Oxidoreductases As A Versatile Biocatalytic

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Review

Received: 16 November 2020 Revised: 26 March 2021 Accepted article published: 29 March 2021 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jctb.6743

Oxidoreductases as a versatile biocatalytic


tool to tackle pollutants for clean
environment – a review
Muhammad Bilal,a* Ahmad Reza Bagheri,b Débora S Vilar,c
Nahal Aramesh,b Katlin Ivon Barrios Eguiluz,c
Luiz Fernando Romanholo Ferreira,d Syed Salman Ashrafe and
Hafiz M N Iqbalf*

Abstract
With the growing population and rapid industrial development of the world, various pollutants — explicitly known as emerg-
ing pollutants (EPs) and including micro and nanoplastics, pharmaceuticals, hazardous dyes, steroid estrogen, and organic pol-
lutants — continue to enter into the environment and water sources. These EPs cause a variety of side effects and diseases, such
as cancer, neurotoxic and mutagenic effects, stomach cramps, intestinal disorders, loss of peripheral vision, deteriorated move-
ment coordination, and weakened muscles, even in low concentrations. The presence of EPs in the environment/water sources
affects humans and animals and disturbs ecological integrity. Therefore, removing these EPs from the environment with a
smart, greener, and environmentally competent technology has become a meaningful goal. Most of the EPs are stable in the
media, and their removal is a considerable scientific challenge. Different treatment methods, like adsorption and degradation
processes, have been used to eliminate these pollutants. Enzyme-mediated approaches hold immense prospects in environ-
mental cleanup and have been keenly explored recently. Many efforts have been made to apply biocatalytic-based materials,
like laccases and peroxidases, as unique tools alongside a powerful oxidation approach for the degradation and treatment of
EPs. These enzymes' unique properties in terms of excellent selectivity and exclusive catalytic features make them robust can-
didates for biocatalytic treatment. This work spotlights the biocatalytic properties and application of oxidoreductases to
remove EPs. The challenges, conclusive remarks, and standpoints for robust biocatalysts are also given.
© 2021 Society of Chemical Industry (SCI).

Keywords: environmental pollution; bioremediation; oxidoreductases; bio-catalysis; mitigation; pollutants; clean environment

INTRODUCTION
The rapid growth of the human population has introduced vari-
ous ecological impacts and affected water resources, which is * Correspondence to: M Bilal, School of Life Science and Food Engineering,
one of the most important resources for life.1 Due to the unprec- Huaiyin Institute of Technology, Huaian 223003, China, E-mail:
edented growth of the population, ecological pollution has also bilaluaf@hotmail.com; or HMN Iqbal, Tecnologico de Monterrey, School of
increased. This pollution has not only severe effects on humans Engineering and Sciences, Monterrey, 64849, Mexico. E-mail: hafiz.
iqbal@tec.mx
but also hazardous side effects on the environment. There are dif-
ferent factors, like human activities and different industries, that a School of Life Science and Food Engineering, Huaiyin Institute of Technology,
have played main roles in causing wastewater pollution. More- Huaian, 223003, China
over, various agricultural and industrial processes produce differ-
b Department of Chemistry, Yasouj University, Yasouj, Iran
ent types of contaminants and dispose them into the
environment. Some of these contaminants include glyphosate, c Graduate Program in Process Engineering, Tiradentes University (UNIT), Av.
acephate, Deet, Propoxur, Metaldehyde, Boric Acid, Diazinon, Murilo Dantas, 300, Farolândia, Aracaju-Sergipe, 49032-490, Brazil
Dursban, Malathion, heavy metals (e.g., arsenic, and mercury),
d Waste and Effluent Treatment Laboratory, Institute of Technology and
formaldehyde, Bisphenol A, Phthalates, fluoride, etc. The partial
Research (ITP), Tiradentes University (UNIT), Av. Murilo Dantas, 300, Farolân-
or incomplete removal of these pollutants can have different dia, Aracaju-Sergipe, 49032-490, Brazil
effects on human health.2 Emerging Pollutants (EPs) are a sub-
class of organic chemicals that have been detected in water e Department of Chemistry, College of Arts and Sciences, Khalifa University, Abu
Dhabi, United Arab Emirates
sources.3 They are a huge concern for water quality.4, 5 The pres-
ence of water pollutants, especially EPs, causes many problems f Tecnologico de Monterrey, School of Engineering and Sciences, Monterrey,
like cancer, stomach cramps, intestinal diseases, loss of peripheral 64849, Mexico
1

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www.soci.org M Bilal et al.

