arXiv subjects

Masakazu Iwai

Publications and source records attributed to Masakazu Iwai.

2 recordsLinked to original sources

arXiv2026

Minor Structural Differences Tune Functional Specialization of Antenna Subunits in the PSII Energy Transfer Network

Photosystem II (PSII) contains a diverse array of pigment-protein subunits with specialized roles in the antenna network. We investigate the functional significance of this subunit diversity in two structurally similar yet functionally distinct PSII subunits: minor light-harvesting complex CP29 and major light-harvesting complex LHCII. We combine two-dimensional electronic-vibrational spectroscopy with lifetime density analysis and structure-based kinetic modeling to assign spectral features to exciton states, providing molecular detail to probed spectral features. We show how the distinct pigment compositions of CP29 and Lhcb1, a monomeric subunit of the major LHCII trimer, reshape excitonic connectivity and energy transfer pathways in the complexes. Compared to Lhcb1, energy transfer pathways in CP29 are more spatially connected and reversible, suggesting CP29 evolved to distribute excitation between the core and periphery of the PSII antenna. We find that small structural modifications from a common framework tune CP29 and Lhcb1 to complementary roles in the PSII supercomplex.

physics.chem-ph↗

arXiv2021

The initial charge separation step in oxygenic photosynthesis

Photosystem II is crucial for life on Earth as it provides oxygen as a result of photoinduced electron transfer and water splitting reactions. The excited state dynamics of the photosystem II-reaction center (PSII-RC) has been a matter of vivid debate because the absorption spectra of the embedded chromophores significantly overlap and hence it is extremely difficult to distinguish transients. Here, we report the two-dimensional electronic-vibrational spectroscopic study of the PSII-RC. The simultaneous resolution along both the visible excitation and infrared detection axis is crucial in allowing for the character of the excitonic states and interplay between them to be clearly distinguished. In particular, this work demonstrates that the mixed exciton-charge transfer state, previously proposed to be responsible for the far-red light operation of photosynthesis, is characterized by the Chl$_{\rm D1}^+$Phe$^-$ radical pair and can be directly prepared upon photoexcitation. Further, we find that the initial electron acceptor in the PSII-RC is Phe, rather than P$_{\rm D1}$, regardless of excitation wavelength.

physics.chem-ph↗