Advancements in the performance and properties of ionenes can be achieved via rational molecular design strategies which combine structural elements of ionic liquids (ILs) and high‐performance polymers. The use of imidazole‐amine molecules with asymmetric reactivity has enabled the synthesis of new bis(imidazole) diimide monomers which are then polymerized via the Menshutkin reaction, followed by anion exchange to various molecular species well known in the IL literature. In this work, three types of imidazolium polyimide‐ionene backbones were synthesized starting from 1‐(3‐aminopropyl)imidazole and pyromellitic dianhydride (PMDA) or 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) or from 1‐(4‐aminophenyl)imidazole and 6FDA, with these monomers then reacted with
The potential applications of cationic poly(ionic liquids) range from medicine to energy storage, and the development of efficient synthetic strategies to target innovative cationic building blocks is an important goal. A post‐polymerization click reaction is reported that provides facile access to trisaminocyclopropenium (TAC) ion‐functionalized macromolecules of various architectures, which are the first class of polyelectrolytes that bear a formal charge on carbon. Quantitative conversions of polymers comprising pendant or main‐chain secondary amines were observed for an array of TAC derivatives in three hours using near equimolar quantities of cyclopropenium chlorides. The resulting TAC polymers are biocompatible and efficient transfection agents. This robust, efficient, and orthogonal click reaction of an ionic liquid, which we term ClickabIL, allows straightforward screening of polymeric TAC derivatives. This platform provides a modular route to synthesize and study various properties of novel TAC‐based polymers.
more » « less- NSF-PAR ID:
- 10037955
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie
- Volume:
- 128
- Issue:
- 40
- ISSN:
- 0044-8249
- Format(s):
- Medium: X Size: p. 12570-12574
- Size(s):
- ["p. 12570-12574"]
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract para ‐dichloroxylene. The Cl−anions on the resultant ionenes were then exchanged with one of six molecular anions yielding a total of 18 distinct polymer compositions. The functional groups present within the cationic backbone as well as the anion type were observed to strongly influence both the thermal and organizational properties of these new ionenes. © 2019 Society of Chemical Industry -
more » « less
Abstract Reversible addition‐fragmentation chain‐transfer (RAFT) polymerization is a commonly used polymerization methodology to generate synthetic polymers. The products of RAFT polymerization, i.e., RAFT polymers, have been widely employed in several biologically relevant areas, including drug delivery, biomedical imaging, and tissue engineering. In this article, we summarize a synthetic methodology to display an azide group at the chain end of a RAFT polymer, thus presenting a reactive site on the polymer terminus. This platform enables a click reaction between azide‐terminated polymers and alkyne‐containing molecules, providing a broadly applicable scaffold for chemical and bioconjugation reactions on RAFT polymers. We also highlight applications of these azide‐terminated RAFT polymers in fluorophore labeling and for promoting organelle targeting capability. © 2020 Wiley Periodicals LLC.
Basic Protocol 1 : Synthesis of the azide derivatives of chain transfer agent and radical initiatorBasic Protocol 2 : Installation of an azide group on the α‐end of RAFT polymersAlternate Protocol : Installation of an azide group on the ω‐end of RAFT polymersBasic Protocol 3 : Click reaction between azide‐terminated RAFT polymers and alkyne derivatives -
We report the facile synthesis and characterization of 1,6-α linked functional stereoregular polysaccharides from biomass-derived levoglucosan via cationic ring-opening polymerization (cROP). Levoglucosan is a bicyclic acetal with rich hydroxyl functionality, which can be synthetically modified to install a variety of pendant groups for tailored properties. We have employed biocompatible and recyclable metal triflate catalysts – scandium and bismuth triflate – for green cROP of levoglucosan derivatives, even at very low catalyst loadings of 0.5 mol%. Combined experimental and computational studies provided key kinetic, thermodynamic, and mechanistic insights into the cROP of these derivatives with metal triflates. Computational studies reveal that ring-opening of levoglucosan derivatives is preferred at the 1,6 anhydro linkage and cROP proceeds in a regio- and stereo-specific manner to form 1,6-α glycosidic linkages. DFT calculations also show that biocompatible metal triflates efficiently coordinate with levoglucosan derivatives as compared to the highly toxic PF 5 used previously. Post-polymerization modification of levoglucosan-based polysaccharides is readily performed via UV-initiated thiol–ene click reactions. The reported levoglucosan based polymers exhibit good thermal stability ( T d > 250 °C) and a wide glass transition temperature ( T g ) window (<−150 °C to 32 °C) that is accessible with thioglycerol and lauryl mercaptan pendant groups. This work demonstrates the utility of levoglucosan as a renewably-derived scaffold, enabling facile access to tailored polysaccharides that could be important in many applications ranging from sustainable materials to biologically active polymers.more » « less
-
more » « less
Abstract Cationic polymers are an interesting class of macromolecules due to their versatility and emerging properties that can be used for various industrial and biomedical purposes. This report is focused on investigating the use of microwave heating in the reversible addition–fragmentation chain transfer polymerization of functional cationic monomers,
N ‐(3‐aminopropyl)methacrylamide hydrochloride (APMA) andN ‐[3‐(dimethylamino)propyl]methacrylamide (DMAPMA). Under comparable polymerization reaction conditions, the microwave‐assisted reaction achieves up to 270% (APMA) and 375% (DMAPMA) rate enhancement over conventional oil‐bath mediated set‐up. Linear relationships are observed between number average molecular weight and monomer conversion for different target degrees of polymerization to give low‐ to high‐molecular‐weight cationic polymers. Chain extension experiments show increase in molecular weight of the cationic polymers with narrow dispersities (Ð < 1.2) indicating retention of the chain transfer agent with no observable aminolysis or hydrolysis during polymerization. -
more » « less
Abstract Recent advances of supramolecular chemistry utilized in the development of self‐healing polymers have revealed that the rate and equilibrium constants of bond dissociation/re‐association, bonding directionality, chain relaxation time, decay rate of chain relaxation after damage, and cluster formation may impact the healing efficiency in a given environment. This review provides an assessment of supramolecular chemistries responsible for self‐healing using H‐bonding, metal–ligand, host–guest, ionic, π–π, and hydrophobic interactions. The impact of these chemistries on self‐healing is examined for various polymeric systems with multifunctional applications which are unique to supramolecular networks. This review also discusses the driving forces leading to physical damage closure in the context of supramolecular bond dynamics, providing insights into the design principles to achieve efficient recovery.
