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.


Title: Organic nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP
Unlike inorganic nanoparticles, organic nanoparticles (oNPs) offer the advantage of “interior tailorability,” thereby enabling the controlled variation of physicochemical characteristics and functionalities, for example, by incorporation of diverse functional small molecules. In this study, a unique inimer-based microemulsion approach is presented to realize oNPs with enhanced control of chemical and mechanical properties by deliberate variation of the degree of hyperbranching or cross-linking. The use of anionic cosurfactants led to oNPs with superior uniformity. Benefitting from the high initiator concentration from inimer and preserved chain-end functionality during atom transfer radical polymerization (ATRP), the capability of oNPs as a multifunctional macroinitiator for the subsequent surface-initiated ATRP was demonstrated. This facilitated the synthesis of densely tethered poly(methyl methacrylate) brush oNPs. Detailed analysis revealed that exceptionally high grafting densities (~1 nm−2) were attributable to multilayer surface grafting from oNPs due to the hyperbranched macromolecular architecture. The ability to control functional attributes along with elastic properties renders this “bottom-up” synthetic strategy of macroinitiator-type oNPs a unique platform for realizing functional materials with a broad spectrum of applications.  more » « less
Award ID(s):
2209587 2202747
PAR ID:
10572055
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
National Academy of Sciences
Date Published:
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
121
Issue:
29
ISSN:
0027-8424
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Durable and conductive interfaces that enable chronic and high‐resolution recording of neural activity are essential for understanding and treating neurodegenerative disorders. These chronic implants require long‐term stability and small contact areas. Consequently, they are often coated with a blend of conductive polymers and are crosslinked to enhance durability despite the potentially deleterious effect of crosslinking on the mechanical and electrical properties. Here the grafting of the poly(3,4 ethylenedioxythiophene) scaffold, poly(styrenesulfonate)‐b‐poly(poly(ethylene glycol) methyl ether methacrylate block copolymer brush to gold, in a controlled and tunable manner, by surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) is described. This “block‐brush” provides high volumetric capacitance (120 F cm─3), strong adhesion to the metal (4 h ultrasonication), improved surface hydrophilicity, and stability against 10 000 charge–discharge voltage sweeps on a multiarray neural electrode. In addition, the block‐brush film showed 33% improved stability against current pulsing. This approach can open numerous avenues for exploring specialized polymer brushes for bioelectronics research and application. 
    more » « less
  2. Abstract A versatile synthetic platform is reported that affords high molecular weight graft copolymers containing polydimethylsiloxane (PDMS) backbones and vinyl‐based polymer side chains with excellent control over molecular weight and grafting density. The synthetic approach leverages thiol‐ene click chemistry to attach an atom‐transfer radical polymerization (ATRP) initiator to a variety of commercially available poly(dimethylsiloxane‐co‐methylvinylsiloxane) backbones (PDMS‐co‐PVMS), followed by controlled radical polymerization with a wide scope of vinyl monomers. Selective degradation of the siloxane backbone with tetrabutylammonium fluoride confirmed the controlled nature of side‐chain growth via ATRP, yielding targeted side‐chain lengths for copolymers containing up to 50% grafting density and overall molecular weights in excess of 1 MDa. In addition, by using a mixture of thiols, grafting density and functionality can be further controlled by tuning initiator loading along the backbone. For example, solid‐state fluorescence of the graft copolymers was achieved by incorporating a thiol‐containing fluorophore along the siloxane backbone during the thiol‐ene click reaction. This simple synthetic platform provides facile control over the properties of a wide variety of grafted copolymers containing flexible PDMS backbones and vinyl polymer side chains. 
    more » « less
  3. Abstract Despite their industrial ubiquity, polyolefin‐polyacrylate block copolymers are challenging to synthesize due to the distinct polymerization pathways necessary for respective blocks. This study utilizes MILRad, metal–organic insertion light‐initiated radical polymerization, to synthesize polyolefin‐b‐poly(methyl acrylate) copolymer by combining palladium‐catalyzed insertion–coordination polymerization and atom transfer radical polymerization (ATRP). Brookhart‐type Pd complexes used for the living polymerization of olefins are homolytically cleaved by blue‐light irradiation, generating polyolefin‐based macroradicals, which are trapped with functional nitroxide derivatives forming ATRP macroinitiators. ATRP in the presence of Cu(0), that is, supplemental activators and reducing agents , is used to polymerize methyl acrylate. An increase in the functionalization efficiency of up to 71% is demonstrated in this study by modifying the light source and optimizing the radical trapping condition. Regardless of the radical trapping efficiency, essentially quantitative chain extension of polyolefin‐Br macroinitiator with acrylates is consistently demonstrated, indicating successful second block formation. 
    more » « less
  4. null (Ed.)
    The synthesis of polymer-grafted nanoparticles (PGNPs) or hairy nanoparticles (HNPs) by tethering of polymer chains to the surface of nanoparticles is an important technique to obtain nanostructured hybrid materials that have been widely used in the formulation of advanced polymer nanocomposites. Ceramic-based polymer nanocomposites integrate key attributes of polymer and ceramic nanomaterial to improve the dielectric properties such as breakdown strength, energy density and dielectric loss. This review describes the ”grafting from” and ”grafting to” approaches commonly adopted to graft polymer chains on NPs pertaining to nano-dielectrics. The article also covers various surface initiated controlled radical polymerization techniques, along with templated approaches for grafting of polymer chains onto SiO2, TiO2, BaTiO3, and Al2O3 nanomaterials. As a look towards applications, an outlook on high-performance polymer nanocomposite capacitors for the design of high energy density pulsed power thin-film capacitors is also presented. 
    more » « less
  5. Abstract Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization (eATRP) to facilitate the regeneration of the activator CuIcomplex on Cu0electrodes. Additionally, Cu0served as a slow supplemental activator and reducing agent (SARA ATRP), enabling the activation of alkyl halides and the regeneration of the CuIactivator through a comproportionation reaction. We harnessed the distinct properties of Cu0dual regeneration, both chemical and electrochemical, by employing sinusoidal, triangular, and square‐wave AC electrolysis alongside some of the most active ATRP catalysts available. Compared to linear waveform (DC electrolysis) or SARA ATRP (without electrolysis), pulsed and AC electrolysis facilitated slightly faster and more controlled polymerizations of acrylates. The same AC electrolysis conditions could successfully polymerize eleven different monomers across different mediums, from water to bulk. Moreover, it proved effective across a spectrum of catalyst activity, from low‐activity Cu/2,2‐bipyridine to highly active Cu complexes with substituted tripodal amine ligands. Chain extension experiments confirmed the high chain‐end fidelity of the produced polymers, yielding functional and high molecular‐weight block copolymers. SEM analysis indicated the robustness of the Cu0electrodes, sustaining at least 15 consecutive polymerizations. 
    more » « less