Chiral polymer self-assembly represents a powerful strategy for constructing chiral nanostructures; however, the mechanism underlying the evolution of chirality from molecular polymers to nanostructures is still not well understood. Especially, regulating the chirality of assemblies under external conditions without changing the chirality of the polymers attracts increasing attentions. In this work, we demonstrate that the degree of polymerization (DP) of the building polymers can effectively modulate the chirality of the nanostructures. It was found that for the nanopatterns assembled by poly(γ-benzyl-l-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) block copolymers on rod-like templates formed by PBLG homopolymers, a chirality transition from left-handed to right-handed is observed upon decreasing the DP of either the PBLG homopolymers, the PBLG blocks, or the PEG blocks. It is revealed that the chirality of the nanopatterns is governed by the chiral arrangement of the pendant phenyl groups of PBLG. Decreasing the DP of PBLG homopolymers or PBLG blocks weakens the dipolar attractions between PBLG chains and the solvents, whereas decreasing the DP of PEG blocks enhances the chain crowding between adjacent PBLG blocks. Both of these effects alter the arrangement of the pendant phenyl groups from an extended right-handed form to a contracted left-handed form, thereby inducing observed chirality inversion in the nanopatterns. This study offers a novel approach to control the chirality of polymer nanostructures through tuning the DP of building polymers and advances our understanding of chirality evolution from polymers to nanostructures.

The evolution ofchirality in supramolecular polymerspresentssignificant complexity and challenges, particularly in elucidatingthe underlying mechanisms. In this study, we investigated the supramolecularassembly of chiral C3 triarylamine tris-amide(TATA) monomers. Homochiral aggregation coupled with temperature-inducedchirality reversal phenomenon was discovered. The enantiomeric monomersform supramolecular polymers with identical chirality, and temperaturevariations rapidly trigger inversion of chirality. These phenomenaoccur simultaneously in a binary solvent system comprising 1,2-dichloroethane(DCE) and a hydrocarbon solvent. The internal structures of the supramolecularpolymers play a vital role in these chirality-related anomalies, andthe fundamental mechanisms were successfully elucidated. Homochiralaggregation results from parallel alignment of adjacent chromophoreswith aligned transition dipole moments in a single column, yieldingan identical positive monosignate Cotton effect in the circular dichroism(CD) spectra. Furthermore, temperature fluctuations influence theconfiguration of central triarylamine moieties, redirecting transitiondipole moments whose directions are entirely inverted, thereby causinga rapid chirality reversal. Our discoveries highlight the crucialrole of internal triarylamine moieties and provide valuable insightsinto mechanisms of chirality-related anomalies.

Abstract Chirality governs physiological processes across scales, yet the ambiguous link between molecular chirality and mesostructured chirality persists. Here, we show that while peptide amphiphiles with molecular chirality can assemble into achiral nanostructures, the co‐assembly with silanes leads to left‐handed helical‐twisted nanoribbons and generates tumor cell activity inhibitory properties. The as‐synthesized micrometer‐long nanoribbons have a uniform morphology with a pitch of ∼340 nm, a width of ∼75 nm, and a thickness of ∼25 nm. An increase in the proportion of silane‐peptide amphiphile modulates the pitch radius ratios from 4.5 to 10.4. It is proposed that the longitudinal stacking force toward the chiral centers during the silane crosslinking can successfully induce chirality transfer from the molecular to the mesostructure. Theoretical calculations confirm this mechanism reduces surface area by 35%. Without drugs, these twisted nanoribbons inhibit tumor cell activity by up to 60%, versus <30% for achiral assemblies. RNA sequencing reveals that mesostructured chirality triggers apoptosis by suppressing cell adhesion and ultimately disrupting cellular metabolism. Our study focuses on the easily overlooked molecular interactions between multiple components during mesostructured chirality formation and the biofeedback role of mesostructured chirality, providing new perspectives for understanding the evolution and significance of chirality in nature.

Chirality governs physiological processes across scales, yet the ambiguous link between molecular chirality and mesostructured chirality persists. Here, we show that while peptide amphiphiles with molecular chirality can assemble into achiral nanostructures, the co-assembly with silanes leads to left-handed helical-twisted nanoribbons and generates tumor cell activity inhibitory properties. The as-synthesized micrometer-long nanoribbons have a uniform morphology with a pitch of ∼340 nm, a width of ∼75 nm, and a thickness of ∼25 nm. An increase in the proportion of silane-peptide amphiphile modulates the pitch radius ratios from 4.5 to 10.4. It is proposed that the longitudinal stacking force toward the chiral centers during the silane crosslinking can successfully induce chirality transfer from the molecular to the mesostructure. Theoretical calculations confirm this mechanism reduces surface area by 35%. Without drugs, these twisted nanoribbons inhibit tumor cell activity by up to 60%, versus <30% for achiral assemblies. RNA sequencing reveals that mesostructured chirality triggers apoptosis by suppressing cell adhesion and ultimately disrupting cellular metabolism. Our study focuses on the easily overlooked molecular interactions between multiple components during mesostructured chirality formation and the biofeedback role of mesostructured chirality, providing new perspectives for understanding the evolution and significance of chirality in nature.

