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Natural diterpenes from Croton ciliatoglanduliferus as photosystem II and photosystem I inhibitors in spinach chloroplasts

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Abstract

In our search for new natural photosynthetic inhibitors that could lead to the development of “green herbicides” less toxic to environment, the diterpene labdane-8α,15-diol (1) and its acetyl derivative (2) were isolated for the first time from Croton ciliatoglanduliferus Ort. They inhibited photophosphorylation, electron transport (basal, phosphorylating and uncoupled) and the partial reactions of both photosystems in spinach thylakoids. Compound 1 inhibits the photosystem II (PS II) partial reaction from water to Na+ Silicomolibdate (SiMo) and has no effect on partial reaction from diphenylcarbazide (DPC) to 2,6-dichlorophenol indophenol (DCPIP), therefore 1 inhibits at the water splitting enzyme and also inhibits PS I partial reaction from reduced phenylmetasulfate (PMS) to methylviologen (MV). Thus, it also inhibits in the span of P700 to Iron sulfur center X (FX). Compound 2 inhibits both, the PS II partial reactions from water to SiMo and from DPC to DCPIP; besides this, it inhibits the photosystem I (PS I) partial reaction from reduced PMS to MV. With these results, we concluded that the targets of the natural product 2 are located at the water splitting enzyme, and at P680 in PS II and at the span of P700 to FX in PS I. The results of compounds 1 and 2 on PS II were corroborated by chlorophyll a fluorescence.

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Abbreviations

ADP:

Adenosine diphosphate

ATP:

Adenosine triphosphate

Chl:

Chlorophyll

DBMIB:

2,5-Dibromo-6-isopropyl-3-methyl-1,4-benzoquinone

DCPIP:

2,6-Dichlorophenol indophenol

DPC:

Diphenylcarbazide

D1 :

Subunit D1 of PS II

EPR:

Electron paramagnetic resonance

F 0 :

Fluorescence level when plastoquinone electron acceptor pool (Q a) is fully oxidized

F 300 :

Fluorescence intensity at 300 μs

F J :

Fluorescence intensity at the J-step (at 2 ms)

F m :

Fluorescence level when Q a is transiently fully reduced

F v :

Variable fluorescence (F m−F 0)

Fv/Fm:

Maximum quantum efficiency of photosystem II

F x :

Iron sulfur center

M 0 :

4(F 300−F 0)/(F m−F 0)

MV:

Methylviologen

OEC:

Oxygen evolving complex

PEA:

Plant efficiency analyzer

PMS:

Phenylmetasulfate

PS I:

Photosystem I

PS II:

Photosystem II

QA (QB):

Primary (secondary) quinone electron acceptor of PS II

P700 :

PS I reaction center

SiMo:

Sodium silicomolybdate

VCC:

Via column chromatography

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Acknowledgements

The authors thank the financial support of the DGAPA-UNAM IN205806 research project. This research was taken in part from the B.Sc. thesis of F. M. F. We also thank to Professor Nelly Diego for the collection and identification of the plant material used in this work and to M en C Yolanda González, M en C Rosa Isela del Villar, M en C Víctor Manuel Arroyo, M en C Georgina Duarte, QFB Marisela Gutiérrez (Facultad de Química, UNAM) for recording the NMR, MS and IR spectra.

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Authors and Affiliations

  1. Department of Biochemistry, National Autonomous University of Mexico, Ciudad Universitaria, Delegación Coyoacán, C.P. 04510, Mexico, D.F., Mexico

    Félix Morales-Flores, Beatriz King-Díaz & Blas Lotina-Hennsen

  2. Pharmacy Department, School of Chemistry, National Autonomous University of Mexico, Ciudad Universitaria, Delegación Coyoacán, C.P. 04510, Mexico, D.F., Mexico

    María Isabel Aguilar

  3. Vascular Plants Laboratory, School of Sciences, National Autonomous University of Mexico, Ciudad Universitaria, Delegación Coyoacán, C.P. 04510, Mexico, D.F., Mexico

    Jesús-Ricardo de Santiago-Gómez

Authors
  1. Félix Morales-Flores
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  2. María Isabel Aguilar
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  3. Beatriz King-Díaz
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  4. Jesús-Ricardo de Santiago-Gómez
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  5. Blas Lotina-Hennsen
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Correspondence to Blas Lotina-Hennsen.

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Morales-Flores, F., Aguilar, M.I., King-Díaz, B. et al. Natural diterpenes from Croton ciliatoglanduliferus as photosystem II and photosystem I inhibitors in spinach chloroplasts. Photosynth Res 91, 71–80 (2007). https://doi.org/10.1007/s11120-007-9143-7

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