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Temperature dependence of light-induced absorbance changes associated with chlorophyll photooxidation in manganese-depleted core complexes of photosystem II

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Abstract

Mid-infrared (4500-1150 cm–1) absorbance changes induced by continuous illumination of Mn-depleted core complexes of photosystem II (PSII) from spinach in the presence of exogenous electron acceptors (potassium ferricyanide and silicomolybdate) were studied by FTIR difference spectroscopy in the temperature range 100–265 K. The FTIR difference spectrum for photooxidation of the chlorophyll dimer P680 was determined from the set of signals associated with oxidation of secondary electron donors (β-carotene, chlorophyll) and reduction of the primary quinone QA. On the basis of analysis of the temperature dependence of the P +680 /P680 FTIR spectrum, it was concluded that frequencies of 131-keto-C=O stretching modes of neutral chlorophyll molecules PD1 and PD2, which constitute P680, are similar to each other, being located at ∼1700 cm–1. This together with considerable difference between the stretching mode frequencies of keto groups of P +D1 and P+ D2 cations (1724 and 1709 cm–1, respectively) is in agreement with a literature model (Okubo et al. (2007) Biochemistry, 46, 4390–4397) suggesting that the positive charge in the P +680 dimer is mainly localized on one of the two chlorophyll molecules. A partial delocalization of the charge between the PD1 and PD2 molecules in P +680 is supported by the presence of a characteristic electronic intervalence band at ∼3000 cm–1. It is shown that a bleaching band at 1680 cm–1 in the P +680 /P680 FTIR spectrum does not belong to P680. A possible origin of this band is discussed, taking into account the temperature dependence (100–265 K) of light-induced absorbance changes of PSII core complexes in the visible spectral region from 620 to 720 nm.

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Abbreviations

ΔA:

absorbance change

Car:

β-carotene

Chl:

chlorophyll a

ChlD1 and ChlD2 :

monomeric chlorophyll molecules bound to D1 and D2 polypeptides of RC

ChlZ :

redoxactive additional chlorophyll molecule of RC

cyt b559:

cytochrome b559

P680 :

dimer of chlorophyll molecules in RC of PSII

PD1, PD2 :

chlorophyll molecules composing P680

Pheo:

pheophytin a

PheoD1 :

pheophytin bound to D1 polypeptide of RC

PSII:

photosystem II

QA :

primary quinone acceptor

RC:

reaction center

SiMo:

silicomolybdate

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Authors and Affiliations

  1. Institute of Basic Biological Problems, Russian Academy of Sciences, 142290, Pushchino, Moscow Region, Russia

    A. A. Zabelin, V. A. Shkuropatova, A. Ya. Shkuropatov & V. A. Shuvalov

  2. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 119991, Moscow, Russia

    V. A. Shuvalov

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  1. A. A. Zabelin
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  2. V. A. Shkuropatova
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  3. A. Ya. Shkuropatov
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  4. V. A. Shuvalov
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Correspondence to A. A. Zabelin.

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Original Russian Text © A. A. Zabelin, V. A. Shkuropatova, A. Ya. Shkuropatov, V. A. Shuvalov, 2015, published in Biokhimiya, 2015, Vol. 80, No. 10, pp. 1551-1560.

Originally published in Biochemistry (Moscow) On-Line Papers in Press, as Manuscript BM15-150, August 23, 2015.

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Zabelin, A.A., Shkuropatova, V.A., Shkuropatov, A.Y. et al. Temperature dependence of light-induced absorbance changes associated with chlorophyll photooxidation in manganese-depleted core complexes of photosystem II. Biochemistry Moscow 80, 1279–1287 (2015). https://doi.org/10.1134/S0006297915100089

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  • DOI: https://doi.org/10.1134/S0006297915100089

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