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51.
Chromatographic reactors are based on coupling chemical reactions with chromatographic separation in fixed-beds. Temperature and flow rate are important parameters for the performance of such reactors. Temperature affects mainly adsorption, chemical equilibria, mass transfer and reaction kinetics, whereas flow rate influences residence time and dispersion. In order to evaluate the mentioned effects, the hydrolysis reactions of methyl formate (MF) and methyl acetate (MA) were chosen as case studies. These reactions were performed experimentally in a lab-scale fixed-bed chromatographic reactor packed with a strong acidic ion exchange resin. The chosen reactions can be considered to represent a relative fast (MF) and a relative slow (MA) reaction. The processes which take place inside the reactor were described and simulated using an isothermal equilibrium dispersive model. The essential model parameters were determined experimentally at different temperatures and flow rates. The performance of the chromatographic reactor was evaluated at several discrete constant temperature levels by quantifying product purity, productivity and yield. The work provides insight regarding the influence of temperature and flow rate on values of the model parameters and the performance criteria. 相似文献
52.
A new two-step synthesis of highly substituted pyrrolidines has been developed. Chiral silane Lewis acid promoted enantioselective Mannich reactions of silyl ketene imines with acylhydrazones may be used to access bishomoallylic benzoic hydrazides that in turn may be cyclized to pyrrolidines by way of the thermal hydroamination reaction reported recently by Beauchemin. Importantly, excellent diastereoselectivity may be realized in the hydroamination reactions. 相似文献
53.
Density functional theory and multiconfigurational CASPT2 and density matrix renormalization group DMRG-CASPT2 have been employed to study the low-lying states of NbGen−/0/+ (n = 1–3) clusters. With the DMRG-CASPT2 method, the active spaces are extended to a size of 20 orbitals. For most of the states, the CASPT2 relative energies are comparable with the DMRG-CASPT2 results. The leading configuration, bond distances, vibrational frequencies, and relative energies of the low-lying states of these clusters were calculated. The ground states of these clusters were computed to be 3Δ, 4Φ, and 5Φ of NbGe−/0/+; 3A2, 4B1, and 3B1 of cyclic-NbGe2−/0/+; and 1A′, 12A″ and 12A′′ (2E), and 3A″ of tetrahedral-NbGe3−/0/+ isomers. For NbGe cluster, our calculations proposed that the 6∑ is almost degenerate with the 4Φ with the CASPT2 and DMRG-CASPT2 relative energies of 0.05 and 0.06 eV. The adiabatic detachment energies of NbGen− (n = 1–3) clusters were estimated to be 1.46, 1.55, and 2.18 eV by the CASPT2 method. The relevant detachment energies of the anionic ground state and the ionization energies of the neutral ground states are evaluated at the CASPT2 level. 相似文献
54.
Duong Quoc Hoan Le Thi Hoa Trinh Thi Huan Nguyen Huu Dinh 《Journal of heterocyclic chemistry》2020,57(4):1720-1728
An efficient and simple method has been reported for the synthesis of 4-(1-Chloro-1-nitroethyl)-6,7-dimethoxy-2-methylquinazoline ( 2 ) as a key compound for further transformation to other novel 6,7-dimethoxy-2-methyl-4-substituted quinazolines. The structure of the synthesized compounds was characterized by spectroscopic methods. The pathway of some unprecedented reactions was proposed. (E)-1-(6,7-dimethoxy-2-methylquinazolin-4-yl)-3-(4-nitrophenyl)prop-2-en-1-one (11) exhibits high in vitro cytotoxicity on three cell lines, Hepatocellular carcinoma (Hep-G2), Human lung carcinoma (LU-1), and Human breast carcinoma (MCF-7) with IC50 of 2.1, 11.6 and 2.2 μM, respectively. 相似文献
55.
