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1.
Studies of breakdown threshold intensity for air at various pressures in the range of 24–760 torr using 0.355, 0.532 and 1.06
μm radiation are reported. We observep
−0.8 scaling ofI
th at 1.06 μm and a weak scaling ofp
−0.4 at 0.532 and 0.355 μm radiation. Strong dependence of breakdown spot size on laser power but weak dependence on air pressure
is observed. 相似文献
2.
3.
Mariappan Periasamy Neela Kishorebabu K. Natarajan Jayakumar 《Tetrahedron letters》2007,48(11):1955-1958
N,N-Dialkylarylamines react with trimethyl orthoformate and TiCl4 under ambient conditions to give the corresponding formyl derivatives in 75-89% yields, whereas the corresponding arylated products are obtained from benzyl ethers and acetals in 42-78% yields. 相似文献
4.
Summary Reduction of anhydrous FeCl3 in THF with sodium naphthalenide under a CO atmosphere at room temperature leads directly to Na2Fe(CO)4, which on reaction with alkyl bromides gives the corresponding aldehydes, ketones and carboxylic acids under appropriate conditions. 相似文献
5.
A model beta-hairpin dodecapeptide [EFGWVpGKWTIK] was designed by including a favorable D-ProGly Type II' beta-turn sequence and a Trp-zip interaction, while also incorporating a beta-strand unfavorable glycine residue in the N-terminal strand. This peptide is highly folded and monomeric in aqueous solution as determined by combined analysis with circular dichroism and 1H NMR spectroscopy. A peptide representing the folded conformation of the model beta-hairpin [cyclic(EFGWVpGKWTIKpG)] and a linear peptide representing the unfolded conformation [EFGWVPGKWTIK] yield unexpected relative deviations between the CD and 1H NMR spectroscopic results that are attributed to variations in the packing interactions of the aromatic side chains. Mutational analysis of the model beta-hairpin indicates that the Trp-zip interaction favors folding and stability relative to an alternate hydrophobic cluster between Trp and Tyr residues [EFGYVpGKWTIK]. The significance of select diagonal interactions in the model beta-hairpin was tested by rearranging the cross-strand hydrophobic interactions to provide a folded peptide [EWFGIpGKTYWK] displaying evidence of an unusual backbone conformation at the hydrophobic cluster. This unusual conformation does not appear to be a result of the glycine residue in the beta-strand, as replacement with a serine results in a peptide [EWFSIpGKTYWK] with a similar and seemingly characteristic CD spectrum. However, an alternate arrangement of hydrophobic residues with a Trp-zip interaction in a similar position to the parent beta-hairpin [EGFWVpGKWITK] results in a folded beta-hairpin conformation. The differences between side chain packing of these peptides precludes meaningful thermodynamic analysis and illustrates the caution necessary when interpreting beta-hairpin folding thermodynamics that are driven, at least in part, by aromatic cross strand interactions. 相似文献
6.
Mariappan PeriasamyN. KishoreBabu Keela Natarajan Jayakumar 《Tetrahedron letters》2003,44(50):8939-8941
The reactions of arylacetic acid esters with tertiary arylamines in the presence of TiCl4 give α-arylated products in 65-90% yields, as well as 10-20% yields of the corresponding benzidines. 相似文献
7.
G. Sivalingam R. Karthik Giridhar Madras 《Journal of Analytical and Applied Pyrolysis》2003,70(2):631-647
The thermal degradation/modification dynamics of poly(-caprolactone) (PCL) was investigated in a thermogravimetric analyzer under non-isothermal and isothermal conditions. The time evolution of the molecular weight distribution during degradation was studied using gel permeation chromatography. Experimental molecular weight evolution and weight loss profile were modeled using continuous distribution kinetics. The degradation exhibited distinctly different behavior under non-isothermal and isothermal heating. Under non-isothermal heating, the mass of the polymer remained constant at initial stages with rapid degradation at longer times. The Friedman and Chang methods of analysis showed a 3-fold change (from 18 to 55–62 kcal mol−1) in the activation energy from low temperatures to high temperatures during degradation. This suggested the governing mechanism changes during degradation and was explained using two parallel mechanisms (random chain scission and specific chain end scission) without invoking the sequential reaction mechanisms. Under isothermal heating, the polymer degraded by pure unzipping of specific products from the chain end. 相似文献
8.
Electronic and structural factors controlling the competition between 5-exo-dig and 6-endo-dig cyclizations of sp2-radicals were analyzed using a combination of available experimental data and computation. Although the stereoelectronically favored 5-exo pathways usually has the lower activation energy, formation of a new aromatic ring not only makes the 6-endo process favorable thermodynamically in conjugated systems but also lowers its activation barrier to the extent where the 5-exo/6-endo selectivity is controlled by subtle factors such as the different sensitivity of the two pathways to strain effects in polycyclic systems. In particular, the stronger sensitivity of the 5-exo pathway to strain leads to a crossover in selectivity. The 6-endo cyclization is kinetically favored in smaller (and strained) cycles, whereas the 5-exo cyclization has lower barriers in the larger rings. 相似文献
9.
10.
G. Madhurambal M. Mariappan S. Hariharan P. Ramasamy S. C. Mojumdar 《Journal of Thermal Analysis and Calorimetry》2013,112(2):1127-1132
Mixed crystals of 0.1 and 0.25 zinc magnesium ammonium sulphate were grown by slow evaporation of aqueous solution at room temperature. The bright and transparent crystals obtained were characterized by thermal (TG–DTA), FTIR and XRD analyses. A fitting decomposition pattern for the compound was formulated on the TG curve which shows two stage mass losses between 133 and 478.75 °C. In this temperature range, DTA curve shows exothermic peaks supporting the formulated decomposition pattern. The FTIR spectra show the vibration frequencies due to the formation of zinc magnesium ammonium sulphate mixed crystals. Detailed structural analysis of the compound is under progress. 相似文献