Linear-dendritic block copolymers (LDBCs) have emerged as promising materials for drug delivery applications, with their hybrid structure exploiting advantageous properties of both linear and dendritic polymers. LDBCs have promising encapsulation efficiencies that can be used to encapsulate both hydrophobic and hydrophilic dyes for bioimaging, cancer therapeutics, and small biomolecules. Additionally, LDBCS can be readily functionalized with varying terminal groups for more efficient targeted delivery. However, depending on structural composition and surface properties, LDBCs also exhibit high dispersities ( Đ ), poor shelf-life, and potentially high cytotoxicity to non-target interfacing blood cells during intravenous drug delivery. Here, we show that choline carboxylic acid-based ionic liquids (ILs) electrostatically solvate LDBCs by direct dissolution and form stable and biocompatible IL-integrated LDBC nano-assemblies. These nano-assemblies are endowed with red blood cell-hitchhiking capabilities and show altered cellular uptake behavior ex vivo . When modified with choline and trans -2-hexenoic acid, IL-LDBC dispersity dropped by half compared to bare LDBCs, and showed a significant shift of the cationic surface charge towards neutrality. Proton nuclear magnetic resonance spectroscopy evidenced twice the total amount of IL on the LDBCs relative to an established IL-linear PLGA platform. Transmission electron microscopy suggested the formation of a nanoparticle surface coating, whichmore »
Understanding the Mechanism of Star-Block Copolymers as Nanoreactors for Synthesis of Well-Defined Silver Nanoparticles
Facile and large-scale synthesis of well-defined, thermally stable silver nanoparticles protected by polymer brushes for use in practical applications is still a challenge. Recent work has reported a nanoreactor approach that can be used to synthesize these silver nanoparticles. This approach uses amphiphilic star-block copolymers, which have a hydrophilic core surrounded by a hydrophobic exterior. These polymers thus can serve as the nanoreactors. In this study, we hypothesize that the local high concentration of silver ions in the inner hydrophilic cores of these star-block copolymers facilitates the nucleation and subsequent growth of silver nanoparticles. When all silver nanoparticles nucleate from the cores of the star-block copolymers in solution, the particle size can be controlled by the core size of the polymer. To test this hypothesis, a polyisoprene-b-poly(p-tert-butylstyrene) (PI-b-PtBS) star-block copolymer was functionalized with carboxylic acid groups using a high-efficiency, photo-initiated thiol-ene click reaction. We characterized this modified polymer using proton nuclear magnetic resonance spectroscopy, and the results indicated that ~60% of the double bonds in the polyisoprene block were successfully functionalized with carboxylic acid groups. When silver ions were added to a solution of these functionalized star-block copolymers, the negatively charged carboxylic acid groups would attract the positively charged silver more »
- Award ID(s):
- 1709420
- Publication Date:
- NSF-PAR ID:
- 10095065
- Journal Name:
- Journal of emerging investigators
- ISSN:
- 2638-0870
- Sponsoring Org:
- National Science Foundation
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Chain exchange behaviors in self-assembled block copolymer (BCP) nanoparticles (NPs) at room temperature are investigated through observations of structural differences between parent and binary systems of BCP NPs with and without crosslinked domains. Pairs of linear diblock or triblock, and branched star-like polystyrene-poly(2-vinylpyridine) (PS-PVP) copolymers that self-assemble in a PVP-selective mixed solvent into BCP NPs with definite differences in size and self-assembled morphology are combined by diverse mixing protocols and at different crosslinking densities to reveal the impact of chain exchange between BCP NPs. Clear structural evolution is observed by dynamic light scattering and AFM and TEM imaging, especially in a blend of triblock + star copolymer BCP NPs. The changes are ascribed to the chain motion inherent in the dynamic equilibrium, which drives the system to a new structure, even at room temperature. Chemical crosslinking of PVP corona blocks suppresses chain exchange between the BCP NPs and freezes the nanostructures at a copolymer crosslinking density (CLD) of ∼9%. This investigation of chain exchange behaviors in BCP NPs having architectural and compositional complexity and the ability to moderate chain motion through tailoring the CLD is expected to be valuable for understanding the dynamic nature of BCP self-assemblies and diversifying themore »
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