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DOI 10.1007/s00253-014-5810-8
MINI-REVIEW
Received: 21 February 2014 / Revised: 30 April 2014 / Accepted: 1 May 2014 / Published online: 20 May 2014
# Springer-Verlag Berlin Heidelberg 2014
Introduction
Physical and chemical processes have been, and continue to
be, an integral aspect of modern life. This is mainly due to
their utility in the conversion of raw materials into valueadded products widely available on the market. However, in
recent years, there has been a growing interest in the use of
bio-based processes, which is attributable to the increasing
evidence of their advantages as alternatives to physicochemical processes and in some cases, the fact that they may
be the only viable option. Unlike physico-chemical processes,
the bio-based processes are considered more efficient, costeffective, environmentally friendly and sustainable; mostly
because they are not overly reliant on non-renewable resources such as fossil fuels. A combination of punitive action
and legislations introduced to improve protection of human
health and the environment, pressure from environmental
protection lobbyists and conscious proactive efforts, have seen
an upsurge in the search for alternative biotechnological processes. Consequently, biotechnology, and in particular biocatalysis, is now established as an important option in many
applications. The main success factors for biocatalytic routes
include the selectivity of the catalyst, the efficiency of the
process (Burton et al. 2002), potential reusability of the enzymes and their biodegradability (once no longer needed), and
general environmental considerations (Pollard and Woodley
2007). Thus, many industries are currently pursuing enzymatic approaches for the development of green chemistry technologies. Laccases are among the enzymes which are being
intensively investigated for various biotechnological
applications.
Laccase (benzenediol: oxygen oxidoreductase, EC
1.10.3.2) is a multi-copper-containing enzyme which performs one-electron oxidation of various substrates such as
diphenols, methoxy-substituted monophenols, as well as aromatic and aliphatic amines to form radicals and at the same
6526
Main reactions
Relevant reviews
6527
6528
Natural mediators include 4-hydroxybenzoic acid, 4hydroxybenzyl alcohol, aniline, phenol and phenolic compounds derived from lignin degradation such as
acetosyringone, acetovanillone, p-coumaric acid, ferulic acid,
syringaldehyde and vanillin (Kunamneni et al. 2008b). It has
been determined that natural mediators act very similar to
synthetic mediators and sometimes have a greater effect
(Fillat et al. 2010). Lignin-derived phenolic mediators have
successfully been applied to fungal laccase reactions involving dye decolourisation, delignification of paper pulp from
wood and non-wood fibres, delignification of flax pulp and
kenaf pulp, delignification of Eucalyptus wood chips, removal
of lipophilic extractives and the oxidation of PAH (Andreu
and Vidal 2011; Fillat et al. 2010; Rico et al. 2014). However,
one potential drawback is that in some instances, an opposite
effect can be achieved when using natural mediators vs synthetic mediators, e.g. Vila et al. (2011) reported on a laccase
that acted as a polymerising agent in the presence of natural
mediators, while acting as a delignifying agent in the presence
of a synthetic mediator. Aracri et al. (2009) reported a
similar result in their study on the bleaching of pulp
and effluents obtained from sisal pulp. In this study,
natural mediators resulted in laccase-mediated coupling
reactions rather than bleaching observed in the presence
of synthetic mediators. This could compromise the use
of the mediators in biofuel production. Such mediators
may be useful in laccase-assisted biografting applications (Aracri et al. 2009). Indeed, we have observed
that lignin model compounds guaiacylglycerol guaiacyl ether (erol) and syringylglycerol -guaiacyl
ether acted as mediators during laccase assisted coupling
of fluorophenols to the models (Kudanga et al. 2010c).
