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: Zwitterionic Sulfonium Sulfonate Polymers: Impacts of Substituents and Inverted Dipole
Research involving polymer zwitterions typically involves the preparation of ammonium-based structures and their study as coatings or gels that impart hydrophilicity and/or antifouling properties to substrates and materials. More recent synthetic advances have produced a significant expansion in polymer zwitterion chemistry, especially with respect to the composition of the cationic moieties that open new possibilities to examine polymer zwitterions as amphiphiles, functional surfactants, and components of complex emulsions. This article describes the synthesis of new zwitterionic sulfonium sulfonate monomers and their use as starting materials in controlled free radical polymerization to yield the corresponding polymers. These novel polymer zwitterions bear sulfonium sulfonate groups, that possess an inverted dipole directionality relative to prior examples that yields different and unexpected physical and chemical properties. For example, the polymer zwitterions described here are soluble in a wide range of nonaqueous solvents and possess significantly greater stability against nucleophiles relative to their dipole-inverted counterparts. Additionally, the amphiphilic character of these sulfonium sulfonate polymers makes them amenable to use as surfactants for stabilizing oil-in-water emulsions, a feature that is not possible using conventional ultrahydrophilic polymer zwitterions.  more » « less
Award ID(s):
2136955
PAR ID:
10478502
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
ACS Macromolecules
Date Published:
Journal Name:
Macromolecules
Volume:
56
Issue:
3
ISSN:
0024-9297
Page Range / eLocation ID:
1105 to 1110
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; (, Macromolecular Rapid Communications)
    Abstract Polymer zwitterions continue to emerge as useful materials for numerous applications, ranging from hydrophilic and antifouling coatings to electronic materials interfaces. While several polymer zwitterion compositions are now well established, interest in this field of soft materials science has grown rapidly in recent years due to the introduction of new structures that diversify their chemistry and architecture. Nonetheless, at present, the variation of the chemical composition of the anionic and cationic components of zwitterionic structures remains relatively limited to a few primary examples. In this article, the versatility of 4‐vinylbenzyl sultone as a precursor to ammonium sulfonate zwitterionic monomers, which are then used in controlled free radical polymerization chemistry to afford “inverted sulfobetaine” polymer zwitterions, is highlighted. An evaluation of the solubility, interfacial activity, and solution configuration of the resultant polymers reveals the dependence of properties on the selection of tertiary amines used for nucleophilic ring‐opening of the sultone precursor, as well as useful properties comparisons across different zwitterionic compositions. 
    more » « less
  2. ; (, Advanced Healthcare Materials)
    Abstract Electrospinning has emerged as a versatile and accessible technology for fabricating polymer fibers, particularly for biological applications. Natural polymers or biopolymers (including synthetically derivatized natural polymers) represent a promising alternative to synthetic polymers, as materials for electrospinning. Many biopolymers are obtained from abundant renewable sources, are biodegradable, and possess inherent biological functions. This review surveys recent literature reporting new fibers produced from emerging biopolymers, highlighting recent developments in the use of sulfated polymers (including carrageenans and glycosaminoglycans), tannin derivatives (condensed and hydrolyzed tannins, tannic acid), modified collagen, and extracellular matrix extracts. The proposed advantages of these biopolymer‐based fibers, focusing on their biomedical applications, are also discussed to highlight the use of new and emerging biopolymers (or new modifications to well‐established ones) to enhance or achieve new properties for electrospun fiber materials. 
    more » « less
  3. ; ; ; ; (, ACS Applied Materials & Interfaces)
    Porous polymers have interesting acoustic properties including wave dampening and acoustic impedance matching and may be used in numerous acoustic applications, e.g., waveguiding or acoustic cloaking. These materials can be prepared by the inclusion of gas-filled voids, or pores, within an elastic polymer network; therefore, porous polymers that have controlled porosity values and a wide range of possible mechanical properties are needed, as these are key factors that impact the sound-dampening properties. Here, the synthesis of acoustic materials with varying porosities and mechanical properties that could be controlled independent of the pore morphology using emulsion templated polymerizations is described. Polydimethylsiloxane-based ABA triblock copolymer surfactants were prepared using reversible addition−fragmentation chain transfer polymerizations to control the emulsion template and act as an additional crosslinker in the polymerization. Acoustic materials prepared with reactive surfactants possessed a storage modulus of ∼300 kPa at a total porosity of 71% compared to materials prepared using analogous nonreactive surfactants that possessed storage modulus values of ∼150 kPa at similar porosities. These materials display very low longitudinal sound speeds of ∼35 m/s at ultrasonic frequencies, making them excellent candidates in the preparation of acoustic devices such as metasurfaces or lenses. 
    more » « less
  4. ; ; ; ; ; ; ; (, Materials Advances)
    2D particle surfactants are attractive for the formation of highly stable emulsions and use as templates to prepare composite structures with performance properties dependent on the composition. Cobalt oxide nanosheets (CONs) are a relatively understudied class of 2D particle surfactants that can be produced by the chemical exfoliation of lithium cobalt oxide, a transition metal oxide known for excellent gas-sensing, catalytic, and electrochemical properties. Here, we report a simple method to access CONs stabilized oil-in-water Pickering emulsions and use these as templates to prepare particles with a core of polymer and shell of CONs. Salt-flocculated CONs produce emulsions with droplets of hydrophobic monomer ( e.g. , styrene) in water that are stable for at least 24 hours, and suspension free radical polymerization is used to produce CON-armored particles. Characterization by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA) confirmed the presence of CONs on the surface of the polymer core. We then demonstrated the CON-armored polymer particles can activate the oxidant peroxymonosulfate (PMS) for the degradation of bisphenol A (BPA). Freshly prepared and artificially aged CON-armored particles showed full degradation of BPA in less than an hour and no decrease in activity was observed after two uses. CON-armored particles combine high surface area of the nanosheets with the ease of recoverability of the particles. 
    more » « less
  5. ; (, Advanced Engineering Materials)
    Smart emulsions are both versatile additives to smart materials and functional smart materials themselves, acting as active components and structural elements driving innovative development. Emulsions offer versatility, ease of manipulation, and stability to smart materials. This review explores the multifaceted roles of emulsions, examining their formulation methods, applications, and role as building blocks in smart materials. The significance of emulsions in smart materials is discussed for applications such as drug delivery and adaptive coatings, as well as their role in stimuli‐responsive colloidal systems and nanocomposites. The smart emulsions reviewed encompass all manner of material types, including fluid and solid/polymerized smart materials. These include both emulsions with dynamic properties and emulsions used in the process of synthesizing other materials. Smart emulsions are categorized by application into shape memory, self‐healing, biological, and stimuli‐responsive, with analysis of formulation methods, metrics, and methods of final incorporation. Smart emulsions can be found initially as fluid systems and some react into solid polymers, tailored to meet functional needs. A comparative analysis reveals emerging trends such as coupling coating self‐healing/corrosion inhibition and use of waterborne polyurethanes. The discussion of smart emulsions concludes by outlining challenges and future directions for leveraging smart emulsions. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email