vision, deteriorated movement coordination, weakened muscles, EPs include three types of compounds: (i) newly developed com-
impaired speech and hearing, endocrine system disruption, and pounds that have entered the environment, (ii) compounds that
liver and nervous system damage and infections.6–8 Based on have been in the environment for a while, but researchers have
advanced analytical technologies, emerging organic micropollu- only recently distinguished them, and (iii) compounds that have
tants are generally defined as non-regulated organic trace pollut- been distinguished, but their effects have only been clarified
ants just recently introduced or newly detected in the recently.34, 36, 37 And now, a different class of EPs has been identi-
environment.9 EPs include different types of compounds and fied and categorized. Depending on the nature of pollutants and
materials.10 For example, micro and nanoplastics (MNPs) are a on the subsequent pollution of environmental components, pol-
kind of EPs detected in water sources. MNPs are a combination lution may be categorized as follows: air pollution, water pollu-
of plastics produced due to photo-oxidation by ultraviolet tion, soil/land pollution, noise pollution, and radioactive
(UV) radiation, physical abrasion by water currents carrying sand pollution. These pollutants can come from various sources.
grains, and biological degradation by organisms that render plas- Among the many different sources of pollutants, wastewater
tics brittle.11 Microplastics are defined as plastics with sizes rang- treatment plants (WWTPs) are the major source. WWTPs cannot
ing from 100 nm to 5 mm, and nanoplastics are materials with completely remove and degrade EPs. Therefore, they can enter dif-
sizes larger than 100 nm.12 This classification is based on the ferent water sources, like rivers and streams.38, 39 Figure 2 represents
European Commission's definition of engineered nanoparticles. different sources of pollutants.35 As can be seen from Fig. 2, EPs can
Due to plastics' broad application in different fields, from consum- be generated by different sources, like agriculture activities, domes-
ables to medical science, global plastic production exceeded tic, hospitals, industries, and spillages. In the following study, EPs are
320 million tons in 2018 and is expected to reach 1800 million collected from landfills, private septic tanks, and sewage treatment
tons in 2050. Only 6–26% of the produced plastics are recycled, plants. So far, different methods have been applied for the treat-
which means that up to 94% ends up in landfills (21–42%) or are ment of different contaminants. These methods include adsorption,
deliberately and/or accidentally released into the environment.13 degradation, and membrane-based methods.23, 24, 40–42 For
The ubiquity of MNPs, which have adverse effects on aquatic spe- instance, Jiang et al. applied the photo-Fenton degradation process
cies, ecosystems, and human health, has given rise to scientific to remove EPs like tetracycline hydrochloride (TCH), atrazin (ATZ),
and public concerns.14 These concerns arise because organisms alachor (ALA), tetrachlorophenol (4-CP), and methyl orange
can ingest MNPs, which causes MNPs to diffuse to cellular bound- (MO).18 They synthesized magnetic composites and applied them
aries and accumulate. These MNPs can then translocate through- for the degradation of pollutants. In the degradation experiment,
out the food chain. MNPs have adverse effects on bacteria, algae, tetracycline hydrochloride (TCH) (20.0 mg/L), atrazin (ATZ)
echinoderms, rotifers, mollusks, and arthropods.15 Pharmaceuti- (5.0 mg/L), alachor (ALA) (10.0 mg/L), tetrachlorophenol (4-CP)
cals are another major category of EPs.10 Pharmaceuticals are sub- (20.0 mg/L), and MO (20.0 mg/L) were selected as model pollutants
stances like antibiotics and disinfectants that have been to represent antibiotic, pharmaceutical, herbicide, industrial, and
discharged from hospitals' effluent into the environment.16 Phar- textile wastewater, respectively. The photo-Fenton degradation effi-
maceutical effluents have hazardous effects on both humans and ciencies of TCH were 52.1%, 60.8%, 85.2%, and 64.0% within 18 min
animals.17 In the case of pharmaceutical residues, it has been for different composites. The mechanism of degradation, the routes,
observed that secondary treatment technologies could degrade and effective factors on the degradation process were investigated.
only 18–32% of the pharmaceutical residues, a percentage that The synthesized photocatalyst improved the reaction rate from
is increased to 30–65% by tertiary treatment. Some of the contam- 0.0950 to 0.1520 min−1. The most important thing about a fabri-
ination effects are unknown, and since they are not monitored, cated catalyst is that it is applicable under visible light irradiation.
they can spread in the environment and water sources.18 Micro- Among the different methods for the removal of pollutants, hybrid
pollutants (MPs) are a kind of pollutant that has garnered much systems are prevalent. These methods are a combination of two
concern recently.19 Some of these pollutants can even enter into strategies that can enhance the efficiency of EPs removal. For
different water matrices of the environment, directly or indi- instance, Pirsaheb and co-workers used the hybrid system as a prac-
rectly.20, 21 These pollutants can form a wide range of compounds, tical way to manage hospital wastewater.43 Due to the low applica-
which can cause harmful side effects.22 These pollutants have bility of traditional systems for EPs treatment, they used a hybrid. In
been found and detected in diverse sources.23, 24 For example, their study, different contaminants, like ceftriaxone (CEF) and amox-
EPs can be found in soil, water, and the atmosphere, and they icillin (AMX), were removed. The removal efficiency was 87.53% (for
cause threats like cancers and chronic diseases.25–28 Based on a AMX) and 93.17% (for CEF). Another method for the removal of EPs
study performed in 2011, perfluorinated compounds can also is photocatalytic degradation. For example, the removal of buspir-
cause hazardous diseases.29 Moreover, pollutants like perfluor- one (anti-anxiety medicine) was performed using TiO2 under a
ooctanoate and perfluorooctane can also reduce humans' repro- xenon lamp.44 As one of the most applicable drugs, diclofenac has
ductive abilities.30 In addition, some pollutants tend to appear in been applied for the treatment of inflammatory diseases. Despite
high concentrations.31, 32 Many studies have focused on EPs its applicability, it has been considered an ecological pollutant that
because they can cause hazardous diseases. For instance, studies causes many concerns. This is because diclofenac can accumulate
showed that the nervous system enzyme in insects could be in the food chain in addition to entering water sources. Its concen-
affected by N, N-Diethyl-meta-toluamide (DEET), which can inhibit tration in water is up to 1.3 μg/L.45 Advanced Oxidation Process
acetylcholinesterase activity.33 To this end, coping with EPs is a (AOP) is another method for the degradation and removal of pollut-
difficult task that needs hard work and presents a variety of draw- ants. AOPs generally use the hydroxyl radicals, the ultimate oxidant
backs. One of the main limitations is that information about the for the remediation of organic contaminants in wastewater. AOP
properties of different methods for removing these pollutants is can combine with ozone (O3), a catalyst, or ultraviolet (UV) irradia-
incomplete.34 Also, these pollutants have different effects on tion to offer a powerful treatment of wastewater. Indeed, AOP is a
humans and animals, and the differences are hard to specify.2 method (which includes Photo-Fenton and photocatalysis using dif-
Figure 1 represents some of the adverse effects of pollutants.35 ferent catalysts, like TiO2) that can have synergistic effects for
2

