全文获取类型
收费全文 | 536篇 |
免费 | 26篇 |
国内免费 | 5篇 |
专业分类
化学 | 372篇 |
晶体学 | 1篇 |
力学 | 15篇 |
数学 | 103篇 |
物理学 | 76篇 |
出版年
2023年 | 3篇 |
2022年 | 11篇 |
2021年 | 13篇 |
2020年 | 6篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2017年 | 12篇 |
2016年 | 15篇 |
2015年 | 12篇 |
2014年 | 19篇 |
2013年 | 21篇 |
2012年 | 37篇 |
2011年 | 39篇 |
2010年 | 21篇 |
2009年 | 20篇 |
2008年 | 36篇 |
2007年 | 30篇 |
2006年 | 39篇 |
2005年 | 33篇 |
2004年 | 28篇 |
2003年 | 29篇 |
2002年 | 19篇 |
2001年 | 13篇 |
2000年 | 14篇 |
1999年 | 4篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 11篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 5篇 |
1978年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1972年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有567条查询结果,搜索用时 15 毫秒
211.
González Álvarez J Blanco Gomis D Arias Abrodo P Díaz Llorente D Busto E Ríos Lombardía N Gotor Fernández V Gutiérrez Álvarez MD 《Analytical and bioanalytical chemistry》2011,400(5):1209-1216
Two ionic liquids (ILs), namely (S,S)-1-butyl-3-(2'-hydroxy-cyclohexyl)-3H-imidazol-1-ium tetrafluoroborate and (S,S)-1-butyl-3-(2'-acetyl-cyclohexyl)-3H-imidazol-1-ium tetrafluoroborate have been employed as stationary phases in capillary gas chromatography. These new phases exhibit a column efficiency of 1,600 and 2,100 plates m(-1) for IL 1 and IL 2, respectively, a wide operating temperature range and good thermal stability (bleeding temperature of 250 °C for IL 1 and 160 °C for IL 2). Inverse gas chromatography (GC) analyses were used to study the solvation properties of these ILs through a linear solvation energy model. The application of these ILs as new GC stationary phases was studied. These stationary phases exhibited unique selectivity for many organic substances, such as alkanes, ketones, esters, and aromatic compounds. The efficient separation of several mixtures containing compounds of different polarities and the good separation of fatty acid methyl esters (FAMEs) and cis/trans isomers indicate that these ILs may be applicable as a new type of GC stationary phases. 相似文献
212.
Cebolla VL Jarne C Domingo P Domínguez A Delgado-Camón A Garriga R Galbán J Membrado L Gálvez EM Cossío FP 《Journal of chromatography. A》2011,1218(19):2668-2675
Changes in emission of berberine cation, induced by non-covalent interactions with lipids on silica gel plates, can be used for detecting and quantifying lipids using fluorescence scanning densitometry in HPTLC analysis. This procedure, referred to as fluorescence detection by intensity changes (FDIC) has been used here in combination with automated multiple development (HPTLC/AMD), a gradient-based separation HPTLC technique, for separating, detecting and quantifying lipids from different families. Three different HPTLC/AMD gradient schemes have been developed for separating: neutral lipid families and steryl glycosides; different sphingolipids; and sphingosine-sphinganine mixtures. Fluorescent molar responses of studied lipids, and differences in response among different lipid families have been rationalized in the light of a previously proposed model of FDIC response, which is based on ion-induced dipole interactions between the fluorophore and the analyte. Likewise, computational calculations using molecular mechanics have also been a complementary useful tool to explain high FDIC responses of cholesteryl and steryl-derivatives, and moderate responses of sphingolipids. An explanation for the high FDIC response of cholesterol, whose limit of detection (LOD) is 5 ng, has been proposed. Advantages and limitations of FDIC application have also been discussed. 相似文献
213.