Martin Krtký Katarína Svr
kov Quynh Anh Vu rka tpnkov Jarmila Vinov 《Molecules (Basel, Switzerland)》2021,26(4)
Based on the broad spectrum of biological activity of hydrazide–hydrazones, trifluoromethyl compounds, and clinical usage of cholinesterase inhibitors, we investigated hydrazones obtained from 4-(trifluoromethyl)benzohydrazide and various benzaldehydes or aliphatic ketones as potential inhibitors of acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE). They were evaluated using Ellman’s spectrophotometric method. The hydrazide–hydrazones produced a dual inhibition of both cholinesterase enzymes with IC50 values of 46.8–137.7 µM and 19.1–881.1 µM for AChE and BuChE, respectively. The majority of the compounds were stronger inhibitors of AChE; four of them (2-bromobenzaldehyde, 3-(trifluoromethyl)benzaldehyde, cyclohexanone, and camphor-based 2o, 2p, 3c, and 3d, respectively) produced a balanced inhibition of the enzymes and only 2-chloro/trifluoromethyl benzylidene derivatives 2d and 2q were found to be more potent inhibitors of BuChE. 4-(Trifluoromethyl)-N’-[4-(trifluoromethyl)benzylidene]benzohydrazide 2l produced the strongest inhibition of AChE via mixed-type inhibition determined experimentally. Structure–activity relationships were identified. The compounds fit physicochemical space for targeting central nervous systems with no apparent cytotoxicity for eukaryotic cell line together. The study provides new insights into this CF3-hydrazide–hydrazone scaffold. 相似文献
56.
57.
Hoang Nam Nhat Phung Quoc Thanh Le Thi Anh Thu 《Journal of magnetism and magnetic materials》2009,321(24):4123-4127
The spin chain systems with one-dimensional magnetic ordering are promising candidates for quantum optical devices. This paper shows how the optical excitation can induce various phonon modes in an ideal Cu-O chain at various lengths. The calculation was carried out at different level theories including configuration interaction singles for excited states, density functional theory and second-order Möller-Plesset perturbation. In general, the number of modes increases with chain length due to growing asymmetry of atomic positions when chain exceeds 5 nm. There were, however, only two basic modes: one is associated with the symmetric oscillation of oxygen and another with the asymmetric motion of the same along the chain. At the length below 4.3 nm, the Raman activity of the symmetric mode (440 cm−1) dominates. From analysis of density of states, this mode may be associated with the excitation across the lowest LUMO bands with changing in spin state. 相似文献
58.
S. Issing F. Fuchs C. Ziereis E. Batke A. Pimenov Y. Vu. Ivanov A. A. Mukhin J. Geurts 《The European Physical Journal B - Condensed Matter and Complex Systems》2010,73(3):353-360
A systematic and detailed study of Raman and infrared active lattice excitations in the orthorhombic multiferroic manganite
Eu1−xYxMnO3 (0 ≤ x ≤ 0.5) was carried out at room temperature. For the infrared active phonon modes the eigenfrequencies, damping constants
and oscillator strengths were analyzed by Fourier-Transform Infrared Spectroscopy in the far infrared frequency range. For
the Raman active phonons the same analysis for eigenfrequencies and damping constants was carried out using Raman spectroscopy
in the range from 200 cm−1 to 700 cm−1. Y doping leads to mode-dependent phonon frequency shifts up to 8%. These are interpreted in terms of the interplay between
the decrease of the reduced ion masses and the axis-dependent change of bond lengths. The latter leads to a bond softening
along the a-axis and a strengthening along the c-axis, for which the highest phonon frequency increase is observed. The application
of both Raman and Infrared Spectroscopy gives us sensitivity not only to symmetry properties via the selection rules but also
to the involvement of different ion types within the unit cell. It is clearly shown that the disorder induced effects are
of minor impact on the lattice properties and solely detected on the rare earth sites. The MnO6 octahedra remain unaffected and show the same behavior as in the stochiometric RMnO3 making Eu1−xYxMnO3 an excellent model system for a quasi-continuous fine-tuning of the lattice parameters relevant for the appearance of multiferroicity. 相似文献
59.
Applying Kontsevich's iterated integral for tangles, we get an isotopy invariant of tangles. We give a method to compute the integral of a tangle combinatorially from modified integrals of some simple tangles. We localize the integral by moving the end points of the tangle to an extreme configuration, and modify the integral so that it is convergent. By using a similar technique, we generalize Kontsevich's invariant to a framed tangle. 相似文献
60.