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281.
Wehlan H Jezek E Lebrasseur N Pavé G Roulland E White AJ Burrows JN Barrett AG 《The Journal of organic chemistry》2006,71(21):8151-8158
A concise and efficient synthesis of the tetracyclic CDEF ring system of lactonamycin (1) is described. The key step involved the Lewis acid mediated, intramolecular Friedel-Crafts acylation of carboxylic acid 6 to produce the tetracyclic CDEF core structure of target 1. The synthesis of 6 was carried out using a high-yielding Negishi coupling of benzyl bromide 7 with triflate 8, which was accessible in 11 steps and 31% overall yield on a multigram scale starting from trihydroxy acid 9. 相似文献
282.
Nathalie Solladié Mathieu E. Walther Emmanuelle Leize Teresa M. Figueira Duarte 《Tetrahedron》2006,62(9):1979-1987
A methanofullerene derivative with an ammonium subunit (1) has been prepared and its ability to form a supramolecular complex with a porphyrin-crown ether conjugate evidenced by NMR, UV-vis, electrospray mass spectrometry (ES-MS) and luminescence experiments. Interestingly, in addition to the ammonium-crown ether recognition, intramolecular stacking of the fullerene moiety and the porphyrin subunit has been evidenced. Due to this additional recognition element, the association constant for the supramolecular complex is increased by two orders of magnitude when compared to the Ka values found for the complexation of 1 with benzo-18-crown-6. Finally, non-covalent systems resulting from the association of cation 1 with porphyrin derivatives bearing two crown ether subunits have been investigated. Intramolecular C60-porphyrin interactions have also been evidenced within these supramolecular complexes. As a result, the 2:1 complexes are very stable as shown by the ES-MS studies. 相似文献
283.
Van Lierde V Chéry CC Roche N Monstrey S Moens L Vanhaecke F 《Analytical and bioanalytical chemistry》2006,384(2):378-384
Since the species that trigger chromium allergy are not yet known, it is important to gain more of an insight into the mechanism
of chromium transport through the skin and into the relationship between chromium allergy and chromium species. In vitro permeation
studies with porcine and human skin were performed using a Franz static diffusion cell. Investigations attempted to elucidate
(i) which Cr compounds are able to permeate through skin, (ii) the influence the Cr concentration in the donor solution has
on the Cr permeation, and (iii) the effect that the time of exposure to the donor solution has on Cr permeation. Capillary
electrophoresis hyphenated to inductively coupled plasma–sector field mass spectrometry (CE–ICP–SFMS) was used to separate
and quantify the Cr species in the receptor fluid. 50 mmol L−1 phosphate buffer (pH 2.5) was used for CE separation, and two different electrophoretic runs were carried out (in the positive
and negative modes). Pneumatic nebulization (PN)-ICP-SFMS was used in order to quantify the total amount of Cr absorbed by
the skin after microwave-assisted acid digestion of the tissue. Cr(VI) was found to pass most easily through the skin. Nevertheless,
Cr(VI) was also shown to be absorbed more efficiently by the skin than Cr(III), an observation attributed to a more pronounced
rejection of the positively charged Cr(III) ions by the skin barrier. These results were in good agreement with in vitro permeation
studies previously reported in the literature in which other analytical techniques were used. Differences observed in the
permeation of Cr following the application of aqueous Cr donor solutions and Cr-containing simulated sweat donor solutions
are also described.
相似文献
284.
Photooxidation of polypropylene/layered double hydroxide nanocomposites: Influence of intralamellar cations 总被引:1,自引:0,他引:1
Sunil P. Lonkar Sandrine Therias Nathalie Caperaa Fabrice Leroux Jean-Luc Gardette 《European Polymer Journal》2010,46(7):1456-135
The influence of layered double hydroxides (LDHs) on the photooxidation of polypropylene (PP)/LDH nanocomposites was studied under irradiation at long wavelengths (λ > 300 nm, 60 °C and in the presence of oxygen). The influence of hybrid LDHs containing different divalent cations (Mg, Zn or both Mg and Zn) on the photooxidation mechanism of PP and on the rates of oxidation of the matrix was characterised based on infrared analysis. The presence of LDHs modifies the photoproducts accumulating in the PP and the rates of oxidation of PP were changed depending on the divalent cations in the LDH layers. Whereas natural clays, such as montmorillonite (MMt), can lead to a faster degradation of the materials, LDHs (Zn2-Al-DS, for example) appear to have no inductive effect on polymer oxidation. 相似文献
285.
