全文获取类型
收费全文 | 157篇 |
免费 | 2篇 |
专业分类
化学 | 100篇 |
力学 | 4篇 |
数学 | 24篇 |
物理学 | 31篇 |
出版年
2022年 | 3篇 |
2021年 | 4篇 |
2020年 | 1篇 |
2019年 | 4篇 |
2018年 | 3篇 |
2017年 | 4篇 |
2016年 | 7篇 |
2015年 | 2篇 |
2014年 | 5篇 |
2013年 | 7篇 |
2012年 | 10篇 |
2011年 | 13篇 |
2010年 | 8篇 |
2009年 | 6篇 |
2008年 | 13篇 |
2007年 | 15篇 |
2006年 | 6篇 |
2005年 | 9篇 |
2004年 | 12篇 |
2003年 | 7篇 |
2002年 | 3篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1992年 | 2篇 |
1989年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
排序方式: 共有159条查询结果,搜索用时 46 毫秒
31.
Neto BA Lapis AA Mancilha FS Vasconcelos IB Thum C Basso LA Santos DS Dupont J 《Organic letters》2007,9(20):4001-4004
4,7-Disubstituted benzothiadiazoles containing 1-arylethynyl and 4-methoxyphenyl groups are selective photoluminescent "light up" probes to duplex DNA with unprecedented sensibility in both spectrophotometric and spectrofluorimetric measurements. 相似文献
32.
Cristoni S Basso E Gerthoux P Mocarelli P Gonella E Brambilla M Crotti S Bernardi LR 《Rapid communications in mass spectrometry : RCM》2007,21(15):2515-2523
Surface-activated chemical ionization (SACI) was employed for the analysis of cocaine and its metabolite, benzoylecgonine, extracted from hair. Following decontamination and acid hydrolysis procedures on the hair sample, the sample solution was diluted (1:10) and directly analyzed by liquid chromatography/surface-activated chemical ionization multiple collisional stage single reaction monitoring mass spectrometry (LC/SACI-MS(3)-SRM) without solid-phase extraction (SPE) pre-purification and concentration procedures. To increase the selectivity of the method, MS(3) was chosen instead of the less selective MS/MS. This data was compared with that achieved using gas chromatography/mass spectrometry (GC/MS), the reference method used by the Italian Government Institute of Health protocol. The limits of detection (LODs) were 0.003 ng/(mg hair) for cocaine and 0.02 ng/(mg hair) for benzoylecgonine and the limits of quantitation (LOQs) were 0.01 ng/(mg hair) for cocaine and 0.04 ng/(mg hair) for benzoylecgonine. The squared correlation coefficient (R(2)) of the calibration curve was 0.9887-0.9980 for cocaine and 0.9987-0.9997 for benzoylecgonine. The percent accuracy error was 2-5% for both cocaine and benzoylecgonine using the LC/SACI-MS(3)-SRM approach, whereas it was higher for benzoylecgonine (20-25%) using the LC/SACI-MS/MS-SRM approach compared with the GC/MS data due to hair matrix contamination. In both cases, high precision was achieved (1-3% precision error), which confirmed the stability of the developed methods. 相似文献
33.
The solvent effect on rotation about the conjugated C-N bond has been studied for methyl N,N-dimethylcarbamate (1), S-methyl N,N-dimethylthiocarbamate (2), O-methyl N,N-dimethylthiocarbamate (3), and methyl N,N-dimethyldithiocarbamate (4). The present investigation included experimental determination of activation parameters (DeltaH, DeltaS, and DeltaG) combined with theoretical calculations via both quantum and classical approaches. Rotational barriers were measured through dynamic NMR experiments in solvents of varied polarity and proton donor ability. In the less polar solvents, the values were 15.3+/-0.5 (CS2), 14.0+/-1.1 (CS2), 17.5+/-0.4 (CCl4), and 14.6+/-0.5 kcal/mol (CCl4) for 1, 2, 3, and 4, respectively. Upon changing to an aqueous solution, the greatest variations occurred for 2 and 4, whereas for 1 and 3, there was no observable effect. Quantum chemical calculations at the HF/6-311+G(2d,p) and B3LYP/6-311+G(2d,p) levels, with the inclusion of solvation effects via the isodensity polarizable continuum model (IPCM), correctly reproduced the experimentally observed trends but failed to account for some of the measured rotational barrier's magnitudes. Hydrogen-bonding effects were included by performing molecular dynamic simulations. For these latter calculations, it was necessary to parametrize the force field against energies of water-solute complexes calculated at B3LYP/6-31+G(d,p). Through the results of radial distribution functions, solution rotational barriers could be calculated, presenting good agreement with experimental determinations and revealing the role of hydrogen bonding. Interestingly, only for 2, the rotational barrier is predicted to increase as a result of complexation with water. For the remaining compounds, hydrogen bonding causes the barrier to decrease, contrasting with most of the molecular systems studied up to now. 相似文献
34.
