Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(<i>ε</i>-caprolactone)-<i>b</i>-polysarcosine Block Copolymers
Poly(ε-caprolactone)-<i>b</i>-polysarcosine (PCL-<i>b</i>-PSar) block copolymers (BCPs) emerge as a promising alternative to conventional poly(<i>ε</i>-caprolactone)-<i>b</i>-poly(ethylene oxide) BCPs for biomedical applications, leveraging superior bi...
Saved in:
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-07-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/30/15/3108 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849770724979376128 |
|---|---|
| author | Zi-Xian Li Chen Yang Lei Guo Jun Ling Jun-Ting Xu |
| author_facet | Zi-Xian Li Chen Yang Lei Guo Jun Ling Jun-Ting Xu |
| author_sort | Zi-Xian Li |
| collection | DOAJ |
| description | Poly(ε-caprolactone)-<i>b</i>-polysarcosine (PCL-<i>b</i>-PSar) block copolymers (BCPs) emerge as a promising alternative to conventional poly(<i>ε</i>-caprolactone)-<i>b</i>-poly(ethylene oxide) BCPs for biomedical applications, leveraging superior biocompatibility and biodegradability. In this study, we synthesized two series of PCL-<i>b</i>-PSar BCPs with controlled polymerization degrees (<i>DP</i> of PCL: 45/67; <i>DP</i> of PSar: 28–99) and low polydispersity indexes (<i>Đ</i> ≤ 1.1) and systematically investigated their crystallization-driven self-assembly (CDSA) in alcohol solvents (ethanol, <i>n</i>-butanol, and <i>n</i>-hexanol). It was found that the limited solubility of PSar in alcohols resulted in competition between micellization and crystallization during self-assembly of PCL-<i>b</i>-PSar, and thus coexistence of lamellae and spherical micelles. To overcome this morphological heterogeneity, we developed a modified self-seeding method by employing a two-step crystallization strategy (i.e., <i>T</i><sub>c1</sub> = 33 °C and <i>T</i><sub>c2</sub> = 8 °C), achieving conversion of micelles into crystals and yielding uniform self-assembled structures. PCL-<i>b</i>-PSar BCPs with short PSar blocks tended to form well-defined two-dimensional lamellar crystals, while those with long PSar blocks induced formation of hierarchical structures in the PCL<sub>45</sub> series and polymer aggregation on crystal surfaces in the PCL<sub>67</sub> series. Solvent quality notably influenced the self-assembly pathways of PCL<sub>45</sub>-<i>b</i>-PSar<sub>28</sub>. Lamellar crystals were formed in ethanol and <i>n</i>-butanol, but micrometer-scale dendritic aggregates were generated in <i>n</i>-hexanol, primarily due to a significant Hansen solubility parameter mismatch. This study elucidated the CDSA mechanism of PCL-<i>b</i>-PSar in alcohols, enabling precise structural control for biomedical applications. |
| format | Article |
| id | doaj-art-a4b60ab2d2fd4d03ae8cbb579274a5da |
| institution | DOAJ |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj-art-a4b60ab2d2fd4d03ae8cbb579274a5da2025-08-20T03:02:55ZengMDPI AGMolecules1420-30492025-07-013015310810.3390/molecules30153108Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(<i>ε</i>-caprolactone)-<i>b</i>-polysarcosine Block CopolymersZi-Xian Li0Chen Yang1Lei Guo2Jun Ling3Jun-Ting Xu4State Key Laboratory of Biobased Transportation Fuel Technology, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, ChinaState Key Laboratory of Biobased Transportation Fuel Technology, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, ChinaState Key Laboratory of Biobased Transportation Fuel Technology, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, ChinaMOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, ChinaState Key Laboratory of Biobased Transportation Fuel Technology, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, ChinaPoly(ε-caprolactone)-<i>b</i>-polysarcosine (PCL-<i>b</i>-PSar) block copolymers (BCPs) emerge as a promising alternative to conventional poly(<i>ε</i>-caprolactone)-<i>b</i>-poly(ethylene oxide) BCPs for biomedical