wileyonlinelibrary.com/jctb © 2021 Society of Chemical Industry (SCI). J Chem Technol Biotechnol 2021
Oxidoreductases as a versatile biocatalytic tool www.soci.org

Figure 1. The side effects of different EPs. Reproduced from Ref. 35 with permission from Elsevier. Copyright © 2020 Elsevier B.V. License Number:
4992070890024.

degradation and removal of pollutants. Much effort has gone into peroxidase (HRP), are investigated and their application in the
investigating the ability of AOPs in the degradation of diclofenac. removal of EPs is assessed.
This degradation method is cheap and straightforward, while other
methods (like filtration and osmosis) are applicable but expensive.46
Despite the applicability and efficiency of different physical and
OXIDOREDUCTASES-MEDIATED
chemical methods, they are faced with main drawbacks. For exam-
ple, these methods are expensive and have insufficient affectivity, REMEDIATION — A BETTER STRATEGY FOR
they produce high amounts of sludge and form toxic materials A SAFE ENVIRONMENT
and products. To address these problems, the design and develop- As a new and promising method, the biological process uses dif-
ment of new approaches is vital. One of the most promising ferent enzymes (such as peroxidases) to remove EPs. Many differ-
methods for the degradation of different kinds of EPs is biological ent enzyme systems have been used in recent years and all the
systems, especially systems based on enzymes.21, 47 For the treat- approaches that use enzymes have unique features. One of the
ment and removal of EPs (like pharmaceuticals, Anthraquinone main advantages is that these methods apply to a wide range of
dyes, and organic contaminants) from the environment, and espe- concentrations of pollutants. They are also safe, cheap, easy, and
cially from the water, degradation, or remediation processes based can produce low levels of sludge.21, 52 Despite the unique advan-
on biosystems have been successfully applied. In biosystems, micro- tages of enzymatic remediation, it also has some limitations. For
organisms, such as enzymes, are applied.48–50 In the biodegradation instance, some of the catalysts are expensive and cannot be used
process, the microorganisms use the contaminants as a substrate, for several cycles. Also, enzymes may change under different con-
which can induce enzymes, and then transformed into materials ditions.36 To address these limitations, immobilization of the
with low toxicity.24, 27 Compared to other physiochemical methods, enzymes on various supports is an alternative method.53, 54
biodegradation processes have many unique advantages. For Recently, laccase and peroxidases have been extensively applied
instance, these methods are simple, easy, safe, and considered to to remove different pollutants.55, 56 The main application of these
be green methods.47, 51 Despite the unique advantages of biological enzymes is to catalyze the reactions based on the oxidation–
methods, however, they also have some limitations. For example, reduction process.57 Oxidoreductases include oxidases, peroxi-
dases, dehydrogenases, and oxygenases. Two of the most
they are longer processes, and some of the microorganisms may
important and common enzymes for enzymatic-remediation stud-
not be stable in different conditions.51 This manuscript begins by
ies are peroxidases and laccases due to their excellent ability to
investigating different treatment approaches for the removal of pol-
degrade various contaminants.58 The mechanism of action of these
lutants. In the next step, different oxidoreductases, like laccases, lig-
enzymes involves forming radicals that can degrade pollutants.
nin peroxidase (LiP), soybean peroxidase (SBP), and horseradish
3

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www.soci.org M Bilal et al.

Figure 2. Various sources of ECs/EPs, whereas ECs and EPs represent the same type of emerging compounds with hazardous concern. Reproduced from
Ref. 35 with permission from Elsevier. Copyright © 2020 Elsevier B.V. License Number: 4992070890024.

