Daniel Strub

Biotransformations of monoterpenes by photoautotrophic micro‐organisms

Monoterpenes are widely used in food technology, cosmetic and pharmaceutical industries and as compounds of agricultural importance. It is known that compounds comprising this class can be transformed by a variety of organisms, namely by: bacteria, fungi, yeasts, plants or isolated enzymes. Biotransformations, as one of the most important tools of green chemistry, allow obtaining new products using whole cells of micro‐organisms or isolated enzymes in mild reaction conditions. Therefore, biotransformations of monoterpenes, by different type of reaction such as: epoxidation, oxidation and stereoselective hydroxylation, resulted in the production of so desired, enantiomerically defined compounds that can be advised as natural seem to be interesting. Bearing in mind that such processes are carried out also by easy to maintain, photoautotrophic micro‐organisms cultivated at large scale, this paper is focused on biotransformations of acyclic, monocyclic and bicyclic monoterpenes by freshwater or haliphylic cyanobacteria and microalgae on the way of mainly stereoselective hydroxylation. Moreover, aspects of potential industrial application of obtained products in medicine, perfume, cosmetics and food industry are discussed.

Application of microorganisms towards synthesis of chiral terpenoid derivatives.

Biotransformations are a standard tool of green chemistry and thus are following the rules of sustainable development. In this article, we describe the most common types of reactions conducted by microorganisms applied towards synthesis of chiral terpenoid derivatives. Potential applications of obtained products in various areas of industry and agriculture are shown. We also describe biological activity of presented compounds. Stereoselective hydroxylation, epoxidation, Baeyer–Villiger oxidation, stereo- and enantioselective reduction of ketones, and various kinetic resolutions carried out by bacteria and fungi have been reviewed. Mechanistic considerations regarding chemical and enzymatic reactions are presented. We also briefly describe modern approaches towards enhancing desired enzymatic activity in order to apply modified biocatalysts as an efficient tool and green alternative to chemical catalysts used in industry.

Evaluation of the irritating influence of carane derivatives and their antioxidant properties in a deoxyribose degradation test

Previous studies of the propranolol monoterpene derivative (-)-4-[2-hydroxy-3-(N-isopropylamino)-propoxyimino]-cis-carane hydrochloride (KP-23) and its diastereoisomers, KP-23R and KP-23S, demonstrated different effects on the cyclic AMP generating system as well as anti-inflammatory, analgesic, antihistaminic and antioxidant activity. The present study examined the influence of KP-23 and its diastereoisomers KP-23R and KP-23S on the skin-irritating activity and the mucous membrane-irritating activity as well as their influence on a late-type contact allergy in the in vivo tests. The hydroxyl radical scavenging potential of the three analogues was evaluated using their ability to inhibit Fe(II)/H2O2-induced oxidative degradation of 2-deoxyribose (2-DR) in the in vitro tests. The results obtained indicated that the hydroxyamine carane derivative did not evoke irritative changes and did not induce a late-type contact allergy in the guinea-pig. Diastereoisomers of KP-23 exhibit antioxidant properties in a dose-dependent manner and protected against OH-radicals generated from the Fenton reaction.

Synthesis of the aggregation pheromone of the Colorado potato beetle from its degradation product

Incubation of the Colorado potato beetle aggregation pheromone, (S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one, with antennal or leg extracts from this beetle gave 6-methyl-5-hepten-2-one as the major product. This ketone was used as a substrate in a stereoselective synthesis of the pheromone. It was attached to the butanediacetal of glycolic acid with good stereoselectivity and the desired isomer was further enriched by purification of the product of this reaction on silica gel.