Depolymerization of lignin for biological conversion through sulfonation and a chelator-mediated Fenton reaction

Martinez, Daniella V.; Rodriguez, Alberto; Juarros, Miranda A.; Martinez, Estevan J.; Alam, Todd M.; Simmons, Blake A.; Sale, Kenneth L.; Singer, Steven W.; Kent, Michael S.

doi:10.1039/d1gc03854k

Depolymerization of lignin for biological conversion through sulfonation and a chelator-mediated Fenton reaction

Journal Article · Sun Jan 30 23:00:00 EST 2022 · Green Chemistry

DOI:https://doi.org/10.1039/d1gc03854k· OSTI ID:1845395

Martinez, Daniella V. ^[1]; ^[2]; Juarros, Miranda A. ^[1]; Martinez, Estevan J. ^[1]; ^[3]; ^[4]; Sale, Kenneth L. ^[5]; Singer, Steven W. ^[4]; ^[5]

Sandia National Laboratories (SNL), Albuquerque, NM, and Livermore, CA (United States)
Sandia National Laboratories (SNL), Albuquerque, NM, and Livermore, CA (United States); Joint BioEnergy Institute, Emeryville, CA (United States)
Sandia National Laboratories, Livermore, CA and Albuquerque, NM 87185, USA
Joint BioEnergy Institute, Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Joint BioEnergy Institute, Emeryville, CA (United States); Sandia National Laboratories (SNL), Albuquerque, NM, and Livermore, CA (United States)

The generating value from lignin through depolymerization and biological conversion to valuable fuels, chemicals, or intermediates has great promise but is limited by several factors including lack of cost-effective depolymerization methods, toxicity within the breakdown products, and low bioconversion of the breakdown products. High yield depolymerization of natural lignins requires cleaving carbon-carbon bonds in addition to ether bonds. To address that need, we report that a chelator-mediated Fenton reaction can efficiently cleave C-C bonds in sulfonated polymers at or near room temperature, and that unwanted repolymerization can be minimized through optimizing reaction conditions. This method was used to depolymerize lignosulfonate from M_w = 28,000 g/mol to M_w = 800 g/mol. The breakdown products were characterized by SEC, FTIR and NMR and evaluated for bioavailability. The breakdown products are rich in acid, aldehyde, and alcohol functionalities but are largely devoid of aromatics and aliphatic dienes. A panel of nine organisms were tested for the ability to grow on the breakdown products. Growth at a low level was observed for several monocultures on the depolymerized LS in absence of glucose. Much stronger growth was observed in the presence of 0.2% glucose and for one organism we demonstrate doubling of melanin production in the presence of depolymerized LS. The results suggest that this chelator-mediated Fenton method is a promising new approach for biological conversion of lignin into higher value chemicals or intermediates.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525; AC02-05CH11231

OSTI ID:: 1845395

Alternate ID(s):: OSTI ID: 1842866

Report Number(s):: SAND2022-0904J; 703249

Journal Information:: Green Chemistry, Journal Name: Green Chemistry Journal Issue: 4 Vol. 24; ISSN 1463-9262

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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