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1.
Karthikeyan G. Anbalagan K. Elango K. P. 《Russian Journal of Coordination Chemistry》2003,29(4):237-244
Photoreduction of [Co(En)2Cl(RC6H4NH2)]2+ ions (where R = p-OMe, p-OEt, p-Me, m-Me, H, p-F, and m-OMe) in varying compositions of water–methanol and water–1,4-dioxane mixtures containing 15–40% (vol.) of organic co-solvent is carried out. Ultraviolet excitation of the above complexes in air-equilibrated solutions causes bleaching of its intense LMCT excited states with concurrent production of Co2+ion. As seen from the quantum yield data, Co(II) increases smoothly with increasing content of organic co-solvent in the binary mixtures. The observed values indicate that the metal center is reduced by both ligands and solvent. The quantum yield Co(II) is considerably affected by the substituent R of the amine, RC6H4NH2 ligand. The effects of solvent and substituted ligands on the Co(II) are estimated quantitatively using linear regression and multiple correlation methods. The former analysis was carried out using Grunwald–Winstein (Y) Gutmann donor number (DN
N) and Krygowski–Fawcett E
N
T (solvent empirical parameters). In addition, Kamlet–Taft's , , and * solvatochromic parameters were also used to study the effect of solute–solvent interaction. The effect of substitution on the aromatic amine ligand affects the quantum yield values, which was established using Hammett's substituent constant . Extensive tabulations of percentage contributions of these parameters, calculated using methods reported earlier, provide suitable values which are presumed to explain the quantitative effects of solvent and structural changes in the aromatic ligand on photoreduction of the cobalt(III) complexes. 相似文献
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Carbonate radicals react with aliphatic amines by a dual mechanism, viz. (i) hydrogen abstraction and (ii) electron transfer. The former is more probable with primary amines. Tertiary amines react via electron transfer. Both mechanisms may operate in secondary amines. Cyclic tertiary amines react with different rates and their relative reactivities are explained on the basis of the concept of Hoffmann's ‘through bond’ interaction. 相似文献
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5.
T. P. Elango V. Ramakrishnan S. Vancheesan J. C. Kuriacose 《Journal of Chemical Sciences》1984,93(1):47-52
Rate constants for the reaction of carbonate radical with aniline and some parasubstituted anilines have been determined by
the flash photolysis technique. Using σ+ para values the rate constants at pH 8.5 correlate very well with the Hammett equation yielding ρ= − 1. The carbonate radical oxidises aniline giving the anilino radical. The products so formed have been identified through
studies under conditions of continuous irradiation. 相似文献
6.
Samuel N. Sanders Elango Kumarasamy Kealan J. Fallon Matthew Y. Sfeir Luis M. Campos 《Chemical science》2020,11(4):1079
Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large.We report the synthesis and photophysical characterization of highly exoergic singlet fission in a hexacene dimer revealing exciton dynamics that follow the energy gap law. 相似文献
7.
T. P. Elango S. Vancheesan V. Ramakrishnan J. C. Kuriacose 《Journal of Radioanalytical and Nuclear Chemistry》1988,125(1):151-155
Carbonate radical shows moderate reactivity (k2=1.8·106 M–1 s–1) with nickelglycine complex. As an oxidizing free radical, it may attack the ligand to form Ni(II) coordinated glycine radical or oxidize the metal center to form a Ni(III) glycine transient. Continuous -irradiation of the complex-bicarbonate mixture yields glyoxalic acid (G=1.7) as the major product. The reaction involves an attack of the ligand and precludes the oxidation of metal center. 相似文献
8.
Guan-Yeow Yeap Elango Hrishikesan Yi-Huan Chan Wan Ahmad Kamil Mahmood 《Journal of fluorescence》2017,27(1):105-110
A new chalcone-based probe containing coumarin and naphthol at both ends has been synthesized via aldol condensation. The uniqueness of the newly derived probe can be ascribed to the presence of naphthol and coumarin units acting as binding site and signaling element, respectively. The fluorogenic behaviors toward various anions were investigated. The probe was characterized by various spectroscopic techniques and the in-depth study led to show excellent selectivity and sensitivity for fluoride ions. The hydrogen bonding thus formed with fluoride anion provides remarkable fluorometric responses. The interactions of the probe with fluoride ions were determined by fluorescence, FT-IR and NMR spectroscopic techniques. The exploratory studies by fluorescent spectral changes augur well for the naked-eye sensing applications. 相似文献
9.