Pyridine as novel substrate for regioselective oxygenation with aromatic peroxygenase from Agrocybe aegerita

AbstractAgrocybe aegerita peroxidase (AaP) is a versatile extracellular biocatalyst that can oxygenate aromatic compounds. Here, we report on the selective oxidation of pyridine (PY) yielding pyridine N-oxide as sole product. Using H218O2 as co-substrate, the origin of oxygen was confirmed to be the peroxide. Therefore, AaP can be regarded as a true peroxygenase transferring one oxygen atom from peroxide to the substrate. To our best knowledge, there are only two types of enzymes oxidizing PY at the nitrogen: bacterial methane monooxygenase and a few P450 monooxygenases. AaP is the first extracellular enzyme and the first peroxidase that catalyzes this reaction, and it converted also substituted PYs into the corresponding N-oxides

Characterization of Volatile Compounds and Flavor in Spirits of Old Apple and Pear Cultivars from the Balkan Region

This study was conducted with the aim of developing fruit spirits by utilizing old (autochthonous) apple and pear cultivars that can be attractive to both consumers and producers. Consumers of spirits could enjoy the unique flavor, and producers could gain an opportunity for brand development. In total, eight old apple cultivars (Sarija, Žuja, Samoniklica, Prijedorska zelenika, Bobovec, Masnjača, Lijepocvjetka, and Šarenika) and three pear cultivars (Budaljača, Krakača, and Kalićanka) from Bosnia and Herzegovina were used for the spirits production and for characterizing the flavor of distillates. Golden Delicious was used as a representative of commercial apple cultivar. The aroma profile was conducted through the identification of minor volatile organic compounds (VOCs) and the sensory perception of spirits. Analysis of the VOCs was performed by gas chromatography mass spectroscopy (GC/MS) techniques after enrichment via solid-phase microextraction (SPME). Sensory evaluation was performed by 12 trained panelists. Overall, 35 minor volatile compounds were found in spirits: 13 esters, 7 alcohols, 6 acids, 5 terpenes, and 4 aldehydes. Significant differences were detected in the distribution and quantity of the VOCs, which were fruit cultivar-dependent. Spirits made from Šarenika apple cultivar showed the largest amount of all acids, especially short- and medium-chain fatty acids; however, this richness was not correlated with pleasant sensory attributes. Spirits obtained from Prijedorska zelenika and Masnjača apple cultivars had the best sensory attributes. Budeljača and Krakača pears are promising cultivars as flavoring in spirits production

Hydroxylation of naphthalene by aromatic peroxygenase from Agrocybe aegerita proceeds via oxygen transfer from H(2)O (2) and intermediary epoxidation

6 páginas, 3 figuras -- PAGS nros. 1071-1076A-grocybe aegerita peroxidase/peroxygenase (AaP) is an extracellular fungal biocatalyst that selectively hydroxylates the aromatic ring of naphthalene. Under alkaline conditions, the reaction proceeds via the formation of an intermediary product with a molecular mass of 144 and a characteristic UV absorption spectrum (A (max) 210, 267, and 303 nm). The compound was semistable at pH 9 but spontaneously hydrolyzed under acidic conditions (pH <7) into 1-naphthol as major product and traces of 2-naphthol. Based on these findings and literature data, we propose naphthalene 1,2-oxide as the primary product of AaP-catalyzed oxygenation of naphthalene. Using (18)O-labeled hydrogen peroxide, the origin of the oxygen atom transferred to naphthalene was proved to be the peroxide that acts both as oxidant (primary electron acceptor) and oxygen source.European Union (integrated project BIORENEW), the German Ministry of Education and Research (BMBF, project 0313433D), and the German Environmental Foundation (DBU, project 13225-32).Peer reviewe