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81.
The surface pressure (Π) vs surface concentration (Γs) curves of the hydrogen-bonded polymer blend poly(vinylacetate)+ poly(4-hydro-xystyrene) (PVAc+P4HS) have been measured at
25 °C onto a water subphase at pH=2.0. While PVAc forms extended monolayers, and the free surface of water is found to be
a good solvent for it, P4HS forms compressed monolayers, and the surface is a near Θ-type solvent for it. PVAc and P4HS form
miscible non-ideal monolayers until near the collapse pressure through the whole concentration range. The composition dependence
of the Π–Γs curves is rather complex. Contrary to what might be expected, the addition of PVAc to the blend does not reduce the rigidity
of the monolayer until its weight fraction is larger than 0.5. The compressibility data of the P4HS-rich monolayers suggest
the existence of a second maximum at high surface coverages, a result already observed in some polysiloxanes.
Received: 11 March 1998 Accepted: 7 May 1998 相似文献
82.
S. V. Shishkina T. G. Drushlyak L. A. Kutulya N. S. Pivnenko O. V. Shishkin 《Journal of Structural Chemistry》2004,45(5):889-895
X-ray analysis was carried out to study the molecular structure of β-hydroxyketone, which is one of the minor products of selective aldol condensation of (−)-menthone with 4-carbomethoxybenzaldehyde. The cyclohexanone ring of the compound has a practically undistorted chair conformation with an axial orientation of the 1-methyl group and the bulkiest 2-[1′-hydroxy-1′ -(4-carbomethoxyphenyl)]methyl substituent and the equatorial orientation of the isopropyl group in the 4 position. The stereochemical configuration was found to be (1R,2R,4 R, 1′ S), supporting that the compound belongs to the group of (+)-isomenthones; i.e., the starting (-)-menthone undergoes (to a certain extent) epimerization under the reaction conditions used. In crystal, there is intermolecular hydrogen bonding >C=O...HO- (the -O...H- bond length is 2.15 Å). The molecular conformation in hydroxyketone crystals differs from the one which prevails in solutions (according to previous NMR data) and which is characterized by an inverted cyclohexanone ring and intramolecular hydrogen bonding >C=O...HO.Original Russian Text Copyright © 2004 by S. V. Shishkina, T. G. Drushlyak, L. A. Kutulya, N. S. Pivnenko, and O. V. Shishkin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 933–940, September–October, 2004. 相似文献
83.
McDowell SA 《Journal of computational chemistry》2003,24(10):1201-1207
A theoretical study of the properties of the linear LiH dimer was undertaken. In this dimer, an unusual type of hydrogen bonding (termed "inverse" hydrogen bonding by some authors), which involves the hydrogen bonded molecule acting as an electron donor (rather than as a proton donor), is exhibited. The optimized geometry, dipole moment, interaction energy, atomic charges, harmonic vibrational frequencies, and frequency shifts for the dimer are computed at the SCF, MP2, and QCISD levels of theory using mainly a 6-31++G(d,p) basis set. We also examined the relative stability of the mono-deuterated isotopomers of linear (LiH)(2), i.e., Li-H...Li-D and Li-D...Li-H. Analysis of the normal vibrational modes, changes in the partial atomic charges, and changes in the vibrational frequencies of LiH on complexation were used to gain insight into the bonding and properties of the linear LiH dimer and its isotopomers. 相似文献
84.
The complexation of tetramethylresorc[4]arene with primary and secondary amines in acetonitrile was investigated spectrophotometrically. The stoichiometry of the complexes formed was shown to depend on the amine concentration. Based on the proposed complexation models, the formation constants of the complexes as well as their thermodynamical parameters were determined and discussed. Depending on the amine concentration, two types of solid complexes of tetramethylresorc[4]arene with amines were obtained. The composition of these complexes was confirmed by 1H NMR. 相似文献
85.
A. G. Matveeva E. I. Matrosov Z. A. Starikova G. V. Bodrin S. V. Matveev P. V. Petrovskii E. E. Nifant’ev 《Russian Chemical Bulletin》2005,54(11):2519-2534
The trifunctional ligand, 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol (L
2), forms complexes with cerium(III) nitrate having a ligand to metal ratio of 1: 1, 2: 1, and 3: 1. The structures of these complexes in the solid state and
in solution were studied by X-ray diffraction, IR and NMR (1H and 31P) spectroscopy, and conformational analysis (molecular mechanics). The 2: 1 complexes of L
2 with lanthanum(III) and neodymium(III) nitrates were synthesized and characterized. In all complexes, the neutral ligand is coordinated through both phosphoryl
oxygen atoms. The hydroxy oxygen atom is coordinated only in some complexes, and the hydrogen atom of the hydroxy group is
involved in hydrogen bonding. The compositions and structures of the resulting complexes depend on the method of synthesis
and the nature of solvent. The ligand was found to undergo easy inner-sphere oxidation. The structure of one of the transformation
products was established by X-ray diffraction. Unlike the coordinated ligand, the free ligand is very stable to oxidation.
