Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways
The directed depolymerization of lignin biopolymers is of utmost relevance for the valorization or commercialization of biomass fuels. We present a computational and theoretical screening approach to identify potential cleavage pathways and resulting fragments that are formed during depolymerization...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2016
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| Online Access: | http://hdl.handle.net/1721.1/105336 https://orcid.org/0000-0002-2128-1791 https://orcid.org/0000-0001-9342-0191 |
| _version_ | 1810979837917003776 |
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| author | Liu, Fang Mar, Brendan D. Qi, Helena Wen Kulik, Heather Janine |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Liu, Fang Mar, Brendan D. Qi, Helena Wen Kulik, Heather Janine |
| author_sort | Liu, Fang |
| collection | MIT |
| description | The directed depolymerization of lignin biopolymers is of utmost relevance for the valorization or commercialization of biomass fuels. We present a computational and theoretical screening approach to identify potential cleavage pathways and resulting fragments that are formed during depolymerization of lignin oligomers containing two to six monomers. We have developed a chemical discovery technique to identify the chemically relevant putative fragments in eight known polymeric linkage types of lignin. Obtaining these structures is a crucial precursor to the development of any further kinetic modeling. We have developed this approach by adapting steered molecular dynamics calculations under constant force and varying the points of applied force in the molecule to diversify the screening approach. Key observations include relationships between abundance and breaking frequency, the relative diversity of potential pathways for a given linkage, and the observation that readily cleaved bonds can destabilize adjacent bonds, causing subsequent automatic cleavage. |
| first_indexed | 2024-09-23T09:49:18Z |
| format | Article |
| id | mit-1721.1/105336 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T09:49:18Z |
| publishDate | 2016 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1053362022-09-30T17:04:45Z Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways Liu, Fang Mar, Brendan D. Qi, Helena Wen Kulik, Heather Janine Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Chemistry Kulik, Heather Janine Mar, Brendan D. Qi, Helena Wen Kulik, Heather Janine The directed depolymerization of lignin biopolymers is of utmost relevance for the valorization or commercialization of biomass fuels. We present a computational and theoretical screening approach to identify potential cleavage pathways and resulting fragments that are formed during depolymerization of lignin oligomers containing two to six monomers. We have developed a chemical discovery technique to identify the chemically relevant putative fragments in eight known polymeric linkage types of lignin. Obtaining these structures is a crucial precursor to the development of any further kinetic modeling. We have developed this approach by adapting steered molecular dynamics calculations under constant force and varying the points of applied force in the molecule to diversify the screening approach. Key observations include relationships between abundance and breaking frequency, the relative diversity of potential pathways for a given linkage, and the observation that readily cleaved bonds can destabilize adjacent bonds, causing subsequent automatic cleavage. Massachusetts Institute of Technology (Research Support Corporation, Reed Grant) United States. Dept. of Energy. Computational Science Graduate Fellowship Program (DOE-CSGF) Burroughs Wellcome Fund (Career Award at the Scientific Interface) 2016-11-15T20:32:27Z 2016-11-15T20:32:27Z 2015-05 2015-05 Article http://purl.org/eprint/type/JournalArticle 1089-5639 1520-5215 http://hdl.handle.net/1721.1/105336 Mar, Brendan D., Helena W. Qi, Fang Liu, and Heather J. Kulik. “Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways.” Journal of Physical Chemistry A 119, no. 24 (June 18, 2015): 6551-6562. https://orcid.org/0000-0002-2128-1791 https://orcid.org/0000-0001-9342-0191 en_US http://dx.doi.org/10.1021/acs.jpca.5b03503 Journal of Physical Chemistry A Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Kulik via Erja Kajosalo |
| spellingShingle | Liu, Fang Mar, Brendan D. Qi, Helena Wen Kulik, Heather Janine Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways |
| title | Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways |
| title_full | Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways |
| title_fullStr | Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways |
| title_full_unstemmed | Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways |
| title_short | Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways |
| title_sort | ab initio screening approach for the discovery of lignin polymer breaking pathways |
| url | http://hdl.handle.net/1721.1/105336 https://orcid.org/0000-0002-2128-1791 https://orcid.org/0000-0001-9342-0191 |
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