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981.
Rois Benassi Erika Ferrari Sandra Lazzari Francesca Pignedoli Ferdinando Spagnolo Monica Saladini 《Journal of Physical Organic Chemistry》2011,24(4):299-310
In the present study, we investigate the structures of glucosylated curcumin derivatives with DFT at B3LYP/6‐31G* level. A conformational analysis is performed in order to determine the conformational minimum (GS) and rotational transition state (TS) of curcumin derivatives and then their electronic features are evaluated. HOMO and LUMO frontier orbitals and maps of electron density potential (MEPs) are plotted and compared. In order to correlate their predicted spectroscopic properties with IR, UV–vis and NMR experimental data we extended the theoretical study on electronic properties to different solvents (H2O, MeOH, ACN, DMSO). The main finding is that the curcuminic core maintains the same geometrical and electronic structures in all compounds miming the metal coordination capability showed by curcumin. Therefore, we may confirm that the presence of glucose does not affect the electronic properties of the derivatives. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
982.
Reactions of ·OH/O .? radicals and H‐atoms as well as specific oxidants such as Cl2.? and N3· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 109 dm3 mol?1 s?1 with 2‐HBA and 2 × 109 dm3 mol?1 s?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH2OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO42? ions (k = 2.1 × 107 and 2.8 × 107 dm3 mol?1 s?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H2PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H+ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O .? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O .? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
983.
Radomir Jasiński Magdalena Kwiatkowska Andrzej Barański 《Journal of Physical Organic Chemistry》2011,24(9):843-853
In spite of diversified electrophilicity of E‐2‐arylnitroethenes, their [4 + 2] cycloaddition reactions with cyclopentadiene leads to the corresponding 6‐endo‐aryl‐5‐exo‐nitronorbornenes and 6‐exo‐aryl‐5‐endo‐nitronorbornenes as the only reaction products. Stereoselectivity, substituent and solvent effects, and activation parameters, suggest that these reactions occur via a synchronous concerted mechanism on both competing pathways. The experimental results obtained are consistent with the data from B3LYP/6‐31G(d) calculations. Due to high electrophilicity of E‐2‐arylnitroethenes, the reactions studied should be considered as polar [4 + 2] cycloadditions. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
984.
985.
D. Amaranatha ReddyA. Divya G. MuraliR.P. Vijayalakshmi B.K. Reddy 《Physica B: Condensed Matter》2011,406(10):1944-1949
Nanoparticles of Zn1−xCrxS (x=0.00, 0.005, 0.01, 0.02 and 0.03) were prepared by a chemical co-precipitation reaction from homogenous solutions of zinc and chromium salts. These nanoparticles were sterically stabilized using 2-mercaptoethanol. Here a study of the effect of Cr doping on structural, morphological and optical properties of nanoparticles was undertaken. Elemental analysis, morphological, structural and optical properties have been investigated by energy dispersive analysis of X-rays (EDAX), scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-visible spectroscopy .EDAX measurements confirmed the presence of Cr in the ZnS lattice. XRD showed that ZnS:Cr nanoparticles crystallized in zincblende structure with preferential orientation along (1 1 1) plane. The average sizes of the nanoparticles lay in the range of 3-6 nm and lattice parameters were in the range of 5.2-5.4 Å. Lattice contraction was observed with an increase of Cr concentration. The particle size and lattice parameters obtained from TEM and SAED images were in agreement with the XRD results. The absorption edge shifted to lower wavelengths with an increase in Cr concentration as per UV-Vis spectroscopy. The band gap energy values were in the range of 3.85-4.05 eV. This blueshift is attributed to the quantum confinement effect. 相似文献
986.
First-principle study on the effect of high Li-2N co-doping on the conductivity of ZnO 总被引:1,自引:0,他引:1
Based on the density functional theory (DFT), using first-principles plane-wave ultrasoft pseudopotential method, the models of the unit cell of pure ZnO and two highly Li-2N co-doped supercells of Zn0.9375Li0.0625O0.875N0.125 and Zn0.9167Li0.0833O0.8333N0.1667 were constructed, and the geometry optimization for the three models was carried out. The total density of states (TDOS) and the band structures (BS) were also calculated. The calculation results showed that in the range of high doping concentration, when the co-doping concentration is more than a certain value, the conductivity decreased with the increase of co-doping concentration of Li-2N in ZnO, which agrees with the change trend of the experimental results. 相似文献
987.
