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Holzwarth_2006


The mechanism and kinetics of electron transfer in isolated D1/D2-cytb559 photosystem (PS) II reaction centers (RCs) and in intact PSII cores have been studied by femtosecond transient absorption and kinetic compartment modeling. For intact PSII, a component of .1.5 ps reflects the dominant energy- ...

Holzwarth AR, Mueller, Reus M, Nowaczyk M, Sander J and Roegner M (2006) Kinetics and mechanism of electron transfer in intact photosystem II and in the isolated reaction center: pheophytin is the primary electron acceptor. Proc Natl Acad Sci U S A 103: 6895-6900
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The mechanism and kinetics of electron transfer in isolated D1/D2-cytb559 photosystem (PS) II reaction centers (RCs) and in intact PSII cores have been studied by femtosecond transient absorption and kinetic compartment modeling. For intact PSII, a component of .1.5 ps reflects the dominant energy-trapping kinetics from the antenna by the RC. A 5.5-ps component reflects the apparent lifetime of primary charge separation, which is faster by a factor of 8.12 than assumed so far. The 35-ps component represents the apparent lifetime of formation of a secondary radical pair, and the .200-ps component represents the electron transfer to the QA acceptor. In isolated RCs, the apparent lifetimes of primary and secondary charge separation are .3 and 11 ps, respectively. It is shown (i) that pheophytin is reduced in the first step, and (ii) that the rate constants of electron transfer in the RC are identical for PSII cores and for isolated RCs. We interpret the first electron transfer step as electron donation from the primary electron donor Chlacc D1. Thus, this mechanism, suggested earlier for isolated RCs at cryogenic temperatures, is also operative in intact PSII cores and in isolated RCs at ambient temperature. The effective rate constant of primary electron transfer from the equilibrated RC* excited state is 170.180 ns.1, and the rate constant of secondary electron transfer is 120.130 ns.1.
DOI:10.1073/pnas.0505371103
A photosystem that contains a pheophytin-quinone reaction center with associated accessory pigments and electron carriers. In cyanobacteria and chloroplasts, in the presence of light, PSII functions as a water-plastoquinone oxidoreductase, transferring electrons from water to plastoquinone, whereas other photosynthetic bacteria carry out anoxygenic photosynthesis and oxidize other compounds to re-reduce the photoreaction center.
GO:0009523
Plants are exposed to a temporally and spatially heterogeneous environment, and photosynthesis is well adapted to these fluctuations. Understanding of the complex, non-linear dynamics of photosynthesis in fluctuating light requires novel-modeling approaches that involve not only the primary light and dark biochemical reactions, but also networks of regulatory interactions. This requirement exceeds the capacity of the existing molecular models that are typically reduced to describe a partial process, dynamics of a specific complex or its particular dynamic feature. We propose a concept of comprehensive model that would represent an internally consistent, integral framework combining information on the reduced models that led to its construction. This review explores approaches and tools that exist in engineering, mathematics, and in other domains of biology that can be used to develop a comprehensive model of photosynthesis. Equally important, we investigated techniques by which one can rigorously reduce such a comprehensive model to models of low dimensionality, which preserve dynamic features of interest and, thus, contribute to a better understanding of photosynthesis under natural and thus fluctuating conditions. The web-based platform www.e-photosynthesis.org is introduced as an arena where these concepts and tools are being introduced and tested.
DOI:10.1007/s11120-007-9178-9
The synthesis by organisms of organic chemical compounds, especially carbohydrates, from carbon dioxide (CO2) using energy obtained from light rather than from the oxidation of chemical compounds.
GO:0015979
Absorption and transfer of the energy absorbed from light photons between photosystem reaction centers. [source: GOC:sm]
GO:0009765
Chloroplasts are semiautonomous arganelles comprising an envelope formed of two membranes, an aqueous matrix known as stroma, and an extensive system of internal membranes known as thylakoids. All of the light-harvesting and energy-transducing functions are located in the thylakoids." [source: local, PMID:15187262]
"A homodimer of chlorophyll a (PD1-PD2) originally thought to be the primary electron donor in photosystem II (PSII). However, later studies showed that the primary electron donor in PSII is the accessory chlorophyll in D1 protein of PSII (ChlD1) and not P680. Therefore, P680 is the secondary electron donor in PSII, reducing ChlD1+ and oxidizing tyrosine Z (YZ)." [source: local]

