{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,10]],"date-time":"2026-06-10T01:59:04Z","timestamp":1781056744884,"version":"3.54.1"},"reference-count":49,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2026,6,9]],"date-time":"2026-06-09T00:00:00Z","timestamp":1780963200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>We report di- and triblock copolymers that combine hydrophilic polyethers\u2014poly(ethylene glycol) monomethyl ether (mPEG) and polyglycidol (PGl)\u2014with a hydrophobic, degradable polyester, poly(\u03b2-butyrolactone) (P(\u03b2-BL)). A mild hydrolysis method was developed to selectively remove acetal protecting groups from poly(ethoxy ethyl glycidyl ether) (PEEGE) without cleaving the \u03b2-butyrolactone polyester backbone, enabling the preparation of PGl-b-P(\u03b2-BL) and mPEG-b-PGl-b-P(\u03b2-BL) block copolymers. Thermal analysis revealed that the glass transition temperatures (Tg) of the copolymers could be tuned by varying block composition and length. Diblock copolymers containing the PGl segment were amorphous, with Tg values ranging from \u22122.7 to \u221219.9 \u00b0C. The presence of an mPEG segment in the triblock copolymers resulted in a further decrease in Tg, reaching values between \u221232.3 and \u221238.9 \u00b0C. Solubility and water affinity studies demonstrated that incorporation of hydrophilic polyether blocks enhances copolymer\u2013solvent interactions, leading to increased wettability of the polymer-coated surface. The water contact angle for films formed from PGl-b-P(\u03b2-BL) decreased to 53 \u00b0C, while for mPEG-b-PGl-b-P(\u03b2-BL) copolymers, it was further reduced to 43 \u00b0C compared with the hydrophobic P(\u03b2-BL) film. Hydrolytic degradation experiments showed accelerated cleavage of the P(\u03b2-BL) segment in copolymers containing hydrophilic blocks compared to the P(\u03b2-BL) homopolymer, which is attributed to increased water accessibility and surface hydrophilicity. The most pronounced decrease in molar mass, reaching at least 50% relative to the initial non-degraded sample, was observed for the diblock copolymers, whereas the P(\u03b2-BL) sample showed only a marginal weight reduction of a few percent. Overall, this study demonstrates that the combination of hydrophilic mPEG and PGl blocks with P(\u03b2-BL) enables the design of block copolymers with tunable thermal properties, solubility, and degradation behavior, offering potential for a wide range of applications.<\/jats:p>","DOI":"10.3390\/ma19122467","type":"journal-article","created":{"date-parts":[[2026,6,10]],"date-time":"2026-06-10T00:58:12Z","timestamp":1781053092000},"page":"2467","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Block Copolymers Based on Ethylene Glycol, Glycidol and \u03b2-Butyrolactone with Tunable Thermal Properties, Solubility, and Hydrolytic Degradation"],"prefix":"10.3390","volume":"19","author":[{"given":"Marcelina","family":"Bochenek","sequence":"first","affiliation":[{"name":"Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sk\u0142odowskiej 34, 41-819 Zabrze, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Natalia","family":"Oleszko-Torbus","sequence":"additional","affiliation":[{"name":"Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sk\u0142odowskiej 34, 41-819 Zabrze, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5400-4379","authenticated-orcid":false,"given":"Agnieszka","family":"Kowalczuk","sequence":"additional","affiliation":[{"name":"Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sk\u0142odowskiej 34, 41-819 Zabrze, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3819-9196","authenticated-orcid":false,"given":"Wojciech","family":"Wa\u0142ach","sequence":"additional","affiliation":[{"name":"Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sk\u0142odowskiej 34, 41-819 Zabrze, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,6,9]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"130204","DOI":"10.1016\/j.ijbiomac.2024.130204","article-title":"Synthesis and physical properties of polyhydroxyalkanoate (PHA)-based block copolymers: A review","volume":"263","author":"Mai","year":"2024","journal-title":"Int. J. Biol. Macromol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"e265","DOI":"10.1038\/am.2016.48","article-title":"Polyhydroxyalkanoates: Opening doors for a sustainable future","volume":"8","author":"Li","year":"2016","journal-title":"NPG Asia Mater."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"106","DOI":"10.1021\/sc400340p","article-title":"Polyhydroxyalkanoates: Chemical Modifications Toward Biomedical Applications","volume":"2","author":"Kai","year":"2014","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"29","DOI":"10.1002\/btpr.2565","article-title":"Polyhydroxyalkanoates: Properties and chemical modification approaches for their functionalization","volume":"34","author":"Raza","year":"2018","journal-title":"Biotechnol. Prog."