Well‐Defined Poly(HPMAm) Brushes via Surface‐Initiated RAFT Polymerization; A Mixed‐Chain Transfer Agent (CTA) Approach
Abstract Over three decades, efforts to prevent non‐specific protein adsorption on surfaces have improved; however, developing well‐defined antifouling coatings remains a challenge in biomaterials research. In this study, a rapid and straightforward protocol relying on surface‐initiated reversible a...
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Wiley-VCH
2025-07-01
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| Series: | Advanced Materials Interfaces |
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| Online Access: | https://doi.org/10.1002/admi.202500196 |
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| author | Manisha Singh Zdeňka Sedláková Jan Svoboda Eliezer Jäger Rafal Poreba |
| author_facet | Manisha Singh Zdeňka Sedláková Jan Svoboda Eliezer Jäger Rafal Poreba |
| author_sort | Manisha Singh |
| collection | DOAJ |
| description | Abstract Over three decades, efforts to prevent non‐specific protein adsorption on surfaces have improved; however, developing well‐defined antifouling coatings remains a challenge in biomaterials research. In this study, a rapid and straightforward protocol relying on surface‐initiated reversible addition‐fragmentation chain‐transfer (RAFT) polymerization (S‐RAFT) is demonstrated to fabricate poly(N‐(2‐hydroxypropyl methacrylamide), poly(HPMAm)) brushes employing a mixed‐chain transfer agent (CTA) approach. By systematically evaluating different combinations of surface‐tethered and free CTAs, it is demonstrated that the simultaneous use of structurally distinct CTA classes; dithiobenzoate (DTB) and trithiocarbonate (TTC); enhances polymerization control and brush growth rates. The conditions enable the fabrication of poly(HPMAm) brushes exceeding 70 nm in thickness within only 4 h at 50 °C. Spectroscopic ellipsometry confirmed that the mixed‐CTA approach significantly outperforms single‐CTA systems, yielding higher polymerization efficiency and greater brush thickness. Additionally, size exclusion chromatography (SEC) confirmed that the solution‐born polymers exhibited narrow dispersity (Ð = 1.05–1.15), ensuring well‐defined polymer structures. The findings highlight the advantages of combining different CTAs in a single polymerization system, leading to a more efficient and scalable method for fabricating antifouling poly(HPMAm) coatings. This approach offers a significant potential for biomedical applications, including biosensors, blood‐contacting devices, and implantable materials. |
| format | Article |
| id | doaj-art-b60a9e370c0d4e959a52f8529bebda33 |
| institution | DOAJ |
| issn | 2196-7350 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Wiley-VCH |
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| series | Advanced Materials Interfaces |
| spelling | doaj-art-b60a9e370c0d4e959a52f8529bebda332025-08-20T03:12:49ZengWiley-VCHAdvanced Materials Interfaces2196-73502025-07-011213n/an/a10.1002/admi.202500196Well‐Defined Poly(HPMAm) Brushes via Surface‐Initiated RAFT Polymerization; A Mixed‐Chain Transfer Agent (CTA) ApproachManisha Singh0Zdeňka Sedláková1Jan Svoboda2Eliezer Jäger3Rafal Poreba4Institute of Macromolecular Chemistry Czech Academy of Sciences Heyrovsky sq. 2 Prague 16200 Czech RepublicInstitute of Macromolecular Chemistry Czech Academy of Sciences Heyrovsky sq. 2 Prague 16200 Czech RepublicInstitute of Macromolecular Chemistry Czech Academy of Sciences Heyrovsky sq. 2 Prague 16200 Czech RepublicInstitute of Macromolecular Chemistry Czech Academy of Sciences Heyrovsky sq. 2 Prague 16200 Czech RepublicInstitute of Macromolecular Chemistry Czech Academy of Sciences Heyrovsky sq. 2 Prague 16200 Czech RepublicAbstract Over three decades, efforts to prevent non‐specific protein adsorption on surfaces have improved; however, developing well‐defined antifouling coatings remains a challenge in biomaterials research. In this study, a rapid and straightforward protocol relying on surface‐initiated reversible addition‐fragmentation chain‐transfer (RAFT) polymerization (S‐RAFT) is demonstrated to fabricate poly(N‐(2‐hydroxypropyl methacrylamide), poly(HPMAm)) brushes employing a mixed‐chain transfer agent (CTA) approach. By systematically evaluating different combinations of surface‐tethered and free CTAs, it is demonstrated that the simultaneous use of structurally distinct CTA classes; dithiobenzoate (DTB) and trithiocarbonate (TTC); enhances polymerization control and brush growth rates. The conditions enable the fabrication of poly(HPMAm) brushes exceeding 70 nm in thickness within only 4 h at 50 °C. Spectroscopic ellipsometry confirmed that the mixed‐CTA approach significantly outperforms single‐CTA systems, yielding higher polymerization efficiency and greater brush thickness. Additionally, size exclusion chromatography (SEC) confirmed that the solution‐born polymers exhibited narrow dispersity (Ð = 1.05–1.15), ensuring well‐defined polymer structures. The findings highlight the advantages of combining different CTAs in a single polymerization system, leading to a more efficient and scalable method for fabricating antifouling poly(HPMAm) coatings. This approach offers a significant potential for biomedical applications, including biosensors, blood‐contacting devices, and implantable materials.https://doi.org/10.1002/admi.202500196(surface RAFTpoly(HPMA))poly(HPMAm)polymer brushessacrificial chain transfer agentsurface‐initiated polymerization |
| spellingShingle | Manisha Singh Zdeňka Sedláková Jan Svoboda Eliezer Jäger Rafal Poreba Well‐Defined Poly(HPMAm) Brushes via Surface‐Initiated RAFT Polymerization; A Mixed‐Chain Transfer Agent (CTA) Approach Advanced Materials Interfaces (surface RAFT poly(HPMA)) poly(HPMAm) polymer brushes sacrificial chain transfer agent surface‐initiated polymerization |
| title | Well‐Defined Poly(HPMAm) Brushes via Surface‐Initiated RAFT Polymerization; A Mixed‐Chain Transfer Agent (CTA) Approach |
| title_full | Well‐Defined Poly(HPMAm) Brushes via Surface‐Initiated RAFT Polymerization; A Mixed‐Chain Transfer Agent (CTA) Approach |
| title_fullStr | Well‐Defined Poly(HPMAm) Brushes via Surface‐Initiated RAFT Polymerization; A Mixed‐Chain Transfer Agent (CTA) Approach |
| title_full_unstemmed | Well‐Defined Poly(HPMAm) Brushes via Surface‐Initiated RAFT Polymerization; A Mixed‐Chain Transfer Agent (CTA) Approach |
| title_short | Well‐Defined Poly(HPMAm) Brushes via Surface‐Initiated RAFT Polymerization; A Mixed‐Chain Transfer Agent (CTA) Approach |
| title_sort | well defined poly hpmam brushes via surface initiated raft polymerization a mixed chain transfer agent cta approach |
| topic | (surface RAFT poly(HPMA)) poly(HPMAm) polymer brushes sacrificial chain transfer agent surface‐initiated polymerization |
| url | https://doi.org/10.1002/admi.202500196 |
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