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Atmospheric Low-Temperature Plasma-Induced Changes in the Structure of the Lignin Macromolecule: An Experimental and Theoretical Investigation.

Identifieur interne : 000551 ( Main/Exploration ); précédent : 000550; suivant : 000552

Atmospheric Low-Temperature Plasma-Induced Changes in the Structure of the Lignin Macromolecule: An Experimental and Theoretical Investigation.

Auteurs : Yizhong Cao [République populaire de Chine, États-Unis] ; Miao Tang [République populaire de Chine] ; Pei Yang [République populaire de Chine] ; Minzhi Chen [République populaire de Chine] ; Siqun Wang [États-Unis] ; Haiming Hua [République populaire de Chine] ; Weimin Chen [République populaire de Chine] ; Xiaoyan Zhou [République populaire de Chine]

Source :

RBID : pubmed:31834791

Descripteurs français

English descriptors

Abstract

Atmospheric low-temperature plasma has emerged as a promising pretreatment for lignocellulose to improve bio-refining. Herein, we investigated plasma-induced changes in the chemical structure of lignin to obtain a fundamental understanding of the plasma-lignocellulose interaction. Based on the results, plasma possesses a strong capacity to cleave C-C covalent bonds in the aliphatic region of lignin, accompanied by oxidation. Plasma treatment leads to the degradation and fragmentation of lignin. Pronounced deconstruction of β-O-4 aryl ether is observed in plasma. The relative content of β-O-4 aryl ether was reduced from the initial value of 65.1/100Ar to 58.7/100Ar for lignin from corncob and from the initial value of 72.5/100Ar to 63.8/100Ar for lignin from poplar after plasma treatment, respectively. According to the density functional theory analysis, the oxygen atom of β-O-4 aryl ether is the most likely potential reaction site and the Cβ-O covalent bond exhibits the lowest decomposition free energy (50.5 kcal mol-1), which will easily be cleaved in plasma. The dominant reaction pathway of lignin degradation is the cleavage of the Cβ-O covalent bond followed by the cleavage of the Cβ-Cα bond. We propose that this investigation is beneficial to optimize and expand the applications of plasma treatment in pretreatment of lignocellulose.

DOI: 10.1021/acs.jafc.9b05604
PubMed: 31834791


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<term>Cold Temperature (MeSH)</term>
<term>Lignin (chemistry)</term>
<term>Macromolecular Substances (chemistry)</term>
<term>Models, Molecular (MeSH)</term>
<term>Oxidation-Reduction (MeSH)</term>
<term>Oxygen (chemistry)</term>
<term>Plasma Gases (chemistry)</term>
</keywords>
<keywords scheme="KwdFr" xml:lang="fr">
<term>Basse température (MeSH)</term>
<term>Gaz plasmas (composition chimique)</term>
<term>Lignine (composition chimique)</term>
<term>Modèles moléculaires (MeSH)</term>
<term>Oxydoréduction (MeSH)</term>
<term>Oxygène (composition chimique)</term>
<term>Structures macromoléculaires (composition chimique)</term>
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<term>Lignin</term>
<term>Macromolecular Substances</term>
<term>Oxygen</term>
<term>Plasma Gases</term>
</keywords>
<keywords scheme="MESH" qualifier="composition chimique" xml:lang="fr">
<term>Gaz plasmas</term>
<term>Lignine</term>
<term>Oxygène</term>
<term>Structures macromoléculaires</term>
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<term>Models, Molecular</term>
<term>Oxidation-Reduction</term>
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<div type="abstract" xml:lang="en">Atmospheric low-temperature plasma has emerged as a promising pretreatment for lignocellulose to improve bio-refining. Herein, we investigated plasma-induced changes in the chemical structure of lignin to obtain a fundamental understanding of the plasma-lignocellulose interaction. Based on the results, plasma possesses a strong capacity to cleave C-C covalent bonds in the aliphatic region of lignin, accompanied by oxidation. Plasma treatment leads to the degradation and fragmentation of lignin. Pronounced deconstruction of β-O-4 aryl ether is observed in plasma. The relative content of β-O-4 aryl ether was reduced from the initial value of 65.1/100Ar to 58.7/100Ar for lignin from corncob and from the initial value of 72.5/100Ar to 63.8/100Ar for lignin from poplar after plasma treatment, respectively. According to the density functional theory analysis, the oxygen atom of β-O-4 aryl ether is the most likely potential reaction site and the C
<sub>β</sub>
-O covalent bond exhibits the lowest decomposition free energy (50.5 kcal mol
<sup>-1</sup>
), which will easily be cleaved in plasma. The dominant reaction pathway of lignin degradation is the cleavage of the C
<sub>β</sub>
-O covalent bond followed by the cleavage of the C
<sub>β</sub>
-C
<sub>α</sub>
bond. We propose that this investigation is beneficial to optimize and expand the applications of plasma treatment in pretreatment of lignocellulose.</div>
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<AbstractText>Atmospheric low-temperature plasma has emerged as a promising pretreatment for lignocellulose to improve bio-refining. Herein, we investigated plasma-induced changes in the chemical structure of lignin to obtain a fundamental understanding of the plasma-lignocellulose interaction. Based on the results, plasma possesses a strong capacity to cleave C-C covalent bonds in the aliphatic region of lignin, accompanied by oxidation. Plasma treatment leads to the degradation and fragmentation of lignin. Pronounced deconstruction of β-O-4 aryl ether is observed in plasma. The relative content of β-O-4 aryl ether was reduced from the initial value of 65.1/100Ar to 58.7/100Ar for lignin from corncob and from the initial value of 72.5/100Ar to 63.8/100Ar for lignin from poplar after plasma treatment, respectively. According to the density functional theory analysis, the oxygen atom of β-O-4 aryl ether is the most likely potential reaction site and the C
<sub>β</sub>
-O covalent bond exhibits the lowest decomposition free energy (50.5 kcal mol
<sup>-1</sup>
), which will easily be cleaved in plasma. The dominant reaction pathway of lignin degradation is the cleavage of the C
<sub>β</sub>
-O covalent bond followed by the cleavage of the C
<sub>β</sub>
-C
<sub>α</sub>
bond. We propose that this investigation is beneficial to optimize and expand the applications of plasma treatment in pretreatment of lignocellulose.</AbstractText>
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<li>États-Unis</li>
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<name sortKey="Yang, Pei" sort="Yang, Pei" uniqKey="Yang P" first="Pei" last="Yang">Pei Yang</name>
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