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"2865","DOI":"10.1039\/C5CS00089K","article-title":"Water soluble polyhydroxyalkanoates: Future materials for therapeutic applications","volume":"44","author":"Li","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"144","DOI":"10.1016\/j.msec.2017.12.035","article-title":"Polyhydroxyalkanoates (PHA) for therapeutic applications","volume":"86","author":"Zhang","year":"2018","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Bassett, D.C. (1988). Biologically produced R-3-hydroxyalkanoate polymers and copolymers. Developments in Crystalline Polymers, Springer. [1st ed.]. Chapter 1.","DOI":"10.1007\/978-94-009-1341-7_1"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1021\/bm049700c","article-title":"Bacterial Polyesters: Biosynthesis, Biodegradable Plastics and Biotechnology","volume":"6","author":"Lentz","year":"2005","journal-title":"Biomacromolecules"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1246","DOI":"10.1073\/pnas.45.8.1246","article-title":"The Role of Organic Substrates in Bacterial Photosynthesis","volume":"45","author":"Stanier","year":"1959","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Elustondo, P.A., Angelova, P.R., Kawalec, M., Michalak, M., Kurcok, P., Abramov, A.Y., and Pavlov, E.V. (2013). Polyhydroxybutyrate Targets Mammalian Mitochondria and Increases Permeability of Plasmalemmal and Mitochondrial Membranes. PLoS ONE, 8.","DOI":"10.1371\/journal.pone.0075812"},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Dedkova, E.N., and Blatter, L.A. (2014). Role of \u03b2-hydroxybutyrate, its polymer poly-\u03b2-hydroxybutyrate and inorganic polyphosphate in mammalian health and disease. Front. Physiol., 5.","DOI":"10.3389\/fphys.2014.00260"},{"key":"ref_12","unstructured":"Mark, J.E. (1999). Poly(hydroxybutyrate). Polymer Data Handbook, Oxford University Press."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"791","DOI":"10.3144\/expresspolymlett.2014.82","article-title":"Polyhydroxyalkanoate (PHA): Review of synthesis, characteristics, processing and potential applications in packaging","volume":"8","author":"Bugnicourt","year":"2014","journal-title":"Express Polym. Lett."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"518","DOI":"10.1016\/j.ejpb.2011.11.014","article-title":"Amorphous amphiphilic P(3HV-co-4HB)-b-mPEG block copolymer synthesized from bacterial copolyester via melt transesterification: Nanoparticle preparation, cisplatin-loading for cancer therapy and in vitro evaluation","volume":"80","author":"Shah","year":"2012","journal-title":"Eur. J. Pharm. Biopharm."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1057","DOI":"10.1021\/bm025553b","article-title":"One-Step Synthesis of Amphiphilic Diblock Copolymers from Bacterial Poly([R]-3-hydroxybutyric acid)","volume":"3","author":"Ravenelle","year":"2002","journal-title":"Biomacromolecules"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"856","DOI":"10.1021\/bm034019g","article-title":"Self-Assembly of Poly([R]-3-hydroxybutyric acid)-Block-Poly(ethylene glycol) Diblock Copolymers","volume":"4","author":"Ravenelle","year":"2003","journal-title":"Biomacromolecules"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"278","DOI":"10.1002\/macp.201000562","article-title":"Controlled Synthesis of Well Defined Poly(3-hydroxyalkanoate)s-based Amphiphilic Diblock Copolymers Using Click Chemistry","volume":"212","author":"Babinot","year":"2011","journal-title":"Macromol. Chem. Phys."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"12849","DOI":"10.1039\/c1cc15965h","article-title":"Amphiphilic star-block copolymers and supramolecular transformation of nanogel-like micelles to nanovesicles","volume":"47","author":"Zhu","year":"2011","journal-title":"Chem. Commun."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"88","DOI":"10.1016\/j.jcis.2012.02.042","article-title":"A micellization study of medium chain length poly(3-hydroxyalkanoate)-based amphiphilic diblock copolymers","volume":"375","author":"Babinot","year":"2012","journal-title":"J. Colloid Interface Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"887","DOI":"10.1002\/pi.2424","article-title":"Novel amphiphilic poly(ester-urethane)s based on poly[(R)-3-hydroxyalkanoate]: Synthesis, biocompatibility and aggregation in aqueous solution","volume":"57","author":"Li","year":"2008","journal-title":"Polym. Int."