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11.
ter Wiel MK van Delden RA Meetsma A Feringa BL 《Journal of the American Chemical Society》2005,127(41):14208-14222
To investigate the unidirectional rotation of chiral overcrowded biphenanthrylidenes in more detail, the size of the substituent next to the double bond responsible for the unidirectionality of rotation was varied. The thermal and photochemical isomerization of three sterically overcrowded alkenes is described. The behavior of the biphenanthrylidenes with methyl and ethyl substituents is rather similar, and these compounds undergo a unidirectional 360 degrees rotation around the central double bond in a four-step sequence involving two photochemical cis-trans isomerizations and two thermal helix inversions. The only difference between these two true molecular motors was a small entropic effect, which causes the ethyl substituted molecular motor to rotate slightly faster. The behavior of the i-propyl substituted compound differs significantly from that of the other two. Although not all different isomers of the i-propyl substituted molecular motor were detected spectroscopically, experimental data led to the conclusion that this compound can also be considered as a molecular motor and is capable of performing a 360 degrees unidirectional rotation. (1)H NMR and X-ray analysis show a meso-like form as an intermediate in the unidirectional rotation, which proves that the thermal helix inversion is a stepwise process. 相似文献
12.
Bente A. Somsen Fenna W. B. Craenmehr Wei-Hong W. Liu Auke A. Koops Marloes A. M. Pennings Emira J. Visser Christian Ottmann Peter J. Cossar Luc Brunsveld 《Chemical science》2022,13(44):13122
Molecular glues represent an evolution in drug discovery, however, targeted stabilization of protein complexes remains challenging, owing to a paucity of drug design rules. The functional mapping of hotspots has been critical to protein–protein interaction (PPI) inhibitor research, however, the orthogonal approach to stabilize PPIs has not exploited this information. Utilizing the hub protein 14-3-3 as a case study we demonstrate that functional mapping of hotspots provides a triage map for 14-3-3 molecular glue development. Truncation and mutation studies allowed deconvoluting the energetic contributions of sidechain and backbone interactions of a 14-3-3-binding non-natural peptide. Three central 14-3-3 hotspots were identified and their thermodynamic characteristics profiled. In addition to the phospho-binding pocket; (i) Asn226, (ii) Lys122 and (iii) the hydrophobic patch formed by Leu218, Ile219 and Leu222 were critical for protein complex formation. Exploiting this hotspot information allowed a peptide-based molecular glue that elicits high cooperativity (α = 36) and selectively stabilizes the 14-3-3/ChREBP PPI to be uniquely developed.The functional mapping of a 14-3-3 protein complex, by means of peptide truncations and point mutations, as an approach to identify critical hotspots regions for 14-3-3 molecular glue drug design. 相似文献
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Summary Nine different CuII(sulf)2 and three mixed CuII(sulf)2X2–3 (X=NH3 or pyridine) derivatives were prepared from CuII and sulfanilamides (sulfH=sulfadiazine, sulfadimethoxine, sulfadimidine, sulfamerazine, sulfamethoxydiazine, sulfamethoxypyridazine, sulfapyridine, sulfathiazole and sulfisomidine) in alkaline solution and their e.s.r., i.r. and ligandfield spectroscopic properties were evaluated. Two types of Cu(sulf)2 complexes were formed: dimeric and monomeric/ polymeric species. 相似文献
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Christine C. Mattheus Anne B. Dros Jacob Baas Auke Meetsma Jan L. de Boer Thomas T. M. Palstra 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(8):939-941
Pentacene, C22H14, crystallizes in different morphologies characterized by their d(001)‐spacings of 14.1, 14.5, 15.0 and 15.4 Å. We have studied the crystal structure of the 14.1 and 14.5 Åd‐spacing morphologies grown by vapour transport and from solution. We find a close correspondence between the 14.1 Å structure reported by Holmes, Kumaraswamy, Matzeger & Vollhardt [Chem. Eur. J. (1999), 5 , 3399–3412] and the 14.5 Å structure reported by Campbell, Monteath Robertson & Trotter [Acta Cryst. (1961), 14 , 705–711]. Single crystals commonly adopt the 14.1 Åd‐spacing morphology with an inversion centre on both molecules in the unit cell. Thin films grown on SiO2 substrates above 350 K preferentially adopt the 14.5 Åd‐spacing morphology, with a slightly smaller unit‐cell volume. 相似文献
18.
Bas B. van Aken Auke Meetsma Thomas T. M. Palstra 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(3):230-232
The crystal structure of hexagonal yttrium trioxomanganate has been determined at room temperature and at 180 K. It is isomorphous with LuMnO3. The Mn displacement vector has a frustrated component in the ab plane and a ferroelectric part along the c axis. The net ferroelectricity is zero due to inversion twinning, with 1:1 twin fractions. 相似文献
19.
A procedure has been developed for estimating the information content of retrieval systems with binary-coded mass spectra, as well as mass spectra coded by other methods, from the statistical properties of a reference file. For a reference file, binary-coded with a threshold of 1% of the intensity of the base peak, this results typically in an estimated information content of about 50 bits for 200 selected values. It is shown that, because of errors occurring in the binary-coded spectra, the actual information content is only about 12 bits. This explains the poor performance observed for retrieval systems with binary-coded mass spectra. 相似文献
20.
Otto Bekers Jantina J. Van Den Bosch Kettenes Steven P. Van Helden Don Seijkens Jos H. Beijnen Auke Bulti Willy J. M. Underberg 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(2):185-193
The inclusion complexation of the anthracyline antibiotics doxorubicin and daunorubicin with cyclodextrins has been studied by proton NMR and molecular modelling. The anthracyclines were found to complex with -cyclodextriny-cyclodextrin, whereby the aglyconic part of the molecule is included in the cyclodextrin cavity. Job ratio plots based on NMR data indicate that the complex has a stoichiometry of 1 : 1. Complex constant values of 345 M–1 and 323 M–1 (at pH 3) were found for doxorubicin and daunorubicin, respectively. 相似文献