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  • 1
    ISSN: 1573-5079
    Keywords: cytochrome bf complex ; activated state ; hydrostatic pressure ; activation volume ; reaction volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The effects of pressure on the kinetics of redox reactions in and around the chloroplast cytochrome bf complex were studied using a reconstituted system consisting of Photosystem I (PS I) particles, cytochrome bf complex and plastocyanin (PC), all derived from pea chloroplasts. There were no significant permanent effects of pressure in the range 0.1–191 MPa on the reaction kinetics, or on the shape of the absorption spectra of components studied. Discernable effects on rate-coefficients of increasing pressure were observed on the reduction of P700+ by PCI, on the reduction of PCII by ascorbate, and on the oxidation of decyl plastoquinol by the bf complex. The volumes of activation ΔV# were determined from the dependence of the rate-coefficient on pressure using: $$(\partial lnk/\partial P)_T = - \Delta V^\# /RT.$$ The volume of activation is the difference in partial molar volume between the activated state and the reactants for the redox reaction. Such data was sought to help define in detail those redox reactions and the corresponding activated states. For the reduction of P700+ by PCI and the oxidation of decyl plastoquinol by the bf complex, the rate coefficient decreased with increase in pressure, whilst for the reduction of PCII by ascorbate it increased. The corresponding volumes of activation were 9.6±0.6×10-6 m3 mol-1, 18±2×10-6 m3 mol-1 and -14±1×10-6 m3 mol-1, respectively. Much of the pressure-dependence of PCII reduction by ascorbate was ascribed to an increase in ascorbate ionisation with increase in pressure. There was little effect of pressure on the kinetics of oxidation of ferrocytochrome f by PCII, or on the equilibrium constant of the redox pair ferrocytochrome f/ferricytochrome f: PCII/PCI. Possible physical bases for these activation volumes are discussed, and they are compared with literature values.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Photosynthesis research 40 (1994), S. 199-206 
    ISSN: 1573-5079
    Keywords: cytochrome bf complex ; electron transfers ; kinetics ; quinol oxidation ; Q-cycle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The kinetics of oxidation and reduction of P700, plastocyanin, cytochrome f and cytochrome b-563 were studied in a reconstituted system consisting of Photosystem I particles, cytochrome bf complex and plastocyanin, all derived from pea leaf chloroplasts. Decyl plastoquinol was the reductant of the bf complex. Turnovers of the system were initiated by laser flashes. The reaction between oxidised P700 and plastocyanin was non-homogeneous in that a second-order rate coefficient of c. 5×10−7 M−1 s−1 applied to 80% of the P700+ and c. 0.7×107 M−1 s−1 to the remainder. In the presence of bf complex, but without quinol, the electron transfer between cytochrome f and oxidised plastocyanin could be described by a second-order rate coefficient of c. 4×107 M−1 s−1 (forward), and c. 1.6×107 M−1 s−1 (reverse). The equilibrium coefficient was thus 2.5. Unexpectedly, there was little reduction of cytochrome f + or plastocyanin+ by electrons from the Rieske centre. With added quinol, reduction of cytochrome b-563 occurred. Concomitantly, electrons appeared in the oxidised species. It was inferred that either the Rieske centre was not involved in the high-potential chain of electron transfer events, or that, only in the presence of quinol, electrons were quickly passed from the Rieske centre to cytochrome f +. Additionally, the presence of quinol altered the equilibrium coefficient for the cyt f/PC interaction from 2.5 to c. 5. The reaction between quinol and the bf complex was describable by a second-order rate coefficient of about 3×106 M−1 s−1. The pattern of the redox reactions around the bf complex could be simulated in detail with a Q-cycle model as previously found for chloroplasts.
    Type of Medium: Electronic Resource
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