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51.
A convenient synthesis of 4'-aminopantetheine from commercial D-pantethine is reported. The amino group was introduced by reductive amination in order to avoid substitution at a sterically congested position. Derivatives of 4'-aminopantetheine were also prepared to evaluate the effect of O-to-N substitution on inhibitors of the resistance-causing enzyme aminoglycoside N-6'-acetyltransferase. The biological results combined with docking studies indicate that in spite of its reported unusual flexibility and ability to adopt different folds, this enzyme is highly specific for AcCoA. 相似文献
52.
Salas G Podgoršek A Campbell PS Santini CC Pádua AA Costa Gomes MF Philippot K Chaudret B Turmine M 《Physical chemistry chemical physics : PCCP》2011,13(30):13527-13536
Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface. 相似文献
53.
54.
Lydie Viau Itamar Malkowsky Karine Costuas Stéphanie Boulin Lo?c Toupet Eléna Ishow Keitaro Nakatani Olivier Maury Hubert Le Bozec 《Chemphyschem》2006,7(3):644-657
Two 2,2'-bipyridines, substituted at the 4,4'-positions by p-dialkylaminophenylazostyryl moieties p-R2N-C6H4-N=N-C6H4-CH=CH-[6 a, R2N=nBu2N; 6 b, R2N=(nBu)(C4H8OTHP)N; 6 c, R2N=(nBu)(C4H8OH)N], were successfully synthesized by using Wadworth-Emmons reactions. The X-ray structure of 6 a has been determined. Esterification of 6 c with 2-bromoisobutyroylbromide afforded 6 d. This ligand was used as an initiator for the living radical polymerization of methylmethacrylate (MMA) and gave rise to macroligand 6 e. Thin films of good optical quality were obtained by the spin-coating technique. Photoisomerization experiments were carried out on 6 a in solution and on 6 e in both solution and film, and the kinetics of photochemical (E/Z) and thermal (Z/E) isomerization were investigated. They were found to show Z-E back isomerization typical of aminoazobenzene-type rather than of push-pull-type molecules. Density functional theoretical (TD-DFT) calculations were performed on model compound 6 a' (R2N=Me2N) to understand the structural and electronic transitions of the corresponding E-E, E-Z and Z-Z isomers. It was found that the E-E isomer is almost planar as observed experimentally by X-ray diffraction, whereas the Z-Z isomer, which is 35.4 kcal mol(-1) less stable than the E-E isomer, is nonplanar. The theoretical studies also reveal that several transitions of pi-pi*, n-pi* and charge-transfer (CT) types, are involved in the long-wavelength transition of 6 a (E-E). The same observations can be made for the (Z-Z) isomer, and the TD-DFT simulated spectrum fits quite nicely to the experimental, reproducing and explaining the apparition of a blue-shifted charge-transfer band at 390 nm. 相似文献
55.
Karine L Marques Jo?o L M Santos Jo?o A Lopes José L F C Lima 《Analytical sciences》2008,24(8):985-991
An automated multi-pumping flow system is proposed for the simultaneous chemiluminometric determination of benserazide and levodopa using multivariate calibration methods. The developed methodology is based on chemiluminescence (CL) emission generated by the reaction of benserazide with luminol, and on a concurrent inhibiting effect of levodopa on this reaction. A multi-pumping flow system comprising multiple solenoid micro-pumps as the only active components was developed to implement a stopped-flow approach for signal acquisition and processing. Artificial neural networks were used to establish a relationship between the CL emission profile and the concentration of both drugs. The concentration values used to establish the experimental calibration samples were varied between 5 and 30 mg l(-1) for levodopa and between 2.5 and 20 mg l(-1) for benserazide. The proposed method was successfully applied to the simultaneous determination of levodopa and benserazide in pharmaceutical formulations combining both drugs. 相似文献
56.