Ana M.G. Silva Andreia LeitePablo Gonzalez M. Rosário M. DominguesPaula Gameiro Baltazar de CastroMaria Rangel 《Tetrahedron》2011,67(40):7821-7828
Piperazine and 1,2-diaminobenzene have been previously used as anchoring molecules to synthesize 3-hydroxy-4-pyridinone (3,4-HPO) tetradentate ligands affording ligands with different flexibility and coordination properties. In order to have a relatively rigid and hindered structure, a porphyrin platform was selected to anchor one or two 3,4-HPO chelating units. This platform provides an additional N4 coordination sphere and also very interesting optical properties to the synthesized conjugates. Depending on the metal ion present in the porphyrin core, conjugates with different spectroscopic properties are obtained. EPR spectroscopy has been used to characterize the copper(II) metalloporphyrins and to monitor and identify the species formed upon addition of copper(II) to solutions of two porphyrin conjugates with one and two 3,4-HPO arms. The porphyrin conjugates having two 3,4-HPO units are ligands that provide two separate binding sites with N4 and O4 coordination spheres, which allow accommodation of two metal ion centers that may be distinguished by spectroscopic methods. 相似文献
214.
Zeghada S Bentabed-Ababsa G Derdour A Abdelmounim S Domingo LR Sáez JA Roisnel T Nassar E Mongin F 《Organic & biomolecular chemistry》2011,9(11):4295-4305
Reactions were performed from aryl azides on the one hand, and activated alkenes coming from β-dicarbonyl compounds or malonodinitrile on the other hand, either with recourse to conventional heating or to microwave activation, to afford 1-aryl-1H-1,2,3-triazoles. The mechanism and the regioselectivity of the reactions involving β-dicarbonyl compounds have been theoretically studied using DFT methods at the B3LYP/6-31G* level: they are domino processes comprising a tautomeric equilibrium of the β-dicarbonyl compounds with their enol forms, a 1,3-dipolar cycloaddition of the enol forms with the aryl azides (high activation energy), and a dehydration process (lower activation energy). The effect of non-conventional activation methods on the degradation of 1,2,3-triazolines was next studied experimentally. Finally, some of the 1,2,3-triazoles such synthesized were evaluated for their bactericidal and cytotoxic activities. 相似文献
215.
The role of Ti(Oi-Pr)(4) Lewis acid (LA) in the cooperative N-heterocyclic carbene (NHC)/LA catalyzed addition of enals to enones to yield cis-cyclopentenes has been investigated using DFT methods at the B3LYP/6-31G** computational level. Ti(IV) effectively catalyzes the reaction by formation of a complex with cinnamaldehyde 1, which favors the nucleophilic attack of NHC 5 on 1, and the subsequent proton abstraction to yield the extended Ti(IV)-Breslow intermediate 21. The nature of the metal involved in the LA catalyst plays a relevant role due to the more basic character of NHCs than aldehydes. Thus, strong LAs, such as Zn(OTf)(2), prevent the catalytic behavior of NHCs to form a very stable complex. The subsequent formation of a complex between chalcone 2 and the extended Ti(IV)-Breslow intermediate 21 favors the cis stereoselective C-C bond-formation. Analysis of the structures of Ti(IV)-complex precursors for the cis and trans C-C bond-formation steps allows for an explanation of the unexpected cis stereoselectivity. 相似文献
216.
Domingo LR Pérez-Ruiz R Argüello JE Miranda MA 《The journal of physical chemistry. A》2011,115(21):5443-5448
The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4+2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b(?+) is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b(?+) (ii). Calculations support that 1a(?+) follows reaction pathway ii (leading to the formal [4+2] cycloadducts 5a). By contrast, 1b(?+) follows pathway i, leading to trans-stilbene radical cation (2b(?+)) and thiobenzophenone. 相似文献
217.
Rafael Block SamulewskiJúlio César da Rocha Rafael StielerErnesto Schulz Lang David John EvansGiordano Poneti Otaciro Rangel NascimentoRonny Rocha Ribeiro Fábio Souza Nunes 《Polyhedron》2011,30(12):1997-2006
Herein we report on the synthesis, single crystal X-ray structure, spectroscopic and magnetic properties of [{Cu2(tidf)(H2O)}2(μ-CN)2Fe(CN)4]·6H2O (1), [Cu2(tidf)(H2O)2][Ni(CN)4] (2) and [Cu2(tidf)(H2O)2][Fe(CN)5NO]·H2O (3) (tidf = a Robson type macrocyclic ligand obtained on condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane). Complex (1) is pentanuclear; two paramagnetic dicopper(II) units are linked by a hexacyanoferrate(II) ion through two cyano-bridges. All compounds exhibit extensive, three-dimensional, supramolecular structures supported by classic hydrogen bonding between the coordinated aqua ligands, water molecules and cyano groups. Magnetism as a function of the temperature of complexes 1-3 is consistent with a strong antiferromagnetism with exchange parameters 2J estimated −783(29), −913(2), −905(1), respectively. 相似文献
218.