The geometric chirality of nanoscale materials originates from the asymmetric structures of the enantiomeric molecules. Herein, we introduce a universal strategy for fabricating in situ-synthesized Au nanostructures (issAu) on biological substrates using a simple staining solution of Au precursors, surfactant, and reductant. As a proof-of-concept, we integrated this staining reaction into bacterial systems, achieving the oriented growth of issAu on organism skeletons. With the involvement of exogenous cysteine enantiomers in the staining solution, enantiomeric molecules contribute to anisotropic growth of branched issAu and the evolution of plasmonic chirality. Through reaction optimization, we successfully engineer chiral issAu onto bacteria, constructing these nanobioheterostructures as versatile, bacterium-derived nanomaterials. The simple and rapid staining method based on chiral issAu growth solutions facilitates the in situ plasmonic engineering of pathogenic bacteria, enabling optical microscopy imaging of individual microbes. Our protocol provides an approach for the chiral nanoengineering of biological entities and exhibits high potential in antimicrobial and bioanalytical applications.

Chiral assemblies are increasingly recognized for their ability to dictate photophysical processes, notably by enhancing triplet generation in intercalated chromophores for applications in phototherapeutics and chiral optoelectronics. However, the precise mechanism of chirality-enhanced intersystem crossing (ISC) remains elusive, as deciphering it requires resolving the complex coupling between ultrafast excited-state dynamics and the evolution of excited-state chirality. Herein, by integrating femtosecond time-resolved circularly polarized luminescence (fs-TRCPL) spectroscopy with transient absorption (TA) spectroscopy and quantum chemical calculations, we directly correlate the chiral gradient imposed by DNA assemblies with enhanced ISC kinetics for the first time. Using a natural antibiotic gilvocarcin V (GV) intercalated into a B-typed dA18•dT18 duplex, a pronounced increase of triplet quantum yield of GV from 7.6% in the solution to 25.8% in DNA is observed. Such enhancement is driven by an amplification of GV's excited-state chirality, leading to direct ISC from the Franck-Condon (FC) region and spin-orbit charge transfer ISC from charge-transfer state simultaneously. This work elucidates the mechanism of excited-state chirality on triplet-state generation and offers a novel design principle for high-performance triplet sensitizers leveraging chiral assemblies.

Chiral gold (Au) nanostructures are typically synthesized via the addition of growth seeds to reaction solutions containing Au precursors, surfactants, and enantiomeric molecules, and the geometric chirality of these nanostructures arises from enantiomer-induced asymmetric growth. However, the influence of coexisting nonchiral surfactants in reaction solutions on the chirality evolution of nanomaterials is rarely discussed. Herein, taking cysteine and hexadecyl trimethylammonium bromide (CTAB) as examples of enantiomeric molecule and surfactant, respectively, the Au reaction solution related to the growth of chiral Au nanostructures was studied in depth. Our findings reveal that increasing concentrations of cysteine promote the formation of branched Au nanostructures. With only micromolar cysteine, it is sufficient to induce the anisotropic branched growth. Nevertheless, when the reaction rates are rapid, the impacts of cysteine on branched growth are weakened. Fortunately, CTAB with the optimal concentration (1.0 mM) serves a reaction modulator, slowing asymmetric growth while enhancing the geometric chirality features of those branched Au nanostructures. When CTAB concentrations surpass 10.0 mM, the products are mainly characterized with the assembled architectures, which detrimentally affect the chirality characteristics. This work is crucial to reveal the chirality evolution mechanism of chiral nanomaterials, remarkably guiding the mediated synthesis of unprecedent chiral nanomaterials on emerging substrates.

