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Four-arm star poly(ε-caprolactone) with a central poly(ethylene glycol) PEG unit bridged with 2,2-bis(methyl) propionic acid, (PCL)2-b-PEG-b-(PCL)2, and six-arm star PCL homopolymer with a central dipentaerythritol units were hydrolysed using a lipase from Pseudomonas cepacia and the Thermobifida cellulosilytica cutinase Thc_Cut1. For comparative analysis, Y-shaped copolymers containing methylated PEG bridged with bisMPA, MePEG-(PCL)2, and linear triblock copolymers PCL-b-PEG-b-PCL were also subjected to enzymatic hydrolysis. The hydrophilic nature of the polymers was determined using contact angle analysis, showing that a higher PEG content exhibited a lower contact angle and higher surface wettability. Enzymatic hydrolysis was monitored by % mass loss, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). A higher rate of mass loss was found for lipase catalysed hydrolysis of those polymers with the highest PEG content, leading to significant surface erosion and increase in crystallinity within the first two days. Liquid chromatography (LC) and size exclusion chromatography (SEC) of samples incubated with the cutinase showed a significant decrease in molecular weight, increase in dispersity, and release of ε-CL monomer units after 6 h of incubation.

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