Influence of CdSe and CdSe/CdS nanocrystals on the optical activity of chiral organic molecules

Visheratina, Anastasia; Орлова, А. О.; Purcell-Milton, Finn; Кузнецова, Вера; Visheratin, Alexander A.; Kundelev, Evgeny V.; Маслов, В. Г.; Баранов, А. В.; Fedorov, Anatoly V.; Gun’ko, Yurii K.

doi:10.1039/c7tc03457a

Cited by 9 publications

(20 citation statements)

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“…Similar results were also obtained by Martynenko et al [68]. This model is often used to explain a wide range of observed phenomena including influence of QD size [62], shell thickness [62,69], nature and binding mode of ligands [70][71][72][73][74] on the position, shape and intensity of CD peaks, as well as the influence of QDs on the properties of chiral molecules [75], which will be discussed in the present review. In addition, this method allows the investigation of the QD energy structure using CD spectra [68].…”

Section: The Mechanisms Of Ligand-induced Chirality In Qdssupporting

confidence: 84%

“…Moreover, it has been theoretically predicted by Govorov et al [88][89][90] that a nonchiral planar molecule can become optically active when it forms a complex and couples via dipole and multipole Coulomb interactions with achiral NCs. In another important piece, it has also been demonstrated that CD signal intensity of the chiral molecule chlorine e6 can be significantly increased due to interaction with QDs [75,91]. Visheratina et al [75] has shown that the effect of QDs on the chlorin e6 weakens with increase in size of CdSe QDs and with an increase in CdS shell thickness of CdSe/CdS QDs.…”

Section: Influence Of Qds On Optical Activity Of Chiral Moleculementioning

confidence: 98%

“…In another important piece, it has also been demonstrated that CD signal intensity of the chiral molecule chlorine e6 can be significantly increased due to interaction with QDs [75,91]. Visheratina et al [75] has shown that the effect of QDs on the chlorin e6 weakens with increase in size of CdSe QDs and with an increase in CdS shell thickness of CdSe/CdS QDs. This was explained by a decrease in the efficiency of hybridization of the electronic levels of the QD and the chiral molecule [62].…”

Section: Influence Of Qds On Optical Activity Of Chiral Moleculementioning

confidence: 98%

“…(C) Circular dichroism (CD) spectra of chlorin e6 in a free form (red) and bound to the QDs. Adapted from a study by Visheratina et al[75] with permission from The Royal Society of Chemistry.V. Kuznetsova et al: Ligand-induced chirality and optical activity…”

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Ligand-induced chirality and optical activity in semiconductor nanocrystals: theory and applications

et al. 2020

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Chirality is one of the most fascinating occurrences in the natural world and plays a crucial role in chemistry, biochemistry, pharmacology, and medicine. Chirality has also been envisaged to play an important role in nanotechnology and particularly in nanophotonics, therefore, chiral and chiroptical active nanoparticles (NPs) have attracted a lot of interest over recent years. Optical activity can be induced in NPs in several different ways, including via the direct interaction of achiral NPs with a chiral molecule. This results in circular dichroism (CD) in the region of the intrinsic absorption of the NPs. This interaction in turn affects the optical properties of the chiral molecule. Recently, studies of induced chirality in quantum dots (QDs) has deserved special attention and this phenomenon has been explored in detail in a number of important papers. In this article, we review these important recent advances in the preparation and formation of chiral molecule–QD systems and analyze the mechanisms of induced chirality, the factors influencing CD spectra shape and the intensity of the CD, as well as the effect of QDs on chiral molecules. We also consider potential applications of these types of chiroptical QDs including sensing, bioimaging, enantioselective synthesis, circularly polarized light emitters, and spintronic devices. Finally, we highlight the problems and possibilities that can arise in research areas concerning the interaction of QDs with chiral molecules and that a mutual influence approach must be taken into account particularly in areas, such as photonics, cell imaging, pharmacology, nanomedicine and nanotoxicology.