6529
a
COCH 3
MeO
OMe
HO
OH
CH 2OH
OH
OH
OH
Vanillyl alcohol
OMe
OMe
OH
OH
HO
MeO
OMe
OH
Gallic acid
Acetosyringone
COOH
Syringic acid
Vanillin
COCH 3
OH
OH
OH
NH 2
OH
MeO
OMe
OMe
OH
OH
p-coumaric acid
OH
Syringaldehyde Acetovanillone
CHO
OMe
OH
MeO
MeO
OMe
OH
MeO
OH
OH
2,6-dimethylphenol
HO
OCH 2CH 3
OMe
MeO
Sinapic acid
OH
OH
O
O
HO
MeO
OH
OH
HO
MeO
4-hydroxybenzoic acid
Ferulic acid
Cinnamic acid
OH
Coniferyl alcohol
H3C
O
N OH
H3C
CH3
N
H3C
OH
CH3
OH
SO3H
TEMPO
HPI
SPP-m
Violuric acid
OH
H 3C
N
N
OH
OH
OH
HBT
NHA
S
O
O
HO
S
N
N
OH
S
Phenol red
O
N
H3C
CH3
ABTS
6530
Fig. 2 Lignocellulose model structure, delignification strategies, and subsequent steps in the production of bioethanol (Adapted from Du et al. 2013b;
Asgher et al. 2014 with permission from ACS Publications and Elsevier)
through radical coupling to form inter-unit linkages such as O-4, -5, 5-5, -, 5-O-4 and the more recently discovered
dibenzodioxocin 5-5-O-4 (Karhunen et al. 1995a, b) (Fig. 3d
k).
The first comprehensive model of softwood lignin structure
was developed by Sakakibara (1980) based upon the degradation products formed from lignin samples as a result of
hydrolysis in aqueous dioxane and catalytic hydrogenolysis.
According to the Sakakibara model, the most prevalent interunit linkages were thought to be the -O-4 alkyl aryl ether, 5-5
biphenyl, -5 and 1 alkyl arene and -O-4 benzyl aryl ether
linkages. However, recent developments have shown that
there are very low levels, if any of -1 and non-cyclic -O-4
linkages (Kilpelinen et al. 1994; Ede and Kilpelinen 1995)
6531
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Fig. 4 A model of the structural features of gymnosperm lignin and its association with hemicellulose components to form lignin-carbohydrate
complexes (Chen and Sarkanen 2010). Reprinted with permission from Elsevier
from enzymes (Ding et al. 2012; Jung et al. 2000; Chang and
Holtzapple 2000) or by binding cellulolytic enzymes nonproductively (Kumar et al. 2012; Palonen et al. 2004;
Esteghlalian et al. 2001). A number of physical and chemical
pretreatment processes are being considered to minimise the
effect of lignin for example removal or breakdown of the
lignin component in order to expose the carbohydrate component to hydrolytic enzymes or hydrolysis of hemicellulose to
release monomeric sugars and soluble oligomers from the cell
wall matrix into the hydrolysate, leaving the lignin with the
residual substrate for subsequent removal after the hydrolysis
of cellulose or even after distillation. These include mechanical treatment, thermal treatment, acid treatment, alkali treatment, oxidative treatment with hydrogen peroxide or peracetic
acid, ammonia treatment, carbon dioxide treatment and using
various combinations of these physico-chemical processes.
However, these processes are in most cases unattractive as
they fail to meet the basic pretreatment requirements such as
avoiding the degradation or loss of carbohydrates, avoiding
the formation of by-products which are inhibitory to the
subsequent hydrolysis and fermentation processes, and being
cost-effective (Sun and Cheng 2002; Talebnia et al. 2010). For
example, acid treatment causes enzyme inhibition, and condensation and precipitation of solubilised lignin components
which decreases digestibility (Hendriks and Zeeman 2009). In
addition, acid treatment has a risk in the formation of volatile
degradation products and this carbon is lost during conversion
to ethanol (not a major issue in methane production, as volatile
products can be converted to methane). Steam pretreatment
causes production of furfural, hydroxy-methylfurfural and
soluble phenolic compounds which inhibit ethanol or biogas
production. Alkali treatment can cause solubilisation, redistribution and condensation of lignin and modifications in the
crystalline state of the cellulose which counteract the positive
effects of lignin removal and cellulose swelling (Gregg and
Saddler 1996). Oxidative pretreatment causes solubilisation of
lignin which inhibits conversion of the cellulose to ethanol or
methane, and also causes loss of sugars due to non-selective
oxidation. Ammonia treatment can only be carried out at
ambient temperatures for several days while carbon dioxide
treatment is carried out at high temperatures of up to 200 C.
