Supramolecular nanoreactors for intracellular singlet-oxygen sensitization

S. Swaminathan, Colin Fowley, E.R. Thapaliya, Bridgeen McCaughan, S. Tang, A. Fraix, B. Captain, S. Sortino, J Callan, F.M. 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. © The Royal Society of Chemistry 2015.
LanguageEnglish
Pages14071-14079
JournalNanoscale
Volume7
Issue number33
Early online date28 Jul 2015
DOIs
Publication statusE-pub ahead of print - 28 Jul 2015

Fingerprint

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

Keywords

  • Anthracene
  • Cell membranes
  • Chromophores
  • Containers
  • Energy transfer
  • Ethylene
  • Ethylene glycol
  • Infrared devices
  • Lanthanum compounds
  • Nanoparticles
  • Oxygen
  • Photodynamic therapy
  • Solutions
  • Supramolecular chemistry
  • Concomitant production
  • Illumination conditions
  • Inter-system crossings
  • Intracellular spaces
  • Nanoscaled particles
  • Near-infrared photons
  • Oligo(ethylene glycol)
  • Photo-induced generation
  • Molecular oxygen

Cite this

Swaminathan, S., Fowley, C., Thapaliya, E. R., McCaughan, B., Tang, S., Fraix, A., ... Raymo, F. M. (2015). Supramolecular nanoreactors for intracellular singlet-oxygen sensitization. Nanoscale, 7(33), 14071-14079. https://doi.org/10.1039/c5nr02672e
Swaminathan, S. ; Fowley, Colin ; Thapaliya, E.R. ; McCaughan, Bridgeen ; Tang, S. ; Fraix, A. ; Captain, B. ; Sortino, S. ; Callan, J ; Raymo, F.M. / Supramolecular nanoreactors for intracellular singlet-oxygen sensitization. In: Nanoscale. 2015 ; Vol. 7, No. 33. pp. 14071-14079.
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Swaminathan, S, Fowley, C, Thapaliya, ER, McCaughan, B, Tang, S, Fraix, A, Captain, B, Sortino, S, Callan, J & Raymo, FM 2015, 'Supramolecular nanoreactors for intracellular singlet-oxygen sensitization', Nanoscale, vol. 7, no. 33, pp. 14071-14079. https://doi.org/10.1039/c5nr02672e

Supramolecular nanoreactors for intracellular singlet-oxygen sensitization. / Swaminathan, S.; Fowley, Colin; Thapaliya, E.R.; McCaughan, Bridgeen; Tang, S.; Fraix, A.; Captain, B.; Sortino, S.; Callan, J; Raymo, F.M.

In: Nanoscale, Vol. 7, No. 33, 28.07.2015, p. 14071-14079.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Supramolecular nanoreactors for intracellular singlet-oxygen sensitization

AU - Swaminathan, S.

AU - Fowley, Colin

AU - Thapaliya, E.R.

AU - McCaughan, Bridgeen

AU - Tang, S.

AU - Fraix, A.

AU - Captain, B.

AU - Sortino, S.

AU - Callan, J

AU - Raymo, F.M.

N1 - cited By 0

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N2 - 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. © The Royal Society of Chemistry 2015.

AB - 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. © The Royal Society of Chemistry 2015.

KW - Anthracene

KW - Cell membranes

KW - Chromophores

KW - Containers

KW - Energy transfer

KW - Ethylene

KW - Ethylene glycol

KW - Infrared devices

KW - Lanthanum compounds

KW - Nanoparticles

KW - Oxygen

KW - Photodynamic therapy

KW - Solutions

KW - Supramolecular chemistry

KW - Concomitant production

KW - Illumination conditions

KW - Inter-system crossings

KW - Intracellular spaces

KW - Nanoscaled particles

KW - Near-infrared photons

KW - Oligo(ethylene glycol)

KW - Photo-induced generation

KW - Molecular oxygen

U2 - 10.1039/c5nr02672e

DO - 10.1039/c5nr02672e

M3 - Article

VL - 7

SP - 14071

EP - 14079

JO - Nanoscale

T2 - Nanoscale

JF - Nanoscale

SN - 2040-3364

IS - 33

ER -

Swaminathan S, Fowley C, Thapaliya ER, McCaughan B, Tang S, Fraix A et al. Supramolecular nanoreactors for intracellular singlet-oxygen sensitization. Nanoscale. 2015 Jul 28;7(33):14071-14079. https://doi.org/10.1039/c5nr02672e