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Structure, photodynamic reaction and DNA photocleavage properties of a nitrosyl iron-sulfur cluster (Me4N)2[Fe2S2(NO)4]: A DFT calculation and experimental study.

Identifieur interne : 000033 ( Main/Exploration ); précédent : 000032; suivant : 000034

Structure, photodynamic reaction and DNA photocleavage properties of a nitrosyl iron-sulfur cluster (Me4N)2[Fe2S2(NO)4]: A DFT calculation and experimental study.

Auteurs : Qi Jing [République populaire de Chine] ; Lifang Liu [République populaire de Chine] ; Yu Zhang [République populaire de Chine] ; Leilei Xie [République populaire de Chine] ; Luna Song [République populaire de Chine] ; Wenming Wang [République populaire de Chine] ; Yanhong Liu [République populaire de Chine] ; Xuan Zhao [États-Unis] ; Hongfei Wang [République populaire de Chine]

Source :

RBID : pubmed:32408226

Abstract

Density functional theory calculations were performed on the structure of the nitrosyl iron-sulfur cluster (Me4N)2[Fe2S2(NO)4]. The IR spectra were assigned and the electronic ground-state properties in different solvents were analyzed. Dynamic conversion of [Fe2S2(NO)4]2- was analyzed quantitatively using the time-resolved IR spectra in different solvents. Photo irradiation and polarity of solvent obviously affect the reaction rates, which are faster in CH3CN and CH3OH than those in DMSO and water. The calculated orbital energies of HOMOs are higher and those of LUMO-HOMO gap are smaller in CH3CN and CH3OH than those in DMSO and water, which is consistent with the reaction rate and explains the experimental observation. Moreover, the photo-induced nitric oxide (NO) release and cluster conversion was identified using EPR spectra. The photocleavage of pBR322 DNA was observed, both NO and oxygen related free radicals play key roles in the process. The study provides an effective method to monitor the photodynamic reactions for better understanding of the physiological activity of nitrosyl iron-sulfur clusters.

DOI: 10.1016/j.saa.2020.118401
PubMed: 32408226


Affiliations:


