Engineering of inorganic nanostructures with hierarchy of chiral geometries at multiple scales

Visheratina, Anastasia; Kumar, Prashant; Kotov, Nicholas A.

doi:10.1002/aic.17438

Cited by 11 publications

(18 citation statements)

References 180 publications

(262 reference statements)

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“…To mimic and exploit chiral nanostructures of plants, animals and inorganic tissues for the design of nanomaterials, their evolutionary mechanism needs to be understood. The formation of asymmetry at the macroscale is often a result of chirality transfer from small to large scales, for which the nanoscale plays a crucial role 79 . In nature, the generation of chirality is based on hierarchy, with chiral superstructures displaying chirality at the molecular, nanoscale, microscale and macroscale.…”

Section: Introductionmentioning

confidence: 99%

Bioinspired chiral inorganic nanomaterials

Cho

Guerrero‐Martínez

et al. 2023

Nat Rev Bioeng

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From small molecules to entire organisms, evolution has refined biological structures at the nanoscale, microscale and macroscale to be chiral-that is, mirror dissymmetric. Chirality results in biological, chemical and physical properties that can be influenced by circularly polarized electromagnetic fields. Chiral nanoscale materials can be designed that mimic, refine and advance biological chiral geometries, to engineer optical, physical and chemical properties for applications in photonics, sensing, catalysis and biomedicine. In this Review, we discuss the mechanisms underlying chirality transfer in nature and provide design principles for chiral nanomaterials. We highlight how chiral features emerge in inorganic materials during the chemical synthesis of chiral nanostructures, and outline key applications for inorganic chiral nanomaterials, including promising designs for biomedical applications, such as biosensing and immunomodulation. We conclude Nature Reviews Bioengineering Review article nanostructures). We describe hierarchical multiscale chirality in biological systems (for example, cytoskeleton hypothesis and chirality in biominerals), and analyse the most abundant chirality transfer mechanisms in biology, including enantioselective interaction between surfaces and chiral molecules, template-induced synthesis and chirality transfer, and photon-induced chiral nanomaterials. However, as in many natural systems 54 , these transfer mechanisms cannot be analysed separately because a concomitance of effects is responsible for the resulting chiral morphologies, in particular for highly crystalline nanomaterials, for which template-induced and photon-induced syntheses cannot be entirely decoupled from enantioselective interactions at high Miller index surfaces. Finally, we present potential applications in photonics (for example, polarization-control, non-linear optics), sensing (enantiomer discrimination), catalysis (chemical and pharmaceutical) and biomedicine (for example, photothermal and photodynamic therapies). Chirality in biologyChirality exists across multiple size scales in biological entities, dictating their geometries, properties and behaviour. For example, aminoacyl-tRNA synthases, enzymes involved in the selection of amino acids in protein synthesis, preferentially bind to l-amino acids by steric exclusion of d-amino acids 55 . Peptide elongation of d-amino acids at the ribosomes is slow owing to the large distance between the reaction sites 56 , limiting the production of peptides with incorporated d-amino acids 57,58 . The incorporation of some d-amino acids, such as d-Asp and d-Ser, has been linked to amyloid-β peptides present in the brains of patients with Alzheimer disease 59 , indicating that chirality at the molecular level could extend its influence to the organism and its behaviour.Chirality also offers survival advantage(s) for organisms. Fan-like petal arrangements of mutated Arabidopsis thaliana show left-handed chirality and clockwise twisting. The handedness of their asymmetric g...

