Energy Transfer and Radical-Pair Dynamics in Photosystem I with Different Red Chlorophyll a Pigments
Abstract
:1. Introduction
2. Results
2.1. Absorption Spectra
2.2. Chlamydomonas reinhardtii
2.3. Synechocystis PCC6803
2.4. Thermosynechococcus elongatus
2.5. Spirulina Platensis
3. Discussion
3.1. Sub-ps Dynamics
3.2. Thermodynamic Considerations
3.3. Comparison of the RC and RP SADS
4. Materials and Methods
4.1. Transient-Absorption Experiments
4.2. Time-Resolved Fluorescence Spectra
4.3. Global and Target Analysis of Time-Resolved Spectra
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
Appendix A
Model for the Observations
References
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A | species\τ (ps) | 0.28 | 0.38 | 2.65 | 7.92 | 13.3 | 32.3 | long lived | input |
Ant1 | 0.015 | 0.850 | 0.007 | 0.005 | 0.004 | 0 | 0 | 0.88 | |
Bulk Chl a | −0.335 | −0.475 | 0.361 | 0.316 | 0.241 | 0 | 0 | 0.11 | |
Red Chl a | 0.007 | 0.014 | −0.258 | 0.150 | 0.086 | 0 | 0 | 0 | |
WL-RC | 0.418 | −0.589 | 0.075 | 0.055 | 0.051 | 0 | 0 | 0.01 | |
RP1 | −0.108 | 0.208 | −0.242 | −1.826 | 1.968 | 0 | 0 | 0 | |
RP2 | 0.003 | −0.007 | 0.063 | 1.724 | −3.984 | 2.201 | 0 | 0 | |
RP3 | 0.000 | 0.000 | −0.005 | −0.423 | 1.637 | −2.203 | 0.994 | 0 | |
sum | 0 | 0 | 0 | 0 | 0.004 | −0.002 | 0.994 | 1 | |
B | species\τ (ps) | 0.28 | 0.38 | 2.65 | 7.92 | 13.3 | 32.3 | long lived | input |
Ant1 | 0.016 | −0.022 | −0.005 | 0.006 | 0.004 | 0 | 0 | 0 | |
Bulk Chl a | −0.355 | 0.012 | −0.273 | 0.371 | 0.255 | 0 | 0 | 0.01 | |
Red Chl a | 0.008 | 0.000 | 0.195 | 0.177 | 0.091 | 0 | 0 | 0.47 | |
WL-RC | 0.443 | 0.015 | −0.057 | 0.065 | 0.054 | 0 | 0 | 0.52 | |
RP1 | −0.114 | −0.005 | 0.184 | −2.142 | 2.079 | 0 | 0 | 0 | |
RP2 | 0.003 | 0.000 | −0.048 | 2.024 | −4.207 | 2.228 | 0 | 0 | |
RP3 | 0.000 | 0.000 | 0.004 | −0.497 | 1.729 | −2.230 | 0.994 | 0 | |
sum | 0 | 0 | 0 | 0 | 0.005 | −0.002 | 0.994 | 1 |
A | Chlamydomonas reinhardtii | Ant1 | Bulk Chl a | Red Chl a | WL-RC | |
λmax (nm) | 675 | 682 | 689 | 690 | ||
(1/cm) | 14,805 | 14,654 | 14,519 | 14,483 | ||
(kB.T) | 72.7 | 72.0 | 71.3 | 71.1 | ||
ΔH (kB.T) | 0.7 | −0.7 | −0.8 | |||
ΔG (kB.T) | 4.1 | 1.3 | 1.3 | |||
ΔH − ΔG = TΔS (kB.T) | −3.4 | −2.0 | −2.2 | |||
“N” | 2.7 | 78 | 10.4 | 8.7 | ||
B | Synechocystis PCC6803 | Ant1 | Bulk Chl a | Red Chl a1 | Red Chl a2 | WL-RC |
λmax (nm) | 683 | 685 | 701 | 709 | 693 | |
(1/cm) | 14,635 | 14,594 | 14,260 | 14,096 | 14,438 | |
(kB.T) | 71.9 | 71.7 | 70.0 | 69.2 | 70.9 | |
ΔH (kB.T) | 0.2 | −1.6 | −2.4 | −0.8 | ||
ΔG (kB.T) | 4.1 | 1.1 | 1.3 | 1.5 | ||
ΔH – ΔG = TΔS (kB.T) | −3.9 | −2.7 | −3.8 | −2.3 | ||
“N” | 1.6 | 78 | 5.3 | 1.8 | 8.1 | |
C | Thermosynechococcus elongatus | Ant1 | Bulk Chl a | Red Chl a1 | Red Chl a2 | WL-RC |
λmax (nm) | 681 | 686 | 707 | 723 | 693 | |
(1/cm) | 14,682 | 14,581 | 14,152 | 13,824 | 14,438 | |
(kB.T) | 72.1 | 71.6 | 69.5 | 67.9 | 70.9 | |
ΔH (kB.T) | 0.5 | −2.1 | −3.7 | −0.7 | ||
ΔG (kB.T) | 4.1 | 0.2 | 0.6 | 1.5 | ||
ΔH – ΔG = TΔS (kB.T) | −3.6 | −2.3 | −4.3 | −2.2 | ||
“N” | 2.1 | 78 | 7.9 | 1.0 | 8.6 | |
D | Spirulina platensis | Ant1 | Bulk Chl a | Red Chl a1 | Red Chl a2 | WL-RC |
λmax (nm) | 679 | 684 | 713 | 732 | 693 | |
(1/cm) | 14,722 | 14,630 | 14,031 | 13,670 | 14,438 | |
(kB.T) | 72.3 | 71.8 | 68.9 | 67.1 | 70.9 | |
ΔH (kB.T) | 0.5 | −2.9 | −4.7 | −0.9 | ||
ΔG (kB.T) | 4.1 | 0.1 | −0.4 | 1.5 | ||
ΔH – ΔG = TΔS (kB.T) | −3.7 | −3.1 | −4.3 | −2.4 | ||
“N” | 2.0 | 78 | 3.6 | 1.0 | 6.8 |
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van Stokkum, I.H.M.; Müller, M.G.; Holzwarth, A.R. Energy Transfer and Radical-Pair Dynamics in Photosystem I with Different Red Chlorophyll a Pigments. Int. J. Mol. Sci. 2024, 25, 4125. https://doi.org/10.3390/ijms25074125
van Stokkum IHM, Müller MG, Holzwarth AR. Energy Transfer and Radical-Pair Dynamics in Photosystem I with Different Red Chlorophyll a Pigments. International Journal of Molecular Sciences. 2024; 25(7):4125. https://doi.org/10.3390/ijms25074125
Chicago/Turabian Stylevan Stokkum, Ivo H. M., Marc G. Müller, and Alfred R. Holzwarth. 2024. "Energy Transfer and Radical-Pair Dynamics in Photosystem I with Different Red Chlorophyll a Pigments" International Journal of Molecular Sciences 25, no. 7: 4125. https://doi.org/10.3390/ijms25074125