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Title: Defining lignin nanoparticle properties through tailored lignin reactivity by sequential organosolv fragmentation approach (SOFA)

Abstract

Sustainable biorefinery heavily depends on the generation of value-added products, particularly from lignin. Despite considerable efforts, the production of fungible lignin bioproducts is still hindered by the poor fractionation and low reactivity of lignin. To address these challenges, the sequential organosolv fragmentation approach (SOFA) using ethanol plus different-stage catalysts was explored to selectively dissolve lignin for producing multiple uniform lignin streams, and to tailor its chemistry and reactivity for fabricating lignin nanoparticles (LNPs) with desired quality features. In a biorefinery concept, the carbohydrate output is taken into consideration. SOFA significantly increased the glucose and xylose yields, suggesting an improved monomer-sugar release. The fractionated lignin was used to fabricate LNPs via self-assembly. Although these LNPs were derived from the same substrate, they exhibited different properties. The effective diameter almost followed the order of stage 1, stage 3, and stage 2 in each SOFA, and the smallest effective diameter was approximately 130 nm from SOFA using ethanol plus sulfuric acid. The polydispersity index and zeta potential were less than 0.08 and –50 mV, respectively, suggesting good uniformity and stability of the LNPs. Lignin characterization results suggested that SOFA using ethanol plus sulfuric acid produced high-molecular-weight lignin, decreased S/G ratio, and β-O-4 andmore » β–β linkage abundance, yet produced the condensed lignin and enhanced its hydrophobicity. More importantly, it exposed more phenolic OH groups and enhanced the stability of LNPs, likely due to the hydrogen bond networks. Together with enriched COOH groups, it promoted the formation of electrical double layers and increased the zeta potential of LNPs. In conclusion, by tailoring the lignin chemistry using SOFA to enhance the self-assembling process, high-quality LNPs of a spherical shape, small effective diameters, and good stability have been fabricated, which represents a sustainable means for upgrading the low-value lignin and thus contributes to the profitability of biorefineries.« less

