p-Nitro-tetradecyloxy-calix[4]arene as a highly selective stationary phase for gas chromatographic separations
NEW JOURNAL OF CHEMISTRY
Authors: Sun, Tao; Shuai, Xiaomin; Bin, Li; Ren, Kaixin; Jiang, Xingxing; Chen, Haipeng; Hu, Shaoqiang; Cai, Zhiqiang
Abstract
Here, we report the first example of the utilization of p-nitro-tetradecyloxy-calix[4]arene (C4A-NO2) as a stationary phase for capillary gas chromatographic (GC) separations. The statically coated C4A-NO2 column exhibited a high column efficiency of 3815 plates per m and moderate polarity. The C4A-NO2 column was investigated for its separation performance and retention behaviours by utilizing a wide variety of isomer mixtures, covering alkylated benzenes and naphthalenes, alkenes, furans, alcohols, benzaldehydes, phenols and halogenated anilines. Importantly, the C4A-NO2 column exhibited high resolving capability for both aliphatic and aromatic isomers. Particularly, it displayed advantageous resolving capability over the commercial DB-17 column for halogenated aniline isomers. This work provides a good reference for designing calixarene derivatives as GC stationary phases, which is important for developing a family of stationary phases with specific selectivity.
Insights in the kinetic mechanism of the eukaryotic Baeyer-Villiger monooxygenase BVMOAf1 from Aspergillus fumigatus Af293
BIOCHIMIE
Authors: Laura Mascotti, Maria; Kurina-Sanz, Marcela; Juri Ayub, Maximiliano; Fraaije, Marco W.
Abstract
This work reports a detailed kinetic study of the recently discovered BVMOAf1 from Aspergillus fumigatus Af293. By performing steady state and pre-steady state kinetic analyses, it was demonstrated that the rate of catalysis is partially limited by the NADPH-mediated reduction of the flavin cofactor, a unique hallmark of BVMOAf1. In addition, the oxygenating C4a-(hydro)peroxyflavin intermediate could be spectrophotometrically detected and it was found to be the most stable among all analyzed BVMOs. To assess the possible influence of some residues on the kinetic features, model-inspired site-directed mutagenesis was performed. Among the mutants, the Q436A variant showed a slightly broader substrate scope and a better catalytic efficiency. In summary, this study describes for the first time the kinetic parameters for an eukaryotic BVMO. (C) 2014 Elsevier B.V. and Societe francaise de biochimie et biologie Moleculaire (SFBBM). All rights reserved.