Lignin peroxidase produced from the fungal isolation of Trichoderma citrinoviride


Lignin peroxidase (LiP EC 1.11.1.14), also known as diarylpro- AJAC3 from sewage showed high efficiency (99.6%) degradation
pane oxygenase, is a glycoprotein belonging to a group of heme of 17 ⊎-estradiol (E2). In another study, authors reported that LiP
fungal peroxidases.59 White-rot fungi (WRF) are the most effec- could effectively remove E2, and such reactions are significantly
tive for delignification due to ligninolytic extracellular oxidative enhanced in the presence of VA.68, 69 It was also possible to
enzymes' production. Different types of WRF, like Phanerochaete observe the catalytic efficiency of LiP produced by Ganoderma
chrysosporium, Pleurotus ostreatus, Coriolus versicolor, Cyathus applanatum and Laetiporus sulphureus in the removal of cele-
stercoreus, and Ceriporiopsis subvermispora, can degrade lignin. coxib, diclofenac, and ibuprofen. Results indicated a reduction
WRF can also produce monomeric hemoproteins as multiple iso- of approximately 98%, 96%, and 95%, respectively, by combin-
enzymes and isoforms.60 In addition, WRF show higher efficiency ing the fungal intercropping.70, 71
than bacteria due to their strong ability to degrade and remove In another applicability, Shaheen et al.72 reported that Gano-
lignin through the delignification process.61 Figure 3 shows that derma lucidum IBL-05 immobilized LiP has catalytic potential in
this group uses H2O2 as a co-substrate and it catalyzes the oxida- the degradation of effluents (dye molecules). It was also an effi-
tion of veratryl alcohol (VA), which means a low molecular mass cient biocatalyst in the significant reduction of biochemical
redox mediator is generated endogenously.61 During catalysis, oxygen demand (BOD) (66.44–98.22%), chemical oxygen
organic acids can displace electrons from various organic com- demand (COD) (81.34–98.82%), and total organic carbon (TOC)
pounds, such as phenols (e.g., guaiacol, VA, catechol, singaric (80.21–97.77%) values. In general, the immobilized LiP deriva-
acid, and acetosyringone), aromatic amines, sulfur compounds, tives produced by the WRF exhibit higher catalytic efficiencies,
and non-saturated fatty acids. This, in turn, promotes highly term stability, and reusability.73 In another work, Ferreira-Leitao
reactive radicals that facilitate the oxidation of recalcitrant com- et al.74 determined that, although both biocatalysts were able to
pounds.62, 63 Catalytically, fungal peroxidase with higher oxida- oxidize the methylene blue (MB) dye, LiP presented good perfor-
tive potential stands out in its ability to destroy the plant cell mance. In addition, the increased capacity of purified LiP of
wall of lignin (phenolic compounds).62, 64 Its persistence in the Kocuria rosy MTCC 1532 was evident by the discoloration of
environment can promote breast carcinoma in female fish, 11 different dyes.75 LiP crude enzymatic extract contributes to
which propitiates the extermination of these organisms.65, 66 In improving the efficiency for the enhanced biodegradation of
the study conducted by Chatterjee and Abraham,67 crude LiP contaminants.74–76
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Figure 3. Mechanism of the catalyzing reaction of LiP in the degradation process. The compound undergoes oxidation by hydrogen peroxide to produce
the compound FeIV (Fe4 + − oxo and cationic radical porphyrin). The reduction of FeIV happens in two stages of an electron, which results in the formation
of another compound, FeIV (Fe4+ after the reduction of porphyrin cation radical), which is then converted to the native state of the enzyme. During the
catalytic cycle, two substrate molecules are oxidized by veratryl alcohol.