Vera DM Haynes MH Ball AR Dai T Astrakas C Kelso MJ Hamblin MR Tegos GP 《Photochemistry and photobiology》2012,88(3):499-511
Conventional antimicrobial strategies have become increasingly ineffective due to the emergence of multidrug resistance among pathogenic microorganisms. The need to overcome these deficiencies has triggered the exploration of alternative treatments and unconventional approaches towards controlling microbial infections. Photodynamic therapy (PDT) was originally established as an anticancer modality and is currently used in the treatment of age-related macular degeneration. The concept of photodynamic inactivation requires cell exposure to light energy, typically wavelengths in the visible region that causes the excitation of photosensitizer molecules either exogenous or endogenous, which results in the production of reactive oxygen species (ROS). ROS produce cell inactivation and death through modification of intracellular components. The versatile characteristics of PDT prompted its investigation as an anti-infective discovery platform. Advances in understanding of microbial physiology have shed light on a series of pathways, and phenotypes that serve as putative targets for antimicrobial drug discovery. Investigations of these phenotypic elements in concert with PDT have been reported focused on multidrug efflux systems, biofilms, virulence and pathogenesis determinants. In many instances the results are promising but only preliminary and require further investigation. This review discusses the different antimicrobial PDT strategies and highlights the need for highly informative and comprehensive discovery approaches. 相似文献
219.
SD de Souza AM de Souza AC de Sousa AC Sodero LM Cabral MG Albuquerque HC Castro CR Rodrigues 《Molecules (Basel, Switzerland)》2012,17(8):9529-9539
Hologram QSAR models were developed for a series of 36 inhibitors (29 training set and seven test set compounds) of acetyl/butyrylcholinesterase (AChE/BChE) enzymes, an attractive molecular target for Alzheimer's disease (AD) treatment. The HQSAR models (N = 29) exhibited significant cross-validated (AChE, q2 = 0.787; BChE, q2 = 0. 904) and non-cross-validated (AChE, r2 = 0.965; BChE, r2 = 0.952) correlation coefficients. The models were used to predict the inhibitory potencies of the test set compounds, and agreement between the experimental and predicted values was verified, exhibiting a powerful predictive capability. Contribution maps show that structural fragments containing aromatic moieties and long side chains increase potency. Both the HQSAR models and the contribution maps should be useful for the further design of novel, structurally related cholinesterase inhibitors. 相似文献
220.
Chafia Sobhi Abdelmalek Khorief Nacereddine Abdelhafid Djerourou M. José Aurell Luis R. Domingo 《Tetrahedron》2012,68(40):8457-8462
The role of the trifluoromethyl group in reactivity, regio-, and stereoselectivity in cycloaddition reactions has been analyzed by studying the 1,3-dipolar cycloaddition (13DC) reactions of nitrone 4 with 3,3,3-trifluoro-1-nitropropene 7b and 3,3,3-trifluoro-2-nitropropene 14 using density functional theory (DFT) methods at the B3LYP/6-311G(d) level. The recent M06-2X functional has also been evaluated but, although the thermodynamic performance is improved, the kinetic data are not necessarily better than those obtained by the popular B3LYP functional for cycloaddition reactions. Four reactive channels associated with the meta and ortho regio- and endo and exo stereoselective approach modes of the nitro group of these disubstituted ethylenes relative to nitrone 4 have been explored and characterized. Unlike other electron-withdrawing groups, the trifluoromethyl group increases the reactivity of the nitroethylene, but it does not modify the meta and endo selectivities when it is located at the β conjugated position of nitroethylene. Analysis of the global and local electrophilicity indices allows for an explanation of the role of the trifluoromethyl group in reactivity and regioselectivity of electrophilically activated ethylenes. 相似文献