The influence of selected ω-mercaptocarboxylate ligands on physicochemical properties and biological activity of Cd-free, zinc‑copper‑indium sulfide colloidal nanocrystals

Kalinowska, Dominika; Drozd, Marcin; Grabowska-Jadach, Ilona; Pietrzak, Mariusz; Dybko, Artur; Malinowska, Elżbieta; Brzózka, Zbigniew

doi:10.1016/j.msec.2018.12.043

Cited by 8 publications

(6 citation statements)

References 67 publications

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“…Examples include thiols from mercapto carboxylic acids (MCAs, e.g., 3-mercaptopropionic acid MPA) or other compounds bearing thiol groups, such as penicillamine (a mercapto amino acid). In these cases, particle stabilization in the aqueous phase is achieved by the hydrophilic functional groups on the side facing the aqueous medium [24][25][26][27][28][29][30][31]. For example, Kalinowska et al demonstrated a ligand exchange on ZnCuInS/ZnS QDs using MPA and 6-mercaptohexanoic acid.…”

Section: Introductionmentioning

confidence: 99%

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Mixed Mercaptocarboxylic Acid Shells Provide Stable Dispersions of InPZnS/ZnSe/ZnS Multishell Quantum Dots in Aqueous Media

et al. 2020

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Highly luminescent indium phosphide zinc sulfide (InPZnS) quantum dots (QDs), with zinc selenide/zinc sulfide (ZnSe/ZnS) shells, were synthesized. The QDs were modified via a post-synthetic ligand exchange reaction with 3-mercaptopropionic acid (MPA) and 11-mercaptoundecanoic acid (MUA) in different MPA:MUA ratios, making this study the first investigation into the effects of mixed ligand shells on InPZnS QDs. Moreover, this article also describes an optimized method for the correlation of the QD size vs. optical absorption of the QDs. Upon ligand exchange, the QDs can be dispersed in water. Longer ligands (MUA) provide more stable dispersions than short-chain ligands. Thicker ZnSe/ZnS shells provide a better photoluminescence quantum yield (PLQY) and higher emission stability upon ligand exchange. Both the ligand exchange and the optical properties are highly reproducible between different QD batches. Before dialysis, QDs with a ZnS shell thickness of ~4.9 monolayers (ML), stabilized with a mixed MPA:MUA (mixing ratio of 1:10), showed the highest PLQY, at ~45%. After dialysis, QDs with a ZnS shell thickness of ~4.9 ML, stabilized with a mixed MPA:MUA and a ratio of 1:10 and 1:100, showed the highest PLQYs, of ~41%. The dispersions were stable up to 44 days at ambient conditions and in the dark. After 44 days, QDs with a ZnS shell thickness of ~4.9 ML, stabilized with only MUA, showed the highest PLQY, of ~34%.

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Section: Introductionmentioning

confidence: 99%

“…For example, Kalinowska et al demonstrated a ligand exchange on ZnCuInS/ZnS QDs using MPA and 6-mercaptohexanoic acid. The resulting particles are stable in the aqueous phase for several months and show a high PLQY, even after phase transfer [26].…”

Section: Introductionmentioning

confidence: 99%

Mixed Mercaptocarboxylic Acid Shells Provide Stable Dispersions of InPZnS/ZnSe/ZnS Multishell Quantum Dots in Aqueous Media

et al. 2020

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“…[ 97 ] During direct ligand exchange, the native hydrophobic surface ligands are directly exchanged for more hydrophilic surface ligands. The most commonly used ligands are water‐soluble ligands containing thiol groups, including monodentate thiols like 3‐Mercaptopropionic acid (MPA), [ 117 ] glutathione (GSH), [ 118 ] and bidentate thiols like dihydrolipoic acid (DHLA), [ 86 ] and multidentate ligands. [ 97 ] Ligand exchange does not significantly change the hydrodynamic radius of the QDs, which has important implications for the biodistribution and excretion of dosed QDs, [ 93 ] and also facilitates fluorescence resonance energy transfer (FRET)‐based applications.…”

Section: Modification Strategies For Qdsmentioning

confidence: 99%

Recent Advances in Metal Chalcogenide Quantum Dots: From Material Design to Biomedical Applications

