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Ohne Zusammenfassung 相似文献
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Wolfgang Holzer Constanze Kautsch Rosa M. Claramunt Ibon Alkorta José Elguero 《Tetrahedron》2004,60(32):6791-6805
The tautomerism of pyrazolones unsubstituted at position 3(5) has been investigated by 13C- and 1H NMR spectroscopic methods. Apart from chemical shift considerations and NOE effects the magnitude of the geminal 2J[pyrazole C-4,H3(5)] spin coupling constant permits the unambiguous differentiation between 1H-pyrazol-5-ol (OH) and 1,2-dihydro-3H-pyrazol-3-one (NH) forms. Whereas 1H-pyrazol-5-ols and 2,4-dihydro-3H-pyrazol-3-ones (CH-form) exhibit 2J values of approximately 9-11 Hz, in 1,2-dihydro-3H-pyrazol-3-ones this coupling constant is considerably reduced to 4-5 Hz. This can be mainly attributed to the removal of the lone-pair at pyrazole N−1 in the latter due to protonation or alkylation. According to the data obtained, 2-substituted 4-acyl-1,2-dihydro-3H-pyrazol-3-ones exist predominantly as pyrazol-5-ols in CDCl3 or benzene-d6 solution, whereas in DMSO-d6 also minor amounts of NH tautomer may contribute to the tautomeric composition. 2,4-Dihydro-2-phenyl-3H-pyrazol-3-one (1-phenyl-2-pyrazolin-5-one) exists in benzene-d6 solely in the CH-form, in CDCl3 as a mixture of CH and OH-form, whereas in DMSO-d6 a fast equilibrium between OH and NH isomer (with the former far predominating) is probable. For 11 compounds, including neutral and protonated molecules, we have calculated at the B3LYP/6-311++G** level, the 2J(1H,13C) coupling constants which are in good agreement with those measured experimentally. 相似文献
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Laschat S Baro A Steinke N Giesselmann F Hägele C Scalia G Judele R Kapatsina E Sauer S Schreivogel A Tosoni M 《Angewandte Chemie (International ed. in English)》2007,46(26):4832-4887
Most associate liquid crystals with their everyday use in laptop computers, mobile phones, digital cameras, and other electronic devices. However, in contrast to their rodlike (calamitic) counterparts, first described in 1907 by Vorl?nder, disklike (discotic, columnar) liquid crystals, which were discovered in 1977 by Chandrasekhar et al., offer further applications as a result of their orientation in the columnar mesophase, making them ideal candidates for molecular wires in various optical and electronic devices such as photocopiers, laser printers, photovoltaic cells, light-emitting diodes, field-effect transistors, and holographic data storage. Beginning with an overview of the various mesophases and characterization methods, this Review will focus on the major classes of columnar mesogens rather than presenting a library of columnar liquid crystals. Emphasis will be given to efficient synthetic procedures, and relevant mesomorphic and physical properties. Finally, some applications and perspectives in materials science and molecular electronics will be discussed. 相似文献
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Dr. Wolfgang Jahnke Dr. Guido Bold Dr. Andreas L. Marzinzik Dr. Silvio Ofner Xavier Pellé Dr. Simona Cotesta Emmanuelle Bourgier Sylvie Lehmann Chrystelle Henry René Hemmig Dr. Frédéric Stauffer Dr. J. Constanze D. Hartwieg Dr. Jonathan R. Green Dr. Jean‐Michel Rondeau 《Angewandte Chemie (International ed. in English)》2015,54(48):14575-14579
Targeting drugs to their desired site of action can increase their safety and efficacy. Bisphosphonates are prototypical examples of drugs targeted to bone. However, bisphosphonate bone affinity is often considered too strong and cannot be significantly modulated without losing activity on the enzymatic target, farnesyl pyrophosphate synthase (FPPS). Furthermore, bisphosphonate bone affinity comes at the expense of very low and variable oral bioavailability. FPPS inhibitors were developed with a monophosphonate as a bone‐affinity tag that confers moderate affinity to bone, which can furthermore be tuned to the desired level, and the relationship between structure and bone affinity was evaluated by using an NMR‐based bone‐binding assay. The concept of targeting drugs to bone with moderate affinity, while retaining oral bioavailability, has broad application to a variety of other bone‐targeted drugs. 相似文献
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A. Carel N. Kwamen Gilles S. de Macedo Constanze Wiederhold Prof. Dr. Iris M. Oppel Prof. Dr. Markus Albrecht 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3829-3833
The thioester moiety is introduced as a lithium binding unit for the hierarchical formation of titanium(IV) catecholate-based lithium-bridged helicates. In solution, the coordination compounds show a monomer–dimer equilibrium which —in comparison to the oxo esters— is significantly shifted towards the monomers. In addition, the influence of the thioester side chain on the dimerization behavior is investigated and an expansible/compressible molecular switch is synthesized. In the latter case expansion and compression are performed reversibly in methanol, whereas in DMSO spontaneous expansion occurs. 相似文献