Polyelectrolyte layer-by-layer deposition in cylindrical nanopores

T. D. Lazzara, K. H. A. Lau, A. I. Abou-Kandil, A. M. Caminade, J. P. Majoral, W. Knoll

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.
LanguageEnglish
Pages3909-3920
Number of pages12
JournalACS Nano
Volume4
Issue number7
DOIs
Publication statusPublished - 16 Jun 2010

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Nanopores
Polyelectrolytes
Ionic strength
Aluminum Oxide
Dendrimers
hydrazine
Optical waveguides
Aluminum
Oxides
porosity
Multilayers
aluminum oxides
dendrimers
Membranes
optical waveguides
Planar waveguides
Hydrazine
Coulomb interactions
Phosphorus
Nanotubes

Keywords

  • microporous membranes
  • porous substrates
  • cylindrical pores
  • polyelectrolytes
  • dendrimers
  • layer-by-layer self-assembly
  • optical lightmode waveguide spectroscopy
  • phosphorus-containing dendrimers
  • thiol-terminated dendrimer
  • optical wave-guide
  • on-a-chip
  • ionic-strength template synthesis
  • anodic
  • alumina electrostatic interactions
  • nanostructured materials

Cite this

Lazzara, T. D., Lau, K. H. A., Abou-Kandil, A. I., Caminade, A. M., Majoral, J. P., & Knoll, W. (2010). Polyelectrolyte layer-by-layer deposition in cylindrical nanopores. ACS Nano, 4(7), 3909-3920. https://doi.org/10.1021/nn1007594
Lazzara, T. D. ; Lau, K. H. A. ; Abou-Kandil, A. I. ; Caminade, A. M. ; Majoral, J. P. ; Knoll, W. / Polyelectrolyte layer-by-layer deposition in cylindrical nanopores. In: ACS Nano. 2010 ; Vol. 4, No. 7. pp. 3909-3920.
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Lazzara, TD, Lau, KHA, Abou-Kandil, AI, Caminade, AM, Majoral, JP & Knoll, W 2010, 'Polyelectrolyte layer-by-layer deposition in cylindrical nanopores' ACS Nano, vol. 4, no. 7, pp. 3909-3920. https://doi.org/10.1021/nn1007594

Polyelectrolyte layer-by-layer deposition in cylindrical nanopores. / Lazzara, T. D.; Lau, K. H. A.; Abou-Kandil, A. I.; Caminade, A. M.; Majoral, J. P.; Knoll, W.

In: ACS Nano, Vol. 4, No. 7, 16.06.2010, p. 3909-3920.

Research output: Contribution to journalArticle

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T1 - Polyelectrolyte layer-by-layer deposition in cylindrical nanopores

AU - Lazzara, T. D.

AU - Lau, K. H. A.

AU - Abou-Kandil, A. I.

AU - Caminade, A. M.

AU - Majoral, J. P.

AU - Knoll, W.

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N2 - Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.

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KW - microporous membranes

KW - porous substrates

KW - cylindrical pores

KW - polyelectrolytes

KW - dendrimers

KW - layer-by-layer self-assembly

KW - optical lightmode waveguide spectroscopy

KW - phosphorus-containing dendrimers

KW - thiol-terminated dendrimer

KW - optical wave-guide

KW - on-a-chip

KW - ionic-strength template synthesis

KW - anodic

KW - alumina electrostatic interactions

KW - nanostructured materials

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DO - 10.1021/nn1007594

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VL - 4

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Lazzara TD, Lau KHA, Abou-Kandil AI, Caminade AM, Majoral JP, Knoll W. Polyelectrolyte layer-by-layer deposition in cylindrical nanopores. ACS Nano. 2010 Jun 16;4(7):3909-3920. https://doi.org/10.1021/nn1007594