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Section: The Mechanisms Of Ligand-induced Chirality In Qdssupporting

confidence: 84%

Section: Influence Of Qds On Optical Activity Of Chiral Moleculementioning

confidence: 98%

Section: Influence Of Qds On Optical Activity Of Chiral Moleculementioning

confidence: 98%

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Ligand-induced chirality and optical activity in semiconductor nanocrystals: theory and applications

et al. 2020

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“…Optical activity can be induced in QDs by functionalization with chiral ligands via a relatively simple post-synthetic phase-transfer ligand exchange. ,,− In this process, the initial hydrophobic ligands in QDs produced by the hot injection synthesis in organic medium are typically exchanged by chiral hydrophilic ligands, accompanied by the transfer of QDs into the aqueous phase. ,,, In this case, QDs exhibit optical activity in their absorption region, unlike the chiral ligand molecules, which typically absorb light only in the deep UV region. , The origin of induced chirality can be explained by the chiral distortion of QD surface atoms upon the adsorption of chiral ligands, ,,, or the hybridization of the energy levels of the QD and chiral ligand molecules leading to the splitting of QD hole–electron levels into two sublevels with different absorptions of circularly polarized light. ,,,− …”

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Effect of Chiral Ligand Concentration and Binding Mode on Chiroptical Activity of CdSe/CdS Quantum Dots

et al. 2019

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Chiroptically active fluorescent semiconductor nanocrystals, quantum dots (QDs), are of high interest, from a theoretical and technological point of view, because they are promising candidates for a range of potential applications. Optical activity can be induced in QDs by capping them with chiral molecules, resulting in circular dichroism (CD) signals in the range of the QD ultraviolet−visible (UV-vis) absorption. However, the effects of the chiral ligand concentration and binding modes on the chiroptical properties of QDs are still poorly understood. In the present study, we report the strong influence of the concentration of a chiral amino acid (cysteine) on its binding modes upon the surface of CdSe/CdS QDs, resulting in varying QD chiroptical activity and corresponding CD signals. Importantly, we demonstrate that the increase of cysteine concentration is accompanied by the growth of the QD CD intensity, reaching a certain critical point, after which it starts to decrease. The intensity of the CD signal varies by almost an order of magnitude across this range. Nuclear magnetic resonance and Fourier transform infrared data, supported by density functional theory calculations, reveal a change in the binding mode of cysteine molecules from tridentate to bidentate when going from low to high concentrations, which results in a change in the CD intensity. Hence, we conclude that the chiroptical properties of QDs are dependent on the concentration and binding modes of the capping chiral ligands. These findings are very important for understanding chiroptical phenomena at the nanoscale and for the design of advanced optically active nanomaterials.

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Expanding the Horizons of Machine Learning in Nanomaterials to Chiral Nanostructures

Kuznetsova,

Coogan,

Botov

et al. 2024

Advanced Materials

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Machine learning holds significant research potential in the field of nanotechnology, enabling nanomaterial structure and property predictions, facilitating the design of novel materials, and reducing the need for time‐consuming and labour‐intensive experiments and simulations. In contrast to their achiral counterparts, the application of machine learning for chiral nanomaterials and nanostructures is still in its infancy, with a limited number of publications to date. This is despite the great potential of machine learning to advance the development of new sustainable chiral materials with high values of optical activity, circularly polarised luminescence, and enantioselectivity, as well as for the analysis of structural chirality by electron microscopy. In this review, we provide an analysis of machine learning methods used in studying achiral nanomaterials, subsequently offering guidance on adapting and extending this work to chiral nanomaterials. We present an overview of chiral nanomaterials within the framework of synthesis‐structure‐property‐application relationships and provide insights on how to leverage machine learning for the study of these highly complex relationships. We also review and discuss some key recent publications on the application of machine learning for chiral nanomaterials. Finally, the review captures the key achievements, ongoing challenges, and the prospective outlook for this very important research field.This article is protected by copyright. All rights reserved

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Influence of CdSe and CdSe/CdS nanocrystals on the optical activity of chiral organic molecules

Abstract: Influence of semiconductor nanocrystal diameter and shell thickness on optical activity of chiral organic molecule is reported.

Cited by 9 publications

References 43 publications

Ligand-induced chirality and optical activity in semiconductor nanocrystals: theory and applications

Ligand-induced chirality and optical activity in semiconductor nanocrystals: theory and applications

Effect of Chiral Ligand Concentration and Binding Mode on Chiroptical Activity of CdSe/CdS Quantum Dots

Expanding the Horizons of Machine Learning in Nanomaterials to Chiral Nanostructures

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