Microstructure—Thermal Property Relationships of Poly (Ethylene Glycol-<i>b</i>-Caprolactone) Copolymers and Their Micelles
The crystallinity of polymers strongly affects their properties. For block copolymers, whereby two crystallisable blocks are covalently tethered to one another, the molecular weight of the individual blocks and their relative weight fraction are important structural parameters that control their cry...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-10-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/14/20/4365 |
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| author | Khandokar Sadique Faisal Andrew J. Clulow Stephanie V. MacWilliams Todd A. Gillam Ashlyn Austin Marta Krasowska Anton Blencowe |
| author_facet | Khandokar Sadique Faisal Andrew J. Clulow Stephanie V. MacWilliams Todd A. Gillam Ashlyn Austin Marta Krasowska Anton Blencowe |
| author_sort | Khandokar Sadique Faisal |
| collection | DOAJ |
| description | The crystallinity of polymers strongly affects their properties. For block copolymers, whereby two crystallisable blocks are covalently tethered to one another, the molecular weight of the individual blocks and their relative weight fraction are important structural parameters that control their crystallisation. In the case of block copolymer micelles, these parameters can influence the crystallinity of the core, which has implications for drug encapsulation and release. Therefore, in this study, we aimed to determine how the microstructure of poly(ethylene glycol-<i>b</i>-caprolactone) (PEG-<i>b-</i>PCL) copolymers contributes to the crystallinity of their hydrophobic PCL micelle cores. Using a library of PEG-<i>b</i>-PCL copolymers with PEG number-average molecular weight (<i>M<sub>n</sub></i>) values of 2, 5, and 10 kDa and weight fractions of PCL (<i>f<sub>PCL</sub></i>) ranging from 0.11 to 0.67, the thermal behaviour and morphology were studied in blends, bulk, and micelles using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WXRD), and Synchrotron wide-angle X-ray scattering (WAXS). Compared to PEG and PCL homopolymers, the block copolymers displayed reduced crystallinity in the bulk phase and the individual blocks had a large influence on the crystallisation of one another. The <i>f<sub>PCL</sub></i> was determined to be the dominant contributor to the extent and order of crystallisation of the two blocks. When <i>f<sub>PCL</sub></i> < 0.35, the initial crystallisation of PEG led to an amorphous PCL phase. At <i>f<sub>PCL</sub></i> values between 0.35 and 0.65, PEG crystallisation was followed by PCL crystallisation, whereas this behaviour was reversed when <i>f<sub>PCL</sub></i> > 0.65. For lyophilised PEG-<i>b</i>-PCL micelles, the crystallinity of the core increased with increasing <i>f<sub>PCL</sub></i>, although the core was predominately amorphous for micelles with <i>f<sub>PCL</sub></i> < 0.35. These findings contribute to understanding the relationships between copolymer microstructure and micelle core crystallinity that are important for the design and performance of micellar drug delivery systems, and the broader application of polymer micelles. |
| first_indexed | 2024-03-09T19:33:03Z |
| format | Article |
| id | doaj.art-cfd678c249e44606a7164db819593847 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-09T19:33:03Z |
| publishDate | 2022-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-cfd678c249e44606a7164db8195938472023-11-24T02:08:00ZengMDPI AGPolymers2073-43602022-10-011420436510.3390/polym14204365Microstructure—Thermal Property Relationships of Poly (Ethylene Glycol-<i>b</i>-Caprolactone) Copolymers and Their MicellesKhandokar Sadique Faisal0Andrew J. Clulow1Stephanie V. MacWilliams2Todd A. Gillam3Ashlyn Austin4Marta Krasowska5Anton Blencowe6Applied Chemistry and Translational Biomaterials (ACTB) Group, Centre for Pharmaceutical Innovation (CPI), UniSA Clinical and Health Sciences, University of South Australia, Adelaide, SA 5000, AustraliaBioSAXS Beamline, Australian Synchrotron, Australian Nuclear Science and Technology Organisation (ANSTO), Clayton, VIC 3168, AustraliaSurface Interactions and Soft Matter (SISM) Group, Future Industries Institute, UniSA STEM, University of South Australia, Mawson Lakes, SA 5095, AustraliaApplied Chemistry and Translational Biomaterials (ACTB) Group, Centre for