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Self Assembly of Coiled-Coil Peptide−Porphyrin Complexes
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Current Address: Department of Chemistry, Lewis and Clark College, 0615 SW Palatine Hill Rd., Portland, OR 97219.
Abstract

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).

Characterization of Mesoscale Coiled-Coil Peptide–Porphyrin Complexes
Brian J. Pepe-Mooney, Bashkim Kokona, and Robert FairmanBiomacromolecules2011 12 (12), 4196-4203Characterization of Mesoscale Coiled-Coil Peptide–Porphyrin Complexes
Brian J. Pepe-Mooney, Bashkim Kokona, and Robert FairmanBiomacromolecules2011 12 (12), 4196-4203Photoelectronically 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-...

Thermodynamic Analysis of Self-Assembly in Coiled-Coil Biomaterials
Betty P. Tsang, Heidi S. Bretscher, Bashkim Kokona, Robert S. Manning, and Robert FairmanBiochemistry2011 50 (40), 8548-8558Thermodynamic Analysis of Self-Assembly in Coiled-Coil Biomaterials
Betty P. Tsang, Heidi S. Bretscher, Bashkim Kokona, Robert S. Manning, and Robert FairmanBiochemistry2011 50 (40), 8548-8558Coiled-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 ...

Polystyrene Sulfonate–Porphyrin Assemblies: Influence of Polyelectrolyte and Porphyrin Structure
Christian Ruthard, Michael Maskos, Ute Kolb, and Franziska GröhnThe Journal of Physical Chemistry B2011 Article ASAPPolystyrene Sulfonate–Porphyrin Assemblies: Influence of Polyelectrolyte and Porphyrin Structure
Christian Ruthard, Michael Maskos, Ute Kolb, and Franziska GröhnThe Journal of Physical Chemistry B2011 Article ASAPIn 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 ...

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

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