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"7489","DOI":"10.1021\/jp1018247","article-title":"Designing Poly[(R)-3-hydroxybutyrate]-Based Polyurethane Block Copolymers for Electrospun Nanofiber Scaffolds with Improved Mechanical Properties and Enhanced Mineralization Capability","volume":"114","author":"Liu","year":"2010","journal-title":"J. Phys. Chem. B"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"2740","DOI":"10.1021\/bm050234g","article-title":"Poly(ester urethane)s Consisting of Poly[(R)-3-hydroxybutyrate] and Poly(ethylene glycol) as Candidate Biomaterials: Characterization and Mechanical Property Study","volume":"6","author":"Li","year":"2005","journal-title":"Biomacromolecules"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"10561","DOI":"10.1016\/j.polymer.2005.08.014","article-title":"Synthesis and characterization of biodegradable poly(3-hydroxybutyrate) and poly(ethylene glycol) multiblock copolymers","volume":"46","author":"Zhao","year":"2005","journal-title":"Polymer"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"194","DOI":"10.1021\/ma8019865","article-title":"Synthesis of Novel Biodegradable Thermoresponsive Triblock Copolymers Based on Poly[(R)-3-hydroxybutyrate] and Poly(N-isopropylacrylamide) and Their Formation of Thermoresponsive Micelles","volume":"42","author":"Li","year":"2009","journal-title":"Macromolecules"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1092","DOI":"10.1002\/mabi.201300050","article-title":"Incorporation of Poly[(R)-3-hydroxybutyrate] into Cationic Copolymers Based onPoly(2-(dimethylamino)ethyl methacrylate) to Improve Gene Delivery","volume":"13","author":"Loh","year":"2013","journal-title":"Macromol. Biosci."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2564","DOI":"10.1039\/c3py00096f","article-title":"Dual responsive micelles based on poly[(R)-3-hydroxybutyrate] and poly(2-(di-methylamino)ethyl methacrylate) for effective doxorubicin delivery","volume":"4","author":"Loh","year":"2013","journal-title":"Polym. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"8681","DOI":"10.1021\/la0515266","article-title":"Micellization Phenomena of Biodegradable Amphiphilic Triblock Copolymers Consisting of Poly(\u03b2-hydroxyalkanoic acid) and Poly(ethylene oxide)","volume":"21","author":"Li","year":"2005","journal-title":"Langmuir"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1365","DOI":"10.1002\/macp.201500033","article-title":"Peptide Dendrimer Functionalized with Amphiphilic Triblock Copolymers: Synthesis and Characterization","volume":"216","author":"Oledzka","year":"2015","journal-title":"Macromol. Chem. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2661","DOI":"10.1021\/ma025725x","article-title":"Synthesis and Characterization of New Biodegradable Amphiphilic Poly(ethylene oxide)-b-poly[(R)-3-hydroxy butyrate]-b-poly(ethylene oxide) Triblock Copolymers","volume":"36","author":"Li","year":"2003","journal-title":"Macromolecules"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"732","DOI":"10.1016\/j.polymer.2007.12.017","article-title":"Controlled synthesis and characterizations of amphiphilic poly[(R,S)-3-hydroxybutyrate]-poly(ethylene glycol)-poly[(R,S)-3-hydroxybutyrate] triblock copolymers","volume":"49","author":"Liu","year":"2008","journal-title":"Polymer"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"6288","DOI":"10.1002\/anie.200902672","article-title":"Poly(ethylene glycol) in drug delivery: Pros and cons as well as potential alternatives","volume":"49","author":"Knop","year":"2010","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"198","DOI":"10.1016\/j.actbio.2023.02.012","article-title":"NIR-II light evokes DNA cross-linking for chemotherapy and immunogenic cell death","volume":"160","author":"Huang","year":"2023","journal-title":"Acta Biomater."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"96","DOI":"10.1016\/j.msec.2018.10.092","article-title":"Delivery of platinum (II) drugs with bulky ligands in trans-geometry for overcoming cisplatin drug resistance","volume":"96","author":"Yang","year":"2019","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2300","DOI":"10.1039\/b923472a","article-title":"Elucidating rheological property enhancements in supramolecular hydrogels of short poly[(R,S)-3-hydroxybutyrate]-based amphiphilic triblock copolymer and \u03b1-cyclodextrin for injectable hydrogel applications","volume":"6","author":"Liu","year":"2010","journal-title":"Soft Matter"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"4804","DOI":"10.1016\/j.biomaterials.2006.04.039","article-title":"Biodegradable nanoparticles of amphiphilic triblock copolymers based on poly(3-hydroxybutyrate) and poly(ethylene glycol) as drug carriers","volume":"27","author":"Chen","year":"2006","journal-title":"Biomaterials"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1466","DOI":"10.1021\/bm034247a","article-title":"Recent Developments in Ring Opening Polymerization of Lactones for Biomedical Applications","volume":"4","author":"Albertsson","year":"2003","journal-title":"Biomacromolecules"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"4113","DOI":"10.1016\/j.biomaterials.2007.05.016","article-title":"Hydrolytic degradation and protein release studies of thermogelling polyurethane copolymers consisting of poly[(R)-3-hydroxybutyrate], poly(ethylene glycol), and poly(propylene glycol)","volume":"28","author":"Loh","year":"2007","journal-title":"Biomaterials"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"112116","DOI":"10.1016\/j.eurpolymj.2023.112116","article-title":"Controlled \u201cone-pot\u201d block copolymerization of \u03b2-butyrolactone and oxiranes via quantitative active centers transformation","volume":"194","author":"Bochenek","year":"2023","journal-title":"Eur. Polym. J."