An enzymatically controlled one-step synthesis of a non-isocyanate polyurethane monomer from sustainable resources is feasible under mild reaction conditions.

Singlet oxygen is a reactive oxygen species undesired in living cells but a rare and valuable reagent in chemical synthesis. We present a fluorescence spectroscopic analysis of the singletoxygen formation activity of commercial peroxidases and novel peroxygenases. Singlet-oxygen sensor green (SOSG) is used as fluorogenic singlet oxygen trap. Establishing a kinetic model for the reaction cascade to the fluorescent SOSG endoperoxide permits a kinetic analysis of enzymatic singlet-oxygen formation. All peroxidases and peroxygenases show singlet-oxygen formation. No singlet oxygen activity could be found for any catalase under investigation. Substrate inhibition is observed for all reactive enzymes. The commercial dye-decolorizing peroxidase industrially used for dairy bleaching shows the highest singlet-oxygen activity and the lowest inhibition. This enzyme was immobilized on a textile carrier and successfully applied for a chemical synthesis. Here, ascaridole was synthesized via enzymatically produced singlet oxygen.

Background Polyesters with pendant hydroxyl groups are attractive materials which offer additional functionalization points in the polymer chain. In contrast to chemical polycondensation, lipase regioselectivity enables the synthesis of these materials as certain hydroxyl groups remain unaffected during the enzymatic process. Methods and Major Results In this study, a combination of synthesis development and reactor design was used for the enzymatic synthesis of an aliphatic‐aromatic polyester with two different classes of pendant hydroxyl groups. Using 2,6‐bishydroxy(methyl)‐p‐cresol as diol in lipase catalyzed polycondensation with adipic acid required the addition of hexane diol as third monomer for polycondensation to take place. Reaction conditions were explored in order to identify the preferred reaction conditions for the incorporation of the aromatic diol and the enhancement of the hydroxyl group density. Post‐polymerization with glycerol at low temperature integrated additional aliphatic hydroxyl groups, reduced the polydispersity and increased the end group functionality. Conclusion A new material with aromatic building blocks and boosted polymer chain reactivity was obtained, which is suggested to find application in various areas of material development from coatings to adhesives.