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1.
The fluorescence lifetime of Nile Red (NR) is not sensitive to dielectric solvent–solute interactions but markedly decreases with the increase of the hydrogen bond donating ability in alcohols because vibrations associated with hydrogen bonding are involved in the deactivation process. The negligible viscosity effect indicates that twisting of the diethylamino moiety of NR does not play significant role in the dissipation of the excitation energy. 相似文献
2.
The fluorescent properties of 2-hydroxy Nile red dye (HONR) proved to be highly sensitive to the basicity of hydrogen bond acceptors. Fluorescence quantum yields and fluorescence decay profiles were measured as the function of the concentration of organic nitrogen compounds in solvents of various polarities. The detailed mechanism and the kinetics of the fluorescence quenching were revealed with the combined analysis of the steady-state and time-resolved spectroscopic data. The relative contribution of the competing reaction steps was found to be very sensitive to the basicity of the additive and to solvent polarity. The most profound change appeared in the unimolecular deactivation pathways of the excited hydrogen-bonded HONR, whereas the formation rate of this species varied to a lesser extent. The dissociation into excited HONR and ground-state base was able to compete with the energy dissipation only when 2,4,6-trimethylpyridine was used as hydrogen bond acceptor in toluene. The bimolecular quenching of the excited hydrogen-bonded complex played significant role in apolar solvents. Proton displacement along the hydrogen bond in the excited complex led to excited ion pairs in polar media. 相似文献
3.
Amyes TL Diver ST Richard JP Rivas FM Toth K 《Journal of the American Chemical Society》2004,126(13):4366-4374
We report second-order rate constants kDO (M-1 s-1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 degrees C and I = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 10(11) s-1. The data were used to calculate reliable carbon acid pK(a)s for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pKa = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 x 10(16) for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes. 相似文献
4.
István Szilágyi Krisztina Imrik Dariusz Sarzisky Sándor Dóbé Tibor Bérces 《Reaction Kinetics and Catalysis Letters》2002,77(2):341-345
The title reactions have been studied at room temperature by applying the discharge flow method coupled with laser induced fluorescence detection of methoxy radicals and resonance fluorescence detection of bromine atoms. The following rate constants were determined: CH3O + Br Õ products (1) k
1 (298 K) = (3.4 ± 0.4 (1)) × 1013 cm3 mol-1 s-1, CH3O + Br2 Õ products (2) k
2 (298 K) £ 5 × 108 cm3 mol-1 s-1. 相似文献
5.
6.
Krisztina Sebk‐Nagy Lszl Biczk Akimitsu Morimoto Tetsuya Shimada Haruo Inoue 《Photochemistry and photobiology》2004,80(1):119-126
Effects of solvent, pH and hydrogen bonding with N‐methylimidazole (MIm) on the photophysical properties of 1‐hydroxyfluorenone (1HOF) have been studied. Fluorescence lifetime, fluorescence quantum yield and triplet yield measurements demonstrated that intersystem crossing was the dominant process in apolar media and its rate constant significantly diminished with increasing solvent polarity. The acceleration of internal conversion in alcohols paralleled the strength of intermolecular hydrogen bonding. The faster energy dissipation from the singlet‐excited state in cyclohexane was attributed to intramolecular hydrogen bonding. The pKa of 1HOF decreased from 10.06 to 5.0 on light absorption, and H3O+ quenched the singletexcited molecules in a practically diffusion‐controlled reaction. On addition of MIm in toluene, dual fluorescence was observed, which was attributed to reversible formation of excited hydrogen‐bonded ion pair. Rate constants for the various deactivation pathways were derived from the combined analysis of the steady‐state and the time‐resolved fluorescence results. 相似文献
7.
Truong Son Pham Katalin Gönczi György Kardos Krisztina Süle László Hegedűs Mihály Kállay Miklós Kubinyi Pál Szabó Imre Petneházy László Tőke Zsuzsa Jászay 《Tetrahedron: Asymmetry》2013,24(24):1605-1614
Several cinchona based squaramide catalysts were applied to the asymmetric Michael addition of α-nitroethylphosphonates to acrylic acid aryl esters, resulting in high yields and enantioselectivities. The absolute configuration of one of the quaternary α-nitrophosphonate adducts was deduced from its experimental and calculated CD spectra. The adducts were reduced to their cyclic aminophosphonates by catalytic hydrogenation. 相似文献
8.
Dávid Illés Nagy Alajos Grün Krisztina Lévay Sándor Garadnay István Greiner 《合成通讯》2018,48(6):663-671
The reaction of 1H-imidazol-1-ylacetic acid and two equivalents of phosphorus trichloride/phosphorous acid at 75?°C in sulfolane, or in the presence of catalytic amounts of [bmim][BF4] afforded zoledronic acid in yields up to 75%. The joint use of the ionic liquid additive and sulfolane as the solvent was synergetic affording highly valuable zoledronic acid in a record yield of 93%. 相似文献
9.
Alexander A. Kamnev Roman L. Dykman Krisztina Kovács Alexei N. Pankratov Anna V. Tugarova Zoltán Homonnay Ernő Kuzmann 《Structural chemistry》2014,25(2):649-657
Iron(III)-containing aqueous solutions of 5-methylresorcinol (5-MR), 5-n-propylresorcinol (5-n-PR) and 4-n-hexylresorcinol (4-n-HR) at pH ~ 3 were studied by means of 57Fe transmission Mössbauer spectroscopy. Kinetic considerations were applied to the redox reactions. Density Functional Theory (DFT) calculations were performed for the alkylresorcinol (AR) molecules and their non-alkylated analogue (resorcinol). Mössbauer spectra consisted of quadrupole doublets assigned to high-spin Fe(III) and Fe(II) species. From changes in their relative spectral areas, a gradual reduction of Fe(III) by all the ARs studied was observed. However, significant differences were found for the reduction rates among the ARs. The following series of the reduction rates was established by means of Mössbauer spectroscopy: 4-n-HR ? 5-MR > 5-n-PR, supplemented by rate constants calculated using a kinetic model. DFT calculations resulted in the following series: 4-n-HR ? 5-n-PR > 5-MR ? resorcinol (the latter is not oxidised under the conditions applied). The reversed order of the experimentally observed 5-MR and 5-n-PR oxidation rates may be explained in terms of their different kinetic parameters related to their structure. 相似文献
10.