chemical entity:chlorophyll a
compound:chlorophyll a
"The primary quinone electron acceptor in photosystem II (PSII). It accepts electrons from reduced primary electron acceptor in PSII, pheophytin (Pheo) and it donates electrons to the secondary quinone electron acceptor in PSII, QB." [source: local, PMID:9351808 ]

compound:plastoquinone
"Is the primary electron acceptor of photosystem II (PS II). When the primary charge separation in PSII occurs, the ChlD1+Pheo- state is formed and the electron of reduced Pheo is then transported to the primary quinone electron acceptor in PSII, QA. Chemical formula: C56H76N4O6" [source: local, PMID:19805064 ]

compound:pheophytin a
"The core (proximal) antenna complex of photosystem II (PSII) participates in light harvesting and in excitation energy transfer from distal antenna of PSII (LHCII) to the reaction center of PSII (RC II). The core antenna is composed of the CP43 and CP47 proteins which are tightly associated with RCII and CP43 and CP47 contains only chlorophyll a molecules (no chlorophyll b)." [source: local, GOC:lr, PMID:20080575]

cellular component:PSII light-harvesting complex
"Chlorophyll a, the primary electron donor in photosystem II (PSII). When oxidized by the primary charge separation in PSII, it is reduced by P680." [source: local, PMID:18339736 ]

compound:chlorophyll a
a) Fluorescence emission is the radiative transition from the excited singlet state to the ground state. The released energy is emitted in form of fluorescence photon. b) Heat dissipation is the non-radiative transition from the excited singlet state to the ground state. The released energy is dissipated to vibrations of the nuclei in the pigment and its surroundings. [source: local]

Reaction Rate
P680 / Core Antenna* / ChlD / Qa / Pheo -> P680 / Core Antenna / ChlD / Qa / Pheo 2.00e+5 mol/s-1 (Fluorescence: 6.70e+7 mol/sec-1)
P680 / Core Antenna* / ChlD / Qa / Pheo
P680 / Core Antenna / ChlD / Qa / Pheo
A process in which a interaction between two pigment molecules (typically dipole-dipole) causes simultaneous de-excitation of the donor molecule from the excited singlet state to the ground state and excitation of the acceptor molecule from the ground state to the excited singlet state. [source: local]

biological process:photosynthesis,light harvesting
Reaction Rate
P680 / Core Antenna* / ChlD / Qa / Pheo -> P680 / Core Antenna / ChlD* / Qa / Pheo 1.92e+10 mol/s-1
P680 / Core Antenna* / ChlD / Qa / Pheo
P680 / Core Antenna / ChlD* / Qa / Pheo
A process in which a interaction between two pigment molecules (typically dipole-dipole) causes simultaneous de-excitation of the donor molecule from the excited singlet state to the ground state and excitation of the acceptor molecule from the ground state to the excited singlet state. [source: local]

biological process:photosynthesis,light harvesting
Reaction Rate
P680 / Core Antenna / ChlD* / Qa / Pheo -> P680 / Core Antenna* / ChlD / Qa / Pheo 2.50e+10 mol/s-1
P680 / Core Antenna / ChlD* / Qa / Pheo
P680 / Core Antenna* / ChlD / Qa / Pheo
Reaction Rate
P680 / Core Antenna / ChlD* / Qa / Pheo -> P680 / Core Antenna / ChlD / Qa / Pheo 2.00e+5 mol/s-1 (Fluorescence: 6.70e+6 mol/sec-1)
P680 / Core Antenna / ChlD* / Qa / Pheo
P680 / Core Antenna / ChlD / Qa / Pheo
Charge recombination is an inverse process to charge separation: One negatively charged molecule (electron acceptor) reacts with one positively charged molecule (electron donor) returning to the electrically neutral states of both donor and acceptor. After the process, one of the molecules (typically the electron donor) occurs in its singlet excited state.

