Toward the origin of exciton electronic structure in phycobiliproteins

The Journal of Chemical Physics
Jordan M WomickAndrew M Moran

Abstract

Femtosecond laser spectroscopies are used to examine the electronic structures of two proteins found in the phycobilisome antenna of cyanobacteria, allophycocyanin (APC) and C-phycocyanin (CPC). The wave function composition involving the pairs of phycocyanobilin pigments (i.e., dimers) found in both proteins is the primary focus of this investigation. Despite their similar geometries, earlier experimental studies conducted in our laboratory and elsewhere observe clear signatures of exciton electronic structure in APC but not CPC. This issue is further investigated here using new experiments. Transient grating (TG) experiments employing broadband quasicontinuum probe pulses find a redshift in the signal spectrum of APC, which is almost twice that of CPC. Dynamics in the TG signal spectra suggest that the sub-100 fs dynamics in APC and CPC are respectively dominated by internal conversion and nuclear relaxation. A specialized technique, intraband electronic coherence spectroscopy (IECS), photoexcites electronic and nuclear coherences with nearly full suppression of signals corresponding to electronic populations. The main conclusion drawn by IECS is that dephasing of intraband electronic coherences in APC occurs in less than 25 ...Continue Reading

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Citations

Dec 15, 2010·The Journal of Physical Chemistry. B·Carsten OlbrichUlrich Kleinekathöfer
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Apr 21, 2011·The Journal of Physical Chemistry Letters·Sandeep VermaHirendra N Ghosh
Jan 28, 2011·The Journal of Physical Chemistry. B·Jordan M Womick, Andrew M Moran
Mar 9, 2011·The Journal of Physical Chemistry. a·Jordan M WomickAndrew M Moran
Sep 3, 2010·The Journal of Physical Chemistry. B·Brantley A WestAndrew M Moran

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