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41.
Waldemar Hoffmann Johanna Hofmann Kevin Pagel 《Journal of the American Society for Mass Spectrometry》2014,25(3):471-479
Recent works using ion mobility-mass spectrometry (IM-MS) have highlighted the power of this instrumental configuration to tackle one of the greatest challenges in glycomics and glycoproteomics: the existence of isobaric isomers. For a successful separation of species with identical mass but different structure via IM-MS, it is crucial to have sufficient IM resolution. In commercially available IM-MS instruments, however, this resolution is limited by the design of the instrument and usually cannot be increased at-will without extensive modifications. Here, we present a systematic approach to improve the resolving capability of IM-MS instruments using so-called energy-resolved ion mobility-mass spectrometry. The technique utilizes the fact that individual components in an isobaric mixture fragment at considerably different energies when activated in the gas phase via collision-induced dissociation (CID). As a result, certain components can be suppressed selectively at increased CID activation energy. Using a mixture of four isobaric carbohydrates, we show that each of the individual sugars can be resolved and unambiguously identified even when their drift times differ by as little as 3 %. However, the presented results also indicate that a certain difference in the gas-phase stability of the individual components is crucial for a successful separation via energy-resolved IM-MS. Figure
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42.
Ewa esawska Izabela Korona-Gowniak Wojciech Nitek Waldemar Tejchman 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(4):359-366
Derivatives of pyrimidine‐2(1H)‐selenone are a group of compounds with very strong antimicrobial activity. In order to study the effect of the position of the methoxy substituent on biological activity, molecular geometry and intermolecular interactions in the crystal, three derivatives were prepared and evaluated with respect to their antimicrobial activities, and their crystal structures were determined by X‐ray diffraction. The investigated compounds, namely, 1‐(X‐methoxyphenyl)‐4‐methyl‐6‐phenylpyrimidine‐2(1H)‐selenones (X = 2, 3 and 4 for 1 , 2 and 3 , respectively), C18H16N2OSe, showed very strong activity against selected strains of Gram‐positive bacteria and fungi. Two compounds, 1 and 2 , crystallize in the monoclinic space group P21/c, while 3 crystallizes in the space group P21/n; 1 has two molecules in the asymmetric unit and the other two ( 2 and 3 ) have one molecule. The geometries of the investigated compounds differ slightly in the mutual orientations of the aromatic and pyrimidineselenone rings. The O atom in 1 stabilizes the conformation of the molecules via intramolecular C—H…O hydrogen bonding. The packing of molecules is determined by weak C—H…N and C—H…Se intermolecular interactions and additionally in 1 and 2 by C—H…O intermolecular interactions. The introduction of the methoxy substituent results in greater selectivity of the investigated compounds. 相似文献
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Waldemar Wolczyski 《Crystal Research and Technology》1989,24(11):1113-1120
In order to find a generalized entropy production for steady-state eutectic growth the entropy production per unit time and volume is to be determined. A relationship which expresses the entropy production per unit time and volume as a function of KRUPKOWSKI 's equations is shown. It is in a qualitative accuracy with LESOULT -TURPIN 's theory. The above quantity is to be integrated over a distinguished volume of the unidirectionally solidified eutectic structure. A correlation between this volume and entropy production is discussed. 相似文献
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Adam W Bargon RM Bosio SG Schenk WA Stalke D 《The Journal of organic chemistry》2002,67(20):7037-7041
The direct molybdenum-catalyzed sulfuration of a variety of isonitriles with elemental sulfur or propene sulfide as sulfur donors affords the corresponding isothiocyanates in good yields and under mild reaction conditions. A catalytic cycle is suggested, in which the molybdenum oxo disulfur complex operates as the active sulfur-transferring species. A novel adduct between the isonitrile and the molybdenum complex has been characterized by X-ray analysis and its association constant determined by UV-vis spectroscopy, but this adduct appears not to be involved in the sulfur-transfer process. 相似文献
47.
Adam W García H Diedering M Martí V Olivucci M Palomares E 《Journal of the American Chemical Society》2002,124(41):12192-12199
The photochemical denitrogenation of the cyclopentene-annelated DBH-type azoalkanes 1 has been examined in solution as a function of bridgehead substitution and temperature. For all derivatives, namely, the unsubstituted 1a(H/H), monomethyl 1b(Me/H) dimethyl 1c(Me/Me), monophenyl 1d(Ph/H), and diphenyl 1e(Ph/Ph), the temperature-dependent ratio of syn and anti housanes 2 provides experimental support for a competition between the singlet (high temperature) and triplet (low temperature) reaction channels in the direct photolysis. The syn/anti ratio of the housanes 2 depends on the extent and type of bridgehead substitution; the amount of the anti diastereomer (retention) follows the order Ph > Me > H, and double substitution is more effective than single. This stereochemical memory is interpreted in terms of the mass effect (inertia) of the substituents and steric interaction (size) between the substituents at the bridgehead and the methylene bridge during the deazetation step of the transient diazenyl diradical conformations (1)DZ (exo-ax) and (1)DZ (exo-eq). These conformers are impulsively generated upon decay of the (1)(n,pi)-excited azoalkane, a trajectory assessed through computational work. The new mechanistic feature disclosed by the unprecedented anti stereoselectivity (retention) is the intervention of a puckered 1,3-cyclopentanediyl singlet diradical (1)DR as product bifurcation step, whose conformational relaxation to the planar species (loss of stereochemical memory) is encumbered by bridgehead substitution. 相似文献
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Zusammenfassung Es wird auf Grund der Untersuchung der Polymerisation, des thermischen Verhaltens und der Photolyse der Stabilitätsbereich von Chlorisocyanat, Cl-N=C=O, umgrenzt und dadurch die Möglichkeiten der Aufbewahrung und Werwendung für Reaktionen mit anderen Substanzen aufgezeigt.
Chemistry of chloro-isocyanate, I: Polymerisation, thermic behaviour, and photolysis
The stability of chloro-isocyanate, Cl-N=C=O, is determined by investigating its polymerisation and thermic and photolytic behaviour. The possibilities of storing and using for reactions with other substances are discussed.相似文献