T. Raghavendra RaoCh. Rama Krishna U.S. Udayachandran ThampyCh. Venkata Reddy Y.P. ReddyP. Sambasiva Rao R.V.S.S.N. Ravikumar 《Physica B: Condensed Matter》2011,406(11):2132-2137
The effect of Li2O content in vanadyl doped 20ZnO+xLi2O+(30−x)Na2O+50B2O3 (5≤x≥25) glasses has been studied with respect to their physical and structural properties. The absence of sharp peaks in XRD spectra of these glass samples confirms the amorphous nature. The physical parameters like density, refractive index, ionic concentration and electronic polarizability vary non-linearly with x mol% depending on the diffusivities of alkali ions. EPR and optical absorption spectra reveal that the resonance signals are characteristics of VO2+ ions in tetragonally compressed octahedral site. Spin-Hamiltonian, crystal field, tetragonal field and bonding parameters are found to be in good agreement with the other reported glass systems. The tetragonal distortion (g⊥-g∥) and Dt reveals that their values vary non-linearly with Li2O content and reaches a minimum at x=10 mol%. An anomaly of character has been observed in all the properties of vanadyl doped glass systems, which gives a clear indication of mixed alkali effect. 相似文献
988.
Qinqin Liu Juan YangXiaonong Cheng Xiujuan SunChuanliang Zang 《Physica B: Condensed Matter》2011,406(18):3458-3464
ZrW2O8 displays the unusual property of an isotropic bulk contraction in volume as a function of temperature. We report here on the positive thermal expansion (PTE) property caused by substituting Mo for W sites in ZrW2O8 at room temperature. The room temperature crystal structure of ZrW2−xMoxO8 compounds, which were synthesized using a low temperature route, could be divided into ordered phase with α-ZrW2O8 structure (0≤x≤0.5) and disordered phase with β-ZrW2O8 (0.5<x≤1.5) and c-ZrMo2O8 structure (1.5<x≤2). ZrW2−xMoxO8 adopting β-ZrW2O8 structure shows abnormal PTE property at room temperature due to the existence of water molecules, while ZrW2−xMoxO8 adopting the other two structures (α-ZrW2O8 and c-ZrMo2O8) shows negative thermal expansion (NTE) property from room temperature until decomposition for α-ZrW2O8 structure or trigonal phase transition for c-ZrMo2O8 structure. The reason lies in the fact that the oxygen migration caused by the Mo substitution leads to the re-arrangement of W(Mo)O4 tetrahedra lying along the 3-fold axis, only particular W/Mo ratio (0.5<x≤1.5) produces a special crystal structure, which allows the entrance of water molecules. 相似文献
989.
Bo ZhuChun-Mei Liu Ming-Bang LvXiang-Rong Chen Jun Zhu Guang-Fu Ji 《Physica B: Condensed Matter》2011,406(18):3508-3513
We investigate the structural, phase transition and elastic properties of SnO2 in the rutile-type, pyrite-type, ZrO2-type and cotunnite-type phases by the plane-wave pseudopotential density functional theory method. The lattice constants, bulk modulus and its pressure derivative are well consistent with the available experimental and other theoretical data. Also, we find that the rutile→pyrite, pyrite→ZrO2 and ZrO2→cotunnite phase transition occur at 12.9, 59.1 and 111.1 GPa, which are in better agreement with the experimental results than those of Gracia et al. (2007). Moreover, we obtain the pressure dependences of elastic constants for the four structures. 相似文献
990.
T. SrikumarM.G. Brik Ch. Srinivasa RaoN. Venkatramaiah Y. GandhiN. Veeraiah 《Physica B: Condensed Matter》2011,406(19):3592-3598
Li2O-ZrO2-SiO2: Ho3+ glasses mixed with three interesting d-block elemental oxides, viz., Nb2O5, Ta2O5 and La2O3, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb2O5 and Ta2O5 mixed Li2O-ZrO2-SiO2 glasses (free of Ho3+ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta5+ and Nb5+ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho3+ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio βr and the radiative lifetime τr, for 5S2 emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for 5S2 level of Ho3+ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La2O3 mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho3+ ions. 相似文献