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41.
Xiao-Shu He Dragana Tadi Malgorzata Brzostowska Arnold Brossi Maureen Bell Cyrus Creveling 《Helvetica chimica acta》1991,74(7):1399-1411
O-Methylation of the optically active 3′-hydroxycoclaurines 3a and 3b and of the N-methylated analogs 5a,b with S-adenosyl-L -[methyl-14C]methionine in presence of mammalian COMT was investigated in vitro. The N-unsubstituted (1S)- and (1R )-isomers 3a and 3b , respectively, afforded almost equal amounts of the corresponding N-norreticuline 4 and N-nororientaline 19 , besides two unknown by-products (see Fig. and Table 1). The N-methylated (1S)-isoquinoline 5a , on the other hand, afforded largely (S)-orientaline ((S)- 19 ), while an almost equal mixture of (R)-reticuline ( 6b ) and (R)-orientaline ((R)- 19 ) was obtained from the (1R)-enantiomer 5b . The isoquinolines 3a,b and 5a,b were prepared by a Bischler-Napieralski cyclization yielding O-benzyl-protected isoquinoline 10 (Scheme 1). The optical resolution of 10 was accomplished with 2′-bromotartranilic acid. The N-methylated isoquinolines were prepared by N-formylation of 10a,b and reduction of the formamides 13a,b with diborane (→ 14a,b ). Deblocking of the benzyl-ether moieties of 10a,b and 14a,b was accomplished by catalytic hydrogenation in presence of HCl, affording directly 3a,b ·HCl and 5a,b ·HCl, respectively. 相似文献
42.
Thierry Meylheuc Christophe Methivier Margareth Renault Jean-Marie Herry Claire-Marie Pradier Marie Noëlle Bellon-Fontaine 《Colloids and surfaces. B, Biointerfaces》2006,52(2):128
The ability of adsorbed biosurfactants (Pf and Lb) obtained from gram-negative bacterium (Pseudomonas fluorescens) or gram-positive bacterium (Lactobacillus helveticus) to inhibit adhesion of four listerial strains to stainless steel was investigated. These metallic surfaces were characterized using the following complementary analytical techniques: contact-angle measurements (CAM), atomic force microscopy (AFM), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) and X-ray photoelectron spectroscopy (XPS). Contact-angles with polar liquids (water and formamide) indicated that the stainless steel surface covered with adsorbed biosurfactant was more hydrophilic and electron-donating than bare stainless steel. The surface characterization by XPS and PM-IRRAS revealed that conditioning the stainless steel changes the substrate in two ways, by modifying the surface alloy composition and by leaving an thin adsorbed organic layer. AFM observations enabled to say that the layer covered entirely the surface and was probably thicker (with patches) in the case of Pf-conditioned surfaces compared to the Lb-conditioned ones, which seemed to be less homogeneous. Though the added layer was thin, significant chemical changes were observed that can account for drastic modifications in the surface adhesive properties. As a matter of fact, adhesion tests showed that both used biosurfactants were effective by decreasing strongly the level of contamination of stainless steel surfaces by the four strains of Listeria monocytogenes. The more important decrease concerned the CIP104794 and CIP103573 strains (>99.7%) on surface conditioned by L. helveticus biosurfactant. A less reduced phenomenon (75.2%) for the CIP103574 strain on stainless steel with absorbed biosurfactant from P. fluorescens was observed. Whatever the strain of L. monocytogenes and the biosurfactant used, this antiadhesive biologic coating reduced both total adhering flora and viable and cultivable adherent bacteria on stainless steel surfaces. This study confirms that biosurfactants constitute an effective strategy to prevent microbial colonization of metallic surfaces by pathogenic bacteria like the food-borne pathogen L. monocytogenes. 相似文献
43.
This work investigated the chemiluminescent reaction of free chlorine with bis(2,4,6-(trichlorophenyl)oxalate) (TCPO) in the presence of 9,10-diphenylanthracene in acetonitrile/water medium, with analytical application for free chlorine in tap water. In the absence of free chlorine, the background signal increased with the pH and the chemiluminescence emission showed strong dependence with the sample acidity. A flow injection analysis system, for free chlorine determination, was developed. The linear range for free chlorine was (0.2-3.0)×10−5 mol l−1. Chloramine 1.0×10−5 mol l−1 and chlorite 1.0×10−6 mol l−1 also enhanced the chemiluminescence intensity. 相似文献
44.