35.
Luca Banfi Andrea Basso Chiara Lambruschini Lisa Moni Renata Riva 《Chemical science》2021,12(47):15445
This perspective aims at celebrating the 100th anniversary of the discovery of the Passerini three component reaction. After being nearly neglected for many years, now this reaction has become quite popular, thanks to the achievements of the last 30 years, which have revealed several chances of exploitation in organic synthesis. Though not being comprehensive, this review means to show the various ways that have been used in order to expand the utility of the Passerini reaction. Post-MCR transformations to give heterocycles or peptidomimetics, variants through single component replacement, stereochemical issues, and applications in total syntheses will be especially covered.This perspective aims at celebrating the 100th anniversary of the discovery of the Passerini three component reaction. 相似文献
36.
Maria Valeria De Bonis Maria Cefola Bernardo Pace Gianpaolo Ruocco 《Heat and Mass Transfer》2013,49(6):799-808
Perishable bio-substrate behavior can be modeled during packaged storage. Local mass and heattransfer have been coupled to respiration rate and microbial growth. Validating measurements have also been performed, and a multi-objective optimization was employed to tune the model. The model is able to simulate gas composition history and local bacteria spoilage in storage modes commonly adopted by the food industry, depending on product features and temperature. Exploitation of this mathematical tool would allow for informed technical and management decisions. 相似文献
37.
Development of a stereoselective Ugi reaction starting from an oxanorbornene β-amino acid derivative
Banfi L Basso A Chiappe C De Moliner F Riva R Sonaglia L 《Organic & biomolecular chemistry》2012,10(19):3819-3829
We have synthesised a novel oxanorbornene β-aminoacid derivative and employed it in a stereoselective Ugi reaction. Hypothesis regarding the mechanism taking place during the reaction have been made and validated through the determination of the relative and absolute configuration of the Ugi adducts. Use of the correct choice of solvents can increase stereoselection. The resulting bicyclic peptidomimetics can be used as a novel class of pluripotent substrates to be elaborated according to the synthetic strategies previously elaborated in our laboratories. 相似文献
38.
J.F. Bobo D. Basso E. Snoeck C. Gatel D. Hrabovsky J.L. Gauffier L. Ressier R. Mamy S. Visnovsky J. Hamrle J. Teillet A.R. Fert 《The European Physical Journal B - Condensed Matter and Complex Systems》2001,24(1):43-49
Magnetite Fe3O4 films were grown on single crystal MgO (001) substrates using facing target sputtering technique. Conversion Electron M?ssbauer
Spectroscopy and magneto optical polar Kerr spectra have confirmed the stoichiometric repartition of Fe cations corresponding
to the inverse spinel structure and the electronic structure characteristic of bulk Fe3O4. Hysteresis loops carried out at room temperature show that, in a 1 T applied magnetic field, only 60% of the saturation
magnetization is detected. This behavior is discussed in correlation to the antiphase boundaries (APBs) observed by electron
microscopy. Magnetic force microscopy studies show that magnetic domains are larger than the mean distance between APBs.
Received 2 July 2001 相似文献
39.
40.
Pierpaolo Caricato Gianpaolo Ghiani Antonio Grieco Roberto Musmanno 《European Journal of Operational Research》2007
The single loop material flow system design is a combinatorial optimization problem, arising in material handling system design, which amounts to designing an unidirectional loop flow pattern as well as to locate pickup and delivery stations. The objective is to minimize the time required to carry out all material flow movements between cells. In this paper, we develop valid inequalities for a previously proposed formulation. The valid inequalities are then embedded into a branch-and-cut framework which is shown to solve much larger instances to optimality than those reported in the literature. A tailored tabu search heuristic is also illustrated and computationally assessed. 相似文献