Chiral nanostructures hold transformative potential across diverse fields, yet their assembly construction remains hindered by the high entropic barrier of dissymmetric building units. Inspired by biological structural dynamics, we construct two chiral copper-based hydrogen-bonded frameworks [D(L)-Cu-crystals] via hydrogen-bonded assembly using chiral metal-organic helical as the building unit. Single-crystal X-ray diffraction elucidates hierarchical chirality evolution from asymmetric coordinations to helical chains and framework packing. Furthermore, disassembling D(L)-Cu-crystals yields corresponding single-unit chiral metal-organic helices [D(L)-Cu-SMOHs], fully exposed active sites and well-preserved helical architectures. Notably, D(L)-Cu-SMOHs inhibit amyloid fibrillization effectively with pronounced chirality discrimination, driven by entropy-favored hydrophobic interaction. Molecular docking reveals that D-Cu-SMOH exhibits enhanced binding to critical amyloidogenic regions relative to the L-enantiomer. This work establishes a dynamic and reversible assembly-disassembly approach applicable for constructions of chiral nanomaterials. Moreover, it provides insights into understanding enantioselective amyloid inhibition, extending applications in asymmetric catalysis, enantioselective separation and chiroptical devices.

The transformation of metal nanocluster (MNC)-based heterochiral assemblies into their homochiral analogues is a compelling goal inspired by the ubiquitous homochirality observed in living systems. Owing to the intricate factors governing nanomaterial chirality, the precise control of supramolecular chirality in MNCs remains rarely demonstrated. Herein, we demonstrated the coassembly behavior of AuNCs protected by 6-propyl-2-thiouracil (Au3PRT3) with chiral mandelic acid (MA), which revealed the formation of hybrid chiral superstructures of P- and M-helices in a single system. Combined experimental and theoretical studies comprehensively reveal that the enol-keto isomerization of the Au3PRT3 staple motif is primarily responsible for the emergence of P- and M-helices during coassembly. The negatively charged enol-type Au3PRT3 (Au3PRT3enol) interacts directly with S-MA molecules and forms parallel malposed dimers, resulting in the formation of P-helices. In contrast, the dissociation of H+ ions triggers enol-keto isomerization within the PRT ligand. The resulting keto-type isomer (Au3PRT3keto) then interacts with S-MA molecules, promoting vertical stacking of dimers that lead to the formation of M-helices. Based on this observation, the addition of S-MA molecules with the preformed Au3PRT3keto exclusively induces the formation of homochiral M-helices. In this way, the toggling of multiple chiral superstructures was achieved by leveraging facile Au3PRT3enol-Au3PRT3keto isomerization. This work elucidates the precise control of chiral structures by isomerization of surface motifs of AuNCs and presents a paradigm for investigating the structure-property relationship of AuNC materials. This approach offers a strategic pathway for constructing artificial supramolecular composite systems with diverse chiral architectures, potentially advancing our understanding of chirality evolution in natural systems and aiding its biomimetic replication.

Abstract Achieving precise control over chirality evolution in supramolecular polymers that exhibit circularly polarized luminescence (CPL) inversion during aggregation remains a critical yet challenging endeavor. Herein, the construction of coordinated supramolecular polymers derived from homochiral dimers of four Schiff base derivatives and Zn(II) ions, assembled via dynamic chloride bridges is reported. These supramolecular systems exhibit multiple chiroptical inversions in their aggregated states upon exposure to xylene isomers, a process facilitated by solvent‐induced dimer rotation and reversible dissociation of the chloride bridges. Single‐crystal X‐ray diffraction (SCXRD) analysis reveals that xylene isomers act as molecular actuators, triggering rotational motion of the dimers within the assemblies through hydrogen bonding and C─H···π interactions. By modulating the type of xylene isomer and applying thermal stimuli, precise control over both the CPL inversion and emissive wavelength of these coordinated supramolecular polymers is achieved. This work demonstrates precise control over the chiroptical properties of coordinated supramolecular materials, offering a promising platform for the development of stimuli‐responsive CPL‐active systems with dynamically tunable chirality, particularly for applications in information storage and encryption.

Preparing multi‐color and multi‐stimuli‐responsive circularly polarized luminescence (CPL) materials and understanding the evolution of chirality through the visualized mode is still a challenge. Here, an encapsulation engineering approach of chiral metal‐organic frameworks (MOFs) is proposed to confine guest emitters to realize multi‐color and multi‐stimuli‐responsive CPL. Based on triplet‐triplet energy transfer (TTET), white CPL and near‐infrared circularly polarized room temperature phosphorescence (NIR‐CPRTP) can be obtained by introducing the pyrene derivatives. With the introduction of the guest containing vinylpyrene group, the light‐ and thermal‐responsive CPL with the signal inversion can be realized through the reversible [2+2] cycloaddition reaction between the ligand and guest triggered by visible light/ultraviolet light or heating. Furthermore, the excitation‐dependent CPL is successfully achieved with the incorporation of excited state intramolecular proton transfer (ESIPT) molecules into nanopores. Importantly, the chirality magnification can be greatly enhanced through the chiral spatial confinement, the accurate host‐guest single crystal structures of FLT@DCF‐12 and FLT@LCF‐12 provide the visualized mode to understand the mechanism of chirality transfer, amplification and responsiveness. White LED and multiple information display and encryption are further demonstrated. This breakthrough provides a new perspective to guest‐encapsulated chiral MOFs and contributes to the construction of stimuli‐responsive CPL‐active materials.

