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Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers

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Abstract

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M n 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by 1H NMR, quantitative 13C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (< 2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers.

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Acknowledgements

This work was financially supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia (Project No. 172062 and 173048).

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Authors and Affiliations

  1. Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, Belgrade, 11000, Serbia

    Marijana Ponjavic, Marija S. Nikolic & Jasna Djonlagic

  2. Institute of Molecular Genetics and Genetic Engineering, University of Belgrade, P. O. Box 23, Belgrade, 11010, Serbia

    Sanja Jeremic, Lidija Djokic & Jasmina Nikodinovic-Runic

  3. Institute of Chemistry, Technology and Metallurgy, University of Belgrade, P. O. Box 473, Belgrade, 11010, Serbia

    Vladan R. Cosovic

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  1. Marijana Ponjavic
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  2. Marija S. Nikolic
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Correspondence to Jasna Djonlagic.

Electronic supplementary material

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Figure S1. FTIR spectra of PCL and PCECs copolymers before and after hydrolytic and enzymatic degradation. (TIF 133 KB)

10924_2017_1130_MOESM2_ESM.tif

Figure S2. Enzymatic degradation of PCL and PCEC copolymers within agar-based medium using cell free extracts (CFE) of P. aeruginosa PAO1 grown on glucose and oil as a carbon source. (TIF 516 KB)

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Ponjavic, M., Nikolic, M.S., Jeremic, S. et al. Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers. J Polym Environ 26, 2346–2359 (2018). https://doi.org/10.1007/s10924-017-1130-2

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