The instant controlled pressure drop (DIC) technology enabled both the extraction of essential oil and the expansion of the matrix itself which improved solvent extraction. The sequential use of DIC and Ultrasound Assisted Extraction (UAE) triggered complementary actions materialized by supplementary effects. We visualized these combination impacts by comparing them to standard techniques: Hydrodistillation (HD) and Solvent Extraction (SE). First, the extraction of orange peel Essential Oils (EO) was achieved by HD during 4 h and DIC process (after optimization) during 2 min; EO yields was 1.97 mg/g dry material (dm) with HD compared to 16.57 mg/g dm with DIC. Second, the solid residue was recovered to extract antioxidant compounds (naringin and hesperidin) by SE and UAE. Scanning electron microscope showed that after HD the recovered solid shriveled as opposite to DIC treatment which expanded the product structure. HPLC analyses showed that the best kinetics and yields of naringin and hesperidin extraction was when DIC and UAE are combined. Indeed, after 1 h of extraction, DIC treated orange peels with UAE were 0.825 ± 1.6 × 10?2 g/g of dry material (dm) for hesperidin and 6.45 × 10?2 ± 2.3 × 10?4 g/g dm for naringin compared to 0.64 ± 2.7 × 10?2 g/g of dry material (dm) and 5.7 × 10?2 ± 1.6 × 10?3 g/g dm, respectively with SE. By combining DIC to UAE, it was possible to enhance kinetics and yields of antioxidant extraction. 相似文献
57.
Sebastian Prinz Karine M. Sparta Georg Roth 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(3):i27-i29
Dirubidium divanadyl phyllooctasilicate, Rb2(VO)2[Si8O19], is the first known anhydrous diphyllosilicate containing VIV. The structure consists of silicate double layers which are separated by [V2O8]8− dimers and is related to that of the compounds A2Cu2[Si8O19] (A = Rb or Cs), although the title compound crystallizes in a noncentrosymmetric orthorhombic space group. The silicate double layers contain four tetrahedrally coordinated Si sites in general positions and 12 O sites, nine in general positions and the other three on mirror planes. The vanadyl dimers have two square‐pyramidally coordinated V sites (site symmetry m). There are two different 10‐ and 12‐fold coordinated Rb sites with site symmetry m, one of which is a split position located between the dimers in the interlayer space, while the other is in a channel within the silicate layer. 相似文献
58.
Vidic J Grosclaude J Monnerie R Persuy MA Badonnel K Baly C Caillol M Briand L Salesse R Pajot-Augy E 《Lab on a chip》2008,8(5):678-688
The molecular mechanisms underlying odorant detection have been investigated using the chip based SPR technique by focusing on the dynamic interactions between transmembrane Olfactory Receptor OR1740, odorant ligands and soluble Odorant-Binding Protein (OBP-1F). The OR1740 present in the lipid bilayer of nanosomes derived from transformed yeasts specifically bound OBP-1F. The receptor preferential odorant ligand helional released bound OBP-1F from the OR-OBP complex, while unrelated odorants failed to do so. OBP-1F modified the functional OR1740 dose-response to helional, from a bell-shaped to a saturation curve, thus preserving OR activity at high ligand concentration. This unravels an active role for OBPs in olfaction, in addition to passive transport or a scavenger role. This sensorchip technology was applied to assessing native OBP-1F in a biological sample: rat olfactory mucus also displayed significant binding to OR1740 nanosomes, and the addition of helional yielded the dissociation of mucus OBP from the receptor. 相似文献
59.
Le Dévédec F Bazinet L Furtos A Venne K Brunet S Mateescu MA 《Journal of chromatography. A》2008,1194(2):165-171
A novel approach for chitosan oligosaccharide (COS) separation by immobilized metal affinity chromatography (IMAC) based on the differences in the interactions of chelated copper (II) ions with various COS (dimers, trimers, tetramers) is described. Polyhydroxylic chromatographic supports (agarose CL-6B and silica) were functionalized with various chelating functions such as iminodiacetate (IDA), carboxymethyl-aspartate (CM-Asp) and tris(carboxymethyl)ethylenediamine (TED). The COS retention capacities of the columns were between 2 and 6 mg/cm(3), depending on the chelating group. The COS were separated and/or enriched up to 95% for dimer and trimer and 90% for the tetramer, with yields of 60-95%. 相似文献
60.
Karine Scarpellini‐Charras Gérard Boyer Nathalie Filloux Jean‐Pierre Galy 《Journal of heterocyclic chemistry》2008,45(1):67-70
The preparation of symmetric 2,2′‐dimethoxy‐10,10′‐biacridinyl‐9,9′‐dione atropisomers were obtained by the oxidative coupling of 9(10H)‐acridinone with 1,3‐dibromo‐5,5‐dimethyl‐imidazolidine‐2,4‐dione 相似文献