Piao

Yang

Cui

et al. 2022

Adv Funct Materials

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With the rapid progress in nanomaterials and biochemistry, there has been an explosion of interest in biomolecule-modified quantum dots (QDs) for biomedical applications. Metal chalcogenide quantum dots (MCQDs), as the most widely studied QDs, have attracted tremendous attention in the biomedical field on account of their unique and excellent optical properties and the ease of biomolecular modifications. Herein, important advances in MCQDs over recent years are reviewed, from materials design to biomedical applications. Especially, this review focuses on the challenges encountered in the applications of MCQDs in biomedical fields and how these problems can be solved by rational design of synthesis methods and modifications, which have opened a universal route to develop the functionalized MCQDs. Moreover, recent processes in bioimaging, biosensing, and cancer therapy based on MCQDs are examined, including the rapid detection and diagnosis of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). This review provides broad insights into MCQDs in the biomedical field and will inspire material researchers to develop MCQDs in the future.

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“…Recently, also the organic-to-aqueous phase transfer of ZAIS QDs was assessed by NMR spectroscopy for the hydrophilic ligands 11-mercaptoundecanoic acid, DHLA, and cysteine, and the efficiency of the ligand exchange and its influence on the PL QY were determined . Other studies of ligand exchange procedures for ternary or quaternary QDs focus on the impact of this exchange on QD performance in applications such as hydrogen production, optoelectronic devices, ,, and bioimaging. ,,− However, life sciences application-dedicated studies of the effect of biocompatible surface ligands are still scarce, especially the systematic exploration of the influence of ligand denticity on the colloidal stability and optoelectronic properties of ternary and quaternary QDs.…”

Section: Introductionmentioning

confidence: 99%

Influence of Hydrophilic Thiol Ligands of Varying Denticity on the Luminescence Properties and Colloidal Stability of Quaternary Semiconductor Nanocrystals

et al. 2022

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Binary photoluminescent semiconductor nanocrystals (quantum dots, QDs) are one of the best studied fluorescent nanomaterials, and their unique optoelectronic properties paved the road to many applications in (bio)nanophotonics, optoelectronics, and photovoltaics. However, concerns related to their toxic constituents like cadmium or lead and the emerging interest in greener chemistry synthesis approaches hamper their future applicability. Interesting alternatives for some applications like biosensing or bioimaging are heavy-metal-free ternary QDs like AgInS2 (AIS), CuInS2 (CIS), and quaternary QDs such as AIS-ZnS (ZAIS). In this context, we explored the effect of ligand denticity on the organic-to-aqueous phase transfer of oleylamine-stabilized ZAIS QDs with the hydrophilic ligands mercaptopropionic acid (MPA), dihydrolipoic acid (DHLA), and 3-mercapto-2,2-bis(mercaptomethyl)propanoic acid (3MPA), bearing mono-, bi-, and trialkyl thiol groups. Spectroscopic studies of the resulting water-dispersible ZAIS QDs revealed a considerable influence of ligand denticity and ligand-to-QD ratio on the spectral position and width (FWHM; full width at half-maximum) of the photoluminescence (PL) bands, the PL quantum yields (PL QY), and the PL decay kinetics. Thiol capping and phase transfer resulted in a loss in PL by at least a factor of 2. The ligand-induced PL quenching observed particularly for ligands bearing two or three thiol groups was attributed to the facilitated formation of surface-bound disulfides. The best colloidal stability under high dilution conditions was observed for 3MPA.

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The influence of selected ω-mercaptocarboxylate ligands on physicochemical properties and biological activity of Cd-free, zinc‑copper‑indium sulfide colloidal nanocrystals

Cited by 8 publications

References 67 publications

Mixed Mercaptocarboxylic Acid Shells Provide Stable Dispersions of InPZnS/ZnSe/ZnS Multishell Quantum Dots in Aqueous Media

Mixed Mercaptocarboxylic Acid Shells Provide Stable Dispersions of InPZnS/ZnSe/ZnS Multishell Quantum Dots in Aqueous Media

Recent Advances in Metal Chalcogenide Quantum Dots: From Material Design to Biomedical Applications

Influence of Hydrophilic Thiol Ligands of Varying Denticity on the Luminescence Properties and Colloidal Stability of Quaternary Semiconductor Nanocrystals

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