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States)
  2. Univ. of Tennessee, Knoxville, TN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Texas A & M Univ., College Station, TX (United States); Northwest Univ. (People's Republic of China)
  5. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1489102
Alternate Identifier(s):
OSTI ID: 1483017
Grant/Contract Number:  
AC05-00OR22725; EE0006112; EE0007104; EE0008250
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 21; Journal Issue: 2; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Zhi -Hua, Hao, Naijia, Shinde, Somnath, Pu, Yunqiao Joseph, Kang, Xiaofeng, Ragauskas, Arthur J., and Yuan, Joshua S. Defining lignin nanoparticle properties through tailored lignin reactivity by sequential organosolv fragmentation approach (SOFA). United States: N. p., 2018. Web. doi:10.1039/c8gc03290d.
Liu, Zhi -Hua, Hao, Naijia, Shinde, Somnath, Pu, Yunqiao Joseph, Kang, Xiaofeng, Ragauskas, Arthur J., & Yuan, Joshua S. Defining lignin nanoparticle properties through tailored lignin reactivity by sequential organosolv fragmentation approach (SOFA). United States. https://doi.org/10.1039/c8gc03290d
Liu, Zhi -Hua, Hao, Naijia, Shinde, Somnath, Pu, Yunqiao Joseph, Kang, Xiaofeng, Ragauskas, Arthur J., and Yuan, Joshua S. Thu . "Defining lignin nanoparticle properties through tailored lignin reactivity by sequential organosolv fragmentation approach (SOFA)". United States. https://doi.org/10.1039/c8gc03290d. https://www.osti.gov/servlets/purl/1489102.
@article{osti_1489102,
title = {Defining lignin nanoparticle properties through tailored lignin reactivity by sequential organosolv fragmentation approach (SOFA)},
author = {Liu, Zhi -Hua and Hao, Naijia and Shinde, Somnath and Pu, Yunqiao Joseph and Kang, Xiaofeng and Ragauskas, Arthur J. and Yuan, Joshua S.},
abstractNote = {Sustainable biorefinery heavily depends on the generation of value-added products, particularly from lignin. Despite considerable efforts, the production of fungible lignin bioproducts is still hindered by the poor fractionation and low reactivity of lignin. To address these challenges, the sequential organosolv fragmentation approach (SOFA) using ethanol plus different-stage catalysts was explored to selectively dissolve lignin for producing multiple uniform lignin streams, and to tailor its chemistry and reactivity for fabricating lignin nanoparticles (LNPs) with desired quality features. In a biorefinery concept, the carbohydrate output is taken into consideration. SOFA significantly increased the glucose and xylose yields, suggesting an improved monomer-sugar release. The fractionated lignin was used to fabricate LNPs via self-assembly. Although these LNPs were derived from the same substrate, they exhibited different properties. The effective diameter almost followed the order of stage 1, stage 3, and stage 2 in each SOFA, and the smallest effective diameter was approximately 130 nm from SOFA using ethanol plus sulfuric acid. The polydispersity index and zeta potential were less than 0.08 and –50 mV, respectively, suggesting good uniformity and stability of the LNPs. Lignin characterization results suggested that SOFA using ethanol plus sulfuric acid produced high-molecular-weight lignin, decreased S/G ratio, and β-O-4 and β–β linkage abundance, yet produced the condensed lignin and enhanced its hydrophobicity. More importantly, it exposed more phenolic OH groups and enhanced the stability of LNPs, likely due to the hydrogen bond networks. Together with enriched COOH groups, it promoted the formation of electrical double layers and increased the zeta potential of LNPs. In conclusion, by tailoring the lignin chemistry using SOFA to enhance the self-assembling process, high-quality LNPs of a spherical shape, small effective diameters, and good stability have been fabricated, which represents a sustainable means for upgrading the low-value lignin and thus contributes to the profitability of biorefineries.},
doi = {10.1039/c8gc03290d},
journal = {Green Chemistry},
number = 2,
volume = 21,
place = {United States},
year = {2018},
month = {11}
}

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Works referenced in this record:

Biological valorization strategies for converting lignin into fuels and chemicals
journal, June 2017


Lignin Biosynthesis
journal, June 2003


Recent advances in understanding the pseudo-lignin formation in a lignocellulosic biorefinery
journal, January 2018

  • Shinde, Somnath D.; Meng, Xianzhi; Kumar, Rajeev
  • Green Chemistry, Vol. 20, Issue 10
  • DOI: 10.1039/C8GC00353J

Application of quantitative 31P NMR in biomass lignin and biofuel precursors characterization
journal, January 2011

  • Pu, Yunqiao; Cao, Shilin; Ragauskas, Arthur J.
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c1ee01201k

Lignification and lignin topochemistry — an ultrastructural view
journal, July 2001


Revealing the structure and distribution changes of Eucalyptus lignin during the hydrothermal and alkaline pretreatments
journal, April 2017


Phase Separation Behavior and Crew-Cut Micelle Formation of Polystyrene- b -poly(acrylic acid) Copolymers in Solutions
journal, February 1997

  • Zhang, Lifeng; Shen, Hongwei; Eisenberg, Adi
  • Macromolecules, Vol. 30, Issue 4
  • DOI: 10.1021/ma961413g

Transforming biomass conversion with ionic liquids: process intensification and the development of a high-gravity, one-pot process for the production of cellulosic ethanol
journal, January 2016

  • Xu, Feng; Sun, Jian; Konda, N. V. S. N. Murthy
  • Energy & Environmental Science, Vol. 9, Issue 3
  • DOI: 10.1039/C5EE02940F

Ethanol from lignocellulosic biomass techno-economic performance in short-, middle- and long-term
journal, April 2005

  • Hamelinck, Carlo N; Hooijdonk, Geertje van; Faaij, André PC
  • Biomass and Bioenergy, Vol. 28, Issue 4, p. 384-410
  • DOI: 10.1016/j.biombioe.2004.09.002

