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Initiated Chemical Vapor Deposition (iCVD) is a free-radical polymerization technique used to synthesize functional polymer thin films. In the context of drug delivery, the conformality of iCVD coatings and the variety of functional chemical moieties make them excellent materials for encapsulating pharmaceutics. Poly(4-aminostyrene) (PAS) belongs to a class of functionalizable materials, whose primary amine allows decoration of the delivery vehicles with biomolecules that enable targeted delivery or biocompatibility. Understanding kinetics of PAS polymerization in iCVD is crucial for such deployments because drug release kinetics in thin-film encapsulation have been shown to be determined by the film thickness. Nevertheless, the effects of deposition conditions on PAS growth kinetics have not been studied systematically. To bridge that knowledge gap, we report the kinetics of iCVD polymerization as a function of fractional saturation pressure of the monomer (i.e., P m /P sat ) in a dual-regime fashion, with quadratic dependence under low P m /P sat and linear dependence under high P m /P sat . We uncovered the critical P m /P sat value of 0.2, around which the transition also occurs for many other iCVD monomers. Because existing theoretical models for the iCVD process cannot fully explain the dual-regime polymerization kinetics, we drew inspiration from solution-phase polymerization and proposed updated termination mechanisms that account for the transition between two regimes. The reported model builds upon existing iCVD theories and allows the synthesis of PAS thin films with precisely controlled growth rates, which has the potential to accelerate the deployment of iCVD PAS as a novel biomaterial in controlled and targeted drug delivery with designed pharmacokinetics.
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This content will become publicly available on November 8, 2025
Single-step synthesis of shaped polymeric particles using initiated chemical vapor deposition in liquid crystals
We elucidate a previously unknown synthesis pathway that leads to polymeric nanospheres, orientation-controlled microgels, or microspheroids via single-step polymerization of divinylbenzene (DVB) using initiated chemical vapor deposition (iCVD) in liquid crystals (LC). iCVD supplies vapor-phase reactants continuously, avoiding the critical limitation of reactant-induced disruption of LC structure that has plagued past LC-templated polymerization processes. LC is leveraged as a real-time display of the polymerization conditions and particle emergence, captured using an in situ long–focal range microscope. Detailed image analysis unravels key LC-guided mechanisms during polymerization. pDVB forms nanospheres due to poor solubilization by nematic LC. The nanospheres partition to the LC-solid interface and further assemble into microgel clusters whose orientation is guided by the LC molecular alignment. On further polymerization, microgel clusters transition to microspheroids that resemble liquid drops. We identify key energetic factors that guide trajectories along the synthesis pathway, providing the fundamental basis of a framework for engineering particle synthesis with shape control.
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- Award ID(s):
- 2229092
- PAR ID:
- 10561366
- Publisher / Repository:
- American Association for the Advancement of Science
- Date Published:
- Journal Name:
- Science Advances
- Volume:
- 10
- Issue:
- 45
- ISSN:
- 2375-2548
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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