67253-09-2Relevant academic research and scientific papers
Crystal structure of H2O2-dependent cytochrome P450SPαwith its bound fatty acid substrate: Insight into the regioselective hydroxylation of fatty acids at the α position
Fujishiro, Takashi,Shoji, Osami,Nagano, Shingo,Sugimoto, Hiroshi,Shiro, Yoshitsugu,Watanabe, Yoshihito
experimental part, p. 29941 - 29950 (2012/04/10)
Cytochrome P450SPα (CYP152B1) isolated from Sphingomonas paucimobilis is the first P450 to be classified as a 2O 2-dependent P450. P450SPα hydroxylates fatty acids with high α-regioselectivity. Herein we report the crystal structure of P450SPαwith palmitic acid as a substrate at a resolution of 1.65 A. The structure revealed that the Cα of the bound palmitic acid in one of the alternative conformations is 4.5 A from the heme iron. This conformation explains the highly selective α-hydroxylation of fatty acid observed in P450SPα. Mutations at the active site and the F-G loop of P450SPα did not impair its regioselectivity. The crystal structures of mutants (L78F and F288G) revealed that the location of the bound palmitic acid was essentially the same as that in the WT, although amino acids at the active site were replaced with the corresponding amino acids of cytochrome P450BSβ (CYP152A1), which shows β-regioselectivity. This implies that the high regioselectivity of P450SPα is caused by the orientation of the hydrophobic channel, which is more perpendicular to the heme plane than that of P450 BSβ.
α hydroxylation of carboxylic acids with molecular oxygen catalyzed by the α oxidase of peas (Pisum sativum): A novel biocatalytic synthesis of enantiomerically pure (R)-2-hydroxy acids
Adam, Waldemar,Boland, Wilhelm,Hartmann-Schreier, Jenny,Humpf, Hans-Ulrich,Lazarus, Michael,Saffert, Alexander,Saha-M?ller, Chantu R.,Schreier, Peter
, p. 11044 - 11048 (2007/10/03)
The substrate selectivities of the α oxidation of saturated, unsaturated, and heteroatom-containing (oxygen, sulfur) carboxylic acids 1 by the enzyme extract of peas (Pisum sativum) indicate that this biotransformation proceeds highly enantioselectively. For the first time, the synthesis of optically pure 2-hydroxy acids 2 has been achieved on the semipreparative scale (1 mmol) by α hydroxylation of long-chain carboxylic acids with molecular oxygen, catalyzed by the α oxidase of peas. For derivatives with sulfur atom in the chain, no sulfoxidation is observed. The functionalities (carbon double and triple bonds, oxygen, and sulfur atoms) must be at least three carbon atoms away from the carboxylic acid group to achieve efficient asymmetric hydroxylation. The absolute configuration of the 2-hydroxy acids 2 was assigned by comparison of the gaschromatographic data with that of authentic reference compounds and by application of the exciton- coupled-circular-dichroism (ECCD) method. This unprecedented asymmetric biocatalytic methodology should be valuable for the preparation of enantiomerically pure (R)-2-hydroxy acids.
Enantioselective α hydroxylation of carboxylic acids with molecular oxygen catalyzed by the α oxidation enzyme system of young pea leaves (Pisum sativum): A substrate selectivity study
Adam, Waldemar,Lazarus, Michael,Saha-Moeller, Chantu R.,Schreier, Peter
, p. 2287 - 2292 (2007/10/03)
The substrate selectivity of the α oxidation of carboxylic acids 1 by crude homogenate of young pea leaves was investigated. Saturated fatty acids with 7 to 16 carbon atoms and oleic acid were transformed to the enantiomerically pure (R)-2-hydroxy acids 2 in the presence of molecular oxygen.
Cerebrosides from Fomitopsis pinicola (Sw. Ex Fr.) Karst.
Striegler, S.,Haslinger, E.
, p. 755 - 762 (2007/10/03)
A cerebroside fraction was obtained from the bruit bodies of fomitopsis pinicola using column chromatography and then separated into six compounds by reversed-phase HPLC.The sugar component of all cerebrosides was D-glucose.The major fatty acids were 2-hydroxyfatty acids (C14-C18), the long chain base was identified as 9-methyl-C18-4,8-sphingadienine which is widely distributed in fungi and reported to be essential for the fruit-inducing activity of fungi.Based on degradation studies, fast atom bombardment mass spectrometry, and different 1H and 13C NMR investigations, the structure of the main cerebroside (1) was determined to be (4E,8E,2S,3R,2'R)-N-2'-hydroxypalmityl-1-O-β-D-glucopyranosyl-9-methyl-4,8-sphingadienine. - Keywords: Cerebroside; Glycolipid; Fomitopsis pinicola; 1H and 13C NMR