A simple process for lignin nanoparticle preparation
journal, January 2016

  • Lievonen, Miikka; Valle-Delgado, Juan José; Mattinen, Maija-Liisa
  • Green Chemistry, Vol. 18, Issue 5
  • DOI: 10.1039/C5GC01436K

Renewable acrylonitrile production
journal, December 2017

  • Karp, Eric M.; Eaton, Todd R.; Sànchez i. Nogué, Violeta
  • Science, Vol. 358, Issue 6368
  • DOI: 10.1126/science.aan1059

Persistence of engineered nanoparticles in a municipal solid-waste incineration plant
journal, May 2012

  • Walser, Tobias; Limbach, Ludwig K.; Brogioli, Robert
  • Nature Nanotechnology, Vol. 7, Issue 8
  • DOI: 10.1038/nnano.2012.64

Reductive lignocellulose fractionation into soluble lignin-derived phenolic monomers and dimers and processable carbohydrate pulps
journal, January 2015

  • Van den Bosch, S.; Schutyser, W.; Vanholme, R.
  • Energy & Environmental Science, Vol. 8, Issue 6
  • DOI: 10.1039/C5EE00204D

Synergetic Effects of Alcohol/Water Mixing on the Catalytic Reductive Fractionation of Poplar Wood
journal, October 2016

  • Renders, Tom; Van den Bosch, Sander; Vangeel, Thijs
  • ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 12
  • DOI: 10.1021/acssuschemeng.6b01844

Structural Characterization and Comparison of Switchgrass Ball-milled Lignin Before and After Dilute Acid Pretreatment
journal, August 2009

  • Samuel, Reichel; Pu, Yunqiao; Raman, Babu
  • Applied Biochemistry and Biotechnology, Vol. 162, Issue 1
  • DOI: 10.1007/s12010-009-8749-y

Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
journal, October 2015


Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production
journal, February 2007

  • Himmel, M. E.; Ding, S.-Y.; Johnson, D. K.
  • Science, Vol. 315, Issue 5813, p. 804-807
  • DOI: 10.1126/science.1137016

Effects of organosolv and ammonia pretreatments on lignin properties and its inhibition for enzymatic hydrolysis
journal, January 2017

  • Yoo, Chang Geun; Li, Mi; Meng, Xianzhi
  • Green Chemistry, Vol. 19, Issue 8
  • DOI: 10.1039/C6GC03627A

Lignin Structural Modifications Resulting from Ethanol Organosolv Treatment of Loblolly Pine
journal, January 2010

  • Sannigrahi, Poulomi; Ragauskas, Arthur J.; Miller, Stephen J.
  • Energy & Fuels, Vol. 24, Issue 1, p. 683-689
  • DOI: 10.1021/ef900845t

Effects of Two-Stage Dilute Acid Pretreatment on the Structure and Composition of Lignin and Cellulose in Loblolly Pine
journal, September 2008

  • Sannigrahi, Poulomi; Ragauskas, Arthur J.; Miller, Stephen J.
  • BioEnergy Research, Vol. 1, Issue 3-4, p. 205-214
  • DOI: 10.1007/s12155-008-9021-y

Understanding Lignin Fractionation and Characterization from Engineered Switchgrass Treated by an Aqueous Ionic Liquid
journal, March 2018


New Mechanism for the Catalytic Oxidation of Lignin to Vanillin
journal, July 2004


Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading
journal, January 2018

  • Schutyser, W.; Renders, T.; Van den Bosch, S.
  • Chemical Society Reviews, Vol. 47, Issue 3
  • DOI: 10.1039/C7CS00566K

Techno-economic evaluation of thermo-chemical biomass-to-ethanol
journal, April 2011


Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: A review
journal, July 2010


Alkaline lignin extracted from furfural residues for pH-responsive Pickering emulsions and their recyclable polymerization
journal, January 2012

  • Wei, Zengjiang; Yang, Yu; Yang, Rui
  • Green Chemistry, Vol. 14, Issue 11
  • DOI: 10.1039/c2gc36278c

