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Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures

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Abstract

Lignin is one of the most abundant natural materials around the world, accounting for about a quarter of the woody tissue. In general, it is well known that these highly branched aromatic bio-polymers are formed from the polymerization of p-coumaryl, coniferyl, and sinapyl alcohols; however, the connection between these structures are still not known in detail. In this work, we have employed electronic structure calculations to investigate local reactivities and details regarding the connectivity between the basic structures of lignin (unmodified mono and dilignols as well as dehydrogenated monolignols). Condensed-to-atoms Fukui indexes, local softness and hard and soft acids and bases principle were employed in the analyses. The results allow identifying reactive sites on the lignin subunits and access details on the synthesis and degradation of this bio-material. In particular, it is possible to identify a strong influence of the dehydrogenation and monomer dimerization on the monolignols reactivities, which activate the O–C4 and C5 positions.

The local reactivities of lignin subunits were evaluated via DFT calculations.

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Funding

The authors thank the Brazilian National Council for Scientific and Technological Development (CNPq) [grant numbers 448310/2014-7 and 420449/2018-3] and the Pro-Rectory of Research (PROPe) of the São Paulo State University (UNESP) for the financial support and student scholarship. This research was also supported by resources supplied by the Center for Scientific Computing (NCC/GridUNESP) of the São Paulo State University (UNESP).

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  1. Campus of Itapeva, São Paulo State University (UNESP), Itapeva, SP, 18409-010, Brazil

    Rosangela A. Maia, Gustavo Ventorim & Augusto Batagin-Neto

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  1. Rosangela A. Maia
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  2. Gustavo Ventorim
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  3. Augusto Batagin-Neto
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Correspondence to Augusto Batagin-Neto.

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Maia, R.A., Ventorim, G. & Batagin-Neto, A. Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures. J Mol Model 25, 228 (2019). https://doi.org/10.1007/s00894-019-4130-4

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