In general, these physico-chemical processes are energy intensive, uneconomical and environmentally unfriendly.
In light of this, enzymatic approaches, using lignin
oxidising or delignifying enzymes are being considered for
the pretreatment of lignocellulosic materials either alone or in
combination with other pretreatment methods. Laccase is one
enzyme which is being intensively investigated for the pretreatment of lignocellulosic materials in bioethanol or biogas
production since it is one of the most common ligninolytic
enzymes. Table 2 summarises some of the research output in
the application of laccases in biogas and bioethanol production. As shown in Table 2, a number of substrates have been
6533
P. cinnabarinus
P. cinnabarinus
P. cinnabarinus
Modified strains of
Cerrena unicolor
Trametes versicolor
immobilised
Pycnoporus sp.
SYBC-L3
Streptomyces
griseorubens ssr38
P. cinnabarinus and
Trametes villosa
T. villosa
Trametes hirsuta
Ganoderma lucidum
Yarrowia lipolytica
Wheat straw
Wheat straw
Wheat straw
Switchgrass
Paddy straw
Wheat straw
Eucalypt (Eucalyptus
globulus) and
elephant grass
(Pennisetum
purpureum)
Perennial weed
Parthenium sp.
Steam explosion
Alone or with mediators; mild
acid/steam explosion
Steam explosion
Myceliophthora
thermophila
Eucalyptus
Combination treatment/mediator
Source of laccase
Substrate
Delignification
Removal of phenolic compounds
Delignification
Delignification
Delignification
Adsorption; polymerisation;
oligomerisation and removal
of phenolics
Delignification; modification
of biomass (increased porosity)
Delignification
Mode of action
Reference
6534
Appl Microbiol Biotechnol (2014) 98:65256542
Sclerotium sp.
Trametes sp.
T. versicolor
Wheat straw
Newspaper
Corn stover
Corncob residue
Commercial Novozyme
51003
Phellinus robustus, Pleurotus
eryngii, Irpex lacteus and
Poria subvermispora
Pleurotus ostreatus
Manure
None
Trametes hirsuta
Cyathus stercoreus
Trametes versicolor
Pycnoporus sanguineus
H275
Steam-pretreated
softwood
Sugarcane bagasse
Willow pretreated
with steam and
SO2
Wheat straw and
corn stover
N-hydroxy-N-phenylacetamide
(NHA) and N-acetoxy-Nphenylacetamide
Acid hydrolysis
Steam explosion
Wheat straw
Delignification
Delignification (partial)
Polymerisation of phenolic
compounds
Delignification
Delignification
Ceriporiopsis subvermispora
ATCC 90467, CZ-3 and
CBS 347.63
Delignification
Delignification
Delignification
Lignin modification
Delignification (probable;
not investigated)
Delignification
Loosening of lignin-carbohydrate
complex
Delignification/lignin
modification; de-inking
Mode of action
None
None
Japanese cedar
wood
Rice hull
Wheat straw
Pleurotus sp.
Ricinus communis
Steam explosion
Coltricia perennis
Commercial
Novozym 51003
Rice straw
(O. sativa L.)
Steam explosion
Combination treatment/mediator
Source of laccase
Substrate
Table 2 (continued)
Lu et al. (2010)
Yu et al. (2009)
Mukhopadhyay
et al. (2011)
Bruni et al. (2010)
Reference
Not stated
Pleurotus sp.