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Le document en format XML

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[Fe
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S
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<sub>4</sub>
N)
<sub>2</sub>
[Fe
<sub>2</sub>
S
<sub>2</sub>
(NO)
<sub>4</sub>
]: A DFT calculation and experimental study.</title>
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<div type="abstract" xml:lang="en">Density functional theory calculations were performed on the structure of the nitrosyl iron-sulfur cluster (Me
<sub>4</sub>
N)
<sub>2</sub>
[Fe
<sub>2</sub>
S
<sub>2</sub>
(NO)
<sub>4</sub>
]. The IR spectra were assigned and the electronic ground-state properties in different solvents were analyzed. Dynamic conversion of [Fe
<sub>2</sub>
S
<sub>2</sub>
(NO)
<sub>4</sub>
]
<sup>2-</sup>
was analyzed quantitatively using the time-resolved IR spectra in different solvents. Photo irradiation and polarity of solvent obviously affect the reaction rates, which are faster in CH
<sub>3</sub>
CN and CH
<sub>3</sub>
OH than those in DMSO and water. The calculated orbital energies of HOMOs are higher and those of LUMO-HOMO gap are smaller in CH
<sub>3</sub>
CN and CH
<sub>3</sub>
OH than those in DMSO and water, which is consistent with the reaction rate and explains the experimental observation. Moreover, the photo-induced nitric oxide (NO) release and cluster conversion was identified using EPR spectra. The photocleavage of pBR322 DNA was observed, both NO and oxygen related free radicals play key roles in the process. The study provides an effective method to monitor the photodynamic reactions for better understanding of the physiological activity of nitrosyl iron-sulfur clusters.</div>
</front>
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<ArticleTitle>Structure, photodynamic reaction and DNA photocleavage properties of a nitrosyl iron-sulfur cluster (Me
<sub>4</sub>
N)
<sub>2</sub>
[Fe
<sub>2</sub>
S
<sub>2</sub>
(NO)
<sub>4</sub>
]: A DFT calculation and experimental study.</ArticleTitle>
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<AbstractText>Density functional theory calculations were performed on the structure of the nitrosyl iron-sulfur cluster (Me
<sub>4</sub>
N)
<sub>2</sub>
[Fe
<sub>2</sub>
S
<sub>2</sub>
(NO)
<sub>4</sub>
]. The IR spectra were assigned and the electronic ground-state properties in different solvents were analyzed. Dynamic conversion of [Fe
<sub>2</sub>
S
<sub>2</sub>
(NO)
<sub>4</sub>
]
<sup>2-</sup>
was analyzed quantitatively using the time-resolved IR spectra in different solvents. Photo irradiation and polarity of solvent obviously affect the reaction rates, which are faster in CH
<sub>3</sub>
CN and CH
<sub>3</sub>
OH than those in DMSO and water. The calculated orbital energies of HOMOs are higher and those of LUMO-HOMO gap are smaller in CH
<sub>3</sub>
CN and CH
<sub>3</sub>
OH than those in DMSO and water, which is consistent with the reaction rate and explains the experimental observation. Moreover, the photo-induced nitric oxide (NO) release and cluster conversion was identified using EPR spectra. The photocleavage of pBR322 DNA was observed, both NO and oxygen related free radicals play key roles in the process. The study provides an effective method to monitor the photodynamic reactions for better understanding of the physiological activity of nitrosyl iron-sulfur clusters.</AbstractText>
<CopyrightInformation>Copyright © 2020 Elsevier B.V. All rights reserved.</CopyrightInformation>
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<LastName>Jing</LastName>
<ForeName>Qi</ForeName>
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<Affiliation>Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry and Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.</Affiliation>
</AffiliationInfo>
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<LastName>Liu</LastName>
<ForeName>Lifang</ForeName>
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<Affiliation>Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry and Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.</Affiliation>
</AffiliationInfo>
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<LastName>Zhang</LastName>
<ForeName>Yu</ForeName>
<Initials>Y</Initials>
<AffiliationInfo>
<Affiliation>Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry and Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.</Affiliation>
</AffiliationInfo>
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<Affiliation>Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry and Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.</Affiliation>
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<ForeName>Luna</ForeName>
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<ForeName>Wenming</ForeName>
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<Affiliation>Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry and Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.</Affiliation>
</AffiliationInfo>
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<ForeName>Yanhong</ForeName>
<Initials>Y</Initials>
<AffiliationInfo>
<Affiliation>Technical Institute of Physics & Chemistry, CAS, Beijing 100190, China.</Affiliation>
</AffiliationInfo>
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<Author ValidYN="Y">
<LastName>Zhao</LastName>
<ForeName>Xuan</ForeName>
<Initials>X</Initials>
<AffiliationInfo>
<Affiliation>Department of Chemistry, University of Memphis, Memphis, TN 38152, USA.</Affiliation>
</AffiliationInfo>
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<Author ValidYN="Y">
<LastName>Wang</LastName>
<ForeName>Hongfei</ForeName>
<Initials>H</Initials>
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<Affiliation>Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry and Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China. Electronic address: wanghf@sxu.edu.cn.</Affiliation>
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<Language>eng</Language>
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<Year>2020</Year>
<Month>05</Month>
<Day>04</Day>
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<Country>England</Country>
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<KeywordList Owner="NOTNLM">
<Keyword MajorTopicYN="N">Iron-sulfur clusters</Keyword>
<Keyword MajorTopicYN="N">NO donor</Keyword>
<Keyword MajorTopicYN="N">Nitrosyl</Keyword>
<Keyword MajorTopicYN="N">Photodynamic</Keyword>
<Keyword MajorTopicYN="N">Spectroscopy</Keyword>
</KeywordList>
<CoiStatement>Declaration of competing interest All of the authors declare that they have no competing interests. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. The manuscript is not currently under consideration for publication elsewhere.</CoiStatement>
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