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"3112","DOI":"10.1021\/bm060675f","article-title":"Synthesis, Characterization, and Morphology Studies of Biodegradable Amphiphilic Poly[(R)-3-hydroxybutyrate]-alt-Poly(ethylene glycol) Multiblock Copolymers","volume":"7","author":"Li","year":"2006","journal-title":"Biomacromolecules"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"665","DOI":"10.1016\/S0142-9418(01)00142-8","article-title":"Correlation between degree of crystallinity, morphology, glass temperature, mechanical properties and biodegradation of poly (3-hydroxyalkanoate) PHAs and their blends","volume":"21","author":"Schnabel","year":"2002","journal-title":"Polym. Test."},{"key":"ref_41","doi-asserted-by":"crossref","unstructured":"Zhuikov, V.A., Zhuikova, Y.V., Makhina, T.K., Myshkina, V.L., Rusakov, A., Useinov, A., Voinova, V.V., Bonartseva, G.A., Berlin, A.A., and Bonartsev, A.P. (2020). Comparative Structure-Property Characterization of Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate)s Films under Hydrolytic and Enzymatic Degradation: Finding a Transition Point in 3-Hydroxyvalerate Content. Polymers, 12.","DOI":"10.3390\/polym12030728"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1140","DOI":"10.1055\/s-1987-28203","article-title":"Synthesis of Simple Oxetanes Carrying Reactive 2-Substituents","volume":"12","author":"Fitton","year":"1987","journal-title":"Synthesis"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"31","DOI":"10.1016\/S1381-5148(98)00060-1","article-title":"Polyglycidol-block-poly(ethylene oxide)-block-polyglycidol: Synthesis and swelling properties","volume":"42","author":"Dworak","year":"1999","journal-title":"React. Funct. Polym."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"139","DOI":"10.1002\/macp.1994.021950111","article-title":"Synthesis of chiral and racemic functional polymers from glycidol and thioglycidol","volume":"195","author":"Taton","year":"1994","journal-title":"Macromol. Chem. Phys."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"1184","DOI":"10.1021\/ma702308g","article-title":"Double-Hydrophilic Linear-Hyperbranched Block Copolymers Based on Poly(ethylene oxide) and Poly(glycerol)","volume":"41","author":"Wurm","year":"2008","journal-title":"Macromolecules"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"6","DOI":"10.1186\/1754-1611-3-6","article-title":"Reusable, polyethylene glycol-structured microfluidic channel for particle immunoassays","volume":"3","author":"Han","year":"2009","journal-title":"J. Biol. Eng."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"9285","DOI":"10.1021\/la200290k","article-title":"Highly Hydrophilic Surfaces from Polyglycidol Grafts with Dual Antifouling and Specific Protein Recognition Properties","volume":"27","author":"Gosecka","year":"2011","journal-title":"Langmuir"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"1602","DOI":"10.1016\/j.polymdegradstab.2011.06.001","article-title":"Crystallization behavior, thermal property and biodegradation of poly(3-hydroxybutyrate)\/poly(ethylene glycol) grafting copolymer","volume":"96","author":"Zhijiang","year":"2011","journal-title":"Polym. Degrad. Stab."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"1841","DOI":"10.1016\/j.biomaterials.2005.10.038","article-title":"The in vitro hydrolysis of poly(ester urethane)s consisting of poly[(R)-3-hydroxybutyrate] and poly(ethylene glycol)","volume":"27","author":"Loh","year":"2006","journal-title":"Biomaterials"}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/19\/12\/2467\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,6,10]],"date-time":"2026-06-10T01:06:23Z","timestamp":1781053583000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/19\/12\/2467"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,6,9]]},"references-count":49,"journal-issue":{"issue":"12","published-online":{"date-parts":[[2026,6]]}},"alternative-id":["ma19122467"],"URL":"https:\/\/doi.org\/10.3390\/ma19122467","relation":{},"ISSN":["1996-1944"],"issn-type":[{"value":"1996-1944","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,6,9]]}}}