title: Conformational Analysis, Thermal Rearrangement, and EI-MS Fragmentation Mechanism of (1(10)E,4E,6S,7R)-Germacradien-6-ol by (13)C-Labeling Experiments.
abstract: An uncharacterized terpene cyclase from Streptomyces pratensis was identified as (+)-(1(10)E,4E,6S,7R)-germacradien-6-ol synthase. The enzyme product exists as two interconvertible conformers, resulting in complex NMR spectra. For the complete assignment of NMR data, all fifteen ((13)C1)FPP isotopomers (FPP=farnesyl diphosphate) and ((13)C15)FPP were synthesized and enzymatically converted. The products were analyzed using various NMR techniques, including (13)C, (13)C COSY experiments. The ((13)C)FPP isotopomers were also used to investigate the thermal rearrangement and EI fragmentation of the enzyme product.
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Patrick
authors.initials: P
authors.lastname: Rabe
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Lena
authors.initials: L
authors.lastname: Barra
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Jan
authors.initials: J
authors.lastname: Rinkel
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Ramona
authors.initials: R
authors.lastname: Riclea
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Christian A
authors.initials: CA
authors.lastname: Citron
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Tim A
authors.initials: TA
authors.lastname: Klapschinski
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Aron
authors.initials: A
authors.lastname: Janusko
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany). dickschat@uni-bonn.de.
authors.forename: Jeroen S
authors.initials: JS
authors.lastname: Dickschat
mesh_terms: D019883:Alkyl and Aryl Transferases / Q000737:chemistry / Q000378:metabolism*; D002247:Carbon Isotopes; D066241:Carbon-13 Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D011106:Polyisoprenyl Phosphates / Q000138:chemical synthesis / Q000737:chemistry; D012717:Sesquiterpenes / Q000138:chemical synthesis / Q000737:chemistry; D045788:Sesquiterpenes, Germacrane / Q000737:chemistry* / Q000378:metabolism; D021241:Spectrometry, Mass, Electrospray Ionization; D013696:Temperature
chemical_list: D002247:Carbon Isotopes; D011106:Polyisoprenyl Phosphates; D012717:Sesquiterpenes; D045788:Sesquiterpenes, Germacrane; C004808:farnesyl pyrophosphate; D019883:Alkyl and Aryl Transferases
keywords: NMR spectroscopy; conformation analysis; isotopic labeling; mass spectrometry; terpenoids