Reaction Rate
P680 / Core Antenna / ChlD+ / Qa / Pheo- -> P680 / Core Antenna / ChlD* / Qa / Pheo 5.00e+11 mol/s-1
P680 / Core Antenna / ChlD+ / Qa / Pheo-
P680 / Core Antenna / ChlD* / Qa / Pheo
Reaction Rate
P680 / Core Antenna / ChlD+ / Qa / Pheo- -> Core Antenna / P680+ / ChlD / Qa / Pheo- 2.50e+11 mol/s-1
P680 / Core Antenna / ChlD+ / Qa / Pheo-
Core Antenna / P680+ / ChlD / Qa / Pheo-
Reaction Rate
Core Antenna / P680+ / ChlD / Qa / Pheo- -> Core Antenna / P680+ / ChlD / Qa- / Pheo 4.80e+9 mol/s-1
Core Antenna / P680+ / ChlD / Qa / Pheo-
Core Antenna / P680+ / ChlD / Qa- / Pheo
molecular function:electron transporter
Reaction Rate
Core Antenna / P680+ / ChlD / Qa- / Pheo -> Core Antenna / P680+ / ChlD / Qa / Pheo- 2.40e+9 mol/s-1
Core Antenna / P680+ / ChlD / Qa- / Pheo
Core Antenna / P680+ / ChlD / Qa / Pheo-
biological process:charge separation
Reaction Rate
P680 / Core Antenna / ChlD* / Qa / Pheo -> P680 / Core Antenna / ChlD+ / Qa / Pheo- 5.00e+11 mol/s-1
P680 / Core Antenna / ChlD* / Qa / Pheo
P680 / Core Antenna / ChlD+ / Qa / Pheo-
molecular function:electron transporter
Reaction Rate
Core Antenna / P680+ / ChlD / Qa / Pheo- -> P680 / Core Antenna / ChlD+ / Qa / Pheo- 6.70e+10 mol/s-1
Core Antenna / P680+ / ChlD / Qa / Pheo-
P680 / Core Antenna / ChlD+ / Qa / Pheo-

State Variable value
P680, Qa, Pheo, Ac, ChlD* 0
P680, Qa, Pheo-, Ac, ChlD+ 0
P680+, Qa, Pheo-, Ac, ChlD 0
P680, Qa, Pheo, Ac*, ChlD 1
P680+, Qa-, Pheo, Ac, ChlD 0
P680, Qa, Pheo, Ac, ChlD 0
Name Rate
Primary charge separation 5.00e+11 mol/s-1 (Fluorescence: 0.00e+0 mol/s-1)
Energy transfer between ChlD and A 2.50e+10 mol/s-1 (Fluorescence: 0.00e+0 mol/s-1)
RC de-excitation 2.00e+5 mol/s-1 (Fluorescence: 6.70e+6 mol/s-1)
Antenna de-excitation 2.00e+5 mol/s-1 (Fluorescence: 6.70e+7 mol/s-1)
Charge recombination 5.00e+11 mol/s-1 (Fluorescence: 0.00e+0 mol/s-1)
Reverse electron flow from ChlD to P680+ 6.70e+10 mol/s-1 (Fluorescence: 0.00e+0 mol/s-1)
QA reduction by Pheo- 4.80e+9 mol/s-1 (Fluorescence: 0.00e+0 mol/s-1)
Reverse electron flow from QA- to Pheo- 2.40e+9 mol/s-1 (Fluorescence: 0.00e+0 mol/s-1)
ChlD+ reduction by P680 2.50e+11 mol/s-1 (Fluorescence: 0.00e+0 mol/s-1)
Energy transfer between A and ChlD 1.92e+10 mol/s-1 (Fluorescence: 0.00e+0 mol/s-1)