Self Assembly of Coiled-Coil Peptide−Porphyrin Complexes

Bashkim Kokona, Andrew M. Kim, R. Claire Roden, Joshua P. Daniels, Brian J. Pepe-Mooney, Brian C. Kovaric, Julio C. de Paula§, Karl A. Johnson and Robert Fairman*
Department of Biology, Haverford College, 370 Lancaster Avenue, Haverford, Pennsylvania 19041
Biomacromolecules, 2009, 10 (6), pp 1454–1459
DOI: 10.1021/bm9000553
Publication Date (Web): April 17, 2009
Copyright © 2009 American Chemical Society
* To whom correspondence should be addressed. Tel.: (610) 896-4205. Fax: (610) 896-4963. E-mail: rfairman@haverford.edu., §

Current Address: Department of Chemistry, Lewis and Clark College, 0615 SW Palatine Hill Rd., Portland, OR 97219.

Abstract

Abstract Image

We are interested in the controlled assembly of photoelectronic materials using peptides as scaffolds and porphyrins as the conducting material. We describe the integration of a peptide-based polymer strategy with the ability of designed basic peptides to bind anionic porphyrins in order to create regulated photoelectronically active biomaterials. We have described our peptide system in earlier work, which demonstrates the ability of a peptide to form filamentous materials made up of self-assembling coiled-coil structures. We have modified this peptide system to include lysine residues appropriately positioned to specifically bind meso-tetrakis(4-sulfonatophenyl)porphine (TPPS4), a porphyrin that contains four negatively charged sulfonate groups at neutral pH. We measure the binding of TPPS4 to our peptide using UV−visible and fluorescence spectroscopies to follow the porphyrin signature. We determine the concomitant acquisition of helical secondary structure in the peptide upon TPPS4 binding using circular dichroism spectropolarimetry. This binding fosters polymerization of the peptide, as shown by absorbance extinction effects in the peptide CD spectra. The morphologies of the peptide/porphyrin complexes, as imaged by atomic force microscopy, are consistent with the coiled-coil polymers that we had characterized earlier, except that the heights are slightly higher, consistent with porphyrin binding. Evidence for exciton coupling in the copolymers is shown by red-shifting in the UV−visible data, however, the coupling is weak based on a lack of fluorescence quenching in fluorescence experiments.

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This article has been cited by 7 ACS Journal articles (5 most recent appear below).

  • Cover Image

    Characterization of Mesoscale Coiled-Coil Peptide–Porphyrin Complexes

    Brian J. Pepe-Mooney, Bashkim Kokona, and Robert Fairman
    Biomacromolecules2011 12 (12), 4196-4203
    • Characterization of Mesoscale Coiled-Coil Peptide–Porphyrin Complexes

      Brian J. Pepe-Mooney, Bashkim Kokona, and Robert Fairman
      Biomacromolecules2011 12 (12), 4196-4203

      Photoelectronically conductive self-assembling peptide–porphyrin assemblies have great potential in their use as biomaterials, owing largely to their environmentally responsive properties. We have successfully designed a coiled-coil peptide that can self-...

  • Cover Image

    Thermodynamic Analysis of Self-Assembly in Coiled-Coil Biomaterials

    Betty P. Tsang, Heidi S. Bretscher, Bashkim Kokona, Robert S. Manning, and Robert Fairman
    Biochemistry2011 50 (40), 8548-8558
    • Thermodynamic Analysis of Self-Assembly in Coiled-Coil Biomaterials

      Betty P. Tsang, Heidi S. Bretscher, Bashkim Kokona, Robert S. Manning, and Robert Fairman
      Biochemistry2011 50 (40), 8548-8558

      Coiled-coil protein structural motifs have proven amenable to the design of structurally well-defined biomaterials. Mesoscale structural properties can be fairly well predicted based on rules governing the chemical interactions between the helices that ...

  • Cover Image

    Polystyrene Sulfonate–Porphyrin Assemblies: Influence of Polyelectrolyte and Porphyrin Structure

    Christian Ruthard, Michael Maskos, Ute Kolb, and Franziska Gröhn
    The Journal of Physical Chemistry B2011 Article ASAP
    • Polystyrene Sulfonate–Porphyrin Assemblies: Influence of Polyelectrolyte and Porphyrin Structure

      Christian Ruthard, Michael Maskos, Ute Kolb, and Franziska Gröhn
      The Journal of Physical Chemistry B2011 Article ASAP

      In this study, electrostatic self-assembly of different polystyrene sulfonates and a set of tetravalent cationic porphyrins is investigated. It is shown that association of linear polystyrene sulfonates of different molar masses yields finite size ...

  • Cover Image

    Scaling the Chirality in Porphyrin J-Nanoaggregates

    Maria Angela Castriciano, Andrea Romeo, Giovanna De Luca, Valentina Villari, Luigi Monsù Scolaro, and Norberto Micali
    Journal of the American Chemical Society2011 133 (4), 765-767
    • Scaling the Chirality in Porphyrin J-Nanoaggregates

      Maria Angela Castriciano, Andrea Romeo, Giovanna De Luca, Valentina Villari, Luigi Monsù Scolaro, and Norberto Micali
      Journal of the American Chemical Society2011 133 (4), 765-767
  • Cover Image

    Exciton Annihilation and Energy Transfer in Self-Assembled Peptide−Porphyrin Complexes Depends on Peptide Secondary Structure

    Darius Kuciauskas, Juris Kiskis, Gregory A. Caputo, and Vidmantas Gulbinas
    The Journal of Physical Chemistry B2010 114 (48), 16029-16035
    • Exciton Annihilation and Energy Transfer in Self-Assembled Peptide−Porphyrin Complexes Depends on Peptide Secondary Structure

      Darius Kuciauskas, Juris Kiskis, Gregory A. Caputo, and Vidmantas Gulbinas
      The Journal of Physical Chemistry B2010 114 (48), 16029-16035

      We used picosecond transient absorption and fluorescence lifetime spectroscopy to study singlet exciton annihilation and depolarization in self-assembled aggregates of meso-tetra(4-sulfonatophenyl)porphine (TPPS4) and a synthetic 22-residue polypeptide. ...

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History

  • Published In Issue June 08, 2009
  • Article ASAPApril 17, 2009
  • Received: January 14, 2009
    Revised: March 13, 2009

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