We describe single‐chain polymer nanoparticles (SCNPs) possessing intramolecular dynamic covalent crosslinks that can transform into polymer films through a molecular recognition‐mediated crosslinking process. The SCNPs utilise molecular recognition with surface‐immobilised proteins to concentrate upon a substrate, bringing the SCNPs into close spatial proximity with one another and allowing their dynamic covalent crosslinkers to undergo intra‐ to interpolymer chain crosslinking leading to the formation of polymeric film. SCNPs must possess both the capacity for specific molecular recognition and a dynamic nature to their intramolecular crosslinkers to form polymer films, and an investigation of the initial phase of film formation indicates it proceeds from features which form upon the surface then grow predominantly in the xy directions. This approach to polymer film formation presents a potential method to “wrap” surfaces displaying molecular recognition motifs—which could potentially include viral, cellular and bacterial surfaces or artificial surfaces displaying multivalent recognition motifs—within a layer of polymer film.
A series of new two-dimensional coordination framework materials, based on Ag(I)-N bond formation, has been synthesized and structurally characterized by single crystal methods. Reactions between the poly-monodentate bridging ligand N,N'-((1r,4r)-cyclohexane-1,4-diyl)bis(1-(pyridin-3-yl)methanimine), L1, and silver salts yield compounds {[Ag(L1)(MeCN)](CFSO)}, 1, {[Ag(L1)(PFO)]·HO}, 2, and {Ag(L1)(tosylate)}, 3. The frameworks of these materials exhibit two distinct net topologies: 3.4.5 (1 and 2) and 4.6 (3). In all cases, L1 ligands are found to be fully saturated, in terms of metal ion binding, with both sets of pyridyl and imino N atoms involved, though in 1 and 2, crystallographically independent L1 moieties also display pyridyl-only binding. Either solvent (1) or the anion (2 and 3) acts as a terminal ligand to support interlayer interactions in the solid state. For 2 and 3 the molecular sheet orientation lies in the plane of the largest crystal face, indicating that crystal growth is preferentially driven by coordinate bond formation. Despite the relatively labile nature, typical of such Ag(I)-N bonds, solvent-based exfoliation of crystals of 3 was shown to provide dispersions of large, μm, flakes which readily deposit on oxide surfaces as single-molecule sheets, as revealed by atomic force microscopy.
We describe single-chain polymer nanoparticles (SCNPs) possessing intramolecular dynamic covalent crosslinks that can transform into polymer films through amolecular recognition-mediated crosslinking process.T he SCNPs utilise molecular recognition with surface-immobilised proteins to concentrate upon as ubstrate,b ringing the SCNPs into close spatial proximitywith one another and allowing their dynamic covalent crosslinkers to undergo intra-to interpolymer chain crosslinking leading to the formation of polymeric film. SCNPs must possess both the capacity for specific molecular recognition and ad ynamic nature to their intramolecular crosslinkers to form polymer films,and an investigation of the initial phase of film formation indicates it proceeds from features whichform upon the surface then grow predominantly in the xy directions.T his approach to polymer film formation presents ap otential method to "wrap" surfaces displaying molecular recognition motifs-which could potentially include viral, cellular and bacterial surfaces or artificial surfaces displaying multivalent recognition motifs-within al ayer of polymer film.Polymer films are ubiquitous in the modern world, acting as barriers to protect objects from their environments or improve performance.[1] Ap lethora of methods exist to prepare polymer films upon surfaces such as solvent casting, [2] thermal spraying [3] or by vapour deposition techniques [4] and self-assembly methods such as Langmuir-Blodgett [5] or layerby-layer [6] approaches.Alimitation of these methods is that deposition of polymers upon the surfaces is driven by relatively unselective interactions and additional chemical processes may have to be performed if acrosslinked nature to the coating is desired. Here,wereport amethod for polymer film formation in which so-called single-chain polymer nanoparticles (SCNPs) [7] are transformed into crosslinked polymeric films.W es how that film formation only occurs in the presence of complementary molecular recognition between the SCNPs and functionalities displayed on the surface,a nd that the dynamic covalent nature of intramolecular crosslinks contained within the SCNPs is crucial for film formation. We anticipate that this method will enable the "wrapping" of av ariety of surfaces displaying molecular recognition motifs-which could include the surfaces of viruses,c ellular and bacterial surfaces or artificial surfaces displaying multivalent recognition motifs-within alayer of polymer film.We utilise SCNPs (Figure 1a,t op right) which are nanostructures composed of intramolecularly crosslinked linear polymer chains.W eu se dynamic covalent acylhydrazone bonds as intramolecular cross-linkers within our SCNPs on account of the well-known ability of this bond to undergo component exchange processes in aqueous solution (Figure 1b). [8] Thed ynamic nature of the acylhydrazone linkage endows SCNPs with the capacity for structural reconfiguration, facilitating intra-to intermolecular crosslinking of polymer chains.Indilute solution SCNPs po...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.