Horseradish peroxidase
General reaction : 2 Mn2 + +2 H + +H2 O2 →2 Mn3 + +2 H2 O ð1Þ
Horseradish peroxidase (HRP EC 1.11.1.7) is a metalloenzyme
studied extensively in the last several decades. It can be employed
In general, white-rot fungi MnP is considered one of the main
as both a fluid-phase and receptor-mediated probe. It is a
enzymes involved in biotechnology. Its ability to oxidize several
convenient tracer for immunocytochemistry; in situ, HRP
toxic compounds can be used in the biodegradation of lignin
can be detected by reaction with diamino-benzidine. Its concen-
humic acids.87 The ability to synthesize MnP is widespread among
tration can be measured by colorimetric assay using
the different taxonomic groups of WRF basidiomycetes and
O-phenylenediamine (OPD) and hydrogen peroxide.77, 78 Agostini
their potential interaction with a carbon source.87–89 Table 1
et al. investigated the ability of peroxidases for the effective reme-
represents the removal of EPs by several fungi of the basidiomy-
diation of 2,4-dichlorophenol. A high removal efficiency (93–95%)
cete class.90-96 One study found that MnP of P. Chrysosporium
was observed in a broad pH range of 3.0 to 9.0.79 The ability of
was the main enzyme involved in the discoloration of textile
HRP for the degradation of diclofenac was investigated using
dyes.97 This crude or purified enzyme's potential has also been
stopped-flow spectrometry. Results proved that diclofenac could
reported, mainly to discolor various types of synthetic dyes.93 In
be transformed into the dark, orange-colored product by using
the study directed by Zhang et al.,85 MnP crude and purified from
HRP in the presence of H2O2.80 In another study, Li and co-workers
the fungus Cerrena unicolor BBP6 was used in the discoloration of
immobilized HRP on electrospun magnetic nanofibers and used it
solutions of Congo red dyes, MO, Remazol bright blue R, bromo-
to remove phenols.81 Magnetic nanofibers were constructed
phenol blue, and crystal violet. The results proved that the puri-
using the electrospinning method and used for the immobiliza-
fied enzyme's presence favored the discoloration process
tion of HRP. The obtained nanofibers had a 200–400 nm diameter
(53.9%, 77.6%, 81%, 62.2%, and 80.9% removal efficiency, respec-
with a magnetic strength of 19.03 emu·g−1. The modified HRP
tively). Bilal et al.98 investigated the degradation of endocrine-
represented high catalytic activity. In another work, HRP has
disrupting compounds (EDCs), triclosan (TCS), and nonylphenol
immobilized on an alginate/chitosan/montmorillonite (SA/CS/
(NP). The results indicated that, after 1 h of incubation, the
MON) hybrid microsphere and used to remove Aflatoxin B1
enzyme removed about 70% of NP. From this, it was possible to
(AFB1).82 Figure 4 shows the fabrication process of (SA/CS/MON)
confirm that MnP was the enzyme that presented the highest
hybrid microsphere (a) and AFB1 immobilization (b).82 The immo-
TCS removal effect (94%) after 30 min of incubation.99 The same
bilization of HRP was carried out using covalent interactions. MON
TCS removal rate was achieved in the later study by Melo and
has a negative charge that can adsorb AFB1 along with CS chains.
Dezotti;100 meanwhile for TCS with HRP, about 45% of removal
Recently, Liu et al.83 used nanoencapsulation of HRP to improve
was obtained and, in 1 h, MnP reached 0.5 h (94%). This only
the removal of pollutants.
proves that MnP is promising in the removal of TCS compounds.
In another experiment proposed by Tsutsumi et al.,101 some pol-
Manganese peroxidase
lutants were removed. The results indicated that MnP provided
Manganese peroxidase (MnP) (or oxidoreductases, EC 1.11.1.13) is
the complete removal of both compounds, while the laccase
a glycated heme protein with a high molecular mass (ranges from
could only oxidize 70% and 60% of bisphenol A (BPA) and NP,
40–50 kDa) that has 43% of identity with LiP sequences.84 Its cat-
respectively. MnP was also studied in encapsulated form for the
alytic site promotes the oxidation of Mn2+ ions to Mn3+ (mainly
degradation of bisphenol A. The results indicated that these
chelated by oxalic acid) through the substrate H2O285 (Eqn 1).86
enzymes encapsulated in polyacrylamide hydrogel and pectin
5

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www.soci.org M Bilal et al.

Figure 4. Fabrication process of (SA/CS/MON) hybrid microsphere (a) and AFB1 immobilization (b). Reproduced from Ref. 82 with permission from Amer-
ican Chemical Society. Copyright © 2019 American Chemical Society.

achieved about 90% BPA degradation after 8 h of the process.102 could degrade SMX.47 Results showed that, in the presence of
In another study, Tran et al.103 studied the degradation of H2O2 and 1-hydroxybenzotriazole, SBP could degrade >80% of
10 selected pharmaceutically active compounds by whole fungal SMX. In other work, Mashhadi and co-workers applied SBP to treat
culture Trametes versicolor. It is vital to track the fungal species and HAs pyridines and quinolines, both of which have nitrogen.105
their variants to select the organisms that produce these lignin- According to mass spectrometry analysis, the obtained products
modifying enzymes. Thus, the use of enzymatic extracts of MnP of the treated process were dimers and trimmers.
in biotechnological processes can be the basis for developing One of the most common EDCs is TCS, which is an antibacterial
more efficient methods when applied in the degradation of recal- agent. Treatment of TCS can be done using the SBP-assisted bio-
citrant compounds, which is of great interest to the biochemical catalytic process.106 Moreover, SBP is useful for several cycles as a
and related industries. catalyst in different pH levels. It is worth mentioning that, from the
catalytic aspect, SBP was more useful than HRP towards TCS,
Soybean peroxidase which can be related to catalytic efficiency. SBP can facilitate the
Peroxidases are useful for the degradation of different EPs because oxidation of TCS using H2O2, which can produce phenoxyl radi-
they can catalyze oxidation–reduction reactions. Fungal laccase, cals. The other application of systems based on SBP is to remove
SBP (EC 1.11. 1.7), and HRP are the three classes of enzymes that various materials in different areas, like refinery and coal tar
have been widely studied. SBP has been extensively studied wastewater.107, 108 In earlier studies, the effects of dissolved
between these enzymes because it can be found in soybean hulls. organic matter (DOM) on removing TCS by SBP have been evalu-
In 2013, the mechanism of degradation of Crystal Ponceau 6R ated.106, 109 In systems that are based on SBP and use DOM, the
(CP6R) using commercially-available SBP enzymes was investigated products of transformation of TCS are not changed. All these com-
by Ali and co-workers.104 According to their results, the degradation pounds can be found in water. As a porotype thiazole pollutant,
of CP6R was based on two different routes: (i) cleavage of the sym- Thioflavin T's degradation was investigated using SBP and chloro-
metric azo bond, and (ii) cleavage of the asymmetric azo bond. peroxidase (CPO) to investigate the mechanism of degradation of
Results showed that SBP was able to complete the degradation of peroxidases.110 Results proved that SBP and CPO showed a high
the azo dye. Sulfamethoxazole (SMX) is a drug widely applied to ability to degrade Thioflavin T. 2-mercaptobenzothiazole (MBT)
treat various bacterial infections that can be found in wastewater. is another pollutant present in the environment and water. The
A study conducted by Al-Maqdi and co-workers proved that SBP main application of MBT is by companies in the construction of
6

