Engineering precise sequence-defined polymers for advanced functions

Shi, Qiangqiang; Deng, Zhicheng; Hou, Mingxuan; Hu, Xianglong; Liu, Shiyong

doi:10.1016/j.progpolymsci.2023.101677

Cited by 25 publications

(23 citation statements)

References 542 publications

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“…Inspired by the precise synthesis of natural biomacromolecules like DNA and proteins, unnatural precision sequence-defined polymers have emerged as biomimetics with advanced functions . For example, they can serve as alternative information storage media due to their chemical diversity and durability . To this end, the development and use of sequencing methods to decipher the sequence information is of great significance .…”

Section: Precision Sequence-defined Depolymerizable Oligomersmentioning

confidence: 99%

Emerging Trends in the Chemistry of End-to-End Depolymerization

Deng,

Gillies

2023

JACS Au

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Over the past couple of decades, polymers that depolymerize end-to-end upon cleavage of their backbone or activation of a terminal functional group, sometimes referred to as "self-immolative" polymers, have been attracting increasing attention. They are of growing interest in the context of enhancing polymer degradability but also in polymer recycling as they allow monomers to be regenerated in a controlled manner under mild conditions. Furthermore, they are highly promising for applications as smart materials due to their ability to provide an amplified response to a specific signal, as a single sensing event is translated into the generation of many small molecules through a cascade of reactions. From a chemistry perspective, end-to-end depolymerization relies on the principles of self-immolative linkers and polymer ceiling temperature (T c ). In this article, we will introduce the key chemical concepts and foundations of the field and then provide our perspective on recent exciting developments. For example, over the past few years, new depolymerizable backbones, including polyacetals, polydisulfides, polyesters, polythioesters, and polyalkenamers, have been developed, while modern approaches to depolymerize conventional backbones such as polymethacrylates have also been introduced. Progress has also been made on the topological evolution of depolymerizable systems, including the introduction of fully depolymerizable block copolymers, hyperbranched polymers, and polymer networks. Furthermore, precision sequence-defined oligomers have been synthesized and studied for data storage and encryption. Finally, our perspectives on future opportunities and challenges in the field will be discussed.

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Section: Precision Sequence-defined Depolymerizable Oligomersmentioning

confidence: 99%

Emerging Trends in the Chemistry of End-to-End Depolymerization

Deng,

Gillies

2023

JACS Au

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“…The structure of SDPs, especially the sequence, is of great significance in the identification and screening of bioactive substances. And many innovative studies have been reported recently in the screening of small molecule drugs [2a] . In this section, we mainly focus on the prospective applications of SDPs in protein identification and screening.…”

Section: Sdps For Biological Functionsmentioning

confidence: 99%

Precision Sequence‐Defined Polymers: From Sequencing to Biological Functions

Shi,

Zhang,

Liu

2023

Angewandte Chemie

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Precise sequence‐defined polymers (SDPs) with uniform chain‐to‐chain structure including chain length, unit sequence and end functionalities, represent the pinnacle of sophistication in the realm of polymer science. For example, the absolute control over the unit sequence of SDPs allows for bottom‐up design of polymers with hierarchical microstructures and functions. Accompanied with the development of synthetic techniques towards precision SDPs, the decoding of SDP sequences and construction of advanced functions irreplaceable with other synthetic materials is of central importance. In this Minireview, we focus on recent advances in SDP sequencing techniques including tandem mass spectrometry (MS), chemically assisted primary MS, as well as other non‐destructive sequencing methods such as nuclear magnetic resonance (NMR) spectroscopy, circular dichroism (CD), and nanopore sequencing. Additionally, we delve into the promising prospects of SDP functions in the area of cutting‐edge biological research. Topics of exploration include gene delivery systems, the development of hybrid materials combining SDPs and nucleic acids, protein recognition and regulation, as well as the interplay between chirality and biological functions. A brief outlook towards the future directions of SDPs is also presented.

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“…Sequence-defined polymers have gradually developed with precise chain length and sequence, thereby holding great promise to reach the precision, complexity, and functionality of biopolymers. 29 β-appended oligothiophenes, and oligo(ether-sulfone)s, have been reported. 30−38 Various functional polymers with welldefined molecular weights are given by repeated coupling and substitution reactions.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Parameters, such as number-average molecular weight ( M n ), weight-average molecular weight ( M w ), and polydispersity ( M w / M n ), are of critical importance for the solid-state properties of oligomers and polymers. − Furthermore, structurally defined oligomers and polymers with low polydispersities can be used for guided investigation of structure–property relationships and supramolecular self-assembly processes. , However, in the fundamental study of linear molecular structures, the synthesis of functional monodisperse oligomers with precisely defined structures is extremely difficult by conventional means. Sequence-defined polymers have gradually developed with precise chain length and sequence, thereby holding great promise to reach the precision, complexity, and functionality of biopolymers . Such synthetic research is still limited.…”

Section: Introductionmentioning

confidence: 99%

Systematic Order-Made Synthesis of Sequence-Defined Polyurethanes with Length, Types, and Topologies

Yamauchi,

Inayama,

Nakabayashi

et al. 2023

ACS Macro Lett.

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Polyurethanes are industrially and academically important as soft materials. They are conventionally synthesized by a process based on step-growth polymerization; thus, molecular weight and structural control are impossible. However, the development of a synthetic strategy for polyurethanes remains a big challenge in designing soft materials. Herein, we demonstrate a synthetic methodology for generating polyurethanes with selectable lengths and termini characteristics. The multistep synthetic process offered the systematic synthesis of high-molecular weight, regioregular, and α,ω-urethane telechelics. Various oligomers with order-made repeating units revealed the effective length of the polymer properties. To demonstrate the scope of our methodology, it was also applied to the synthesis of block co-oligomers, three-armed star oligomers, and miktoarm star co-oligomers. Thus, our method allows the synthesis of high-molecular-weight oligomers with complete structural and molecular weight control, which is of enormous value to materials science; particularly the study and application of structure−property relationships in polyurethanes.

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Engineering precise sequence-defined polymers for advanced functions

Cited by 25 publications

References 542 publications

Emerging Trends in the Chemistry of End-to-End Depolymerization

Emerging Trends in the Chemistry of End-to-End Depolymerization

Precision Sequence‐Defined Polymers: From Sequencing to Biological Functions

Systematic Order-Made Synthesis of Sequence-Defined Polyurethanes with Length, Types, and Topologies

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