Experimental data about branching ratios for the products of dissociative recombination of polyatomic ions are presently the unique information source available to modelers of natural or laboratory chemical plasmas. Yet, because of limitations in the measurement techniques, data for many ions are incomplete. In particular, the repartition of hydrogen atoms among the fragments of hydrocarbons ions is often not available. A consequence is that proper implementation of dissociative recombination processes in chemical models is difficult, and many models ignore invaluable data. We propose a novel probabilistic approach based on Dirichlet-type distributions, enabling modelers to fully account for the available information. As an application, we consider the production rate of radicals through dissociative recombination in an ionospheric chemistry model of Titan, the largest moon of Saturn. We show how the complete scheme of dissociative recombination products derived with our method dramatically affects these rates in comparison with the simplistic H-loss mechanism implemented by default in all recent models. 相似文献
286.
Djukic JP Michon C Ratkovic Z Kyritsakas-Gruber N de Cian A Pfeffer M 《Dalton transactions (Cambridge, England : 2003)》2006,(12):1564-1573
The thermolytic coupling of Ph(2)CN(2) and (t-Bu)(Ph)CN(2) with doubly cyclomanganated 2,5-diphenylpyrazine and 4,6-diphenylpyrimidine afforded substantial amounts of new triple decker compounds of either C(i) and C(2) symmetry respectively containing, in both series, two eta(3)-bonded Mn(CO)(3) fragments which intervene as scaffolds sustaining the helical non-conjugated triaryl backbone. The molecular structures of two pyrazine derivatives show a typical non-parallel stacking of the aromatic rings and the encapsulation of the central pyrazyl fragment with interplanar centroid-to-centroid distances of ca. 3.5 A. The stacking of the aromatics in the triple-decker pyrimidine derivatives has been assessed by (1)H NMR experiments at low temperature. All the triple-decker-type compounds are electroactive. Pyrimidine triple-deckers can reversibly be electrochemically reduced to the corresponding anions. 相似文献
287.
Stéphane GuillarmeStéphanie Legoupy Nathalie BourgougnonAnne-Marie Aubertin François Huet 《Tetrahedron》2003,59(48):9635-9639
Acyclonucleosides 4 have been obtained by a short way starting from ethyl 2-hydroxymethyl acrylate 5. The key intermediate was acetate 9. Its reaction with free or protected nucleic bases gave either the expected compounds or unusual regioisomers. 相似文献
288.
2,2,2-Trifluorodiazoethane was investigated as a reagent for sulfo group protection on hexosamine monosaccharides. The synthesis of glucosamine and galactosamine building blocks fully differentiated for glycosaminoglycan synthesis and the synthesis of glycosyl donors are described. The compatibility of trifluoroethylsulfonate under a variety of reaction conditions has also been investigated. [structure: see text] 相似文献
289.
An efficient synthesis of diarylmethanes under classical thermal conditions and under microwave heating is described from diarylcarbinols via a new disproportionation reaction. The key step involves a selective hydride transfer of isopropyl ether intermediates. Mild reaction conditions i.e., catalytic CBr4 or TfOH in i-PrOH and good yields render this method useful and competitive to the conventional approaches relying on application of external reducing agents. 相似文献
290.
Ferlay S Félix O Hosseini MW Planeix JM Kyritsakas N 《Chemical communications (Cambridge, England)》2002,(7):702-703
Neutral hybrid 2-D networks have been generated using a bis-amidinium capable of chelating M(CN)6(3-) anions via hydrogen bonds: the packing of the achiral 2-D networks leads to channels which are occupied by water molecules forming polymeric H-bonded chains; furthermore, owing to the dihapto mode of H-bonding, the presence of supramolecular chirality of the delta' and lambda' types taking place within the second coordination sphere of the metallic centre has been demonstrated. 相似文献