Interactions of copper(<scp>ii</scp>) and zinc(<scp>ii</scp>) with chlorophyll: insights from density functional theory studies

Bechaieb, Rim; Fredj, A. Ben; Akacha, Azaiez Ben; Gérard, Hélène

doi:10.1039/c5nj03244j

Cited by 19 publications

(18 citation statements)

References 69 publications

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“…Info. ), and in line with our previous studies [31,32], we focused only on the Q y transition. A blue shift is observed when going from Mg to metals of line 4.…”

Section: Electronic Propertiesmentioning

confidence: 59%

“…Calculations were based on a Chla model containing 73 atoms reported in Scheme 1 which was proposed in our previous work [31,32,[39][40][41]. This model retains the structure of Chla except for the phytyl ester side chain which was replaced by a methyl group to reduce the number of atoms for computation.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Chla and its substitution complex (Pheo(M)) can accommodate additional solvent molecules on the central cation, in addition to the tetracoordination of the Pheo ligand through binding of acetonitrile which was used as a model solvent in our previous works about the interaction of different heavy metals with chlorophyll (a) [31,32]. This solvent has been chosen as it cannot form H-bonds with the C=O groups of chlorophyll (which would be artefact toward the examined properties) and has been recently used as solvent for a detailed experimental study of transmetallation of substituted chlorophylls [43].…”

Section: Computational Detailsmentioning

confidence: 99%

“…From a theoretical point of view, we have recently examined the Mg-substitution by Zn and Cu, and its competition with various chelation processes at the periphery [31]. Substitution by Cu and Zn was found to be possible and the most favored process in the case of copper when implicit solvation is included.…”

Section: Introductionmentioning

confidence: 99%

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DFT and TD-DFT Studies of Mg-Substitution in Chlorophyll by Cr(II), Fe(II) and Ni(II)

2018

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Electronic contributions in electronic transitions and energetic data associated to the Mg-substitution in chlorophyll by three transition metals: chrom (Cr 2+), iron (Fe 2+) and nickel (Ni 2+) have been studied theoretically using density functional theory and time dependent density functional theory (TD-DFT) methods. The binding energies are stronger than for Mg 2+ in the case of all three cations especially in the case of Ni 2+. The Mg-substitution process is found to be exergonic for all title elements in gas phase and in acetonitrile using both implicit and explicit models of solvation. The natural population analysis results, which estimated by natural bond orbital analysis, showed significant charge transfer from pheophytin ligand to the central cation. The UV-visible proprieties of the different substitution compounds have been studied using the TD-DFT method evidencing that substitution of Mg by Cr, Fe or Ni is associated to a blue shift of the Q-band for the three cations.

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“…Info. ), and in line with our previous studies [31,32], we focused only on the Q y transition. A blue shift is observed when going from Mg to metals of line 4.…”

Section: Electronic Propertiesmentioning

confidence: 59%

Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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DFT and TD-DFT Studies of Mg-Substitution in Chlorophyll by Cr(II), Fe(II) and Ni(II)

2018

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“…We state, therefore, similarly to other authors who showed the formation of metal-chlorophyll complexes that cadmium eliminates magnesium from chlorophyll and replaces it in the central position of the porphirine ring. Many papers on metaloporphirins have been published (Kang et al 2018;Bechaieb et al 2016b;Zvezdanović et al 2014;Küpper et al 2006). Recently, based on quantum chemical calculations (with Gaussian 09 program, using the density functional theory DFT at B3LYP level) the chemical structures of metaloporphirins (with Hg, Pb and Cd) were described and the reaction of metaloporphirin formation was postulated (Bechaieb et al 2016a).…”

Section: Absorption and Fluorescence Characteristics Of Chlorophyll Dmentioning

confidence: 99%

Chlorophyll degradation by tetracycline and cadmium in spinach (Spinacia oleracea L.) leaves

Rydzyński

Piotrowicz-Cieślak

Grajek

et al. 2018

Int. J. Environ. Sci. Technol.

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Degradation of chlorophyll was studied in leaves of spinach grown in soil containing cadmium and tetracycline, based on spectroscopic measurements and biochemical analyses of plant extracts. It was shown that plant exposure to the highest levels of tetracycline and cadmium resulted in 64% and 68%, respectively, reduction in chlorophyll content. The chlorophyll degradation rate constants were determined, and they were found to increase with increasing doses of tetracycline and cadmium. The rate constant of chlorophyll degradation by tetracycline ranged from k = 960 M −1 day −1 to k = 2180 M −1 day −1 , and the rate constant of chlorophyll degradation by cadmium ranged from k = 1130 M −1 day −1 to k = 2580 M −1 day −1 , depending on dose. Plant stress responses to tetracycline are much stronger than to cadmium, as is visible from the activity of guaiacol peroxidase and catalase. However, phytotoxicity of cadmium, measured by the rate of chlorophyll degradation and enzyme activities, is much higher compared to tetracycline. The spectroscopic measurements were taken 10 days after tetracycline and cadmium were added to the reagent grade chlorophyll which was used at the concentration of chlorophyll in plants. Changes in absorption and fluorescence spectra are likely to result from removal of magnesium from the chlorophyll molecule, and thus they indicate the formation of pheophytin. Cadmium, on the other hand, is probably bound into the chlorophyll molecule, substituting its magnesium.

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Tetrapyrrole pigments of photosynthetic antennae and reaction centers of higher plants: Structures, biophysics, functions, biochemistry, mechanisms of regulation, applications

Fiedor

Zbyradowski

Pilch

2019

Advances in Botanical Research

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Interactions of copper(ii) and zinc(ii) with chlorophyll: insights from density functional theory studies

Abstract: The most favored reaction of chlorophyll is computed to be substitution for Cu2+ and peripheral chelation for Zn2+.

Cited by 19 publications

References 69 publications

DFT and TD-DFT Studies of Mg-Substitution in Chlorophyll by Cr(II), Fe(II) and Ni(II)

DFT and TD-DFT Studies of Mg-Substitution in Chlorophyll by Cr(II), Fe(II) and Ni(II)

Chlorophyll degradation by tetracycline and cadmium in spinach (Spinacia oleracea L.) leaves

Tetrapyrrole pigments of photosynthetic antennae and reaction centers of higher plants: Structures, biophysics, functions, biochemistry, mechanisms of regulation, applications

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