Biomass pretreatments capable of enabling lignin valorization in a biorefinery process
journal, April 2016


Dynamic Model of Lignin Growing in Restricted Spaces
journal, January 1995


Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014

  • Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
  • Science, Vol. 344, Issue 6185, p. 1246843-1246843
  • DOI: 10.1126/science.1246843

Chemical transformations of Populus trichocarpa during dilute acid pretreatment
journal, January 2012

  • Cao, Shilin; Pu, Yunqiao; Studer, Michael
  • RSC Advances, Vol. 2, Issue 29
  • DOI: 10.1039/c2ra22045h

Lignin transformations for high value applications: towards targeted modifications using green chemistry
journal, January 2017

  • Gillet, S.; Aguedo, M.; Petitjean, L.
  • Green Chemistry, Vol. 19, Issue 18
  • DOI: 10.1039/C7GC01479A

Organosolv fractionating pre‐treatment of lignocellulosic biomass for efficient enzymatic saccharification: chemistry, kinetics, and substrate structures
journal, February 2017

  • Zhao, Xuebing; Li, Siming; Wu, Ruchun
  • Biofuels, Bioproducts and Biorefining, Vol. 11, Issue 3
  • DOI: 10.1002/bbb.1768

Formation of uniform colloidal spheres from lignin, a renewable resource recovered from pulping spent liquor
journal, January 2014

  • Qian, Yong; Deng, Yonghong; Qiu, Xueqing
  • Green Chemistry, Vol. 16, Issue 4
  • DOI: 10.1039/c3gc42131g

Steam explosion and its combinatorial pretreatment refining technology of plant biomass to bio-based products
journal, April 2015


Rapid and near-complete dissolution of wood lignin at ≤80°C by a recyclable acid hydrotrope
journal, September 2017


Structural changes of corn stover lignin during acid pretreatment
journal, April 2012

  • Moxley, Geoffrey; Gaspar, Armindo Ribeiro; Higgins, Don
  • Journal of Industrial Microbiology & Biotechnology, Vol. 39, Issue 9
  • DOI: 10.1007/s10295-012-1131-z

Increasing the revenue from lignocellulosic biomass: Maximizing feedstock utilization
journal, May 2017

  • Alonso, David Martin; Hakim, Sikander H.; Zhou, Shengfei
  • Science Advances, Vol. 3, Issue 5
  • DOI: 10.1126/sciadv.1603301

The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010

  • Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
  • Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
  • DOI: 10.1021/cr900354u

Opportunities and challenges in biological lignin valorization
journal, December 2016


Adipic acid production from lignin
journal, January 2015

  • Vardon, Derek R.; Franden, Mary Ann; Johnson, Christopher W.
  • Energy & Environmental Science, Vol. 8, Issue 2
  • DOI: 10.1039/C4EE03230F

Lignocellulose pretreatment severity – relating pH to biomatrix opening
journal, December 2010


Fractionation of Lignocellulosics by Steam-Aqueous Pretreatments [and Discussion]
journal, April 1987

  • Overend, R. P.; Chornet, E.; Gascoigne, J. A.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 321, Issue 1561
  • DOI: 10.1098/rsta.1987.0029

Valorizing Recalcitrant Cellulolytic Enzyme Lignin via Lignin Nanoparticles Fabrication in an Integrated Biorefinery
journal, February 2017


Combinatorial pretreatment and fermentation optimization enabled a record yield on lignin bioconversion
journal, January 2018


Enzymatic hydrolysis of lignocellulosic biomass from low to high solids loading
journal, December 2016


Lignin-first biomass fractionation: the advent of active stabilisation strategies
journal, January 2017

  • Renders, T.; Van den Bosch, S.; Koelewijn, S. -F.
  • Energy & Environmental Science, Vol. 10, Issue 7
  • DOI: 10.1039/C7EE01298E

Organosolv Delignification of Eucalyptus g lobulus :  Kinetic Study of Autocatalyzed Ethanol Pulping
journal, January 2000

