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Peer-reviewedCC BY-NC-NDACS Polymers Au

Composition-Encoded Control of Amphiphilicity and Nanoscale Rigidity in Poly(isobutyl cyanoacrylate)/Poly(butylene oxide)-stat-polyglycidol Nanospheres and Nanoellipsoids

Abstract

High Resolution Image Download MS PowerPoint Slide Tuning the interfacial hydrophobicity and morphology of polymeric nanomaterials remains a central challenge for controlling their structural, mechanical, and biological properties. Here, we introduce poly(isobutyl cyanoacrylate)/(poly(butylene oxide)- stat -polyglycidol) (PIBCA/(PBO- stat -PG)) nanospheres (NSs) and nanoellipsoids (NEs) as a chemically defined platform for decoupling hydrophobic balance, internal architecture, and morphology within a single system. Statistical copolymers with variable butylene oxide (BO) and glycidol (G) content provide precise modulation of amphiphilicity while maintaining water solubility and stability under in situ polymerization conditions. Across the BO:G gradient, multimodal analyses (TEM, cryo-TEM, DLS, AFM, SAXS, SLS, and ITC) reveal a continuous transition from hydrated, deformable G-rich NSs to compact, lamellar BO-rich structures with reduced hydration and enhanced rigidity. SAXS and AFM jointly establish that BO-induced hydrophobic interactions drive internal densification and structural ordering. Mechanical stretching of embedded NSs yielded NEs with modest aspect ratios (1.6–1.9), compared with previous reports on PIBCA/chitosan NEs. ITC experiments showed a correlation between the aspect ratio and the strength of interaction between PVA and the copolymers. The combined results demonstrate that copolymer architecture alone can encode interfacial structure and mechanical response without altering size or charge. This work establishes PIBCA/(PBO- stat -PG) as a predictive, composition-tunable model for probing how nanoscale amphiphilicity and rigidity govern morphological stability and mechanical behavior in polymeric nanomaterials.

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BibTeX
@article{khelifa2026compositionencoded,
  title = {{Composition-Encoded Control of Amphiphilicity and Nanoscale Rigidity in Poly(isobutyl cyanoacrylate)/Poly(butylene oxide)-stat-polyglycidol Nanospheres and Nanoellipsoids}},
  author = {Hiba Khélifa and Nicolas Illy and Véronique Bennevault and Cécile Huin and Guillaume Tresset and Jean-Michel Guigner and Frédéric Foucher and Philippe Guégan and Kawthar Bouchemal},
  journal = {ACS Polymers Au},
  year = {2026},
  month = nov,
  doi = {10.1021/acspolymersau.6c00014},
  url = {https://hal.science/hal-05853633v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - JOUR
TI  - Composition-Encoded Control of Amphiphilicity and Nanoscale Rigidity in Poly(isobutyl cyanoacrylate)/Poly(butylene oxide)-stat-polyglycidol Nanospheres and Nanoellipsoids
AU  - Hiba Khélifa
AU  - Nicolas Illy
AU  - Véronique Bennevault
AU  - Cécile Huin
AU  - Guillaume Tresset
AU  - Jean-Michel Guigner
AU  - Frédéric Foucher
AU  - Philippe Guégan
AU  - Kawthar Bouchemal
PY  - 2026
DA  - 2026/11/05
JO  - ACS Polymers Au
DO  - 10.1021/acspolymersau.6c00014
UR  - https://hal.science/hal-05853633v1
AB  - High Resolution Image Download MS PowerPoint Slide Tuning the interfacial hydrophobicity and morphology of polymeric nanomaterials remains a central challenge for controlling their structural, mechanical, and biological properties. Here, we introduce poly(isobutyl cyanoacrylate)/(poly(butylene oxide)- stat -polyglycidol) (PIBCA/(PBO- stat -PG)) nanospheres (NSs) and nanoellipsoids (NEs) as a chemically defined platform for decoupling hydrophobic balance, internal architecture, and morphology within a single system. Statistical copolymers with variable butylene oxide (BO) and glycidol (G) content provide precise modulation of amphiphilicity while maintaining water solubility and stability under in situ polymerization conditions. Across the BO:G gradient, multimodal analyses (TEM, cryo-TEM, DLS, AFM, SAXS, SLS, and ITC) reveal a continuous transition from hydrated, deformable G-rich NSs to compact, lamellar BO-rich structures with reduced hydration and enhanced rigidity. SAXS and AFM jointly establish that BO-induced hydrophobic interactions drive internal densification and structural ordering. Mechanical stretching of embedded NSs yielded NEs with modest aspect ratios (1.6–1.9), compared with previous reports on PIBCA/chitosan NEs. ITC experiments showed a correlation between the aspect ratio and the strength of interaction between PVA and the copolymers. The combined results demonstrate that copolymer architecture alone can encode interfacial structure and mechanical response without altering size or charge. This work establishes PIBCA/(PBO- stat -PG) as a predictive, composition-tunable model for probing how nanoscale amphiphilicity and rigidity govern morphological stability and mechanical behavior in polymeric nanomaterials.
SN  - 2694-2453
ER  -