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191.
Simpson CD Brand JD Berresheim AJ Przybilla L Räder HJ Müllen K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(6):1424-1429
In this paper we present the synthesis and characterization of the so far largest polycyclic aromatic hydrocarbon (PAH), containing 222 carbon atoms or 37 separate benzene units. First a suitable three-dimensional oligophenylene precursor molecule is built up by a sequence of Diels-Alder and cyclotrimerization reactions and then planarized in the final step by oxidative cyclodehydrogenation to the corresponding hexagonal PAH. Structural proof is based on isotopically resolved MALDI-TOF mass spectra and electronic characteristics are studied by UV/Vis spectroscopy. 相似文献
192.
Laurent Blasco Lucie Duracher Jean‐Pierre Forestier Laurence Vian Gilberte Marti‐Mestres 《Journal of Dispersion Science and Technology》2013,34(6):811-815
This work aims at presenting the viscoelastic behavior of bio‐mimetic monoglycerides used as emulsifier in a mixture made of two non‐miscible liquids, squalene and water. The measurement of the interfacial tension, carried out by the “pendant drop” method in “dynamic” mode, made it possible to characterize these amphiphilic molecules according to the value of their elastic modulus, ?, as well as their relaxation time, τR. The analysis of these parameters, as well as those developed in the previous publication [L. Blasco et al. (2006) Skin constituents as cosmetic ingredients. Part I: A Study of bio‐mimetic monoglyceride behavior at the squalene‐water interface by the “pendant drop” method in a static mode. J. Dispers. Sci. Technol., 27(6).] shows that the hydrocarbon chain structure, such as its length, the presence of one or more unsaturations, hydroxyl function, affects the behavior of surfactant molecules at the squalene/water interface. 相似文献
193.
ABSTRACT The stepwise synthesis of methyl α-D-glucopyranosyl-(1→3)-α-L-rhamnopyranosyl-(1→3)-α-L-rhamnopyranoside (EBC-OMe, 1), methyl α-L-rhamnopyranosyl-(1→2)-[α-D-glucopyranosyl-(1→3)]-α-L-rhamnopyranosyl-(1→3)-α-L-rhamnopyranoside (A(E)BC-OMe, 2), and methyl 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→2)-α-L-rhamnopyranosyl-(1→2)-[α-D-glucopyranosyl-(1→3)]-α-L-rhamnopyranosyl-(1→3)-α-L-rhamnopyranoside (DA(E)BC-OMe, 3) is described. Compounds 1, 2 and 3 constitute the methyl glycosides of fragments of the O-specific polysaccharide of Shigella flexneri serotype 5a. Methyl 2,4-di-O-benzoyl-α-L-rhamnopyranosyl-(1→3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside was an appropriate BC precursor for the synthesis of 1. For the synthesis of the branched targets 2 and 3, a benzyl group was best suited at position 2 of rhamnose C. Thus, methyl 4-O-benzyl-α-L-rhamnopyranosyl-(1→3)-2,4-di-O-benzyl-α-L-rhamnopyranoside was the key intermediate to the BC portion. In all cases, 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl fluoride was a convenient E precursor, when used in combination with titanium tetrafluoride. All along, attention was paid to steric hindrance as a factor of major impact on the condensation steps outcome. Therefore, based on previous experience, 2-O-acetyl-3,4-di-O-allyl-α-L-rhamnopyranosyl trichloroacetimidate and 3,4,6-tri-O-acetyl-2-deoxy-2-trichloroacetamido-α-D-glucopyranosyl trichloroacetimidate were used as donors. Both suited all requirements when used as key precursors for residues A and D in the synthesis of 3, respectively. 相似文献
194.
João M. Batista Jr. Andrea N.L. BatistaMassuo J. Kato Vanderlan S. BolzaniSilvia N. López Laurence A. NafieMaysa Furlan 《Tetrahedron letters》2012,53(45):6051-6054
A reinvestigation of the monoterpene chromane ester enriched fraction from Peperomia obtusifolia using chiral chromatography led to the identification of a minor peak, which was elucidated by NMR and HRMS as fenchyl-3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3″-methyl-2″-butenyl)-2-(4′-methyl-1′,3′-pentadienyl)-2H-1-benzopyran-6-carboxylate, the same structure assigned to two other fenchyl esters described previously, pointing out a stereoisomeric relationship among them. Further NMR analysis revealed that it was actually a mixture of two compounds, whose absolute configurations were determined by VCD measurements. Although, almost no vibrational transitions could be assigned to the chiral chromane, the experimental VCD spectrum was largely opposite to that obtained for the average experimental VCD [(2S,1?R,2?R,4?S + 2R,1?R,2?R,4?S)/2] for fenchol derivatives. These results allowed us to assign the putative compounds as a racemic mixture of the chiral chromane esterified with the monoterpene (1S,2S,4R)-fenchol, which had not been identified in our early work. 相似文献
195.