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Section: Introductionmentioning

confidence: 99%

Bioinspired chiral inorganic nanomaterials

Cho

Guerrero‐Martínez

et al. 2023

Nat Rev Bioeng

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“…Among those, CNPs are hypothesized to have the tetrahedral coordinated carbon centers inherited from chiral precursors but it is not clear whether these molecular structures can survive the high‐temperature carbonization processes used for their preparation. Additionally, CNPs may also display nanoscale chirality associated both with ligand distribution at the interface and twist‐distortions in the CNP interior 16 . All of these structural features will result in a chiral environment around chromophores that will generate optical activity 17–19 …”

Section: Introductionmentioning

confidence: 99%

“…Additionally, CNPs may also display nanoscale chirality associated both with ligand distribution at the interface and twist-distortions in the CNP interior. 16 All of these structural features will result in a chiral environment around chromophores that will generate optical activity. [17][18][19] The potential use of chiral CNPs for applications in biology, medicine, catalysis, and optics motivates us to determine whether the chiral centers in CNPs are located in the interior or at the interface of the particles.…”

Section: Introductionmentioning

confidence: 99%

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Chiral chromatography and surface chirality of carbon nanoparticles

et al. 2022

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Chiral carbon nanoparticles (CNPs) represent a rapidly evolving area of research for optical and biomedical technologies. Similar to small molecules, applications of CNPs as well as fundamental relationships between their optical activity and structural asymmetry would greatly benefit from their enantioselective separations by chromatography. However, this technique remains in its infancy for chiral carbon and other nanoparticles. The possibility of effective separations using high performance liquid chromatography (HPLC) with chiral stationary phases remains an open question whose answer can also shed light on the components of multiscale chirality of the nanoparticles. Herein, we report a detailed methodology of HPLC for successful separation of chiral CNPs and establish a path for its future optimization. A mobile phase of water/ acetonitrile was able to achieve chiral separation of CNPs derived from L-and D-cysteine denoted as L-CNPs and D-CNPs. Molecular dynamics simulations show that the teicoplanin-based stationary phase has a higher affinity for L-CNPs than for D-CNPs, in agreement with experiments. The experimental and computational findings jointly indicate that chiral centers of chiral CNPs are [This article is part of the Special Issue: Chirality Materials.]

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“…The unique optical, biological, and electrical properties of chiral nanostructured particles strongly depend on the mirror asymmetry of their shapes, which in most cases occurs at multiple levels from nano- to microscale. − Unlike similarly sized chiral objects of (bio)organic origin, the shapes of chiral inorganic particles can be readily identified from electron microscopy (EM) images. This distinction from similarly sized protein complexes and other biological assemblies markedly streamlines the research process and accelerates the discovery of chiral materials.…”

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confidence: 99%

Chirality Analysis of Complex Microparticles using Deep Learning on Realistic Sets of Microscopy Images

Visheratina

Visheratin²,

Kumar

et al. 2023

ACS Nano

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Nanoscale chirality is an actively growing research field spurred by the giant chiroptical activity, enantioselective biological activity, and asymmetric catalytic activity of chiral nanostructures. Compared to chiral molecules, the handedness of chiral nano- and microstructures can be directly established via electron microscopy, which can be utilized for the automatic analysis of chiral nanostructures and prediction of their properties. However, chirality in complex materials may have multiple geometric forms and scales. Computational identification of chirality from electron microscopy images rather than optical measurements is convenient but is fundamentally challenging, too, because (1) image features differentiating left- and right-handed particles can be ambiguous and (2) three-dimensional structure essential for chirality is ‘flattened’ into two-dimensional projections. Here, we show that deep learning algorithms can identify twisted bowtie-shaped microparticles with nearly 100% accuracy and classify them as left- and right-handed with as high as 99% accuracy. Importantly, such accuracy was achieved with as few as 30 original electron microscopy images of bowties. Furthermore, after training on bowtie particles with complex nanostructured features, the model can recognize other chiral shapes with different geometries without retraining for their specific chiral geometry with 93% accuracy, indicating the true learning abilities of the employed neural networks. These findings indicate that our algorithm trained on a practically feasible set of experimental data enables automated analysis of microscopy data for the accelerated discovery of chiral particles and their complex systems for multiple applications.

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Engineering of inorganic nanostructures with hierarchy of chiral geometries at multiple scales

Cited by 11 publications

References 180 publications

Bioinspired chiral inorganic nanomaterials

Bioinspired chiral inorganic nanomaterials

Chiral chromatography and surface chirality of carbon nanoparticles

Chirality Analysis of Complex Microparticles using Deep Learning on Realistic Sets of Microscopy Images

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