全文获取类型
收费全文 | 797篇 |
免费 | 34篇 |
国内免费 | 5篇 |
专业分类
化学 | 736篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 54篇 |
物理学 | 43篇 |
出版年
2023年 | 4篇 |
2022年 | 26篇 |
2021年 | 32篇 |
2020年 | 23篇 |
2019年 | 29篇 |
2018年 | 12篇 |
2017年 | 12篇 |
2016年 | 26篇 |
2015年 | 38篇 |
2014年 | 25篇 |
2013年 | 49篇 |
2012年 | 62篇 |
2011年 | 71篇 |
2010年 | 50篇 |
2009年 | 36篇 |
2008年 | 57篇 |
2007年 | 61篇 |
2006年 | 45篇 |
2005年 | 53篇 |
2004年 | 33篇 |
2003年 | 32篇 |
2002年 | 20篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
排序方式: 共有836条查询结果,搜索用时 11 毫秒
31.
Martín Soto Dr. Raquel G. Soengas Prof. Artur M. S. Silva Prof. Vicente Gotor-Fernández Prof. Humberto Rodríguez-Solla 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(57):13104-13108
In this work, the first example of a radical stereodivergent reaction directed towards the stereoselective synthesis of both (R*,R*)- and (R*,S*)-2,2′-biflavanones promoted by samarium diiodide is reported. Control experiments showed that the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate a variety of 2,2′-biflavanones bearing different substitution patterns at the aromatic ring in good-to-quantitative yields, being both stereoisomers of the desired compounds obtained with total or high control of selectivity. A mechanism that explains both the generation of the corresponding 2,2′-biflavanones and the selectivity is also discussed. The structure and stereochemistry determination of each isomer was unequivocally elucidated by single-crystal X-ray diffraction experiments. 相似文献
32.
Dr. Beatriz Feringán Jesús Cerdá Dr. Beatriz Diosdado Dr. Juan Aragó Prof. Dr. Enrique Ortí Dr. Raquel Giménez Dr. Teresa Sierra 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15313-15322
The ability of a star-shaped tris(triazolyl)triazine derivative to hierarchically build supramolecular chiral columnar organizations through the formation of H-bonded complexes with benzoic acids was studied from a theoretical and experimental point of view. The combined study has been done at three different levels including the study of the structure of the triazine core, the association with benzoic acids in stoichiometry 1:3, and the assembly of 1:3 complexes in helical aggregates. Although the star-shaped triazine core crystallizes in a non-C3 conformation, the C3-symmetric conformation is theoretically predicted to be more stable and gives rise to a favorable C3 supramolecular 1:3 complex upon the interaction with three benzoic acids in their voids. In addition, calculations at different levels (DFT, PM7, and MM3) for the 1:3 host-guest complex predict the formation of large stable columnar helical aggregates stabilized by the compact packing of the interstitial acids by π–π and CH⋅⋅⋅π interactions. The acids restrict the movement of the the star-shaped triazine cores along the stacking axis causing a template effect in the self-assembly of the complex. Theoretical predictions correlate with experimental results, since the interaction with achiral or chiral 3,4,5-(4-alkoxybenzyloxy)benzoic acids gives rise to supramolecular complexes that organize in bulk hexagonal columnar mesophases stable at room temperature with intracolumnar order. The existence of supramolecular chirality in the mesophase was determined for complexes formed by acids derived from (S)-2-octanol. Chiral aggregation was also evidenced for complexes formed in dodecane. 相似文献
33.
Paulo Igor M. Firmino Raquel S. Farias Amanda N. Barros Patrícia G. C. Landim Gervina B. M. Holanda Elisa Rodríguez Alexandre C. Lopes André B. dos Santos 《Applied biochemistry and biotechnology》2018,184(4):1187-1199
As the addition of low concentrations of oxygen can favor the initial degradation of benzene, toluene, ethylbenzene, and xylenes (BTEX) compounds, this work verified the applicability of the microaerobic technology to enhance BTEX removal in an anaerobic bioreactor supplemented with high and low co-substrate (ethanol) concentrations. Additionally, structural alterations on the bioreactor microbiota were assessed throughout the experiment. The bioreactor was fed with a synthetic BTEX-contaminated water (~ 3 mg L?1 of each compound) and operated at a hydraulic retention time of 48 h. The addition of low concentrations of oxygen (1.0 mL min?1 of atmospheric air at 27 °C and 1 atm) assured high removal efficiencies (> 80%) for all compounds under microaerobic conditions. In fact, the applicability of this technology showed to be viable to enhance BTEX removal from contaminated waters, especially concerning benzene (with a 30% removal increase), which is a very recalcitrant compound under anaerobic conditions. However, high concentrations of ethanol adversely affected BTEX removal, especially benzene, under anaerobic and microaerobic conditions. Finally, although bacterial community richness decreased at low concentrations of ethanol, in general, the bioreactor microbiota could deal with the different operational conditions and preserved its functionality during the whole experiment. 相似文献
34.
