Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces

Boyang Mao, David González Calatayud, Vincenzo Mirabello, Navaratnarajah Kuganathan, Haobo Ge, Robert M. J. Jacobs, Ashley M. Shepherd, José Alberto Ribeiro Martins, Jorge Bernardino De La Serna, Benjamin J Hodges, Stanley W. Botchway, Sofia Ioana Pascu

Research output: Contribution to journal › Article

4 Citations (Scopus)
112 Downloads (Pure)

Abstract

Two new routes to functionalized SWNTs have been established using a bulky Zn(II)-porphyrin featuring thiolate groups at the periphery. We probed the optical properties of this Zinc(II)-substituted, bulky aryl porphyrin and those of the corresponding new nano-composites with single walled carbon nanotube (SWNTs) and coronene, as a model for graphene. We report hereby on: (i) the supramolecular interactions between the pristine SWNTs and Zn(II)-porphyrin by virtue of π-π stacking, and (ii) a novel covalent binding strategy based on the Bingel reaction. We investigated the nature of the porphyrin aggregates forming on flat surfaces by Steady-state and time-resolved fluorescence emission spectroscopies and imaging techniques including fluorescence lifetime imaging microscopy (FLIM) together with Atomic Force Microscopy (AFM) and Super Resolution Stimulated Emission Depletion microscopy (STED). X-ray photoelectron spectroscopy (XPS) studies highlighted the differences in the covalent versus non-covalent attachments of functional metalloporphyrins to SWNTs. Gas phase density functional theory (DFT) calculations (implemented in CASTEP) indicated that the Zinc(II) porphyrin interacts non-covalently with SWNT to form a donor-acceptor complex. The appendage of the porphyrin chromophore to the surface of SWNTs affects the absorption and emission properties of the hybrid system to a greater extent than in the case of the supramolecular functionalization of the SWNTs surface.
Original languageEnglish
Pages (from-to)9772-9789
JournalChemistry - A European Journal
Volume23
Issue number41
Early online date25 Apr 2017
DOIs
Publication statusPublished - 21 Jul 2017

Fingerprint

Carbon Nanotubes
Porphyrins
Single-walled carbon nanotubes (SWCN)
Self assembly
Optical microscopy
Fluorescence
Imaging techniques
Zinc
Microscopic examination
Metalloporphyrins
Stimulated emission
Graphite
Fluorescence spectroscopy
Emission spectroscopy
Chromophores
Hybrid systems
Density functional theory
Atomic force microscopy
X ray photoelectron spectroscopy
Optical properties

Cite this

Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces. / Mao, Boyang; Calatayud, David González; Mirabello, Vincenzo; Kuganathan, Navaratnarajah; Ge, Haobo; Jacobs, Robert M. J.; Shepherd, Ashley M.; Ribeiro Martins, José Alberto; Bernardino De La Serna, Jorge; Hodges, Benjamin J; Botchway, Stanley W.; Pascu, Sofia Ioana.

In: Chemistry - A European Journal, Vol. 23, No. 41, 21.07.2017, p. 9772-9789.

Research output: Contribution to journal › Article

Mao, B, Calatayud, DG, Mirabello, V, Kuganathan, N, Ge, H, Jacobs, RMJ, Shepherd, AM, Ribeiro Martins, JA, Bernardino De La Serna, J, Hodges, BJ, Botchway, SW & Pascu, SI 2017, 'Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces', Chemistry - A European Journal, vol. 23, no. 41, pp. 9772-9789. https://doi.org/10.1002/chem.201605232
Mao B, Calatayud DG, Mirabello V, Kuganathan N, Ge H, Jacobs RMJ et al. Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces. Chemistry - A European Journal. 2017 Jul 21;23(41):9772-9789. https://doi.org/10.1002/chem.201605232
Mao, Boyang ; Calatayud, David González ; Mirabello, Vincenzo ; Kuganathan, Navaratnarajah ; Ge, Haobo ; Jacobs, Robert M. J. ; Shepherd, Ashley M. ; Ribeiro Martins, José Alberto ; Bernardino De La Serna, Jorge ; Hodges, Benjamin J ; Botchway, Stanley W. ; Pascu, Sofia Ioana. / Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 41. pp. 9772-9789.
@article{1ada57afcf1e4d1db9d6a9d65cd549d7,
title = "Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces",
abstract = "Two new routes to functionalized SWNTs have been established using a bulky Zn(II)-porphyrin featuring thiolate groups at the periphery. We probed the optical properties of this Zinc(II)-substituted, bulky aryl porphyrin and those of the corresponding new nano-composites with single walled carbon nanotube (SWNTs) and coronene, as a model for graphene. We report hereby on: (i) the supramolecular interactions between the pristine SWNTs and Zn(II)-porphyrin by virtue of π-π stacking, and (ii) a novel covalent binding strategy based on the Bingel reaction. We investigated the nature of the porphyrin aggregates forming on flat surfaces by Steady-state and time-resolved fluorescence emission spectroscopies and imaging techniques including fluorescence lifetime imaging microscopy (FLIM) together with Atomic Force Microscopy (AFM) and Super Resolution Stimulated Emission Depletion microscopy (STED). X-ray photoelectron spectroscopy (XPS) studies highlighted the differences in the covalent versus non-covalent attachments of functional metalloporphyrins to SWNTs. Gas phase density functional theory (DFT) calculations (implemented in CASTEP) indicated that the Zinc(II) porphyrin interacts non-covalently with SWNT to form a donor-acceptor complex. The appendage of the porphyrin chromophore to the surface of SWNTs affects the absorption and emission properties of the hybrid system to a greater extent than in the case of the supramolecular functionalization of the SWNTs surface.",
author = "Boyang Mao and Calatayud, {David Gonz{\'a}lez} and Vincenzo Mirabello and Navaratnarajah Kuganathan and Haobo Ge and Jacobs, {Robert M. J.} and Shepherd, {Ashley M.} and {Ribeiro Martins}, {Jos{\'e} Alberto} and {Bernardino De La Serna}, Jorge and Hodges, {Benjamin J} and Botchway, {Stanley W.} and Pascu, {Sofia Ioana}",
year = "2017",
month = "7",
day = "21",
doi = "10.1002/chem.201605232",
language = "English",
volume = "23",
pages = "9772--9789",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-Blackwell",
number = "41",

