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931.
Lewis Acids as Activators in CBS‐Catalysed Diels–Alder Reactions: Distortion Induced Lewis Acidity Enhancement of SnCl4 下载免费PDF全文
Dr. Alexander R. Nödling Robert Möckel Dr. Ralf Tonner Prof. Dr. Gerhard Hilt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13171-13180
The effect of several Lewis acids on the CBS catalyst (named after Corey, Bakshi and Shibata) was investigated in this study. While 2H NMR spectroscopic measurements served as gauge for the activation capability of the Lewis acids, in situ FT‐IR spectroscopy was employed to assess the catalytic activity of the Lewis acid oxazaborolidine complexes. A correlation was found between the Δδ(2H) values and rate constants kDA, which indicates a direct translation of Lewis acidity into reactivity of the Lewis acid–CBS complexes. Unexpectedly, a significant deviation was found for SnCl4 as Lewis acid. The SnCl4–CBS adduct was much more reactive than the Δδ(2H) values predicted and gave similar reaction rates to those observed for the prominent AlBr3–CBS adduct. To rationalize these results, quantum mechanical calculations were performed. The frontier molecular orbital approach was applied and a good correlation between the LUMO energies of the Lewis acid–CBS–naphthoquinone adducts and kDA could be found. For the SnCl4–CBS–naphthoquinone adduct an unusual distortion was observed leading to an enhanced Lewis acidity. Energy decomposition analysis with natural orbitals for chemical valence (EDA‐NOCV) calculations revealed the relevant interactions and activation mode of SnCl4 as Lewis acid in Diels–Alder reactions. 相似文献
932.
Romuald Bartnik Dariusz Cal 《Phosphorus, sulfur, and silicon and the related elements》2013,188(9):1858-1861
The regioselective synthesis of 3-diethoxyphosphonopyrazoles has been accomplished through the addition of aryl or alkyl hydrazines to (3-ethoxyacryloyl)phosphonic acid diethyl ester. An example of hydrolysis of the pyrazolephosphonic ester to the corresponding acid is described. 相似文献
933.
We comment on the paper [Song et al., J. Comput. Chem. 2009, 30, 399]. and discuss the efficiency of the orbital optimization and gradient evaluation in the Valence Bond Self Consistent Field (VBSCF) method. We note that Song et al. neglect to properly reference Broer et al., who published an algorithm [Broer and Nieuwpoort, Theor. Chim. Acta 1988, 73, 405] to use a Fock matrix to compute a matrix element between two different determinants, which can be used for an orbital optimization. Further, Song et al. publish a misleading comparison with our VBSCF algorithm [Dijkstra and van Lenthe, J. Chem. Phys. 2000, 113, 2100; van Lenthe et al., Mol. Phys. 1991, 73, 1159] to enable them to favorably compare their algorithm with ours. We give detail timings in terms of different orbital types in the calculation and actual timings for the example cases. © 2012 Wiley Periodicals, Inc. 相似文献
934.
Milovan M. Stoiljković Igor A. Pašti Miloš D. Momčilović Jelena J. Savović Mirjana S. Pavlović 《Spectrochimica Acta Part B: Atomic Spectroscopy》2010
Enhancement of emission line intensities by induced oscillations of direct current (DC) arc plasma with continuous aerosol sample supply was investigated using multivariate statistics. Principal component analysis (PCA) was employed to evaluate enhancements of 34 atomic spectral lines belonging to 33 elements and 35 ionic spectral lines belonging to 23 elements. Correlation and classification of the elements were done not only by a single property such as the first ionization energy, but also by considering other relevant parameters. Special attention was paid to the influence of the oxide bond strength in an attempt to clarify/predict the enhancement effect. Energies of vaporization, atomization, and excitation were also considered in the analysis. In the case of atomic lines, the best correlation between the enhancements and first ionization energies was obtained as a negative correlation, with weak consistency in grouping of elements in score plots. Conversely, in the case of ionic lines, the best correlation of the enhancements with the sum of the first ionization energies and oxide bond energies was obtained as a positive correlation, with four distinctive groups of elements. The role of the gas-phase atom-oxide bond energy in the entire enhancement effect is underlined. 相似文献
935.
936.
Francesco De Vincentiis Giorgio Bencivenni Dr. Fabio Pesciaioli Andrea Mazzanti Dr. Giuseppe Bartoli Prof. Patrizia Galzerano Dr. Paolo Melchiorre Prof. Dr. 《化学:亚洲杂志》2010,5(7):1652-1656
The first catalytic method for the asymmetric aziridination of cyclic enones is described. The presented organocatalytic strategy is based on the use of an easily available organocatalyst that is able to convert a wide range of cyclic enones into the desired aziridines with very high enantiomeric purity and good chemical yield. Such a method may very well open up new opportunities to stereoselectively prepare complex chiral molecules that possess an indane moiety, a framework that is found in a large number of bioactive and pharmaceutically important molecules 相似文献
937.
Hydroperoxides, olefins, and arenediazonium salts selectively combine to give azo compounds via an iron(II)-mediated three-component reaction. Starting with a fragmentation liberating acetic acid, the hydroperoxides act as radical source and the diazonium ions as nitrogen-centered radical scavengers. 相似文献
938.
Mohammad Alaghemandi Joachim Schulte Frédéric Leroy Florian Müller‐plathe Michael C. Böhm 《Journal of computational chemistry》2011,32(1):121-133
The thermal conductivity (λ) of carbon nanotubes (CNTs) with chirality indices (5,0), (10,0), (5,5), and (10,10) has been studied by reverse nonequilibrium molecular dynamics (RNEMD) simulations as a function of different bond length alternation patterns (Δri). The Δri dependence of the bond force constant (krx) in the molecular dynamics force field has been modeled with the help of an electronic band structure approach. These calculations show that the Δri dependence of krx in tubes with not too small a diameter can be mapped by a simple linear bond length–bond order correlation. A bond length alternation with an overall reduction in the length of the nanotube causes an enhancement of λ, whereas an alternation scheme leading to an elongation of the tube is coupled to a decrease of the thermal conductivity. This effect is more pronounced in carbon nanotubes with larger diameters. The formation of a polyene‐like structure in the direction of the longitudinal axis has a negligible influence on λ. A comparative analysis of the RNEMD and crystal orbital results indicates that Δri‐dependent modifications of λ and the electrical conductivity are uncorrelated. This behavior is in‐line with a heat transfer that is not carried by electrons. Modifications of λ as a function of the bond alternation in the (10,10) nanotube are explained with the help of power spectra, which provide access to the density of vibrational states. We have suggested longitudinal low‐energy modes in the spectra that might be responsible for the Δri dependence of λ. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
939.
940.
An imaginary potential with universal normalization for dissipative processes in heavy-ion reactions
D. Pereira J. Lubian J.R.B. Oliveira D.P. de Sousa L.C. Chamon 《Physics letters. [Part B]》2009,670(4-5):330-335
In this work we present new coupled channel calculations with the São Paulo potential (SPP) as the bare interaction, and an imaginary potential with system and energy independent normalization that has been developed to take into account dissipative processes in heavy-ion reactions. This imaginary potential is based on high-energy nucleon interaction in nuclear medium. Our theoretical predictions for energies up to ≈100 MeV/nucleon agree very well with the experimental data for the p,n+nucleus, 16O + 27Al, 16O + 60Ni, 58Ni + 124Sn, and weakly bound projectile 7Li + 120Sn systems. 相似文献