  • Oliet, Mercedes; Rodríguez, Francisco; Santos, Aurora
  • Industrial & Engineering Chemistry Research, Vol. 39, Issue 1
  • DOI: 10.1021/ie9905005

Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment
journal, December 2008

  • Donohoe, Bryon S.; Decker, Stephen R.; Tucker, Melvin P.
  • Biotechnology and Bioengineering, Vol. 101, Issue 5
  • DOI: 10.1002/bit.21959

2D NMR characterization of wheat straw residual lignin after dilute acid pretreatment with different severities
journal, June 2017

  • Jensen, Anders; Cabrera, Yohanna; Hsieh, Chia-Wen
  • Holzforschung, Vol. 71, Issue 6
  • DOI: 10.1515/hf-2016-0112

Towards lignin-based functional materials in a sustainable world
journal, January 2016

  • Kai, Dan; Tan, Mein Jin; Chee, Pei Lin
  • Green Chemistry, Vol. 18, Issue 5
  • DOI: 10.1039/C5GC02616D

Lignin depolymerization for phenolic monomers production by sustainable processes
journal, July 2017

  • Fernández-Rodríguez, Javier; Erdocia, Xabier; Sánchez, Cristina
  • Journal of Energy Chemistry, Vol. 26, Issue 4
  • DOI: 10.1016/j.jechem.2017.02.007

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis
journal, June 2016

  • Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.
  • Angewandte Chemie International Edition, Vol. 55, Issue 29
  • DOI: 10.1002/anie.201510351

Fabrication of Environmentally Biodegradable Lignin Nanoparticles
journal, October 2012

  • Frangville, Camille; Rutkevičius, Marius; Richter, Alexander P.
  • ChemPhysChem, Vol. 13, Issue 18
  • DOI: 10.1002/cphc.201200537

Lignin extraction and catalytic upgrading from genetically modified poplar
journal, January 2018


Mass balance and transformation of corn stover by pretreatment with different dilute organic acids
journal, May 2012


Xylose yields and relationship to combined severity for dilute acid post-hydrolysis of xylooligomers from hydrothermal pretreatment of corn stover
journal, January 2015

  • Zhang, Taiying; Kumar, Rajeev; Tsai, Yueh-Du
  • Green Chemistry, Vol. 17, Issue 1
  • DOI: 10.1039/C4GC01283F

Characterization of milled wood lignin and ethanol organosolv lignin from miscanthus
journal, October 2009


Lignin depolymerization/repolymerization and its critical role for delignification of aspen wood by steam explosion
journal, November 2007


Preparation of lignin nanoparticles by chemical modification
journal, March 2014

  • Gilca, Iulian Andrei; Ghitescu, Roxana Elena; Puitel, Adrian Catalin
  • Iranian Polymer Journal, Vol. 23, Issue 5
  • DOI: 10.1007/s13726-014-0232-0

Synthesis and Characterization of Biodegradable Lignin Nanoparticles with Tunable Surface Properties
journal, June 2016


Producing wood-based nanomaterials by rapid fractionation of wood at 80 °C using a recyclable acid hydrotrope
journal, January 2017

  • Bian, Huiyang; Chen, Liheng; Gleisner, R.
  • Green Chemistry, Vol. 19, Issue 14
  • DOI: 10.1039/C7GC00669A

Chemical transformations of Populus trichocarpa during dilute acid pretreatment
text, January 2012

  • Cao, Shilin; Pu, Yunqiao; Studer, Michael Hans-Peter
  • Royal Society of Chemistry
  • DOI: 10.24451/arbor.10124

Works referencing / citing this record:

Cooperative valorization of lignin and residual sugar to polyhydroxyalkanoate (PHA) for enhanced yield and carbon utilization in biorefineries
journal, January 2019

  • Liu, Zhi-Hua; Shinde, Somnath; Xie, Shangxian
  • Sustainable Energy & Fuels, Vol. 3, Issue 8
  • DOI: 10.1039/c9se00021f