[reaction: see text] A new approach to nonracemic [7]helicene-like molecules has been developed. Stereoselective Co(I)-mediated [2 + 2 + 2] cycloisomerization of aromatic triynes containing an asymmetric carbon atom produces [7]helicene-like scaffolds in diastereomeric ratios up to 100:0. This central-to-helical chirality transfer can be controlled by the absolute configuration at the asymmetric center and by the presence of carbon substituents. 相似文献
γ-Irradiation of tris (methylidene)-cyclopropane (‘[3]radialene’) 1 in a rigid electron scavenging matrix (butylchoride/i-pentane, 1:1) at 77 K leads to formation of its molecular cation 1 +. Slight softening of the matrix by a temperature increase of 3–5 K results in formation of a newly absorbing species, tentatively assigned arising from structrral relaxation of 1 + by π-bond rotation: 相似文献
Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) profiles of eye lens proteins showed that both progression of diabetic cataract in rats in vivo and precipitation of soluble eye lens proteins stressed by free radicals in vitro were accompanied by significant protein cross-linking. There was a noticeable contribution of disulfide bridges to protein cross-linking in diabetic eye lens in vivo. In contrast, under conditions in vitro, when eye lens proteins were exposed to hydroxyl or peroxyl radicals, we showed that the participation of reducible disulfide linkages in the formation of high molecular mass products was markedly lower. These in vivo--in vitro differences indicate that the generally accepted role of reactive oxygen species in diabetic cataractogenesis may be overestimated in connection with the processes of protein cross-linking. 相似文献
The new compound CuSb2O3Br crystallize in the monoclinic space group Cc. The unit cell parameters are , , , β=90°, Z=16. The crystal structure is solved from single crystal data, R=0.0490. The compound show a layered structure with slabs from cubic Sb2O3 interspersed in between puckered layers of CuBr. The Sb(III) atoms have tetrahedral [SbO3E] coordination where E is the 5s2 lone pair, these units build up Sb4O4E6 cages. The CuBr layers resemble those in hexagonal CuBr but the Cu(I) ions have actually tetrahedral [CuBr3O] coordination. The Cu-O bonds link the Sb4O6 cages with the CuBr layers. 相似文献
Stereoselective synthesis of cruciferous indole phytoalexin (R)-(+)-1-methoxyspirobrassinin and its unnatural (S)-(−)-enantiomer was achieved by spirocyclization of 1-methoxybrassinin in the presence of (+)- and (−)-menthol and subsequent oxidation of the obtained menthyl ethers. Methanolysis of menthyl ethers in the presence of TFA afforded (2R,3R)-(−)-1-methoxyspirobrassinol methyl ether as well its unnatural (2S,3S)-, (2R,3S)-, and (2S,3R)-isomers. 相似文献
Increased interest in the analysis of aminothiols in body fluids during the last years results in a request for high-throughput analytical methods for their determination. We report here a novel, high-throughput method for the determination of total concentrations of biogenous aminothiols - homocysteine, cysteine, glutathione, cysteinylglycine, gamma-glutamylcysteine, and of penicilamine, mercaptopropionylglycine, and cysteamine, three compounds used to treat disorders of aminothiol metabolism in plasma and urine. Samples were reduced with tris(carboxyethyl)phosphine and labeled with 5-(bromomethyl)fluorescein. Capillary electrophoretic separations were performed in 60 mmol/L borate - 15 mmol/L sodium dodecyl sulfate - 2-amino-2-methyl-1-propanol, pH 10.0, with laser-induced fluorescence detection. Analysis time was less than 2 min. The assay is linear (r > 0.999) up to 500 micromol/L. Reproducibilities of migration times (coefficient of variation, CV) were < 0.5%. Interassay repeatabilities (CV, n = 10) were 5.08% and 6.09% for 5 micromol/L addition of homocysteine and 0.60% and 3.78% for 100 micromol/L addition of cysteine in plasma and urine, respectively. Recovery values were within 94-106% and sensitivity was better than 0.19 micromol/L for all analyzed compounds. Results agreed well with a standard high-performance liquid chromatography (HPLC) method. The diagnostic usefulness of the method has been proven on 79 samples of cystinuric patients and 12 samples of homocystinuric patients. We report here a novel method for the determination of aminothiols in body fluids by capillary electrophoresis (CE). Determination is fast and sensitive enough for diagnostic purposes. 相似文献
The previously discussed principles involved in electrocyclic reactions of openshell ions are exemplified for a type C system, the radical cation couple quadricyclane+ ( Q +)/norbornadiene+ ( NBD +). Exhaustive calculations (MINDO/3) for the various states of the ions support the general predictions for such types of systems. The barrier of interconversion Q + → NBD + is estimated to be significantly lower than that for the corresponding neutrals. Experimental support to this prediction is obtained by γ-irradiation of Q or NBD in an electron scavenging matrix. In both cases only NBD + is observed, indicating that Q + is not stable at 77 K. Previous observations and propositions referring to the system Q +/ NBD + are discussed in view of the present findings. 相似文献