Diverse chirality evolution originating from the same building blocks can be simultaneously triggered, as demonstrated by Chuanliang Feng et al. in their Research Article (e202417876). The study highlights the construction of supramolecular networks composed of M- and P-type nanofibers through the self-assembly of homochiral phenylalanine derivatives. The cover illustration symbolizes this phenomenon, depicting flowers with opposite chirality, all blossoming simultaneously from the same seeds.

Diverse chirality evolution originating from the same building blocks can be simultaneously triggered, as demonstrated by Chuanliang Feng et al. in their Research Article (e202417876). The study highlights the construction of supramolecular networks composed of M- and P-type nanofibers through the self-assembly of homochiral phenylalanine derivatives. The cover illustration symbolizes this phenomenon, depicting flowers with opposite chirality, all blossoming simultaneously from the same seeds.

As nanoparticle morphologies produced by seeded growth expand in number and complexity, tracking their evolution during growth is increasingly important to achieving a mechanistic understanding. However, fast reactions such as chiral growth, in which morphologies change within seconds, remain challenging to monitor at the relevant time scale. We introduce a method based on fast addition of the reducing agent NaBH4, enabling interruption of gold nanoparticle growth, as well as access to reaction intermediates for morphological and optical investigations. We show that NaBH4 reduces the remaining gold salt precursors into achiral nanoparticles and prevents further evolution of the target particles, resulting in a time series with intervals down to seconds. The method is demonstrated on fast, micelle-directed, chiral growth on single-crystalline or penta-twinned nanorod seeds, showing fine variations in the temporal evolution of chirality depending on crystal habit. These series provide representative snapshots from a chirality continuum, offering a platform for studying optical-structural relationships.

Chirality, a pervasive phenomenon in nature, is widely studied across diverse fields including the origins of life, chemical catalysis, drug discovery, and physical optoelectronics. The investigations of natural chiral materials have been constrained by their intrinsically weak chiral effects. Recently, significant progress has been made in the fabrication and assembly of low-dimensional micro and nanoscale chiral materials and their architectures, leading to the discovery of novel optoelectronic phenomena such as circularly polarized light emission, spin and charge flip, advocating great potential for applications in quantum information, quantum computing, and biosensing. Despite these advancements, the fundamental mechanisms underlying the generation, propagation, and amplification of chirality in low-dimensional chiral materials and architectures remain largely unexplored. To tackle these challenges, we focus on employing ultrafast spectroscopy to investigate the dynamics of chirality evolution, with the aim of attaining a more profound understanding of the microscopic mechanisms governing chirality generation and amplification. This review thus provides a comprehensive overview of the chiral micro-/nano-materials, including two-dimensional transition metal dichalcogenides (TMDs), chiral halide perovskites, and chiral metasurfaces, with a particular emphasis on the physical mechanism. This review further explores the advancements made by ultrafast chiral spectroscopy research, thereby paving the way for innovative devices in chiral photonics and optoelectronics.

Chirality evolution is ubiquitous and important in nature, but achieving it in artificial systems is still challenging. Herein, the chirality evolution of supramolecular helices based on l-phenylalanine derivative (LPF) and naphthylamide derivate (NDIAPY) is achieved by the strategy of electron transfer (ET) assisted secondary nucleation. ET from LPF to NDIAPY can be triggered by 5 s UV irradiation on left-handed LPF-NDIAPY co-assemblies, leading to NDIAPY radical anions and partial disassembly of the helices. Meanwhile, spontaneous reversion of radical anions into monomers occurs upon removal of UV light, and the surface of residual co-assemblies can accelerate the reversion process. This surface accelerated reversion of ET further facilitates the secondary nucleation-elongation events, giving rise to the formation of scale-amplified and g vale-increased left-handed helices. Meanwhile, chirality evolution controlled by ET assisted secondary nucleation process can be also realized by adding the prepared LPF-NDIAPY co-assemblies into the total ET system. This study may provide a useful approach to constructing and modulating diverse chiral structures by manipulating the secondary nucleation process.

