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101.
François Clémence Odile Le Martret Jeannine Collard 《Journal of heterocyclic chemistry》1984,21(5):1345-1353
The synthesis of N-aryl and N-heteroaryl substituted 4-hydroxy-3-quinolinecarboxamides 1 is described. The attack of dianions 12 of N-aryl substituted acetamides on the C-4 carbonyl of 4H-3,1-benzoxazin-4-ones 11 gave rise to ketoamides 13 , which smoothly cyclised in the presence of bases to afford quinolinecarboxamides 1 . By this method, a large number of 2-substituted 4-hydroxyquinolinecarboxamides can be prepared. 相似文献
102.
Balcells D Raynaud C Crabtree RH Eisenstein O 《Chemical communications (Cambridge, England)》2008,(6):744-746
DFT studies show that the rebound mechanism for MnO(tpp)(Cl)-catalyzed C-H hydroxylation is favored for spin states with oxyl character. 相似文献
103.
Rubnov S Chevallier C Thoison O Debitus C Laprevote O Guénard D Sévenet T 《Natural product research》2005,19(1):75-79
A new bromoindolesulfonic acid derivative, echinosulfonic acid D (1) was isolated from the New-Caledonian sponge Psammoclemma sp. in a minute quantity. The structure of the alkaloid was established by spectroscopic methods and, in particular, by ESI MSn experiments. Echinosulfonic acid D was cytotoxic to KB cells (IC50 2 microg/mL). 相似文献
104.
Catala L Mathonière C Gloter A Stephan O Gacoin T Boilot JP Mallah T 《Chemical communications (Cambridge, England)》2005,(6):746-748
Nanorods of the photomagnetic coordination network Mo(CN)8Cu2 coated with polyvinylpyrrolidone were prepared and exhibit an enhanced effect upon irradiation when compared to the bulk. 相似文献
105.
Bradley M. Kraft Odile Eisenstein William D. Jones 《Journal of fluorine chemistry》2010,131(11):1122-1548
Cp*2ZrH2 (1) (Cp*: pentamethylcyclopentadienyl) reacts with cyclic perfluorinated olefins to give Cp*2ZrHF (2) and hydrodefluorinated products under very mild conditions. Initial C-F bond activation occurs selectively at the vinylic positions of the cycloolefin to exchange fluorine for hydrogen. Several mechanisms are discussed for this H/F exchange: (a) olefin insertion/β-fluoride elimination, (b) olefin insertion/α-fluoride elimination, and (c) hydride/fluoride σ-bond metathesis. Following H/F σ-bond metathesis exchange of both vinylic C-F bonds of perfluorocyclobutene, 1 then reacts with allylic C-F bonds by insertion/β-fluoride elimination. A similar sequence is observed with perfluorocyclopentene. Cp*2ZrHF reacts selectively with vinylic C-F bonds of perfluorocyclobutene to give 3,3,4,4-tetrafluorocyclobutene and Cp*2ZrF2 without further hydrodefluorination occurring. In the presence of excess 1 and H2, perfluorocyclobutene and perfluorocyclopentene are reduced to cyclobutane and cyclopentane in 46% and 16% yield, respectively. DFT calculations exclude the pathway by way of the olefin insertion/α-fluoride elimination and suggest that the pathway by way of hydride/fluoride σ-bond metathesis is preferred. 相似文献
106.
107.
Woithe K Geib N Meyer O Wörtz T Zerbe K Robinson JA 《Organic & biomolecular chemistry》2008,6(16):2861-2867
OxyB is a cytochrome P450 enzyme that catalyzes the first oxidative phenol coupling reaction during vancomycin biosynthesis. The preferred substrate is a linear peptide linked as a C-terminal thioester to a peptide carrier protein (PCP) domain of the glycopeptide antibiotic non-ribosomal peptide synthetase. Previous studies have shown that OxyB can efficiently oxidize a model hexapeptide-PCP conjugate (R-Leu(1)-R-Tyr(2)-S-Asn(3)-R-Hpg(4)-R-Hpg(5)-S-Tyr(6)-S-PCP) (Hpg = 4-hydroxyphenylglycine) into a macrocyclic product by phenolic coupling of the aromatic rings in residues-4 and -6. In this work, the substrate specificity of OxyB has been explored using a series of N-terminally truncated peptides related in sequence to this model hexapeptide-PCP conjugate. Deletion of one or three residues from the N-terminus afforded a penta- (Ac-Tyr-Asn-Hpg-Hpg-Tyr-S-PCP) and a tri- (Ac-Hpg-Hpg-Tyr-S-PCP) peptide that were also efficiently transformed into the corresponding macrocyclic cross-linked product by OxyB. The tripeptide, representing the core of the macrocycle in vancomycin created by OxyB, is thus sufficient, as a thioester with the PCP domain, for phenol coupling to occur. The related tetrapeptide-PCP thioester was not cyclized by OxyB, neither was a related model hexapeptide containing tryptophan in place of tyrosine-6, nor were tripeptides (related to the natural product K-13) with the sequence Ac-Tyr-Tyr-Tyr-S-PCP cross-linked by OxyB. 相似文献
108.
