Supramolecular nanoreactors for intracellular singlet-oxygen sensitization

Subramani Swaminathan, Colin Fowley, Ek Raj Thapaliya, Bridgeen McCaughan, Sicheng Tang, Aurore Fraix, Burjor Captain, Salvatore Sortino, John F. Callan, Francisco Raymo

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

An amphiphilic polymer with multiple decyl and oligo(ethylene glycol) chains attached to a common poly(methacrylate) backbone assembles into nanoscaled particles in aqueous environments. Hydrophobic anthracene and borondipyrromethene (BODIPY) chromophores can be co-encapsulated within the self-assembling nanoparticles and transported across hydrophilic media. The reversible character of the noncovalent bonds, holding the supramolecular containers together, permits the exchange of their components with fast kinetics in aqueous solution. Incubation of cervical cancer (HeLA) cells with a mixture of two sets of nanoparticles, pre-loaded independently with anthracene or BODIPY chromophores, results in guest scrambling first and then transport of co-entrapped species to the intracellular space. Alternatively, incubation of cells with the two sets of nanocarriers in consecutive steps permits the sequential transport of the anthracene and BODIPY chromophores across the plasma membrane and only then allows their co-encapsulation within the same supramolecular containers. Both mechanisms position the two sets of chromophores with complementary spectral overlap in close proximity to enable the efficient transfer of energy intracellularly from the anthracene donors to the BODIPY acceptors. In the presence of iodine substituents on the BODIPY platform, intersystem crossing follows energy transfer. The resulting triplet state can transfer energy further to molecular oxygen with the concomitant production of singlet oxygen to induce cell mortality. Furthermore, the donor can be excited with two near-infrared photons simultaneously to permit the photoinduced generation of singlet oxygen intracellularly under illumination conditions compatible with applications in vivo. Thus, these supramolecular strategies to control the excitation dynamics of multichromophoric assemblies in the intracellular environment can evolve into valuable protocols for photodynamic therapy.

Original languageEnglish (US)
Pages (from-to)14071-14079
Number of pages9
JournalNanoscale
Volume7
Issue number33
DOIs
StatePublished - Sep 7 2015

Fingerprint

Nanoreactors
Singlet Oxygen
Anthracene
Chromophores
Oxygen
Energy transfer
Containers
Nanoparticles
Photodynamic therapy
Ethylene Glycol
Methacrylates
Molecular oxygen
Cell membranes
Ethylene glycol
Iodine
Encapsulation
Ion exchange
Polymers
Photons
Lighting

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Swaminathan, S., Fowley, C., Thapaliya, E. R., McCaughan, B., Tang, S., Fraix, A., ... Raymo, F. (2015). Supramolecular nanoreactors for intracellular singlet-oxygen sensitization. Nanoscale, 7(33), 14071-14079. https://doi.org/10.1039/c5nr02672e

Supramolecular nanoreactors for intracellular singlet-oxygen sensitization. / Swaminathan, Subramani; Fowley, Colin; Thapaliya, Ek Raj; McCaughan, Bridgeen; Tang, Sicheng; Fraix, Aurore; Captain, Burjor; Sortino, Salvatore; Callan, John F.; Raymo, Francisco.

In: Nanoscale, Vol. 7, No. 33, 07.09.2015, p. 14071-14079.

Research output: Contribution to journalArticle

Swaminathan, S, Fowley, C, Thapaliya, ER, McCaughan, B, Tang, S, Fraix, A, Captain, B, Sortino, S, Callan, JF & Raymo, F 2015, 'Supramolecular nanoreactors for intracellular singlet-oxygen sensitization', Nanoscale, vol. 7, no. 33, pp. 14071-14079. https://doi.org/10.1039/c5nr02672e
Swaminathan S, Fowley C, Thapaliya ER, McCaughan B, Tang S, Fraix A et al. Supramolecular nanoreactors for intracellular singlet-oxygen sensitization. Nanoscale. 2015 Sep 7;7(33):14071-14079. https://doi.org/10.1039/c5nr02672e
Swaminathan, Subramani ; Fowley, Colin ; Thapaliya, Ek Raj ; McCaughan, Bridgeen ; Tang, Sicheng ; Fraix, Aurore ; Captain, Burjor ; Sortino, Salvatore ; Callan, John F. ; Raymo, Francisco. / Supramolecular nanoreactors for intracellular singlet-oxygen sensitization. In: Nanoscale. 2015 ; Vol. 7, No. 33. pp. 14071-14079.
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