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Table 1. Studies of degradation of several emerging pollutants related to the environment by different basidiomycete fungi of WRF

Basidiomycete Contaminant emerging Treatment conditions Removal (%) Reference

Phanerochaete Imidacloprid (IMI) The degradation system consisted of 97.37%, 82.0% and 73.52% at 90
chrysosporium incubation of the 3-day inoculum the initial IMI
fungus with 500 μM quinine and concentration of 10, 20,
10 mg/L IMI. and 30 mg/L, respectively.
Pleurotus pulmonarius Remazol brilliant blue R The conditions of the degradation 100% of RBBR, 47.3% of 91
(RBBR), Congo red, reaction were 0.5 mL of crude Congo red, 67.9% of
methylene blue, and ethyl enzymatic extract with 0.5 mL of each methylene blue, and
violet dye at pH 4.5. Samples incubated 40° 62.5% of ethyl violet.
C for 2 h.
Irpex lacteus Remazol Brilliant Violet 5R The fungus was grown at 28 °C with 90.06% of RBV5R, 91.82% of 92
(RBV5R), Direct Red 5B shaking at 150 rpm for 5 days. The DR5B, and 68.92% of IC.
(DR5B) and Indigo reaction mixture contained purified
Carmine (IC) CD2-MnP (0.25 U/mL) and dye
(50 mg/L).
Trametes sp. Fluorene (FLR), fluoranthene The fungus was grown at 28 °C with 93% of FLR, 96% of FLA, 98% 93
(FLA), pyrene (PYR), shaking at 150 rpm for 5 days. of PYR, 97% of PHE, and
phenanthrene (PHE), and Enzymatic degradation of PAHs was 98% of ANT.
anthracene (ANT) tested in 10% acetonitrile using a
50 mM malonate buffer (pH 4.5).
Nematoloma Glyphosate in vitro conditions after 24 h of 100% of degradation 94
frowardii incubation at 35 °C and 150 rpm. The
standard reaction mixture (1 mL)
contained 0.06 mM glyphosate,
1 mM MnSO4, 1% v/w Tween 80 and
pure enzyme (0.15 U ml-1) in 50 mM
Na acetate buffer (pH 4.5).
Phanerochaete Phenanthrene (PHE) Flasks containing 100 mL of 2% malt 55% of degradation 95
sordida extract liquid medium amended with
50 mg PHE/L. The flasks were
incubated for 14 days at 30 °C and
150 rpm.
Ganoderma lucidum Bentazon Incubation was carried out at 28°C for 90% of removal 96
7 days. The reaction mixture (2.0 mL)
contained (final concentration) in
acetate buffer 50 mM, pH 4.0, 10 mM
bentazon.

rubber products, such as tiers. In work performed for the degrada- compounds (i.e., it combines inorganic chloride substrates with
tion of Thioflavin T, results showed that MBT could also be H2O2).113 This versatile enzyme-containing heme at its active site
degraded using SBP and CPO. Recent research also applied SBP secreted by the marine fungus of Caldariomyces fumago (Leptoxy-
to remove 2,4-DCP (2,4-dichlorophenoxyacetic acid).111 SBP was phium fumago) is recognized as a versatile catalyst to its catalytic
achieved from a transgenic cultivar, and its purification was done activities, which include sulfoxidation, epoxidation, peroxidation,
with enzymatic characterization using pyrogallol as a standard hydroxylation, dismutation, oxidation, and halogenation of vari-
substrate. Based on the results, the optimum pH and temperature ous organic compounds.114, 115 For example, in the halogenation
for achieving SBP were 6.5 and 71.6 °C, respectively. After 1 and process, the catalytic cycle occurs through the in situ generations
24 h bioconversion, the 2,4-DCP was removed by 80% and 96%, of halogenating species, such as X− (Cl or Br), and/or the forma-
respectively. By applying soybean hulls for 24 h, the removal of tion of the hypohalogenate intermediate (HOX); both act as elec-
SBP was about 30%. In another study, pentachlorophenol (PCP) trophiles and then accept electrons, forming a bond with a
was removed from water using SBP.112 In this work, PCP was nucleophile and, thus, aids the halogenation of metabolites
removed in the presence of hydrogen peroxide at pH range 5–7. through the release of water (Fig. 5).116 The catalytic reaction cycle
Results proved that the addition of Fe(II) to the applied system of chloroperoxidase only involves the ferric and superior oxida-
can improve the removal percentage. tion states of iron. CPO initially reacts with hydrogen peroxide to
form a high-valued iron oxo derivative known in the peroxidase
Chloroperoxidase literature as compound I. This compound attacks aliphatic sub-
Chloroperoxidase (CPO) (EC 1.11.1.10) is part of the family of strates (R - H) and converts them to halogenated products
reducing oxide enzymes that catalyze the chlorination of organic (R - X), and the catalytic cycle returns to the resting state since
7

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www.soci.org M Bilal et al.

to cleave different substrates without needing any H2O2 sources.


