Encapsulation of Cadmium Selenide Nanocrystals in Biocompatible Nanotubes: DFT Calculations, X-ray Diffraction Investigations, and Confocal Fluorescence Imaging

David G. Calatayud; Haobo Ge; Navaratnarajah Kuganathan; Vincenzo Mirabello; Robert M.J. Jacobs; Nicholas H. Rees; Craig T. Stoppiello; Andrei N. Khlobystov; Rex M. Tyrrell; Enrico Da Como; Sofia I. Pascu

doi:10.1002/open.201700184

Encapsulation of Cadmium Selenide Nanocrystals in Biocompatible Nanotubes: DFT Calculations, X-ray Diffraction Investigations, and Confocal Fluorescence Imaging

David G. Calatayud, Haobo Ge, Navaratnarajah Kuganathan, Vincenzo Mirabello, Robert M.J. Jacobs, Nicholas H. Rees, Craig T. Stoppiello, Andrei N. Khlobystov, Rex M. Tyrrell, Enrico Da Como, Sofia I. Pascu

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Abstract

The encapsulation of CdSe nanocrystals within single-walled carbon nanotube (SWNT) cavities of varying dimensions at elevated temperatures under strictly air-tight conditions is described for the first time. The structures of CdSe nanocrystals under confinement inside SWNTs was established in a comprehensive study, combining both experimental and DFT theoretical investigations. The calculated binding energies show that all considered polymorphs [(3:3), (4:4), and (4:2)] may be obtained experimentally. The most thermodynamically stable structure (3:3) is directly compared to the experimentally observed CdSe structures inside carbon nanotubes. The gas-phase DFT-calculated energy difference between “free” 3:3 and 4:2 structures (whereby 3:3 models a novel tubular structure in which both Cd and Se form three coordination, as observed experimentally for HgTe inside SWNT, and 4:2 is a motif derived from the hexagonal CuI bulk structure in which both Cd and Se form 4 or 2 coordination) is surprisingly small, only 0.06 eV per formula unit. X-ray powder diffraction, Raman spectroscopy, high-resolution transmission electron microscopy, and energy-dispersive X-ray analyses led to the full characterization of the SWNTs filled with the CdSe nanocrystals, shedding light on the composition, structure, and electronic interactions of the new nanohybrid materials on an atomic level. A new emerging hybrid nanomaterial, simultaneously filled and beta-d-glucan coated, was obtained by using pristine nanotubes and bulk CdSe powder as starting materials. This displayed fluorescence in water dispersions and unexpected biocompatibility was found to be mediated by beta-d-glucan (a biopolymer extracted from barley) with respect to that of the individual inorganic material components. For the first time, such supramolecular nanostructures are investigated by life-science techniques applied to functional nanomaterial characterization, opening the door for future nano-biotechnological applications.

Original language	English
Pages (from-to)	144-158
Number of pages	15
Journal	ChemistryOpen
Volume	7
Issue number	2
Early online date	18 Jan 2018
DOIs	https://doi.org/10.1002/open.201700184
Publication status	Published - 1 Feb 2018
Externally published	Yes

Bibliographical note

© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Funding

This work was financially supported by the Science & Technologies Facilities Council, EPSRC Centre for Doctoral Training Centre for Sustainable Chemical Technologies at Bath, ERC Consolidator grant scheme (O2Sense to S.I.P.) and the University of Bath. The authors would also like to thank some former collaborators, Drs. Christoph Salzmann, Belen-Ballesteros Perez, and Gerard Tobias for helpful discussions and their technical assistance with the initial stages of this research and training for the preliminary samples preparations. Chidambaram Kasimuthu and Gordon Lee are particularly acknowledged for help with some of the very preliminary initial tests and microscopy work during their short-term stay in the S.I.P group at Oxford. Microscopy specialists of Oxford Nanotube Group, Prof John Hutchinson and Dr. Kerstin Jurkschat (Oxford Materials Department), are acknowledged for technical assistance with collection of some of the HRTEM data from initial batches, which proved batch-to-batch consistency. Dr. John Lowe is thanked for technical support with NMR. Prof. Malcolm Green FRS is thanked for invaluable discussions, training, support, and access to Oxford Nanotube Group facilities and expertise. The authors thank EPSRC National Service for Computational Chemistry Software and High-Performance Computational facilities at Imperial College London for support and computational facilities.

