | 60篇 |
国内免费 | 2篇 |
专业分类
化学 | 803篇 |
晶体学 | 2篇 |
力学 | 10篇 |
数学 | 138篇 |
物理学 | 109篇 |
出版年
2023年 | 9篇 |
2022年 | 6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 | 9篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1993年 | 2篇 |
1992年 | 4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1062条查询结果,搜索用时 78 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.
Soxhlet (methanol) and SFE extraction with carbon dioxide in the presence of modifiers at different temperatures (100–200°C) for the extraction of atrazine and its main metabolites from a soil sample were compared. The most effective extraction conditions for both atrazine and its metabolites (i.e. deethylatrazine and deisopropylatrazine) were Co2 modified with 20% molar methanol-trifluoroacetic acid (MeOH-TFA) (TFA 0.65M in MeOH) at 100°C, leading to an extraction efficiency comparable with that of Soxhlet extraction with MeOH for atrazine and ca. 20% higher for its main metabolites. The relative standard deviation (RSD) of SFE was lower than that obtained by Soxhlet extraction, probably because of less interference in the cGC-NPD determination. All the other modifiers evaluated (acetone, triethylamine, and methanol) were less effective than MeOH-TFA for the extraction of atrazine and its metabolites from a soil sample, even at high molar concentrations (20%) and use of higher extraction temperatures (200°C). These results indicate the importance of matrix effects and the need of the selection of an appropriate modifier in order to obtain quantitative extractions by SFE. 相似文献
65.
Nativitat Valls Josep Bonjoch Carlos Del Alamo Joan Bosch 《Helvetica chimica acta》1992,75(1):137-144
A stereodivergent synthesis of enantiomerically pure E-nor-15-azayohimbines via condensation of tryptamine with derivatives of pyroglutamate 4 is reported. When the Pictet-Spengler reaction was induced in refluxing aqueous AcOH a nearly equimolar ratio of lactams 7 and 8 was obtained, whereas under kinetic control (TFA, room temperature) the trans-derivative 8 was the major product. In contrast, cyclization of amido acetal 12 with TsOH gave the cis-derivative 7 as preponderant component. 相似文献
66.
Ventura-Gayete JF Armenta S Garrigues S Morales-Rubio A de la Guardia M 《Talanta》2006,68(5):1700-1706
A multicommutated flow-system was designed in order to increase analytical throughput and for controlling thermal effects on the NIR spectra for determination of Hexythiazox in pesticide formulations. An on-line standard addition was carried out showing the versatility and repeatability of multicommutation for the on-line mixing and dilution of solutions. Results obtained for commercial samples were statistically comparable with those obtained by an HPLC-reference method. Multicommutation-NIR allows the analysis of 52 samples per hour, in front of the 30 samples per hour analyzed by the NIR-batch procedure and the 7 samples per hour analyzed by HPLC-reference method. 相似文献
67.
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
68.
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
69.
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
70.
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