Key Takeaways & Executive Findings
- •• • The review covers recent advances in aromatic foldamers and supramolecular helical assemblies, with a focus on chiral phenomena during helical secondary structure formation, as evidenced by references to studies on chirality transfer and amplification (e.g., Nagata et al., ACS Cent Sci 2019, 5:1235–1240). • • Absolute control of helical handedness in quinoline oligoamides has been achieved using chiral moieties such as β-pinene-derived pyridyl groups and oxazolylaniline, as demonstrated by Kendhale et al. (J Org Chem 2011, 76:195–200) and Zheng et al. (Org Lett 2017, 19:1482–1485). • • Strong chiral amplification in copolymers of biphenylylacetylenes has been reported, with unexpected enhancement/inversion and memory of macromolecular helicity (Ishidate et al., J Am Chem Soc 2019, 141:7605–7614). • • Supramolecular 'sergeants' strategy enables in situ and multi-level induction of chirality in helical assemblies of triarylamine trisamide monomers, as shown by Perennes et al. (Chem Sci 2025, 16:14584–14594).
Abstract
The tertiary spatial structure of biological macromolecules determines their physiological functions. In the formation of the tertiary structure, the secondary structure serves as the assembly foundation, and interactions between secondary structures play a critical role in driving and stabilizing the tertiary architecture. Synthetic foldamers, characterized by their modifiability and structural diversity, can adopt various helical conformations, enabling them to mimic natural protein secondary structures such as the α-helix, while also providing chemical models for studying interactions between secondary structures. This review outlines recent advances in aromatic foldamers and supramolecular helical assemblies formed by helical polymers, with particular attention to unique chiral phenomena observed during the formation of helical secondary structures. It provides a detailed summary of their applications in molecular recognition, ion channels, and circularly polarized luminescence, among others, and discusses future challenges facing aromatic foldamers. The review emphasizes the hierarchical nature of chirality—from primary atomic asymmetry to quaternary higher-order structures—and highlights the importance of understanding non-covalent interactions between helical secondary structures for regulating chiral assembly. Key strategies for constructing chiral helical aromatic foldamers include the use of chiral side chains, terminal groups, and solvent effects, as well as the sergeants-and-soldiers effect and majority-rules principle for chirality amplification. The applications of these foldamers in asymmetric catalysis, chiroptical materials, and biomimetic ion transport are also discussed, underscoring their potential in advanced functional materials.
1. Introduction
Helical foldamers, as one of the most prevalent and extensively studied types within the foldamer systems that mimic biological macromolecules, exhibit considerable application potential and distinct advantages in the functional simulation of peptides. The helical conformation is inherently chiral and is typically denoted as P (right-handed) and M (left-handed) to indicate the absolute configuration of the helix. The helix represents a distinct topological structure observed in biological systems, such as the right-handed double helix of DNA and the right-handed α-helix in proteins. These biological helical polymers further assemble into supramolecular helical architectures, including DNA supercoils and coiled-coil proteins, which play crucial physiological roles in organisms, such as recognition, catalysis, ion transport, as well as the storage and replication of genetic information. For decades, scientists have been dedicated to developing various types of synthetic helical systems, including small molecules, oligomers, polymers, and helical aggregates. With ongoing research, significant progress has been made in the design of synthetic helical systems that exhibit distinctive chiral phenomena and possess specific functional properties.
Chirality is a profoundly fascinating phenomenon in nature, observable across multiple scales from the molecular and supramolecular levels to macroscopic dimensions, and even at the scale of entire galaxies. Currently, chiral substances are widely recognized as the material basis of life and hold significant implications for the origin and evolution of living systems. The fundamental cause of chirality lies in asymmetry, which can be categorized into four hierarchical levels based on scale: primary chirality refers to the asymmetric configuration of atoms; secondary chirality arises from the conformational chirality of entire molecules; tertiary chirality involves chiral supramolecular assemblies formed through non-covalent interactions between molecules; and quaternary chirality denotes higher-order structures resulting from the further organization of secondary or tertiary chiral architectures. Present research on chirality primarily focuses on the helical conformations representative of secondary chirality and the supramolecular assemblies constructed via polymeric systems at the tertiary level. A comprehensive understanding of the non-covalent interactions between helical secondary structures can reveal the mutual influences and regulatory mechanisms among these structures, which is essential for the rational design of functional chiral materials.
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CHEN Jiaxin, DONG Zeyuan (2026). Chiral Helical Aromatic Foldamers: Construction Strategies and Applications. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3854-7
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Frequently Asked Questions
What are the key strategies for achieving absolute control of helical handedness in aromatic foldamers?
Absolute control of helical handedness in aromatic foldamers, such as quinoline oligoamides, can be achieved by introducing chiral moieties at the termini or side chains. For instance, β-pinene-derived pyridyl moieties at the N- and C-termini (Zheng et al., Org Lett 2017, 19:1482–1485) and chiral oxazolylaniline moieties at the C-termini (Zheng et al., Chin Chem Lett 2020, 31:673–676) have been shown to induce a preferred handedness. Additionally, a single stereochemical differentiation, such as H vs. CH3, can bias helix handedness quantitatively (Bindl et al., Chem Commun 2021, 57:5662–5665).
How does chirality amplification work in helical copolymers, and what are the reported magnitudes?
Chirality amplification in helical copolymers, such as those of biphenylylacetylenes, follows the sergeants-and-soldiers or majority-rules principles. Ishidate et al. (J Am Chem Soc 2019, 141:7605–7614) reported unexpectedly strong chiral amplification in chiral/achiral and chiral/chiral copolymers, with further enhancement/inversion and memory of macromolecular helicity. The amplification effect is significant, as even a small excess of chiral units can bias the helix sense of the entire polymer chain.
What are the practical applications of chiral helical aromatic foldamers in materials science?
Chiral helical aromatic foldamers have applications in molecular recognition, ion channels, and circularly polarized luminescence (CPL). For example, they can serve as chiral hosts for enantioselective recognition, as artificial ion channels with controlled transport properties, and as emitters for CPL with high dissymmetry factors. The review also highlights their use in asymmetric catalysis, where helical chirality can induce enantioselectivity in reactions.
What are the main challenges in the field of aromatic foldamers, as discussed in the review?
The review discusses future challenges including the difficulty in achieving precise control over higher-order chiral structures (tertiary and quaternary chirality), the need for scalable synthesis of complex foldamers, and the translation of their unique properties into practical devices. Additionally, understanding the dynamic behavior and stimuli-responsiveness of these systems remains a challenge.
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