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51.
Ciminiello P Dell'Aversano C Fattorusso E Forino M Magno S Di Rosa M Ianaro A Poletti R 《Journal of the American Chemical Society》2002,124(44):13114-13120
A detailed analysis of the causative toxins contained in the hepatopancreas of toxic mussels from the northern Adriatic sea has been carried out. Along with some DSP (diarrhetic shellfish poisoning) type toxins, such as okadaic acid, yessotoxin, and their derivatives, which are involved in a number of human intoxications throughout the world, we have now isolated a new cytotoxin, a polychlorinated sulfolipid 1, whose gross structure has been elucidated by spectral analysis, including various 2D NMR techniques. The relative stereochemistry of 1 was elucidated by successful application of the J-based configuration analysis developed for acyclic compounds using carbon-proton spin-coupling constants ((2,3)J(C,H)) and proton-proton spin-coupling constants ((3)J(H,H)); its absolute stereochemistry was established by the Mosher method. Compound 1 possesses in vitro cytotoxicity against WEHI 164 and RAW 264.7 cells. 相似文献
52.
[reaction: see text] Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pKa = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k2 = 1.8-2.7 x 10(9) M(-1) s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation of the reduced acceptor (methyl viologen radical cation, MV+*), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2*))(OH)CH2(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled with the low rates of beta-fragmentation of the same species have an important bearing in the context of the photoyellowing of lignin containing pulps and papers. 相似文献
53.
(2S)- and (2R)-2-Amino-4-bromobutanoic acid were prepared starting from N-Boc-glutamic acid α tert-butyl ester. The double tert-butyl protection was necessary to prevent a partial racemisation during Barton’s radical decarboxylation used to transform the γ-carboxylic group into a bromide. This bromide reacted with different nitrogen, oxygen and sulphur nucleophiles to give nonnatural amino acids characterised by basic or heterocyclic side chains. The title compound was also used to prepare a conformationally constrained peptidomimetic. 相似文献
54.
The effect of energy exchange on the dynamics of the chemisorption of H2 on Pt (111) is studied within a LEPS potential quasi-classical trajectories treatment. The Einstein model is assumed for the solid. The rigidity of the surfaces is shown to be an acceptable approximation. 相似文献
55.
The paper reports on a structural concept for high stiffness and high damping performance. A stiff external frame and an internal resonating lattice are combined in a beam-like assembly which is characterized by high frequency bandgaps and tuned vibration attenuation at low frequencies. The resonating lattice consists of an elastomeric material arranged according to a chiral topology which is designed to resonate at selected frequencies. The concept achieves high damping performance by combining the frequency-selective properties of internally resonating structures, with the energy dissipation characteristics of their constituent material. The flexible ligaments, the circular nodes and the non-central interactions of the chiral topology lead to dynamic deformation patterns which are beneficial to energy dissipation. Furthermore, tuning and grading of the elements of the lattice allows for tailoring of the resonating properties so that vibration attenuation is obtained over desired frequency ranges. Numerical and experimental results demonstrate the tuning flexibility of this concept and suggest its potential application for load-carrying structural members parts of vibration and shock prone systems. 相似文献
56.
Massimo Curini Francesco Epifano Maria Carla Marcotullio Ornelio Rosati Monia Rossi André Tsadjout 《合成通讯》2013,43(17):3181-3187
Layered zirconium hydrogen phosphonate exchanged with the potassium ion was found to be an efficient heterogeneous catalyst for the hydrolysis of sterically hindered phenolic silyl ethers. 相似文献
57.
Andrea Liscio Massimo Bonini Emanuele Treossi Emanuele Orgiu Marcel Kastler Florian Dötz Vincenzo Palermo Paolo Samorì 《Journal of Polymer Science.Polymer Physics》2012,50(9):642-649
A prototypical semiconducting bicomponent system consisting of a conjugated polymer, that is, poly(3‐hexylthiophene) (P3HT), blended with a small thiophene containing conjugated molecule, that is, an alkyl‐substituted bisphenyl‐bithiophene [phenylene–thiophene–thiophene–phenylene (PTTP)], has been used as an electroactive active layer in field‐effect transistors (FETs). The self‐assembly of this bicomponent system at surfaces has been studied at different length scales, from the nanoscale to the macroscale, and compared with the behavior of monocomponent films of PTTP and P3HT. The correlation between morphology and electric properties of the semiconducting material is explored by fabricating prototypes of FETs varying the relative concentrations of the two‐component blend. The maximum charge carrier mobility value, achieved with a few percent of PTTP component, is not simply due to a uniform dispersion of the molecules in the polymer matrix, but rather to the generation of very long percolation paths, whose composition and electrical properties can be tuned with the PTTP concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
58.
Parviz Holakooei Umberto Tessari Massimo Verde Carmela Vaccaro 《Journal of Thermal Analysis and Calorimetry》2014,118(1):165-176
In this paper, the general rules of phase transformations in calcareous clay bodies during firing were used to estimate the equivalent firing temperature (EFT) of seventeenth century polychrome Persian haft rang tiles based on their X-ray diffraction (XRD) patterns. The novelty of this work is, however, that it handles the XRD patterns of archaeological clay bodies with principal component analysis (PCA) in order to have a new look at their firing and thermal behaviour. Statistically handling the XRD patterns, different clusters were discriminated in the clay bodies whose mineralogical composition showed various proportions of amorphous and quartz contents. The results showed interesting trends in the different clusters in terms of the EFT, quartz content and the density of the bodies. The present work uses PCA to have a new look at XRD patterns of archaeological clay bodies and, moreover, to interpret the PCA results in order to estimate the EFT of a large number of archaeological clay bodies. 相似文献
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