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

Research output: Contribution to journalArticle

3 Citations (Scopus)

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 0.06eV 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.

LanguageEnglish
Pages144-158
JournalChemistryOpen
Volume7
Issue number2
DOIs
StatusPublished - 1 Feb 2018

Fingerprint

Encapsulation
Discrete Fourier transforms
Nanocrystals
Nanotubes
Glucans
Fluorescence
Single-walled carbon nanotubes (SWCN)
Imaging techniques
Nanostructured materials
X ray diffraction
Plasma confinement
Carbon Nanotubes
Biopolymers
High resolution transmission electron microscopy
Polymorphism
Binding energy
Dispersions
Biocompatibility
Powders
X ray powder diffraction

Keywords

  • Beta-d-glucan encapsulation
  • Cadmium selenide functional nanohybrids
  • Density functional calculations
  • Functional and fluorescent biocompatible nanotube hybrids
  • Self-assembly

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Encapsulation of Cadmium Selenide Nanocrystals in Biocompatible Nanotubes : DFT Calculations, X-ray Diffraction Investigations, and Confocal Fluorescence Imaging. / Calatayud, David G.; Ge, Haobo; Kuganathan, Navaratnarajah; Mirabello, Vincenzo; Jacobs, Robert M J; Rees, Nicholas H.; Stoppiello, Craig T.; Khlobystov, Andrei N.; Tyrrell, Rex M.; Como, Enrico Da; Pascu, Sofia I.

In: ChemistryOpen, Vol. 7, No. 2, 01.02.2018, p. 144-158.

Research output: Contribution to journalArticle

Calatayud, David G. ; Ge, Haobo ; Kuganathan, Navaratnarajah ; Mirabello, Vincenzo ; Jacobs, Robert M J ; Rees, Nicholas H. ; Stoppiello, Craig T. ; Khlobystov, Andrei N. ; Tyrrell, Rex M. ; Como, Enrico Da ; Pascu, Sofia I. / Encapsulation of Cadmium Selenide Nanocrystals in Biocompatible Nanotubes : DFT Calculations, X-ray Diffraction Investigations, and Confocal Fluorescence Imaging. In: ChemistryOpen. 2018 ; Vol. 7, No. 2. pp. 144-158.
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