For instance, Fig. 7 shows the hypothetical breakdown of lindane
in the presence of laccase.42 Laccases have been broadly used for
the removal of different EPs. Shao et al. immobilized laccase (Lac)
on hollow mesoporous carbon nanospheres as a noteworthy
immobilization approach and investigated its excellent stability
and efficiency for antibiotic contaminant removal.129 The maxi-
mum loading of Lac on the HMCs materials could reach 835 mg/g.
Figure 5. Catalytic cycle of the enzyme chloroperoxidase. Meanwhile, the immobilized Lac exhibited excellent thermo-sta-
bility, pH stability, storage stability, and reusability. The applied
system showed high efficiency for removing tetracycline hydro-
H2O2 displaces the water molecule.116 Generally, in the literature,
chloride (TCH) and ciprofloxacin hydrochloride (CPH) in the pres-
it is possible to observe the versatility of CPO enzymes, including:
ence of a redox mediator. The oxidation of the piperazinyl
the oxidation of complex oil fractions;117, 118 the generation of
substituent and its hydroxylation represent the major degrada-
bromohydrin, which is useful in the aroma and fragrance indus-
tion of CPH . In another study, Xu et al. assessed the degradation
try;118 and synthesis based on the free radicals of semiconductor
of several polycyclic aromatic hydrocarbons (PAHs) by laccase in
polymers, such as halogenous polyaniline,119 in the enzymatic
a reverse micelle system.130 Reverse micelles were prepared by
oxidation of azo dyes.120 Thus, this wide variety of reactions pro-
using isooctane to simulate oil. In this work, the effects of different
vided by CPO enzymes are of interest to industrial biotransforma-
factors (like pH, temperature, and ionic strength) on the degrada-
tion processes. In addition, its high catalytic activity was noted by
tion rate of PAHs were evaluated. According to the results, the
Li et al.109 Zhang et al.115 achieved high efficiency (98.64%) sulfa-
highest laccase activity was obtained at pH 4.2 and 30 °C with
methoxazole degradation in 20 min. Zhao et al.121 proposed a
60 mmol/L KCl. A facile strategy was performed for the prepara-
promising enzyme-catalyzed degradation of norfloxacin by CPO.
tion of a new class of nanozyme (denoted as CH-Cu) with
The results indicated degradation of 82.18% after 25 min of reac-
laccase-like activity inspired by the structure of the active site
tion at pH 5 and enzymatic concentration of 1.5 × 10−9 mol·L−1.
and the electron transfer pathway of laccase via the coordination
The results showed that all the compounds tested were substrates
of Cu+/Cu2+ with cysteine (Cys)-histidine (His) dipeptide. The pro-
for the oxidation of the enzyme, which was considered catalyti-
posed system represented high efficiency for the degradation of
cally active for transforming pharmaceutical micropollutants with
target pollutants. In other research, Lloret et al.128 investigated
high reaction rates and conversions. Gao et al.122 investigated the
the application of laccase to remove different hormones.
immobilization of CPO with glucose oxidase (GOx) in magnetic
Figure 7 shows the hypothetical breakdown of lindane. Carba-
graphene oxide. Thus, the results showed that immobilized CPO
mazepine (CBZ), as one of the most widely detected materials in
performance was considerably improved by GOx coupling. There-
the environment, is extensively applied in psychiatric medi-
fore, they have shown great potential as biological catalysts that
cine.131 CBZ has hazardous effects on animal and human health.
can be applied in the bioremediation of the emerging organic
The laccase based system was able to transform 95% of CBZ. This
micropollutants present in wastewater. However, additional stud-
process is done under optimum factors (at 35 °C, pH 6, with 60 U/
ies are required to identify the structures of degradation interme-
L).132 Recently, the removal of diclofenac was investigated by
diates produced during the bioremediation of this enzyme and
using laccase from Scytalidium thermophilum.133 Results proved
the approaches involving the use of co-solvents or two-phase sys-
the ability of laccase for the removal of diclofenac for the first time
tems to improve the catalytic reaction from an environmental
under optimum conditions. There are chemical compounds that
point of view.
are regularly used in personal care products and recent studies
are focusing on eco-friendly research for the analysis of these
Laccase compounds.134 Triclosan (TCS) has the main problem of not being
Laccases (Lac) (EC 1.10. 3.2), as a kind of oxidase with different removed using the classical process. regarding other words, when
coppers, are produced from different sources. Laccases are the it is consumed, it enters water sources and has a different concen-
most useful and suitable enzymes for large and industrial scales tration in different effluent (0.027–21.9 μg/L) with a removal per-
due to their unique properties for application in different biotech- centage of 58.0–97.5%.135 It is important to note that the
nological processes.123 The most important property of laccases is proposed wastewater is treated and recycled many times for irri-
that they do not need any nutrient supply while working with oxy- gation applications in arid or semi-arid regions. Therefore, TCS
gen as a co-factor.124 The processes based on the application of can also enter the food chain.136 Many studies have been per-
laccases are fast, and the kinetics of the reaction depends on formed, and the results proved that TCS has hazardous effects
the substrate's affinity. The obtained laccases from wood- due to its potential strength to be endocrine-disrupting.137 BPA
decaying fungi are in the hotspot due to their unique oxidation is a compound that has been extensively applied to different
ability.125 Generally, laccase enzymes can be classified into three industries to produce different products. BPA can enter the envi-
main categories that are based on the copper centers [type ronment from industrial units that produce it or combine it with
1 (blue), type 2 (normal), and type 3 or coupled binuclear]. Type plastics.138, 139 In a study done by Cabana group, NP, TCS, and
1 and type 2 each have only one Cu atom, while type 3 has two BPA were removed using the biocatalytic process based on the
Cu atoms.126 Compared to enzymes based on the plant, the lac- application of the enzyme extracted and obtained from Coriolop-
cases have a higher potential for redox that shows the higher cat- sis polyzona. Based on the statistical analysis, NP and TCS were
alytic efficiency of laccases.127, 128 Atmospheric oxygen can be removed in experimental conditions at 50 °C and the BPA was
applied as electron acceptor and can be used for consumption. removed at 40 °C, while the best removal of these materials
Figure 6 shows some productions of the pollutants after treat- occurred at pH 5.0. In a concentration of 5 mg·L−1 and after the
ment using an enzyme system.42 Laccases have the main property 4-h reaction, the NP and BPA were removed entirely, while
8