Keywords

beta-d-glucan encapsulation
cadmium selenide functional nanohybrids
density functional calculations
functional and fluorescent biocompatible nanotube hybrids
self-assembly

ASJC Scopus subject areas

General Chemistry

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Cite this

Calatayud, D. G., Ge, H., Kuganathan, N., Mirabello, V., Jacobs, R. M. J., Rees, N. H., Stoppiello, C. T., Khlobystov, A. N., Tyrrell, R. M., Como, E. D., & Pascu, S. I. (2018). Encapsulation of Cadmium Selenide Nanocrystals in Biocompatible Nanotubes: DFT Calculations, X-ray Diffraction Investigations, and Confocal Fluorescence Imaging. ChemistryOpen, 7(2), 144-158. https://doi.org/10.1002/open.201700184

Calatayud, DG, Ge, H, Kuganathan, N, Mirabello, V, Jacobs, RMJ, Rees, NH, Stoppiello, CT, Khlobystov, AN, Tyrrell, RM, Como, ED & Pascu, SI 2018, 'Encapsulation of Cadmium Selenide Nanocrystals in Biocompatible Nanotubes: DFT Calculations, X-ray Diffraction Investigations, and Confocal Fluorescence Imaging', ChemistryOpen, vol. 7, no. 2, pp. 144-158. https://doi.org/10.1002/open.201700184

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title = "Encapsulation of Cadmium Selenide Nanocrystals in Biocompatible Nanotubes: DFT Calculations, X-ray Diffraction Investigations, and Confocal Fluorescence Imaging",

abstract = "The encapsulation of CdSe nanocrystals within single-walled carbon nanotube (SWNT) cavities of varying dimensions at elevated temperatures under strictly air-tight conditions is described for the first time. The structures of CdSe nanocrystals under confinement inside SWNTs was established in a comprehensive study, combining both experimental and DFT theoretical investigations. The calculated binding energies show that all considered polymorphs [(3:3), (4:4), and (4:2)] may be obtained experimentally. The most thermodynamically stable structure (3:3) is directly compared to the experimentally observed CdSe structures inside carbon nanotubes. The gas-phase DFT-calculated energy difference between “free” 3:3 and 4:2 structures (whereby 3:3 models a novel tubular structure in which both Cd and Se form three coordination, as observed experimentally for HgTe inside SWNT, and 4:2 is a motif derived from the hexagonal CuI bulk structure in which both Cd and Se form 4 or 2 coordination) is surprisingly small, only 0.06 eV per formula unit. X-ray powder diffraction, Raman spectroscopy, high-resolution transmission electron microscopy, and energy-dispersive X-ray analyses led to the full characterization of the SWNTs filled with the CdSe nanocrystals, shedding light on the composition, structure, and electronic interactions of the new nanohybrid materials on an atomic level. A new emerging hybrid nanomaterial, simultaneously filled and beta-d-glucan coated, was obtained by using pristine nanotubes and bulk CdSe powder as starting materials. This displayed fluorescence in water dispersions and unexpected biocompatibility was found to be mediated by beta-d-glucan (a biopolymer extracted from barley) with respect to that of the individual inorganic material components. For the first time, such supramolecular nanostructures are investigated by life-science techniques applied to functional nanomaterial characterization, opening the door for future nano-biotechnological applications.",

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AU - Calatayud, David G.

AU - Ge, Haobo

AU - Kuganathan, Navaratnarajah

AU - Mirabello, Vincenzo

AU - Jacobs, Robert M.J.

AU - Rees, Nicholas H.