The transfer of chirality from molecules to synthesized nanomaterials has recently attracted significant attention. Although most studies have focused on graphene and plasmonic metal nanostructures, layered transition metal dichalcogenides (TMDs), particularly MoS2, have recently garnered considerable attention due to their semiconducting and electrocatalytic characteristics. Herein, we report a new approach for the synthesis of chiral molybdenum sulfide nanomaterials based on a bottom-up synthesis method in the presence of chiral cysteine enantiomers. In the synthesis process, molybdenum trioxide and sodium hydrosulfide serve as molybdenum and sulfur sources, respectively. In addition, ascorbic acid acts as a reducing agent, resulting in the formation of zero-dimensional MoS2 nanodots. Moreover, the addition of cysteine enantiomers to the growth solutions contributes to the chirality evolution of the MoS2 nanostructures. The chirality is attributed to the cysteine enantiomer-induced preferential folding of the MoS2 planes. The growth mechanism and chiral structure of the nanomaterials are confirmed through a series of characterization techniques. This work combines chirality with the bottom-up synthesis of MoS2 nanodots, thereby expanding the synthetic methods for chiral nanomaterials. This simple synthesis approach provides new insights for the construction of other chiral TMD nanomaterials with emerging structures and properties. More significantly, the as-formed MoS2 nanodots exhibited highly defect-rich structures and chiroptical performance, thereby inspiring a high potential for emerging optical and electronic applications.

Chirality evolution from molecule levels to the nanoscale in an achiral system is a fundamental issue that remains undiscovered. Here, we report the assembly of polyoxometalate (POM) clusters into chiral subnanostructures in achiral systems by programmable single-molecule interactions. Driven by the competing binding of Ca2+ and surface ligands, POM assemblies would twist into helical nanobelts, nanorings, and nanotubes with tunable helicity. Chiral molecules can be used to differentiate the formation energies of chiral isomers and immobilize the homochiral isomer, where strong circular dichroism (CD) signals are obtained in both solutions and films. Chiral helical nanobelts can be used as circularly polarized light (CPL) photodetectors due to their distinct chiroptic responsivity for right and left CPL. By the fine-tuning of interactions at single-molecule levels, the morphology and CD spectra of helical assemblies can be precisely controlled, providing an atomic precision model for investigation of the structure-chirality relationship and chirality manipulation at the nanoscale.

Chiral organic additives have unveiled the extraordinary capacity to form chiral inorganic superstructures, however, complex hierarchical structures have hindered the understanding of chiral transfer and growth mechanisms. This study introduces a simple hydrothermal synthesis method for constructing chiral cobalt superstructures with cysteine, demonstrating specific recognition of chiral molecules and outstanding electrocatalytic activity. The mild preparation conditions allow in situ tracking of chirality evolution in the chiral cobalt superstructure, offering unprecedented insights into the chiral transfer and amplification mechanism. The resulting superstructures exhibit a universal formation process applicable to other metal oxides, extending the understanding of chiral superstructure evolution. This work contributes not only to the fundamental understanding of chirality in self-assembled structures but also provides a versatile method for designing chiral inorganic nanomaterials with remarkable molecular recognition and electrocatalytic capabilities.

Chirality transfer from chiral molecules to chiral nanomaterials represents an important topic for exploring the origin of chirality in many natural and artificial systems. Moreover, developing a promising class of chiral nanomaterials holds great significance for various applications, including sensing, photonics, catalysis, and biomedicine. Here we demonstrate the geometric control and tunable optical chirality of chiral pentatwinned Au nanoparticles with 5-fold rotational symmetry using the seed-mediated chiral growth method. A distinctive growth pathway and optical chirality are observed using pentatwinned decahedra as seeds, in comparison with the single-crystal Au seeds. By employing different peptides as chiral inducers, pentatwinned Au nanoparticles with two distinct geometric chirality (pentagonal nanostars and pentagonal prisms) are obtained. The intriguing formation and evolution of geometric chirality with the twinned structure are analyzed from a crystallographic perspective upon maneuvering the interplay of chiral molecules, surfactants, and reducing agents. Moreover, the interesting effects of the molecular structure of peptides on tuning the geometric chirality of pentatwinned Au nanoparticles are also explored. Finally, we theoretically and experimentally investigate the far-field and near-field optical properties of chiral pentatwinned Au nanoparticles through numerical simulations and single-particle chiroptical measurements. The ability to tune the geometric chirality in a controlled manner represents an important step toward the development of chiral nanomaterials with increasing architectural complexity for chiroptical applications.