skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Hybrid Photoiniferter and Ring‐Opening Polymerization Yields One‐Pot Anisotropic Nanorods
Abstract Polymerization‐induced self‐assembly (PISA) has emerged as a scalable one‐pot technique to prepare block copolymer (BCP) nanoparticles. Recently, a PISA process, that results in poly(l‐lactide)‐b‐poly(ethylene glycol) BCP nanoparticles coined ring‐opening polymerization (ROP)‐induced crystallization‐driven self‐assembly (ROPI‐CDSA), was developed. The resulting nanorods demonstrate a strong propensity for aggregation, resulting in the formation of 2D sheets and 3D networks. This article reports the synthesis of poly(N,N‐dimethyl acrylamide)‐b‐poly(l)‐lactide BCP nanoparticles by ROPI‐CDSA, utilizing a two‐step, one‐pot approach. A dual‐functionalized photoiniferter is first used for controlled radical polymerization of the acrylamido‐based monomer, and the resulting polymer serves as a macroinitiator for organocatalyzed ROP to form the solvophobic polyester block. The resulting nanorods are highly stable and display anisotropy at higher molecular weights (>12k Da) and concentrations (>20% solids) than the previous report. This development expands the chemical scope of ROPI‐CDSA BCPs and provides readily accessible nanorods made with biocompatible materials.  more » « less
Award ID(s):
2238834
PAR ID:
10512619
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Macromolecular Rapid Communications
ISSN:
1022-1336
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; (, Soft Matter)
    Polymerization induced self-assembly (PISA) provides a facile platform for encapsulating therapeutics within block copolymer nanoparticles. 
    more » « less
  2. ; ; ; (, Angewandte Chemie International Edition)
    Abstract Photodegradable nanoparticles with sphere, worm, and vesicle morphologies were synthesized following polymerization induced self‐assembly (PISA), incorporating a photoresponsive phenyl vinyl ketone (PVK) block and a nonphoto responsive 2‐hydroxypropyl methacrylamide (HPMA) block. The photodegradation of nanoparticles under UV revealed that the initial shapes of sphere and vesicle particles are retained even until 7 h and after 24 h of photo‐induced degradation, respectively, despite a significant reduction in molecular weight (Mn). This could be due to the assembly of degraded PVK fragments in the hydrophobic region, maintaining the relative hydrophilic to hydrophobic ratio. However, worm nanoparticles exhibited a fast morphology reversal after 2 min of degradation, yielding sphere nanoparticles. Therefore, photo responsive PVK nanoparticles with morphology and conversion‐dependent degradation behavior were explored. Furthermore, undegraded and degraded nanoparticle coatings exhibited different surface properties, determined by contact angle measurements, with both morphology and degradation impacting the surface properties. Finally, the PVK nanoparticles could encapsulate molecules and release them upon degradation. Therefore, this study can ultimately be applied to numerous fields due to the potential uses of degradable polymers in various material systems, especially for the controlled release of agrochemicals, cleaning agents, or antifungal agents, as well as to enable surface modifications upon degradation. 
    more » « less
  3. ; ; ; ; ; (, Chemical Science)
    Poly( l -lactide) (PLA) is a bioderived and biodegradable polymer that has limited applications due to its hard and brittle nature. Incorporation of 1,3-trimethylene carbonate into PLA, in a block copolymer fashion, improves the mechanical properties, while retaining the biodegradability of the polymer, and broadens its range of applications. However, the preparation of 1,3-trimethylene carbonate (TMC)/ l -lactide (LA) copolymers beyond diblock and triblock structures has not been reported, with explanations focusing mostly on thermodynamic reasons that impede the copolymerization of TMC after lactide. We discuss the preparation of multiblock copolymers via the ring opening polymerization (ROP) of LA and TMC, in a step-wise addition, by a ferrocene-chelating heteroscorpionate zinc complex, {[fc(PPh 2 )(BH[(3,5-Me) 2 pz] 2 )]Zn(μ-OCH 2 Ph)} 2 ([(fc P,B )Zn(μ-OCH 2 Ph)] 2 , fc = 1,1′-ferrocenediyl, pz = pyrazole). The synthesis of up to pentablock copolymers, from various combinations of LA and TMC, was accomplished and the physical, thermal, and mechanical properties of the resulting copolymers evaluated. 
    more » « less
  4. ; ; ; ; ; ; ; (, Angewandte Chemie International Edition)
    Abstract In an effort to synthesize chemically recyclable thermoplastic elastomers, a redox‐switchable catalytic system was developed to synthesize triblock copolymers containing stiff poly(lactic acid) (PLA) end blocks and a flexible poly(tetrahydrofuran‐co‐cyclohexene oxide) (poly(THF‐co‐CHO) copolymer as the mid‐block. The orthogonal reactivity induced by changing the oxidation state of the iron‐based catalyst enabled the synthesis of the triblock copolymers in a single reaction flask from a mixture of monomers. The triblock copolymers demonstrated improved flexibility compared to poly(l‐lactic acid) (PLLA) and thermomechanical properties that resemble thermoplastic elastomers, including a rubbery plateau in the range of −60 to 40 °C. The triblock copolymers containing a higher percentage of THF versus CHO were more flexible, and a blend of triblock copolymers containing PLLA and poly(d‐lactic acid) (PDLA) end‐blocks resulted in a stereocomplex that further increased polymer flexibility. Besides the low cost of lactide and THF, the sustainability of this new class of triblock copolymers was also supported by their depolymerization, which was achieved by exposing the copolymers sequentially to FeCl3and ZnCl2/PEG under reactive distillation conditions. 
    more » « less
  5. ; ; ; ; ; ; (, Journal of Applied Polymer Science)
    Abstract The effect of vortex‐induced mechanical stresses on the fluorescent properties of dye‐containing poly(ethylene glycol)‐block‐poly(lactic acid) (PEG‐b‐PLA) block copolymer micelles has been investigated. PEG‐b‐PLA block copolymer micelles containing fluorescent dyes, 3,3′‐dioctadecyloxacarbocyanine perchlorate (DiO) and/or 1,1′‐dioctadecyl‐3,3,3′,3′‐tetramethylindocarbocyanine perchlorate (DiI), are prepared by a simple one‐step procedure that involves the self‐assembly of block copolymers and spontaneous incorporation of hydrophobic dyes into the core of the micelles. Upon vortexing, the micelle dispersion samples showed a decrease in fluorescence intensity in a rotational speed‐ and time‐dependent manner. The results demonstrated that the vortexing can alter the fluorescent properties of the dye‐containing PEG‐b‐PLA block copolymer micelle dispersion samples, suggesting the potential utility of block copolymer micelles as a mechanical stress‐responsive nanomaterial. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Text Encoded Conversion
  • XML
  • Save / Share this Record
  • Send to Email