applications, leveraging superior biocompatibility and biodegradability. In this study, we synthesized two series of PCL-<i>b</i>-PSar BCPs with controlled polymerization degrees (<i>DP</i> of PCL: 45/67; <i>DP</i> of PSar: 28–99) and low polydispersity indexes (<i>Đ</i> ≤ 1.1) and systematically investigated their crystallization-driven self-assembly (CDSA) in alcohol solvents (ethanol, <i>n</i>-butanol, and <i>n</i>-hexanol). It was found that the limited solubility of PSar in alcohols resulted in competition between micellization and crystallization during self-assembly of PCL-<i>b</i>-PSar, and thus coexistence of lamellae and spherical micelles. To overcome this morphological heterogeneity, we developed a modified self-seeding method by employing a two-step crystallization strategy (i.e., <i>T</i><sub>c1</sub> = 33 °C and <i>T</i><sub>c2</sub> = 8 °C), achieving conversion of micelles into crystals and yielding uniform self-assembled structures. PCL-<i>b</i>-PSar BCPs with short PSar blocks tended to form well-defined two-dimensional lamellar crystals, while those with long PSar blocks induced formation of hierarchical structures in the PCL<sub>45</sub> series and polymer aggregation on crystal surfaces in the PCL<sub>67</sub> series. Solvent quality notably influenced the self-assembly pathways of PCL<sub>45</sub>-<i>b</i>-PSar<sub>28</sub>. Lamellar crystals were formed in ethanol and <i>n</i>-butanol, but micrometer-scale dendritic aggregates were generated in <i>n</i>-hexanol, primarily due to a significant Hansen solubility parameter mismatch. This study elucidated the CDSA mechanism of PCL-<i>b</i>-PSar in alcohols, enabling precise structural control for biomedical applications.https://www.mdpi.com/1420-3049/30/15/3108amphiphilic block copolymerssemicrystalline block copolymerscrystallization-driven self-assemblypoly(<i>ε</i>-caprolactone)polysarcosineself-seeding |
| spellingShingle | Zi-Xian Li Chen Yang Lei Guo Jun Ling Jun-Ting Xu Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(<i>ε</i>-caprolactone)-<i>b</i>-polysarcosine Block Copolymers Molecules amphiphilic block copolymers semicrystalline block copolymers crystallization-driven self-assembly poly(<i>ε</i>-caprolactone) polysarcosine self-seeding |
| title | Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(<i>ε</i>-caprolactone)-<i>b</i>-polysarcosine Block Copolymers |
| title_full | Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(<i>ε</i>-caprolactone)-<i>b</i>-polysarcosine Block Copolymers |
| title_fullStr | Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(<i>ε</i>-caprolactone)-<i>b</i>-polysarcosine Block Copolymers |
| title_full_unstemmed | Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(<i>ε</i>-caprolactone)-<i>b</i>-polysarcosine Block Copolymers |
| title_short | Controlled Synthesis and Crystallization-Driven Self-Assembly of Poly(<i>ε</i>-caprolactone)-<i>b</i>-polysarcosine Block Copolymers |
| title_sort | controlled synthesis and crystallization driven self assembly of poly i ε i caprolactone i b i polysarcosine block copolymers |
| topic | amphiphilic block copolymers semicrystalline block copolymers crystallization-driven self-assembly poly(<i>ε</i>-caprolactone) polysarcosine self-seeding |
| url | https://www.mdpi.com/1420-3049/30/15/3108 |
| work_keys_str_mv | AT zixianli controlledsynthesisandcrystallizationdrivenselfassemblyofpolyieicaprolactoneibipolysarcosineblockcopolymers AT chenyang controlledsynthesisandcrystallizationdrivenselfassemblyofpolyieicaprolactoneibipolysarcosineblockcopolymers AT leiguo controlledsynthesisandcrystallizationdrivenselfassemblyofpolyieicaprolactoneibipolysarcosineblockcopolymers AT junling controlledsynthesisandcrystallizationdrivenselfassemblyofpolyieicaprolactoneibipolysarcosineblockcopolymers AT juntingxu controlledsynthesisandcrystallizationdrivenselfassemblyofpolyieicaprolactoneibipolysarcosineblockcopolymers |