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

التفاصيل البيبلوغرافية
العنوان: Effect of Chiral Ligand Concentration and Binding Mode on Chiroptical Activity of CdSe/CdS Quantum Dots
المؤلفون: Yulia A. Gromova, Nadezda Prochukhan, Eric Mates-Torres, John E. O'Brien, Finn Purcell-Milton, Max García-Melchor, Vera Kuznetsova, A. K. Visheratina, Madeline Marcastel, Yurii K. Gun'ko, Marina Martínez-Carmona
المصدر: ACS Nano. 13:13560-13572
بيانات النشر: American Chemical Society (ACS), 2019.
سنة النشر: 2019
مصطلحات موضوعية: Circular dichroism, Chemistry, Chiral ligand, technology, industry, and agriculture, General Engineering, General Physics and Astronomy, 02 engineering and technology, equipment and supplies, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, Fluorescence, 0104 chemical sciences, Nanomaterials, Quantum dot, Molecule, General Materials Science, Density functional theory, 0210 nano-technology, Chirality (chemistry)
الوصف: 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.
تدمد: 1936-086X
1936-0851
URL الوصول: https://explore.openaire.eu/search/publication?articleId=doi_dedup___::b7d40ee6c2d537c19c1e66b8fd32f2d0
https://doi.org/10.1021/acsnano.9b07513
حقوق: OPEN
رقم الأكسشن: edsair.doi.dedup.....b7d40ee6c2d537c19c1e66b8fd32f2d0
قاعدة البيانات: OpenAIRE