AU - Stoppiello, Craig T.

AU - Khlobystov, Andrei N.

AU - Tyrrell, Rex M.

AU - Como, Enrico Da

AU - Pascu, Sofia I.

N1 - © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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N2 - The encapsulation of CdSe nanocrystals within single-walled carbon nanotube (SWNT) cavities of varying dimensions at elevated temperatures under strictly air-tight conditions is described for the first time. The structures of CdSe nanocrystals under confinement inside SWNTs was established in a comprehensive study, combining both experimental and DFT theoretical investigations. The calculated binding energies show that all considered polymorphs [(3:3), (4:4), and (4:2)] may be obtained experimentally. The most thermodynamically stable structure (3:3) is directly compared to the experimentally observed CdSe structures inside carbon nanotubes. The gas-phase DFT-calculated energy difference between “free” 3:3 and 4:2 structures (whereby 3:3 models a novel tubular structure in which both Cd and Se form three coordination, as observed experimentally for HgTe inside SWNT, and 4:2 is a motif derived from the hexagonal CuI bulk structure in which both Cd and Se form 4 or 2 coordination) is surprisingly small, only 0.06 eV per formula unit. X-ray powder diffraction, Raman spectroscopy, high-resolution transmission electron microscopy, and energy-dispersive X-ray analyses led to the full characterization of the SWNTs filled with the CdSe nanocrystals, shedding light on the composition, structure, and electronic interactions of the new nanohybrid materials on an atomic level. A new emerging hybrid nanomaterial, simultaneously filled and beta-d-glucan coated, was obtained by using pristine nanotubes and bulk CdSe powder as starting materials. This displayed fluorescence in water dispersions and unexpected biocompatibility was found to be mediated by beta-d-glucan (a biopolymer extracted from barley) with respect to that of the individual inorganic material components. For the first time, such supramolecular nanostructures are investigated by life-science techniques applied to functional nanomaterial characterization, opening the door for future nano-biotechnological applications.

AB - The encapsulation of CdSe nanocrystals within single-walled carbon nanotube (SWNT) cavities of varying dimensions at elevated temperatures under strictly air-tight conditions is described for the first time. The structures of CdSe nanocrystals under confinement inside SWNTs was established in a comprehensive study, combining both experimental and DFT theoretical investigations. The calculated binding energies show that all considered polymorphs [(3:3), (4:4), and (4:2)] may be obtained experimentally. The most thermodynamically stable structure (3:3) is directly compared to the experimentally observed CdSe structures inside carbon nanotubes. The gas-phase DFT-calculated energy difference between “free” 3:3 and 4:2 structures (whereby 3:3 models a novel tubular structure in which both Cd and Se form three coordination, as observed experimentally for HgTe inside SWNT, and 4:2 is a motif derived from the hexagonal CuI bulk structure in which both Cd and Se form 4 or 2 coordination) is surprisingly small, only 0.06 eV per formula unit. X-ray powder diffraction, Raman spectroscopy, high-resolution transmission electron microscopy, and energy-dispersive X-ray analyses led to the full characterization of the SWNTs filled with the CdSe nanocrystals, shedding light on the composition, structure, and electronic interactions of the new nanohybrid materials on an atomic level. A new emerging hybrid nanomaterial, simultaneously filled and beta-d-glucan coated, was obtained by using pristine nanotubes and bulk CdSe powder as starting materials. This displayed fluorescence in water dispersions and unexpected biocompatibility was found to be mediated by beta-d-glucan (a biopolymer extracted from barley) with respect to that of the individual inorganic material components. For the first time, such supramolecular nanostructures are investigated by life-science techniques applied to functional nanomaterial characterization, opening the door for future nano-biotechnological applications.

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Encapsulation of Cadmium Selenide Nanocrystals in Biocompatible Nanotubes: DFT Calculations, X-ray Diffraction Investigations, and Confocal Fluorescence Imaging

Abstract

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Funding

Keywords

ASJC Scopus subject areas

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