Dedicated to Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2440–2454, November, 2005. 相似文献
86.
A. A. Vedenyapin M. D. Baturova G. I. Ioseliani G. Kh. Areshidze 《Russian Chemical Bulletin》1997,46(1):76-80
The anodic oxidation of the carbon felt Carbonetcalon results in the formation of surface defects which serve as centers of
strong adsorption of PdII, NiII, and CuII ions. The electrochemical reduction of adsorbed ions makes it possible to obtain metallic catalysts, which undergo multiple
redox cycles without loss of metal. The catalysts are characterized by high dispersity of the reduced phase, high adsorption
capacity with respect to hydrogen, and 100% selectivity in hydrogenation of acetophenone.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 81–85, January 1997 相似文献
87.
88.
Balamurugan V Hundal MS Mukherjee R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1683-1690
Using a group of six neutral M(II)Cl(2)-containing coordination compounds as building blocks, the first systematic investigation of C-H...Cl hydrogen-bonding interactions was performed. Single-crystal X-ray structural analyses of four new compounds (pseudo-tetrahedral Co(II) and Zn(II); distorted trigonal bipyramidal Zn(II)) authenticate the metal coordination geometry. To provide a unified view of the presence of noncovalent interactions in this class of compounds, we have re-examined the packing diagram of two previously reported compounds (a distorted square-pyramidal Cu(II) complex and a trans-octahedral Co(II) complex). The organic ligands of our choice comprise bidentate/tridentate pyrazolylmethylpyridines and an unsymmetrical tridentate pyridylalkylamine. This systematic investigation has allowed us to demonstrate the existence of versatile C-H...Cl(2)M interactions and to report the successful application of such units as inorganic supramolecular synthons. Additional noncovalent interactions such as C-H...O and O-H...Cl hydrogen bonding and pi-pi stacking interactions have also been identified. Formation of novel supramolecular architectures has been revealed: 2D lamellar (p-cyclophane) and 3D lamellar, 3D "stitched staircase" (due to additional hydrogen-bonding interactions by water tetramers, with an average O-O bond length in the tetramer unit of 2.926 A, acting as "molecular clips" between staircases), 3D linked ladder, and single-stranded 1D helix. 相似文献
89.
Highly efficient kinetic resolution of racemic secondary alkyl diazoacetates in intramolecular carbon-hydrogen insertion reactions has been achieved using chiral dirhodium(ii) carboxamidates. Products formed from catalytic diazo decomposition of racemic 2-octyl diazoacetate and, separately, its (2R)- and (2S)-enantiomeric forms, as well as bothcis- andtrans-2-methylcyclohexyl diazoacetates, have been systematically evaluated. Enantioselectivities up to 99 %ee have been obtained for -lactone formation. -Lactone production has been observed and, although minor with cyclohexyl diazoacetates, is the major insertion pathway for diazo decomposition of 2-octyl diazoacetate.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1798–1803, September, 1995.Financial support for this research from the National Institutes of Health (GM 46503) and the National Science Foundation of the United States is gratefully acknowledged. We thank D. A. Pierson for her preparation of 2-methylcyclohexyl diazoacetates and preliminary studies of their diazo decomposition and A. Melekhov from the Higher College of Chemistry for his preparation and catalytic studies of rac-2-octyl diazoacetate. 相似文献
90.
N. I. Golovina R. F. Trofimova L. O. Atovmyan A. G. Korepin P. V. Galkin G. V. Lagodzinskaya M. V. Loginova L. T. Eremenko 《Russian Chemical Bulletin》1994,43(3):398-401
The reaction of -fluorosubstituted polynitroalkylaldimines with HCl results in replacement of the fluorine atom by a chlorine atom. The hitherto unknown -chlorosubstituted polynitroalkylaldimines have been obtained, and their X-ray structural investigation has been performed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 440–443, March, 1994. 相似文献