Organosolv pretreatment of cocoa pod husks: isolation, analysis and use of lignin from an abundant waste product

Daniel James Davidson; Fei Lu; Laura Faas; Daniel McLean Dawson; Geoffrey P.  Warren; Isabella Panovic; James Montgomery; Xiaoyan  Ma; Boris G.  Bosilkov; Alexandra Martha Zoya Slawin; Tomas Lebl; Afroditi  Chatzifragkou; Steve  Robinson; Sharon E. Ashbrook; Liz J.  Shaw; Smilja  Lambert; Isabella  Van Damme; Leonardo D.  Gomez; Dimitris  Charalampopoulos; Nicholas James Westwood

doi:10.1021/acssuschemeng.2c03670

Organosolv pretreatment of cocoa pod husks: isolation, analysis and use of lignin from an abundant waste product

Daniel James Davidson, Fei Lu, Laura Faas, Daniel McLean Dawson, Geoffrey P. Warren, Isabella Panovic, James Montgomery, Xiaoyan Ma, Boris G. Bosilkov, Alexandra Martha Zoya Slawin, Tomas Lebl, Afroditi Chatzifragkou, Steve Robinson, Sharon E. Ashbrook, Liz J. Shaw, Smilja Lambert, Isabella Van Damme, Leonardo D. Gomez, Dimitris Charalampopoulos, Nicholas James Westwood

Research output: Contribution to journal › Article › peer-review

Abstract

Cocoa pod husks (CPHs) represent an underutilized component of the chocolate manufacturing process. While industry’s current focus is understandably on the cocoa beans, the husks make up around 75 wt % of the fruit. Previous studies have been dominated by the carbohydrate polymers present in CPHs, but this work highlights the presence of the biopolymer lignin in this biomass. An optimized organosolv lignin isolation protocol was developed, delivering significant practical improvements. This new protocol may also prove to be useful for agricultural waste-derived biomasses in general. NMR analysis of the high quality lignin led to an improved structural understanding, with evidence provided to support deacetylation of the lignin occurring during the optimized pretreatment. Chemical transformation, using a tosylation, azidation, copper-catalyzed click protocol, delivered a modified lignin oligomer with an organophosphorus motif attached. Thermogravimetric analysis was used to demonstrate the oligomer’s potential as a flame-retardant. Preliminary analysis of the other product streams isolated from the CPHs was also carried out.

Original language	English
Journal	ACS Sustainable Chemistry & Engineering
Early online date	21 Sept 2023
DOIs	https://doi.org/10.1021/acssuschemeng.2c03670
Publication status	E-pub ahead of print - 21 Sept 2023

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Davidson_2023_ACS-SCE_Organosolv-pretreatment_CC
Copyright © 2023 The Authors. This article is licensed under CC-BY 4.0.
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CRITICAT - EASiCAT Studentship: CRITICAT - EASiCAT Studentship
Smith, A. D. (PI)
EPSRC
1/04/21 → 31/10/22
Project: Standard

Organosolv Pretreatment of Cocoa Pod Husks: Isolation, Analysis and Use of Lignin from an Abundant Waste Product (dataset)
Davidson, D. J. (Creator), Lu, F. (Creator), Faas, L. (Creator), Dawson, D. M. (Creator), Warren, G. P. (Creator), Panovic, I. (Creator), Montgomery, J. (Creator), Ma, X. (Creator), Bosilkov, B. G. (Creator), Slawin, A. M. Z. (Creator), Lebl, T. (Creator), Chatzifragkou, A. (Creator), Robinson, S. (Creator), Ashbrook, S. E. (Creator), Shaw, L. J. (Creator), Lambert, S. (Creator), Van Damme, I. (Creator), Gomez, L. D. (Creator), Charalampopoulos, D. (Creator) & Westwood, N. J. (Creator), University of St Andrews, 15 Apr 2024
DOI: 10.17630/83533b33-4273-4cff-95c4-cfda3d44b49e
Dataset