Schröder D Loos J Engeser M Schwarz H Jankowiak HC Berger R Thissen R Dutuit O Döbler J Sauer J 《Inorganic chemistry》2004,43(6):1976-1985
Trimethyl vanadate(V), OV(OCH(3))(3) (1), is examined by various mass spectrometric means. Photoionization experiments yield an ionization energy of IE(OV(OCH(3))(3)) = 9.54 +/- 0.05 eV for the neutral molecule. The primary fragmentation of the molecular cation 1(+), i.e., loss of neutral formaldehyde, can occur via two independent routes of hydrogen migrations to afford the formal V(IV) compounds HOV(OCH(3))(2)(+) and OV(OCH(3))(CH(3)OH)(+), respectively. These two pathways are associated with low-lying activation barriers of almost identical height. At elevated energies, direct V-O bond cleavage of 1(+) allows for expulsion of a methoxy radical concomitant with the generation of the cationic fragment OV(OCH(3))(2)(+), a formal V(V) compound. Trimethyl vanadate can also form a molecular anion, 1(-), whose most abundant dissociation channel involves loss of a methyl radical, thereby leading to the formal V(V) compound OV(OCH(3))(2)O(-). Various mass spectrometric experiments and extensive theoretical studies provide detailed insight into the ion structures and the relative energetics of the primary dissociation reactions of the molecular cations and anions of 1. 相似文献
109.
Mounir Kassir Thibault Roques-Carmes Tayssir Hamieh Angelina Razafitianamaharavo Odile Barres Joumana Toufaily Frédéric Villiéras 《Adsorption》2013,19(6):1197-1209
This paper addresses the surface modification of TiO2 nanoparticles with n-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPS) using various initial aminosilane concentrations. The main objective of this article is to show experimentally the importance of the physisorption during the grafting process. The distinction between chemisorbed and physisorbed aminosilane molecules on TiO2 is thoroughly analyzed. The surface of bare and modified TiO2 particles has been characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) to gain a better understanding of the adsorption mechanism of AHAPS on TiO2. Quantitative information on surface energy of TiO2, in terms of adsorption energy sites and heterogeneity, has been investigated by quasi-equilibrium low-pressure adsorption technique using nitrogen and argon as probe molecules. The FTIR and XPS data are combined to estimate and discuss the chemisorbed and physisorbed contribution. The results demonstrate that both physisorption and chemisorption occurs but they display a different behavior. The physisorbed amounts are much higher than the chemisorbed amounts. This shows that the main part of the adsorbed layer is composed of physisorbed molecules. The physisorbed uptake depends highly on the AHAPS concentration while the chemisorbed amount remains constant. Quasi-equilibrium Ar derivative adsorption isotherms reveal that the AHAPS molecules are mostly located on the {101} and {001} faces of titania and that the two faces display the same reactivity toward AHAPS sorption. Nitrogen adsorption experiments show that the sorption takes place on the three polar surface sites of high energy. The molecules are chemisorbed onto the site displaying the highest energy while they are physisorbed on the two lower energy sites. 相似文献
110.
Measurements of the Protective Effect of Topically Applied Sunscreens using in vitro Three-dimensional Dermal and Skin Equivalents 总被引:4,自引:0,他引:4
Corinne Augustin Christian Collombel Odile Damour 《Photochemistry and photobiology》1997,66(6):853-859
Abstract— For preventing or minimizing acute and chronic skin damage caused by UV radiation, the use of sunscreens is probably the most important measure. To screen the protective efficacy of new sunscreen molecules or formulations against UV rays, we evaluated as in vitro testing methods the use of two three-dimensional models, a dermal equivalent (DE) and a skin equivalent (SE). The DE is composed of a porous collagen-glycosaminoglycans-chitosan matrix populated by normal human fibroblasts. The SE is comprised of a fully differentiated epidermis realized by seeding keratinocytes onto the DE. In this study, we demonstrated that the DE and SE models react to the deleterious effects of UVA and UVB. Then, we extended our research to the evaluation of their usefulness for photoprotection trials. Sunscreen agents (Euso-lex 8020 and 6300) and commercially available sunscreens (chemical and physical filter formulations) that protect the skin against either UVA or UVB were evaluated. The tested products were applied (n = 6) topically (10 μL) and incubated for 30 min prior to irradiation over a range of UVA (0-50 J/cm2 ) or UVB (0-5 J/cm2 ). The photoprotection provided by the tested sunscreen molecules and formulations was evaluated by measurement of residual cellular viability 24 h postirradiation using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetra-zolium bromide (MTT) test and assessment of the inflammation response by interleukin-la release assay. When sunscreens were applied prior to UV exposure, a higher residual cellular viability versus control was obtained, demonstrating the photoprotective effects of the tested products. These in vitro models could be used for screening tests to evaluate the protective effects of sunscreen molecules and formulations, especially for UVA trials because there is a lack of consensus for an in vivo method. 相似文献