Self‐assembled free‐floating nanomaterials from sequence‐defined polymers

Abstract

Sequence‐defined polymers can be programmed to self‐assemble into precise nanostructures for applications in biosensing, drug delivery, optics, and molecular computation. Inspired by the natural self‐assembly processes present in biological protein and DNA systems, sets of molecular design rules have emerged across materials classes as instructions to build a variety of tunable structures. This review highlights recent advances in self‐assembled sequence‐defined and sequence‐specific polymers across peptides, peptoids, DNA, and non‐biological synthetic materials, with a focus on synthesis, assembly processes and overall structure. Specifically, these self‐assembled structures are free‐floating, as such constructs can potentially serve as a platform for the aforementioned applications. Emphasis is placed on the molecular design of polymers that self‐assemble into zero‐dimensional, one‐dimensional, two‐dimensional, or three‐dimensional nanostructures. With the development of automated syntheses and increasing control over self‐assembly, future work may focus on emerging classes of compatible hybrid materials with exciting directions toward new architectures and applications.

Catalytic enrichment of oligothioalkynes: expanding horizons for functionalized oligotriazole synthesis through IrAAC-mediated post-modification

“…The identities of the above two kinds of oligothioalkynes were well confirmed by HRMS analysis. 1 H and 13 C NMR spectra of them as well as crucial intermediates involved in their preparation are also provided in ESI † to elucidate their chemical structure and high purity. Of particular note is that thioalkyne monomers M2 and M4 could be employed in a combinational manner in the construction of each kind of oligothioalkyne, which not only enhance the complexity of the oligomer backbone, but also acts one strategy for adjusting the chemical space between monomers, both of which are critical in determining materials properties.…”

“…3–6 Simultaneously, the creation of non-biological oligomers—like foldamers, π-conjugated oligomers, and sequence-defined oligomers—has spurred the development of an array of advanced materials showcasing a multitude of unprecedented properties. 7–17…”

“…[3][4][5][6] Simultaneously, the creation of non-biological oligomers-like foldamers, π-conjugated oligomers, and sequence-defined oligomers-has spurred the development of an array of advanced materials showcasing a multitude of unprecedented properties. [7][8][9][10][11][12][13][14][15][16][17] To ensure the exacting structural precision of oligomers, a critical factor in deciphering their behaviours and uncovering fundamental structure-property relationships, they are typi-cally synthesized from specialized monomers using iterative elongation strategies (Scheme 1a). 2 However, these laborious stepwise processes not only curtail the yield of desired products but also prove inefficient in generating extensive libraries of uniformly designed oligomers, thereby impeding their practical applications.…”

Mechanistic insights into the pressure-induced polymerization of aryl/perfluoroaryl co-crystals

“…2,3 Such methods offer opportunities toward new donor–acceptor polymers as push–pull chromophores, sequence-defined structures, and structure–function tunable support systems. 4–6 Yet the design of monomers (and/or intricate methods) presents a trade-off between resultant polymer properties, molecular weights, sequential defect sites, and complex design methodologies.…”