Myceliopthera thermophilae
(NS51003 Novozymes A/S)
Basidiomycete Euc-1
Saccharomyces cerevisiae
transformants
(with laccase gene)
T. versicolor, Bjerkandera
adusta, Ganoderma
applanatum and
Phlebia rufa
Cotton stalk
Ricinus communis
Wheat straw
Wheat straw
Spruce hydrolysate
supplemented with
coniferyl aldehyde
Wheat straw
Rhus vernificera
Rice straw
Delignification
None
Result includes effect of other enzymes since whole cells were used
Polymerisation and
detoxification
Delignification
Lignin oxidation
None
None
None
Alkali treatment
None
None
None
Lentinus edodesb
Mushroom logs
Delignification
Detoxification
None
Ureibacillus
thermosphaericus
Mode of action
Combination treatment/mediator
Source of laccase
Substrate
Table 2 (continued)
Haykir (2009)
Mukhopadhyay
et al. (2011)
Kaparaju and
Felby (2010)
Reference
6536
Appl Microbiol Biotechnol (2014) 98:65256542
were not well known at the time and were therefore presented
as suggestions or possible mechanisms. Besides
delignification, laccase or LMS can improve biofuels production through changes in the structure of the lignocellulose
microfiber which modify properties such as porosity, surface
area, and hydrophobicity resulting in the reduction of unproductive binding of cellulases (Moilanen et al. 2011). For
example, it has been observed that laccase-treatment of steam
pretreated spruce resulted in an increase in acidic groups
which would indicate a decrease in lignin hydrophobicity
and an increase in negative surface charge (Palonen and
Viikari 2004). This could result in electrostatic repulsion
toward cellulases which subsequently decreases the unproductive binding of cellulases. It is worth mentioning, however,
that lignin degradation using LMS can also be accompanied
by the release of inhibitory mono-aromatic phenolic compounds in the medium that decreases activity of cellulases
and other hydrolases (Gamble et al. 2000). Similarly, thermochemical pretreatment steps such as acid and steam explosion
typically lead to the production of furans, phenols and weak
acids which can inhibit the activity of cellulases and sugar
fermenting organisms. Treating the steam exploded material is
costly, requires special separation equipment (filtration) and
generates large amounts of wastewater. Subsequently, research efforts are now also being directed towards detoxification of hydrolysates through laccase-catalysed removal of
phenolic compounds and other inhibitory compounds such
as furans and weak acids (Moreno et al. 2013a, c, 2012;
Kolb et al. 2012; Parawira and Tekere 2011; Jnsson et al.
1998). The process involves laccase-catalysed oxidation of
the compounds to unstable radicals which couple to form
oligomeric and polymeric compounds which are less toxic to
enzymes required for subsequent processes than the corresponding monomeric units. The reaction mechanism is well
characterised. For example, we have shown recently that
laccase-catalysed oxidation of the phenolic molecule ferulic
acid led to coupling of the radicals through -5 and -
coupling to form dimers (Adelakun et al. 2012) and the
reaction also produces oligomers and polymers.
Polymerisation of phenolic compounds is so typical of
laccases that we have observed this phenomenon in virtually
all the coupling reactions we carried out with simple phenolic
compounds and oligomeric lignin models (Kudanga et al.
2009, 2010a, b, c; Widsten et al. 2010). Although physicochemical methods are also efficient at removing phenolics,
they also remove compounds such as acetic acid (Chandel
et al. 2007) which are important in biogas production. Some
oxidised mediators such as oxidised N-hydroxy-Nphenylacetamide can also inhibit the cellulases required for
subsequent hydrolysis (Palonen and Viikari 2004). The effect
of such inhibitors can be reduced by using excess substrate
(probably by offering sites for the radical attacks) or by using
acetylated mediators which are slowly released by a lipase in
6537
6538
pretreatment enzyme systems that can be applied in biobased processes for the production of biofuels.
Acknowledgments Financial support from the National Research
Foundation (NRF)South Africa and the Cape Peninsula University of
Technology Research Funding (URF) is gratefully acknowledged. Any
opinion, findings and conclusions or recommendations expressed in this
material are those of the author(s) and therefore the NRF does not accept
any liability in regard thereto.
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