Poly(macrolactone) synthesis and materials

Macrolactones are natural molecules, which can be polymerised enzymatically or, as discovered more recently, by metal or organic catalysts. The obtained semicrystalline aliphatic polyesters combine properties of low density polyethylene (LDPE) and poly(caprolactone). The Heise group has investigated the enzymatic ring-opening polymerisation of unsaturated and saturated macrolactones and to facilitate their use as functional biomaterials. Fundamental aspects such as the optimisation of the polymerisation process as well as the thiol-ene crosslinking and functionalisation were researched.   

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strong fibres by PPDL extrusion

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thermal crosslinking of PGl films 

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thiol-ene chemistry for functional films

Selected publications:

  • Wilson, J. A., Ates, Z., Pflughaupt, R. L., Dove, A. P., Heise, A. Polymers from macrolactones: From pheromones to functional materials. Prog. Polym. Sci. 2019, 91, 29.

  • Ates, Z., Heise, A. Functional films from unsaturated poly(macrolactones) by thiol-ene cross-linking and functionalisation. Polym. Chem. 2014, 5, 2936. 

  • De Geus, M., Van Der Meulen, I., Goderis, B., Van Hecke, K., Dorschu, M., Van Der Werff, H., Koning, C.E., Heise, A. Performance polymers from renewable monomers: High molecular weight poly(pentadecalactone) for fiber applications. Polym. Chem. 2010, 1, 525. 

  • Van Der Meulen, I., Li, Y., Deumens, R., Joosten, E.A.J., Koning, C.E., Heise, A. Copolymers from unsaturated macrolactones: Toward the design of cross-linked biodegradable polyesters. Biomacromolecules 2011, 12, 837. 

  • Van Der Meulen, I., Gubbels, E., Huijser, S., Sablong, R., Koning, C.E., Heise, A., Duchateau, R. Catalytic ring-opening polymerization of renewable macrolactones to high molecular weight polyethylene-like polymers. Macromolecules 2011, 44, 4301.

Poly(macrolactone) biomaterials

Polyesters from unsaturated globalise combine excellent materials properties with an easy handle for chemical functionalisation. The Heise group and collaborators have investigated the potential of poly(globalide) as a platform biomaterial by exploring its processing by electro spinning with in situ crosslinking. These materials revealed promising drug loading and release performance. Moreover, biocompatebility of electrospun poly(globalide) was improved by phosphoester and RGD attachment as well as lamination with cellulose. 

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phosphoster functional fibre meshes

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in situ photocrosslinked PGl fibre meshes

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carbohydrate/PGl bilayer films 

Selected publications:

  • Amaral, H. R., Wilson, J. A., do Amaral, R. J.F.C., Pasçu, I., de Oliveira, F. C.S., Kearney, C. J., Freitas, J. C.C., Heise A. Synthesis of bilayer films from regenerated cellulose nanofibers and poly(globalide) for skin tissue engineering applications. Carbohydrate Polymers 2021, 252, 117201. 

  • de Oliveira, F. C. S., Olvera, D., Sawkins, M., Cryan, S.-A., Kimmins, S. D., Eufrasio da Silva, T., Kelly, D. J., Duffy, J. P., Kearney, C., Heise, A. Direct UV-triggered thiol-ene cross-linking of electrospun polyester fibers from unsaturated poly(macrolactone)s and their drug loading by solvent swelling. Biomacromolecules 2018, 18, 4292. 

  • Polloni, A. E., Chiaradia, V., do Amaral, R. J. F. C., Kearney, C., Gorey, B., de Oliveira, D., de Oliveira, J. V., de Araújo, P. H. H., Sayer, C., Heise, A. Polyesters with main and side chain phosphoesters as structural motives for biocompatible electrospun fibres. Polym. Chem. 2020, 11, 2157.