We present a Molecular Dynamics (MD) study based on Density Functional Theory (DFT) calculations for H(2) interacting with a Pd-Cu(111) surface alloy for low Pd coverages, Θ(Pd). Our results show, in line with recent experimental data, that single isolated Pd atoms evaporated on Cu(111) significantly increase the reactivity of the otherwise inert pure Cu surface. On top of substitutional Pd atoms in the Pd-Cu(111) surface alloy, the activation energy barrier for H(2) dissociation is smaller than the lowest one found on Cu(111) by a factor of two: 0.25 eV vs. 0.46 eV. Also in agreement with experiments, our DFT-MD calculations show that a large fraction of the dissociating H atoms efficiently spillover from Pd (i.e. the active sites), thanks to their extra kinetic energy due to the ~0.50 eV chemisorption exothermicity. Still, our DFT-MD calculations predict a dissociative sticking probability for low energy H(2) molecules that is much smaller than the estimated value from scanning tunneling microscopy experiments. Thus, further theoretical and experimental investigations are required for a complete understanding of H(2) dissociation on low-Θ(Pd) Pd-Cu(111) surface alloys. 相似文献
196.
Inge Cosemans Jimmy Wouters Thomas Cleij Laurence Lutsen Wouter Maes Thomas Junkers Dirk Vanderzande 《Macromolecular rapid communications》2012,33(3):242-247
The anionic polymerization of PPV via the sulfinyl precursor route is further investigated. When LHMDS is employed as the base to form the actively propagating quinodimethane system and THF as the solvent, anionic polymerizations can be observed. With the use of tert‐ butyl‐substituted anionic initiators, specific functional groups can be built in the polymer chain and the chain length can be efficiently controlled, which is demonstrated here for the first time. With introduction of branched side chains on the aromatic core, soluble conjugated PPV material can be obtained with molecular weights in the range of 5000–16 000 g mol−1. 相似文献
197.
Nadia Mayoufi Didier Dalmazzone Walter Fürst Leila Elghoul Adel Seguatni Anthony Delahaye Laurence Fournaison 《Journal of Thermal Analysis and Calorimetry》2012,109(1):481-486
The phase behaviour of the system water?Ctri-n-butylmethylammonium chloride (TBMAC)?CCO2 was investigated by pressure-controlled differential scanning calorimetry in the range 0?C10?mol% TBMAC in water and at CO2 pressures ranging from 0 to 1.5?MPa. In the absence of CO2, an incongruent melting hydrate, which estimated composition corresponds to TBMAC·30H2O, crystallizes at temperatures below ?13.6?°C and forms with ice a peritectic phase at approximately 3.9?mol% TBMAC. In the presence of CO2 at pressures as low as 0.5?MPa, curves evidenced the presence of an additional phase exhibiting congruent melting at temperatures that are strongly pressure dependent and significantly higher than those of hydrates obtained without CO2. This new phase, whose enthalpy of dissociation and CO2 content increase slightly with CO2 pressure, was identified as a mixed semi-clathrate hydrate of TBMAC and CO2 of general formula: (TBMAC?+?xCO2)·30H2O. 相似文献
198.
199.
200.
Catarina I. V. Ramos João P. C. Tomé M. G. Santana‐Marques 《Journal of mass spectrometry : JMS》2012,47(2):173-179
The adduct ions of two tetramolecular G‐quadruplexes formed from the d(TGGGGT) and d(TTGGGGGT) single strands with a group of cationic porphyrins, with different charges and substituents, and one neutral porphyrin, were investigated by ESI‐MS and ESI‐MS/MS in the negative ion mode. Formation of [Q + nNH4++Pp+‐(z + n + p)H+]z‐ adduct ions (where Q = quadruplex, n = number of quartets minus 1, P = porphyrin and p+ =0,1,2,3,4) indicates that the porphyrins are bound outside the quadruplexes providing an additional stabilization to those structures. The fragmentation pathways of the [Q + nNH4++Pp+‐(z + n + p)H+]z‐ adduct ions depend on the number of positive charges (p+) of the porphyrins and on the overall complex charge (z‐), but do not show a significant dependence on the type of the substituent groups in the porphyrins. Formation of the ‘unfilled’ ions [Q + Pp+‐(z + p)H+]z‐ predominates for porphyrins with a higher number of positive charges. Strand separation with the formation of [T + Pp+‐(z‐2 + p)H+](z‐2)‐ and (SS‐2H+)2‐ ions, where T = [d(TG4T)]3 and [d(T2G5T)]3 and SS = d(TG4T) and d(T2G5T) is only observed for the complexes with a higher overall negative charge. Porphyrin loss with the formation of [Q + nNH4+‐(z + n)H+]z‐ ions occurs predominantly for the neutral and monocharged porphyrins. The predominant formation of the ‘unfilled’ ions, [Q + Pp+‐(z + n)H+]z‐, for porphyrins with a higher number of charges shows that these porphyrins can prevent strand separation and preserve, at least partially, the quadruplex structure. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献