}

TY - JOUR

T1 - Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces

AU - Mao, Boyang

AU - Calatayud, David González

AU - Mirabello, Vincenzo

AU - Kuganathan, Navaratnarajah

AU - Ge, Haobo

AU - Jacobs, Robert M. J.

AU - Shepherd, Ashley M.

AU - Ribeiro Martins, José Alberto

AU - Bernardino De La Serna, Jorge

AU - Hodges, Benjamin J

AU - Botchway, Stanley W.

AU - Pascu, Sofia Ioana

PY - 2017/7/21

Y1 - 2017/7/21

N2 - Two new routes to functionalized SWNTs have been established using a bulky Zn(II)-porphyrin featuring thiolate groups at the periphery. We probed the optical properties of this Zinc(II)-substituted, bulky aryl porphyrin and those of the corresponding new nano-composites with single walled carbon nanotube (SWNTs) and coronene, as a model for graphene. We report hereby on: (i) the supramolecular interactions between the pristine SWNTs and Zn(II)-porphyrin by virtue of π-π stacking, and (ii) a novel covalent binding strategy based on the Bingel reaction. We investigated the nature of the porphyrin aggregates forming on flat surfaces by Steady-state and time-resolved fluorescence emission spectroscopies and imaging techniques including fluorescence lifetime imaging microscopy (FLIM) together with Atomic Force Microscopy (AFM) and Super Resolution Stimulated Emission Depletion microscopy (STED). X-ray photoelectron spectroscopy (XPS) studies highlighted the differences in the covalent versus non-covalent attachments of functional metalloporphyrins to SWNTs. Gas phase density functional theory (DFT) calculations (implemented in CASTEP) indicated that the Zinc(II) porphyrin interacts non-covalently with SWNT to form a donor-acceptor complex. The appendage of the porphyrin chromophore to the surface of SWNTs affects the absorption and emission properties of the hybrid system to a greater extent than in the case of the supramolecular functionalization of the SWNTs surface.

AB - Two new routes to functionalized SWNTs have been established using a bulky Zn(II)-porphyrin featuring thiolate groups at the periphery. We probed the optical properties of this Zinc(II)-substituted, bulky aryl porphyrin and those of the corresponding new nano-composites with single walled carbon nanotube (SWNTs) and coronene, as a model for graphene. We report hereby on: (i) the supramolecular interactions between the pristine SWNTs and Zn(II)-porphyrin by virtue of π-π stacking, and (ii) a novel covalent binding strategy based on the Bingel reaction. We investigated the nature of the porphyrin aggregates forming on flat surfaces by Steady-state and time-resolved fluorescence emission spectroscopies and imaging techniques including fluorescence lifetime imaging microscopy (FLIM) together with Atomic Force Microscopy (AFM) and Super Resolution Stimulated Emission Depletion microscopy (STED). X-ray photoelectron spectroscopy (XPS) studies highlighted the differences in the covalent versus non-covalent attachments of functional metalloporphyrins to SWNTs. Gas phase density functional theory (DFT) calculations (implemented in CASTEP) indicated that the Zinc(II) porphyrin interacts non-covalently with SWNT to form a donor-acceptor complex. The appendage of the porphyrin chromophore to the surface of SWNTs affects the absorption and emission properties of the hybrid system to a greater extent than in the case of the supramolecular functionalization of the SWNTs surface.

UR - https://doi.org/10.1002/chem.201605232

U2 - 10.1002/chem.201605232

DO - 10.1002/chem.201605232

M3 - Article

VL - 23

SP - 9772

EP - 9789

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 41

ER -

Access to Document

  • Manuscript SIP ChemEurJ accepted 25 April 2017

    This is the peer reviewed version of the following article: Mao, B., Calatayud, D. G., Mirabello, V., Ge, H., Hodges, B. J., Jacobs, R. M. J., Shepherd, A. M., Ribeiro Martins, J. A., Kuganathan, N., Bernardino De La Serna, J., Botchway, S. W. and Pascu, S. I. (2017), Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces. Chem. Eur. J.. Accepted Author Manuscript. doi:10.1002/chem.201605232, which has been published in final form at: https://doi.org/10.1002/chem.201605232 This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

    Accepted author manuscript, 4 MB