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Immobilized lipase B from Candida antarctica (Novozym® 435, N435) was utilized as part of achemoenzymatic strategy for the synthesis of branched polyesters based on a cyclotetrasiloxane core inthe absence of solvent. Nuclear magnetic resonance spectroscopy and matrix-assisted laser desorptionionization time-of-flight mass spectrometry were utilized to monitor the reactions between tetraestercyclotetrasiloxanes and aliphatic diols. The enzyme-mediated esterification reactions can achieve 65–80% consumption of starting materials in 24–48 h. Longer reaction times, 72–96 h, resulted in theformation of cross-linked gel-like networks. Gel permeation chromatography of the polymers indicatedthat the masses were Mw ¼ 11 400, 13 100, and 19 400 g mol 1 for the substrate pairs of C7D4 ester/octane-1,8-diol, C10D4 ester/pentane-1,5-diol and C10D4 ester/octane-1,8-diol respectively, after 48 h.Extending the polymerization for an additional 24 h with the C10D4 ester/octane-1,8-diol pair gave Mw ¼86 800 g mol 1. To the best of our knowledge this represents the first report using lipase catalysis toproduce branched polymers that are built from a cyclotetrasiloxane core.Natural Sciences and Engineering Research Council (NSERC) of CanadaBrock University Advanced Biomanufacturing Centr

Cyclotetrasiloxane frameworks for the chemoenzymatic synthesis of oligoesters