The efficiency of polysulfane product generation has been investigated for n-propyl thiol reactions with ortho- and para-substituted benzo-1,2-dithiolan-3-one 1-oxides in acetonitrile-water (7:3) mixtures. The reaction is facilitated by reducing the electron density at the para position or by placing substituents bearing lone pair electrons ortho to the dithiolanone-oxide (S1) reaction center. Through-space and through-bond effects both contribute to the conversion of polysulfane products. 相似文献
45.
46.
Brzostowska EM Hoffmann R Parish CA 《Journal of the American Chemical Society》2007,129(14):4401-4409
We expand the scope of the Bergman cyclization by exploring computationally the rearrangement of two osmaenediynes and one rhodaenediyne. The three hypothetical metallaenediynes are constructed by substituting the 14-electron Os(PH3)3 fragment for the C fragment, or the 15-electron Os(PH3)3H or Rh(PH3)3 fragments for the sp2 CH fragment, of 3-ene-1,5-diyne. This replacement is guided by the isolobal analogy and previous metallabenzene chemistry. The rearrangement of osmaenediyne with an Os(PH3)3 fragment in place of C is exothermic by 3 kcal/mol (the parent Bergman reaction is computed to be endothermic by 5 kcal/mol) and associated with a significant decrease in the barrier to rearrangement to 13 kcal/mol (the Ea of the parent reaction computed at the same level of theory is 33 kcal/mol). The replacement of a CH by the isolobal analogue Os(PH3)3H reduces the energy of activation for the rearrangement to 23 kcal/mol and produces a corresponding metalladiradical that is 8 kcal/mol less stable that the corresponding osmaenediyne. The activation energy corresponding to the rearrangement of the rhodaenediyne is the same as that of the organic parent enediyne. Interesting polytopal rearrangements of metallaenediynes and the diradical nature of the resulting intermediates are also explored. 相似文献
47.
Patricia Leme Goto José Mario Carneiro Vilela Margareth Spangler Andrade 《Journal of Dispersion Science and Technology》2013,34(2):228-233
Polymeric nanoparticles constitute an important drug delivery system with controlled release profile. This article describes a new way to produce polymeric nanocapsules using a vegetable oil nanoemulsion as template. The process occurs in two steps: First, a nanoemulsion was obtained with a low-energy method based on phase inversion emulsification, using 2-ethylhexyl acrylate as lipophilic monomer. The in situ polymerization of the nanoemulsion droplets is induced by the addition of polymerization catalyzers. The mean size of the polymeric nanoparticles was evaluated by photon correlation spectroscopy and atomic force microscopy. Both techniques showed the formation of polymeric nanocapsules with a mean particle size less than 300 nm. 相似文献
48.
Identification of fly eggs using scanning electron microscopy for forensic investigations 总被引:1,自引:0,他引:1
Mendonça PM dos Santos-Mallet JR de Mello RP Gomes L de Carvalho Queiroz MM 《Micron (Oxford, England : 1993)》2008,39(7):802-807
Forensic entomology is the science that studies the role of insects in decomposing corpses and one of the most common uses is to estimate the post-mortem interval (PMI) based on insect activity on a decomposing body. Usually, flies are the first insects to reach a carcass and are able to oviposit on carrion within a few hours after death. Scanning electron microscopy (SEM) gives detailed information about morphological characters helping to identify the immature forms of flies and consequently serves as a tool in crime scene investigations. Sometimes, only eggs and larvae are found in corpses. Some dipteral species are important because their larvae develop in organic matter. The aim of this study is to identify eggs of species of forensic importance, such as Chrysomya megacephala, Chrysomya putoria, Lucilia cuprina, Lucilia eximia and Ophyra aenescens, using scanning electron microscopy (SEM). C. megacephala had no anastomosis or holes at the top of the islands and C. putoria had few anastomoses and no holes, whereas L. eximia and O. aenescens were found to have anastomoses and holes and L. cuprina had only anastomoses. The median area was bifurcated anteriorly in C. megacephala, L. eximia and O. aenescens and rounded in C. putoria and L. cuprina. Also the sculptures observed in the chorionic cells, the length and the way that median area ends up posteriorly are characteristics of great diagnostic value to identify muscoids of forensic importance. 相似文献