TY - JOUR
T1 - Unveiling the excited state energy transfer pathways in peridinin-chlorophyll a-protein by ultrafast multi-pulse transient absorption spectroscopy
AU - Redeckas, Kipras
AU - Voiciuk, Vladislava
AU - Zigmantas, Donatas
AU - Hiller, Roger G.
AU - Vengris, Mikas
PY - 2017/4/1
Y1 - 2017/4/1
N2 - Time-resolved multi-pulse methods were applied to investigate the excited state dynamics, the interstate couplings, and the excited state energy transfer pathways between the light-harvesting pigments in peridinin-chlorophyll a-protein (PCP). The utilized pump-dump-probe techniques are based on perturbation of the regular PCP energy transfer pathway. The PCP complexes were initially excited with an ultrashort pulse, resonant to the S0 → S2 transition of the carotenoid peridinin. A portion of the peridinin-based emissive intramolecular charge transfer (ICT) state was then depopulated by applying an ultrashort NIR pulse that perturbed the interaction between S1 and ICT states and the energy flow from the carotenoids to the chlorophylls. The presented data indicate that the peridinin S1 and ICT states are spectrally distinct and coexist in an excited state equilibrium in the PCP complex. Moreover, numeric analysis of the experimental data asserts ICT → Chl-a as the main energy transfer pathway in the photoexcited PCP systems.
AB - Time-resolved multi-pulse methods were applied to investigate the excited state dynamics, the interstate couplings, and the excited state energy transfer pathways between the light-harvesting pigments in peridinin-chlorophyll a-protein (PCP). The utilized pump-dump-probe techniques are based on perturbation of the regular PCP energy transfer pathway. The PCP complexes were initially excited with an ultrashort pulse, resonant to the S0 → S2 transition of the carotenoid peridinin. A portion of the peridinin-based emissive intramolecular charge transfer (ICT) state was then depopulated by applying an ultrashort NIR pulse that perturbed the interaction between S1 and ICT states and the energy flow from the carotenoids to the chlorophylls. The presented data indicate that the peridinin S1 and ICT states are spectrally distinct and coexist in an excited state equilibrium in the PCP complex. Moreover, numeric analysis of the experimental data asserts ICT → Chl-a as the main energy transfer pathway in the photoexcited PCP systems.
KW - Peridinin-chlorophyll α-protein
KW - Pump-probe
KW - Pump-dump-probe
KW - Intramolecular charge transfer
KW - Excited state equilibrium
KW - Excitation energy transfer
UR - http://www.scopus.com/inward/record.url?scp=85012149155&partnerID=8YFLogxK
U2 - 10.1016/j.bbabio.2017.01.014
DO - 10.1016/j.bbabio.2017.01.014
M3 - Article
C2 - 28161327
AN - SCOPUS:85012149155
SN - 0005-2728
VL - 1858
SP - 297
EP - 307
JO - Biochimica et Biophysica Acta - Bioenergetics
JF - Biochimica et Biophysica Acta - Bioenergetics
IS - 4
ER -