Jorge Ferreira Raquel Zilz Igor S. Boeira Sabrina M. da Silva Adriana C.A. Casagrande Osvaldo L. Casagrande 《应用有机金属化学》2019,33(3)
A new set of Cr(III) complexes, {L}CrCl3(THF), based on thiophene–imine ( 2a , L = PhOC6H4(N═CH)‐2‐SC4H3; 2b , L = PhOC2H4(N═CH)‐2‐SC4H3; 2c , L = Ph(NH)C2H4(N═CH)‐2‐SC4H3; 2d , L = PhOC6H4(N═CH)‐2‐SC4H2‐5‐Ph; 2e , L = Ph(NH)C2H4(N═CH)‐2‐SC4H2‐5‐Ph) have been prepared and characterized using elemental analysis and infrared spectroscopy. Upon activation with methylaluminoxane, all the chromium complexes generated active systems affording a nonselective distribution of α‐olefins with turnover frequencies in the range 9500–93 500 (mol ethylene) (mol Cr)?1 h?1, and producing mostly oligomers (95.0–99.3 wt% of total products). Small amounts of polymer were produced in these oligomerization reactions (0.8–8.2 wt%). The catalytic activities were quite sensitive to the ligand environment. Moreover, the effects of oligomerization parameters (temperature, [Al]/[Cr] molar ratio, time) on the activity and on the product distribution were examined. 相似文献
35.
Leonardo C. Simon Raquel S. Mauler Roberto F. De Souza 《Journal of polymer science. Part A, Polymer chemistry》1999,37(24):4656-4663
Different chlorine-free alkylaluminum compounds were active cocatalysts for ethylene polymerization in the presence of 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine-dichloronickel (II) (1). The combination of 1 with trimethylaluminum or triisobutylaluminum produced catalytically active species that polymerized ethylene with productivities up to 469 kgpolymer/(molNi · h). The activity of the catalytic system and the properties of the polymeric materials were influenced strongly by the reaction temperature. The polymers had a high molecular weight (up to 642 × 103 g · mol−1), and the molecular weight increased with the reaction time. The polyethylenes were branched, and the branching could be modulated by the proper choice of reaction parameters. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4656–4663, 1999 相似文献
36.
Andreu R Cerdán MA Franco S Garín J Marco AB Orduna J Palomas D Villacampa B Alicante R Allain M 《Organic letters》2008,10(21):4963-4966
Replacement of the tricyanofuran (TCF) acceptor by its stronger analogue CF 3-TCF results in decreased second-order optical nonlinearities in merocyanines bearing a proaromatic 1,3-dithiole donor. The TCF-containing derivatives display exceptionally high mu beta values up to 31,000 x 10(-48) esu, unprecedented for 1,3-dithiole-based NLO-phores. 相似文献
37.
Ana Luiza Coeli Cruz Ramos Laiza Andrade Nogueira Mauro Ramalho Silva Ana Carolina do Carmo Mazzinghy Ana Paula Xavier Mariano Tssia Nunes de Albuquerque Rodrigues Ana Cardoso Clemente Filha Ferreira de Paula Angelita Cristine de Melo Rodinei Augusti Raquel Linhares Bello de Araújo Inayara Cristina Alves Lacerda Júlio Onsio Ferreira Melo 《Molecules (Basel, Switzerland)》2022,27(15)
Grumixama (Eugenia brasiliensis Lam.) is a native fruit of the Brazilian Atlantic Forest, belonging to the Myrtaceae family, which designatesthe most significant number of species with food potential. It stands out due to its phytochemical characteristics because of the presence of polyphenols and volatile organic compounds. Volatile compounds are substances released by foods that give off an aroma and influence flavor. Solid-phase microextraction is a technique that allows for low-cost, fast, and solvent-free extraction, has an affinity for numerous analytes, and is easily coupled to gas chromatography. The objectives of this work were to evaluate the efficiency of different fibers of SPME (solid-phase microextraction) in the extraction of volatile organic compounds from grumixama pulp; optimize a method for extraction time, temperature, and sample weight; and to determine the characteristic volatile profile of this fruit. For the extraction of volatile compounds, three fibers of different polarities were used: polar polyacrylate (PA) fibers, divinylbenzene/carboxyne/polydimethylsiloxane (DVB/CAR/PDMS) semipolar fibers, and polydimethylsiloxane/divinylbenzene (PDMS/DVB). Fourteen volatile organic compounds (VOCs) were identified by DVB/CAR/PDMS, six by PA, and seven by PDMS/DVB through solid-phase microextraction in the headspace mode (SPME-HS). Considering the total number of compounds identified, regardless of the fiber used, and the optimization of the method, Eugenia brasiliensis presented sesquiterpene fractions (85.7%, 83.3%, and 85.7% of total VOCs) higher than the monoterpene fractions (14.3%, 16.7%, and 14.3%) for DVB/CAR/PDMS, PA, and PDMS/DVB, respectively in its composition. In addition, it was possible to verify that the fiber DVB/CAR/PDMS presented a better efficiency due to the larger chromatographic area observed when the grumixama pulp was subjected to conditions of 75 °C, 2.0 g, and an adsorption time of 20 min. 相似文献
38.