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Davidson, D. J., Lu, F., Faas, L., Dawson, D. M., Warren, G. P., Panovic, I., Montgomery, J., Ma, X., Bosilkov, B. G., Slawin, A. M. Z., Lebl, T., Chatzifragkou, A., Robinson, S., Ashbrook, S. E., Shaw, L. J., Lambert, S., Van Damme, I., Gomez, L. D., Charalampopoulos, D., & Westwood, N. J. (2023). Organosolv pretreatment of cocoa pod husks: isolation, analysis and use of lignin from an abundant waste product. ACS Sustainable Chemistry & Engineering. Advance online publication. https://doi.org/10.1021/acssuschemeng.2c03670

@article{9d92e1a5b210419d84e8e92f6f9364ac,

title = "Organosolv pretreatment of cocoa pod husks: isolation, analysis and use of lignin from an abundant waste product",

abstract = "Cocoa pod husks (CPHs) represent an underutilized component of the chocolate manufacturing process. While industry{\textquoteright}s current focus is understandably on the cocoa beans, the husks make up around 75 wt % of the fruit. Previous studies have been dominated by the carbohydrate polymers present in CPHs, but this work highlights the presence of the biopolymer lignin in this biomass. An optimized organosolv lignin isolation protocol was developed, delivering significant practical improvements. This new protocol may also prove to be useful for agricultural waste-derived biomasses in general. NMR analysis of the high quality lignin led to an improved structural understanding, with evidence provided to support deacetylation of the lignin occurring during the optimized pretreatment. Chemical transformation, using a tosylation, azidation, copper-catalyzed click protocol, delivered a modified lignin oligomer with an organophosphorus motif attached. Thermogravimetric analysis was used to demonstrate the oligomer{\textquoteright}s potential as a flame-retardant. Preliminary analysis of the other product streams isolated from the CPHs was also carried out.",

author = "Davidson, {Daniel James} and Fei Lu and Laura Faas and Dawson, {Daniel McLean} and Warren, {Geoffrey P.} and Isabella Panovic and James Montgomery and Xiaoyan Ma and Bosilkov, {Boris G.} and Slawin, {Alexandra Martha Zoya} and Tomas Lebl and Afroditi Chatzifragkou and Steve Robinson and Ashbrook, {Sharon E.} and Shaw, {Liz J.} and Smilja Lambert and {Van Damme}, Isabella and Gomez, {Leonardo D.} and Dimitris Charalampopoulos and Westwood, {Nicholas James}",

note = "The authors acknowledge the UK Biotechnology and Biological Sciences Research Council (BBSRC) for the financial support through the Global Challenges Research Fund (GCRF) Project “Development of novel value chain from cocoa pod husks in Indonesia: Technological, environmental and socio-economic challenges of a value chain” (BB/P022995/1). EaSI-CAT (Ph.D. studentship to D.J.D.). EPSRC-funded CRITICAT Centre for Doctoral Training (Ph.D. studentship to I.P.; EP/L016419/1).",

year = "2023",

month = sep,

day = "21",

doi = "10.1021/acssuschemeng.2c03670",

language = "English",

journal = "ACS Sustainable Chemistry & Engineering",

issn = "2168-0485",

publisher = "American Chemical Society (ACS)",

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Davidson, DJ, Lu, F, Faas, L, Dawson, DM, Warren, GP, Panovic, I, Montgomery, J, Ma, X, Bosilkov, BG, Slawin, AMZ , Lebl, T, Chatzifragkou, A, Robinson, S, Ashbrook, SE, Shaw, LJ, Lambert, S, Van Damme, I, Gomez, LD, Charalampopoulos, D & Westwood, NJ 2023, 'Organosolv pretreatment of cocoa pod husks: isolation, analysis and use of lignin from an abundant waste product', ACS Sustainable Chemistry & Engineering. https://doi.org/10.1021/acssuschemeng.2c03670

TY - JOUR

T1 - Organosolv pretreatment of cocoa pod husks

T2 - isolation, analysis and use of lignin from an abundant waste product

AU - Davidson, Daniel James

AU - Lu, Fei

AU - Faas, Laura

AU - Dawson, Daniel McLean

AU - Warren, Geoffrey P.

