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141.
Several novel pentamethylcyclopentadienyl complexes of general formula [(C5Me5)IrL3][BF4]2 were prepared including the tris(solvent) precursors [(C5Me5)M(acetone)2(H2O)][BF4]2 (M = Rh, Ir) (1a,b). The X-ray molecular structures of 1a,b were determined at low temperature. Complexes 1a,b are isostructural, and both compounds crystallize in the monoclinic space group P2(1)/c with a = 10.157(3) A, b = 14.038(9) A, c = 16.335(2) A, beta = 99.73(2) degrees, and Z = 4 for 1a and with a = 10.107(9) A, b = 13.994(16) A, c = 15.996(34) A, beta = 99.61(12) degrees, and Z = 4 for 1b. The coordinated water molecule is hydrogen bonded to both BF4(-) anions. Reaction of 1a,b with pyridine (py) afforded the related tris(pyridine) complexes [(C5Me5)M(eta1-(N)-py)3][BF4]2 (M = Rh, Ir) (2a,b). Complex 2b was characterized by X-ray crystallography, monoclinic space group P2(1)/c with a = 8.665(3) A, b = 19.687(7) A, c = 18.408(5) A, beta = 94.17(3) degrees, and Z = 4. Moreover, we prepared the novel neutral compounds (C5Me5)M(eta2-NO3)(eta1-NO3) (M = Rh, Ir) (4a,b) where the anions are bonded to the metal center instead of a coordinating solvent as confirmed by X-ray study on the iridium complex 4b. The latter crystallizes in the orthorhombic space group Pcab with a = 13.032(4) A, b = 14.370(11) A, c = 14.839(18) A, and Z = 8. 相似文献
142.
Supermolecular Columnar Liquid‐Crystalline Phosphorus Dendrimers Decorated with Sulfonamide Derivatives 下载免费PDF全文
Cesar Augusto Hincapié Rosa María Sebastián Joaquín Barberá José Luis Serrano Teresa Sierra Jean‐Pierre Majoral Anne‐Marie Caminade 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17047-17058
A series of supermolecular liquid crystals has been synthesized by combining phosphorus dendrimers of the zero, first, and fourth generations with sulfonamide derivatives, thus generating dendromesogens bearing 6, 12, and 96 mesogenic units on their surfaces. The relevant reactions could be monitored by 1H, 19F, and 31P{1H} NMR spectroscopies. The thermal and mesomorphic properties of the products have been studied by optical microscopy, differential scanning calorimetry, and X‐ray diffraction. All of the new macromolecules prepared in this work have been found to show mesomorphic properties over a wide temperature range; moreover, for all of the compounds, the columnar mesophases observed were maintained or vitrified at room temperature. On increasing the generation of these dendromesogens, mesophases appear at lower temperatures and remain stable over a wider temperature interval. In all cases, on the basis of X‐ray analysis, a cylindrical symmetry of the molecules can be proposed to promote the supramolecular columnar arrangement observed in the mesophases. In this type of model, the height of the dendrimer clearly increases with increasing dendrimer generation, whereas its cross‐ sectional area increases only slightly, probably due to compression of the highly hyperbranched structures as a consequence of their progressive steric constraints. The mesomorphic arrangement is governed by the peripheral sulfonamide units. 相似文献
143.
Exploring the Molecular Structure of Imidazolium–Silica‐Based Nanoparticle Networks by Combining Solid‐State NMR Spectroscopy and First‐Principles Calculations 下载免费PDF全文
Dr. Marie‐Alexandra Neouze Martin Kronstein Dr. Marco Litschauer Dr. Michael Puchberger Dr. Cristina Coelho Prof. Christian Bonhomme Prof. Christel Gervais Dr. Frederik Tielens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15188-15196
A DFT‐based molecular model for imidazolium–silica‐based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small‐angle X‐ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. 11B and 31P HETCOR CP MAS experiments were recorded. Calculated 19F NMR spectroscopy results, combined with the calculated anion–imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π–π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain. 相似文献
144.
Substitution pattern elucidation of hydroxypropyl Pinus pinaster (Ait.) bark polyflavonoid derivatives by ESI(−)‐MS/MS 下载免费PDF全文
Danny E. García Marrero Wolfgang G. Glasser Antonio Pizzi Sebastian Paczkowski Marie‐Pierre G. Laborie 《Journal of mass spectrometry : JMS》2014,49(10):1050-1058
The structure of condensed tannins (CTs) from Pinus pinaster bark extract and their hydroxypropylated derivatives with four degrees of substitution (DS 1, 2, 3 and 4) has been characterized for the first time using negative‐ion mode electrospray ionization tandem mass spectrometry (ESI(?)‐MS/MS). The results showed that P. pinaster bark CTs possess structural homogeneity in terms of monomeric units (C15, catechin). The oligomer sizes were detected to be dimers to heptamers. The derivatives showed typical phenyl‐propyl ether mass fragmentation by substituent elimination (58 amu) and inherent C15 flavonoid fissions. The relative abundance of the product ions revealed a preferential triple, tetra‐/penta‐ and octa‐ hydroxypropylation substitution pattern in the monomer, dimer and trimer derivatives, respectively. A defined order of –OH reactivity towards propylene oxide was established by means of multistage experiments (A‐ring ≥ B‐ring > C‐ring). A high structural heterogeneity of the modified oligomers was detected. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
145.
Vladimír Setni
ka Marie Urbanov Statis Pataridis Vladimír Krl Karel Volka 《Tetrahedron: Asymmetry》2002,13(24):2661-2666
A novel approach to study the sol-gel phase transition of a brucine–porphyrin based gelator, which uses vibrational circular dichroism (VCD) spectroscopy, is described. The gelation process leading to highly ordered chiral supramolecular assemblies was investigated in various solvents at the different temperatures and concentrations. The VCD spectra sensitively reveal the specific parts of molecule whose configuration is influenced by a sol-gel phase transition and chiral supramolecular aggregation and therefore indicate the parts of the molecule responsible for the chiral self-assembly formation. Temperature stability of the organogel studied is discussed on the basis of the VCD and IR absorption spectra. The scanning electron microscopy was used to visualize the structure of brucine–porphyrin conjugate in the gel phase. 相似文献
146.
147.
Marcela Dvorakova Marie Pribylova Radek Pohl Marie E. Migaud Tomas Vanek 《Tetrahedron》2012,68(33):6701-6711
A migration of methyloxycarbonyl group from secondary to primary hydroxyl was observed in furanosides (ribosides and xylosides) under usual desilylation conditions using tetrabutylammonium fluoride. The migration was studied further on several alkyloxycarbonyl furanosides under either basic or acidic conditions. As follows from 13C labelling experiments and product distribution, the migration in xylosides, proceeds intramolecularly via six-membered cyclic carbonate, whereas in ribosides, the migration is intermolecular. Acidic conditions prevented the migration in ribosides whereas the migration in xylosides was circumvented under neutral conditions. 相似文献
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