Reactions of 4-alkylamino-2-phenyl-2-oxazolines 1 with isocyanates and isothiocyanates provide unprecedented efficient and regioselective heterocycle-heterocycle transformations. Compounds 1 reacted rapidly with tosyl isocyanate yielding directly 3-alkyl-4-benzamido-1-tosyl-2-imidazolidinones 4 in almost quantitative yields. The corresponding ureido intermediates 2 were not isolable species. However, the reactions with non-sulfonylated isocyanates or isothiocyanates were slower, leading to the expected ureido and thioureido derivatives 5, which were easily and efficiently transformed to either polysubstituted 2-imino-1,3-oxazolidine or 2-imino-1,3-thiazolidine hydrochlorides 7, respectively, by treatment with hydrochloric acid. The possible reasons for this disparity in chemical behaviour are discussed. X-ray crystallographic structures for 4-benzamido-3-methyl-1-tosyl-2-imidazolidinone 4b, 4-[1-isopropyl-3-(4-nitrophenyl)ureido]-2-phenyl-2-oxazoline 5e, (Z)-3-benzyl-4-benzamido-2-phenylimino-1,3-oxazolidine hydrochloride 7a and (Z)-3-benzyl-4-benzamido-2-phenylimino-1,3-thiazolidine hydrochloride 7b have been determined. 相似文献
39.
Silva AM Filipe P Seixas RS Pinto DC Patterson LK Hug GL Cavaleiro JA Mazière JC Santus R Morlière P 《The journal of physical chemistry. B》2008,112(37):11456-11461
In micellar solutions, one-electron reduction of (*)O 2 (-) radical-anions by 3-alkylpolyhydroxyflavones (FnH) with alkyl chains of n = 1, 4, 6, 10 carbons produces phenoxyl radicals ( (*)Fn) identical to those obtained by one-electron oxidation by (*)Br 2 (-) radical-anions or by repair of tryptophan radicals. In cetyltrimethylammonium bromide (CTAB), F1H localizes in the Stern layer, and alkyl chains of other FnH solubilize in the hydrophobic interior, interacting with cetyl tails. This interaction produces more compact micelles with lower intramicellar fluidity, as suggested by the increase in the pseudo-first-order rate constant of (*)Fn formation ( k 1) from approximately 390 s (-1) for n = 1 to 610 s (-1) for n = 10, leading to an intramicellar bimolecular rate constant of 1 x 10 (5) M (-1) s (-1). Additionally, (*)F1 and (*)F4 decay by intermicellar bimolecular reaction (2 k = 20 and 2 x 10 (5) M (-1) s (-1), respectively) whereas other (*)Fn radicals are stable over seconds due to increased localization with regards to the Stern layer. In contrast, the thick uncharged hydrophilic palisade layer and the compact hydrophobic core of Triton X100 micelles are responsible for a much higher microviscosity resulting in a decrease in k 1 from approximately 15.6 s (-1) for n = 1 to 9.6 s (-1) for n = 10. 相似文献
40.
(1S,2R)-1-Aminoindan-2-ol-derived thioureas behave as efficient H-bonding organocatalysts for the nucleophilic conjugate addition of formaldehyde hydrazones to beta,gamma-unsaturated alpha-keto esters as enoate surrogates, affording the corresponding adducts in good yields and enantioselectivities. 相似文献