Pharmaceutical Innovation (CPI), UniSA Clinical and Health Sciences, University of South Australia, Adelaide, SA 5000, AustraliaApplied Chemistry and Translational Biomaterials (ACTB) Group, Centre for Pharmaceutical Innovation (CPI), UniSA Clinical and Health Sciences, University of South Australia, Adelaide, SA 5000, AustraliaSurface Interactions and Soft Matter (SISM) Group, Future Industries Institute, UniSA STEM, University of South Australia, Mawson Lakes, SA 5095, AustraliaApplied Chemistry and Translational Biomaterials (ACTB) Group, Centre for Pharmaceutical Innovation (CPI), UniSA Clinical and Health Sciences, University of South Australia, Adelaide, SA 5000, AustraliaThe crystallinity of polymers strongly affects their properties. For block copolymers, whereby two crystallisable blocks are covalently tethered to one another, the molecular weight of the individual blocks and their relative weight fraction are important structural parameters that control their crystallisation. In the case of block copolymer micelles, these parameters can influence the crystallinity of the core, which has implications for drug encapsulation and release. Therefore, in this study, we aimed to determine how the microstructure of poly(ethylene glycol-<i>b</i>-caprolactone) (PEG-<i>b-</i>PCL) copolymers contributes to the crystallinity of their hydrophobic PCL micelle cores. Using a library of PEG-<i>b</i>-PCL copolymers with PEG number-average molecular weight (<i>M<sub>n</sub></i>) values of 2, 5, and 10 kDa and weight fractions of PCL (<i>f<sub>PCL</sub></i>) ranging from 0.11 to 0.67, the thermal behaviour and morphology were studied in blends, bulk, and micelles using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WXRD), and Synchrotron wide-angle X-ray scattering (WAXS). Compared to PEG and PCL homopolymers, the block copolymers displayed reduced crystallinity in the bulk phase and the individual blocks had a large influence on the crystallisation of one another. The <i>f<sub>PCL</sub></i> was determined to be the dominant contributor to the extent and order of crystallisation of the two blocks. When <i>f<sub>PCL</sub></i> < 0.35, the initial crystallisation of PEG led to an amorphous PCL phase. At <i>f<sub>PCL</sub></i> values between 0.35 and 0.65, PEG crystallisation was followed by PCL crystallisation, whereas this behaviour was reversed when <i>f<sub>PCL</sub></i> > 0.65. For lyophilised PEG-<i>b</i>-PCL micelles, the crystallinity of the core increased with increasing <i>f<sub>PCL</sub></i>, although the core was predominately amorphous for micelles with <i>f<sub>PCL</sub></i> < 0.35. These findings contribute to understanding the relationships between copolymer microstructure and micelle core crystallinity that are important for the design and performance of micellar drug delivery systems, and the broader application of polymer micelles.https://www.mdpi.com/2073-4360/14/20/4365micellecopolymermicrostructurethermal behaviourcrystallinity |
| spellingShingle | Khandokar Sadique Faisal Andrew J. Clulow Stephanie V. MacWilliams Todd A. Gillam Ashlyn Austin Marta Krasowska Anton Blencowe Microstructure—Thermal Property Relationships of Poly (Ethylene Glycol-<i>b</i>-Caprolactone) Copolymers and Their Micelles Polymers micelle copolymer microstructure thermal behaviour crystallinity |
| title | Microstructure—Thermal Property Relationships of Poly (Ethylene Glycol-<i>b</i>-Caprolactone) Copolymers and Their Micelles |
| title_full | Microstructure—Thermal Property Relationships of Poly (Ethylene Glycol-<i>b</i>-Caprolactone) Copolymers and Their Micelles |
| title_fullStr | Microstructure—Thermal Property Relationships of Poly (Ethylene Glycol-<i>b</i>-Caprolactone) Copolymers and Their Micelles |
| title_full_unstemmed | Microstructure—Thermal Property Relationships of Poly (Ethylene Glycol-<i>b</i>-Caprolactone) Copolymers and Their Micelles |
| title_short | Microstructure—Thermal Property Relationships of Poly (Ethylene Glycol-<i>b</i>-Caprolactone) Copolymers and Their Micelles |
| title_sort | microstructure thermal property relationships of poly ethylene glycol i b i caprolactone copolymers and their micelles |
| topic | micelle copolymer microstructure thermal behaviour crystallinity |
| url | https://www.mdpi.com/2073-4360/14/20/4365 |
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