AU - Panovic, Isabella

AU - Montgomery, James

AU - Ma, Xiaoyan

AU - Bosilkov, Boris G.

AU - Slawin, Alexandra Martha Zoya

AU - Lebl, Tomas

AU - Chatzifragkou, Afroditi

AU - Robinson, Steve

AU - Ashbrook, Sharon E.

AU - Shaw, Liz J.

AU - Lambert, Smilja

AU - Van Damme, Isabella

AU - Gomez, Leonardo D.

AU - Charalampopoulos, Dimitris

AU - Westwood, Nicholas James

N1 - The authors acknowledge the UK Biotechnology and Biological Sciences Research Council (BBSRC) for the financial support through the Global Challenges Research Fund (GCRF) Project “Development of novel value chain from cocoa pod husks in Indonesia: Technological, environmental and socio-economic challenges of a value chain” (BB/P022995/1). EaSI-CAT (Ph.D. studentship to D.J.D.). EPSRC-funded CRITICAT Centre for Doctoral Training (Ph.D. studentship to I.P.; EP/L016419/1).

PY - 2023/9/21

Y1 - 2023/9/21

N2 - Cocoa pod husks (CPHs) represent an underutilized component of the chocolate manufacturing process. While industry’s current focus is understandably on the cocoa beans, the husks make up around 75 wt % of the fruit. Previous studies have been dominated by the carbohydrate polymers present in CPHs, but this work highlights the presence of the biopolymer lignin in this biomass. An optimized organosolv lignin isolation protocol was developed, delivering significant practical improvements. This new protocol may also prove to be useful for agricultural waste-derived biomasses in general. NMR analysis of the high quality lignin led to an improved structural understanding, with evidence provided to support deacetylation of the lignin occurring during the optimized pretreatment. Chemical transformation, using a tosylation, azidation, copper-catalyzed click protocol, delivered a modified lignin oligomer with an organophosphorus motif attached. Thermogravimetric analysis was used to demonstrate the oligomer’s potential as a flame-retardant. Preliminary analysis of the other product streams isolated from the CPHs was also carried out.

AB - Cocoa pod husks (CPHs) represent an underutilized component of the chocolate manufacturing process. While industry’s current focus is understandably on the cocoa beans, the husks make up around 75 wt % of the fruit. Previous studies have been dominated by the carbohydrate polymers present in CPHs, but this work highlights the presence of the biopolymer lignin in this biomass. An optimized organosolv lignin isolation protocol was developed, delivering significant practical improvements. This new protocol may also prove to be useful for agricultural waste-derived biomasses in general. NMR analysis of the high quality lignin led to an improved structural understanding, with evidence provided to support deacetylation of the lignin occurring during the optimized pretreatment. Chemical transformation, using a tosylation, azidation, copper-catalyzed click protocol, delivered a modified lignin oligomer with an organophosphorus motif attached. Thermogravimetric analysis was used to demonstrate the oligomer’s potential as a flame-retardant. Preliminary analysis of the other product streams isolated from the CPHs was also carried out.

U2 - 10.1021/acssuschemeng.2c03670

DO - 10.1021/acssuschemeng.2c03670

M3 - Article

SN - 2168-0485

JO - ACS Sustainable Chemistry & Engineering

JF - ACS Sustainable Chemistry & Engineering

ER -

Organosolv pretreatment of cocoa pod husks: isolation, analysis and use of lignin from an abundant waste product

Abstract

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Projects

CRITICAT - EASiCAT Studentship: CRITICAT - EASiCAT Studentship

Datasets

Organosolv Pretreatment of Cocoa Pod Husks: Isolation, Analysis and Use of Lignin from an Abundant Waste Product (dataset)

Cite this