Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces

Abstract

Precise oligomeric materials constitute a growing area of research with implications for various applications as well as fundamental studies. Notably, this field of science which can be termed macro‐organic chemistry, draws inspiration from both traditional polymer chemistry and organic synthesis, combining the molecular precision of organic chemistry with the materials properties of macromolecules. Discrete oligomers enable access to unprecedented materials properties, for example, in self‐assembled structures, crystallization, or optical properties. The degree of control over oligomer structures resembles many biological systems and enables the design of materials with tailored properties and the development of fundamental structure–property relationships. This Review highlights recent developments in macro‐organic chemistry from synthetic concepts to materials properties, with a focus on self‐assembly and molecular recognition. Finally, an outlook for future research directions is provided.

Sequence-Defined Synthetic Polymers for New-Generation Functional Biomaterials

“…To date, numerous chemical and biological polymerization techniques, such as enzymatic polymerization, templated polymerization, iterative growth, controlled step- or chain-growth polymerization (e.g., atom transfer radical addition, ATRA and photoinduced electron/energy transfer-reversible addition–fragmentation chain transfer-single unit monomer insertion, PET-RAFT-SUMI), molecular machine-mediated synthesis, and very recently self-interrupted living polymerization, have been applied to prepare SDPs. ,,− In this Perspective, we focus on the potential applications of SDPs in biomedical fields such as antimicrobial agents, bioactive ligands, drug delivery carriers, bioimaging agents, and barcoded biomaterials (Figure ). To make this Perspective clear and concise, the recent progress on oligopeptides, oligonucleotides, and oligosaccharides will not be discussed in-depth; this information can be accessed from several comprehensive reviews. − In addition, the synthesis and applications of dendrimers , and discrete π-conjugated oligomers − are beyond the scope of this Perspective as well.…”

Spatially Controlled Highly Branched Vinylsilicones

“…We expanded this concept to create a library of silicone crosslinkers possessing dendritic branches with different degrees of vinyl and alkoxy functionalization and show that, at lower generations, steric problems with functionalization are avoided. The concept of properly controlling polymer synthesis using the perspective of synthetic organic chemists is gaining traction [27]. In the case of silicones, Skov and co-workers initially reported a strategy for synthesizing siloxane copolymers with spatially distributed pendent functional groups, including alkyl chloride and alkyl azide, using the PR reaction [26].…”

Unraveling Sequence Effect on Glass Transition Temperatures of Discrete Unconjugated Oligomers

“…[1][2] The successful preparation of these polymer materials using various biological and organic synthetic techniques has made it possible to investigate their macroscopic properties (e.g., physical, chemical, and biological properties) as well as their applications at different scales, which range from molecular storage to drug delivery. [3][4][5][6][7][8][9][10][11][12][13] The importance and significance of controlling monomer sequence in SCPs is well known and has been extensively demonstrated in recent decades. It is common knowledge that di-or multiblock copolymers generally present more organized self-assembly than statistical copolymers in both bulk and solution systems.…”

“…Probing the corresponding discrete oligomers can facilitate understanding of the properties of assembled high molecular weight polymers. [5,20,32,49] Most importantly, analysis of these small-molecule discrete oligomers will significantly reduce the difficulties in the structure elucidation and mechanistic insight by utilizing widely used analytical instrumentation (e.g., NMR, XRD, etc.). [30] For SDPs, monomer sequence undoubtedly plays an important role in their properties.…”