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: Molecular design principles of ionic liquids with a sulfonyl fluoride moiety
The continued success of ionic liquids in applications ranging from energy to medicine poses the challenge to rapidly find new functional ionic liquids with desirable properties while developing practical, scalable syntheses. As a SuFExable functionality, the sulfonyl fluoride has become widely adopted throughout the field of chemical biology due, in part, to its unique stability–reactivity pattern, highlighting the underappreciated potential of the S VI –F motif in materials chemistry. For the first time, we herein report the development of a set of sulfonyl fluoride-functionalized ionic liquids with considerable structural diversity via an efficient, modular, and orthogonal fluorosulfonylethylation procedure. The resulting SO 2 F-functionalized ionic milieu has properties consistent with its classification as ionic liquids. We employed a combination of molecular design, synthesis, computational modeling, and X-ray crystallographic studies to gain in-depth understanding of their structure–property correlations. The diversification of the SO 2 F-bearing salts is extended to include active pharmaceutical precursors, allowing for access to functional materials with a priori low toxicity.  more » « less
Award ID(s):
1919785 1952846
PAR ID:
10275391
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
New Journal of Chemistry
Volume:
45
Issue:
5
ISSN:
1144-0546
Page Range / eLocation ID:
2443 to 2452
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; (, Small)
    Abstract Electrically accelerated self‐healable poly(ionic liquids) copolymers that exhibit resistor‐capacitor (RC) circuit properties are developed. At low alternating current (AC) frequencies these materials behave as a resistor (R), whereas at higher frequencies as a capacitor (C). These properties are attributed to a combination of dipolar and electrostatic interactions in (1‐[(2‐methacryloyloxy)ethyl]‐3‐butylimidazolium bis(trifluoromethyl‐sulfonyl)imide) copolymerized with methyl methacrylate (MMA) monomers to form p(MEBIm‐TSFI/MMA)] copolymers. When the monomer molar ratio (MEBIm‐TSFI:MMA) is 40/60, these copolymers are capable of undergoing multiple damage‐repair cycles and self‐healing is accelerated by the application of alternating 1.0–4.0 V electric field (EF). Self‐healing in the absence of EFs is facilitated by van der Waals (vdW) interactions, but the application of AC EF induces back and forth movement of charges against the opposing force that result in dithering of electrostatic dipoles giving rise to interchain physical crosslinks. Electrostatic inter‐ and intrachain interactions facilitated by copolymerization of ionic liquid monomers with typically dielectric acrylic‐based monomers result in enhanced cohesive energy densities that accelerate the recovery of vdW forces facilitating self‐healing. Incorporating ionic liquids into commodity polymers offers promising uses as green conducting solid polyelectrolytes in self‐healable energy storage, energy‐harvesting devices, and many other applications. 
    more » « less
  2. ; ; ; ; ; (, ECS Meeting Abstracts)
    Ionic liquids (ILs) are highly tailorable materials with unique physical and chemical properties that set them apart from conventional organic solvents. As the library of readily accessible ILs continues to grow, so too does their relevance in applications ranging from material processing to electrochemical energy storage as solvents capable of accessing new chemistries disallowed by traditional chemicals. While a great deal of interest has been directed towards imidazolium and quaternary ammonium based ionic liquids, there are other understudied classes of cations which have potentially favorable properties for energy related applications. One such class is that with boronium cations. These cations have a unique structure with a formally negative boron flanked by positive nitrogens. This inherently zwitterionic structure presents interesting possibilities for electrochemical applications. To date only a handful of boronium cation-based ionic liquids have been thoroughly characterized despite exhibiting impressive electrochemical stabilities (> 5.0 V). In the present study we synthesized a series of ILs with novel boronium cations coupled with the bis(trifluoro-methanesulfonyl)imide anion. We then characterized the electrochemical and physical properties of these boronium ionic liquids by techniques such as cyclic voltammetry, broadband dielectric spectroscopy, oscillatory shear rheology, and thermogravimetric analysis. We will discuss how systematic variations in boronium cation structure impacted electrochemical and physical properties. 
    more » « less
  3. ; ; ; ; (, Molecules)
    null (Ed.)
    Natural biomacromolecules such as structural proteins and polysaccharides are composed of the basic building blocks of life: amino acids and carbohydrates. Understanding their molecular structure, self-assembly and interaction in solvents such as ionic liquids (ILs) is critical for unleashing a flora of new materials, revolutionizing the way we fabricate multi-structural and multi-functional systems with tunable physicochemical properties. Ionic liquids are superior to organic solvents because they do not produce unwanted by-products and are considered green substitutes because of their reusability. In addition, they will significantly improve the miscibility of biopolymers with other materials while maintaining the mechanical properties of the biopolymer in the final product. Understanding and controlling the physicochemical properties of biopolymers in ionic liquids matrices will be crucial for progress leading to the ability to fabricate robust multi-level structural 1D fiber materials. It will also help to predict the relationship between fiber conformation and protein secondary structures or carbohydrate crystallinity, thus creating potential applications for cell growth signaling, ionic conductivity, liquid diffusion and thermal conductivity, and several applications in biomedicine and environmental science. This will also enable the regeneration of biopolymer composite fiber materials with useful functionalities and customizable options critical for additive manufacturing. The specific capabilities of these fiber materials have been shown to vary based on their fabrication methods including electrospinning and post-treatments. This review serves to provide basic knowledge of these commonly utilized protein and polysaccharide biopolymers and their fiber fabrication methods from various ionic liquids, as well as the effect of post-treatments on these fiber materials and their applications in biomedical and pharmaceutical research, wound healing, environmental filters and sustainable and green chemistry research. 
    more » « less
  4. ; ; ; ; ; (, New Journal of Chemistry)
    In this study, magnetic ionic liquids (MILs) consisting of Ni( ii ), Co( ii ), and Mn( ii ) and paired with the bis[(trifluoromethyl)sulfonyl]imide [NTf 2 − ] anion were synthesized from their water soluble chloride intermediates. The MILs feature low viscosity, high hydrophobicity, and hydrolytic stability making them attractive candidates for a number of highly interdisciplinary applications. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; (, Advanced Intelligent Systems)
    Ionic liquids (ILs) exhibit unique properties of good ionic conductivity, electrochemical and thermal stability, and nonflammability, which make them promising candidates for biomedical applications. The limitations of their cytocompatibility are enhanced by using bioionic liquids (BILs) derived from biological molecules such as amines, sugars, and organic acids. BILs can be synthesized using tailorable chemistries that enable their immobilization onto biopolymers. For example, the cholinium ion and its derivatives have found significant interest in tissue engineering and drug delivery systems. Ion‐doped BIL‐functionalized polymers and their composites can also be used to design pH and electrical responsive actuators and sensors. The cytocompatibility and low immunogenicity of BIL‐functionalized polymers enable the possibilities of their use for power storage devices as well as implantable devices. These devices are gaining recognition and importance in nucleic acid delivery and molecular medicine. This review focuses on the recent advances of BILs in biomedical applications. Specifically, the review explores BILs as agents for biopolymer functionalization and highlights BILs as solvents for supermolecular ionic networks. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email