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Figure 6. Some productions of the pollutants after treatment using enzyme system. Reprinted from Ref. 42 with permission under Creative Commons
Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). Copyright (2019) the authors. Licensee MDPI, Basel, Switzerland.

complete removal of TCS occurred after either 4 or 8 h by laccase- complexes were able to remove 99% and 93.3% of
assisted treatment.140 The removal of NP and TCS as two EDCs was 2,4-dinitrophenol, respectively. To date, different reports have
investigated using the biotechnological aptitude of different lac- focused on the degradation of alkylphenols. There are a few stud-
cases that were thermally stable. Their names were LacI and LacII. ies about the scrutinization of transformation products like oligo-
Based on the HPLC analysis, NP and TCS were degraded using LacI mers and polymers. Molecular docking was employed to provide
and LacII more than 95%. Also, compared to LacII, LacI repre- an insight into the detailed interaction mechanism between these
sented more biocatalyst activity for the oxidation target com- isomers and laccase. Results revealed that the interactions
pound.141 In a study that was carried out by Saito and co- between laccase and isomers were affected by structural charac-
workers, NP was removed completely.142 By applying ABTS as a teristics of the alkyl chain (position and branching degree). The
mediator and laccase as a catalytic agent, TCS was obliterated binding affinities between linear isomers and laccase were para-
after 30 min at pH 5.0 and 25 °C.143 Moreover, results proved that position < meta-position < ortho-position. In addition, hydropho-
the application of different ions could decrease the removal per- bic contacts between laccase and NP or OP isomers were found to
centage. Tsutsumi et al. investigated removing BPA and NP be necessary, while H-bonds were optional.146 Table 2 shows stud-
(5 ppm), and results showed that they can both be removed ies aimed at using bioassays with different test organisms that
completely.101 NPs and Ops as alkylphenols are distinctive EDCs have already been performed in several chemical compounds pre-
that are extensively present in the environment. Dubroca and sent in wastewater after synthesis with oxidoreductases
co-workers proved that T. versicolor laccase could degrade NP into enzymes.99,100,115,121,133,147-149
CO2 in an oxidation-dependent process.144 In another study,
2,4-dinitrophenol was removed from water using free and immo- ANALYTICAL CONSIDERATIONS –
bilized laccases.145 2,4-dinitrophenol is very toxic and shows high
resistance to degradation. Laccase enzyme can decompose phe- QUANTIFICATION AND TOXICITY
nolic compounds. Laccase complexes with montmorillonite K10 EVALUATION MEASURES
and zeolite were used for the decomposition of Different techniques can investigate the performance of the degra-
2,4-dinitrophenol. Figure 8 represents the immobilization process dation of the polymer that is catalyzed by microorganisms. These
of laccase.145 Laccase-zeolite and laccase-montmorillonite techniques can evaluate various aspects of the formation of products
9

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www.soci.org M Bilal et al.

Figure 7. The hypothetical breakdown of lindane in the presence of laccase. Reprinted from Ref. 42 with permission under Creative Commons Attribu-
tion (CC BY) license (http://creativecommons.org/licenses/by/4.0/). Copyright (2019) the authors. Licensee MDPI, Basel, Switzerland.

and can alter the properties (thermodynamics, rheological, and CHALLENGES AND STANDPOINTS FOR
mechanical) of microorganisms' growth on the chemical com-
ROBUST BIOCATALYSTS
pound.150 However, few reports exist regarding the follow-up of bio-
The degradation of organic pollutants by enzymes is a versatile
logical degradation because this process depends on external factors
method. However, the application of oxidoreductase enzymes
(oxygen, temperature, pH, and inoculum) that will dictate aerobiosis
has not been carried out on a large scale. It is essential to direct
conditions. In this sense, several traditional techniques (such as
future studies for alternative biodegradation processes or to
chemical and physical methods) are used to analyze the degradation
improve existing treatment approaches to enhance mineraliza-
by-products catalyzed by oxidoreductase enzymes.151, 152 It is indis-
tion.154 Significant bottlenecks in protein engineering include
pensable for economically viable production on a large scale to eval- increased operational stability, (explicitly, H2O2 stability in the
uate the toxic by-products generated or the remnants of the case of peroxidases), expansion of the variety of substrates by
biological process because of various chemicals. In this case, it is nec- increasing the enzyme's redox potential, and the constitution of
essary to employ bioassays using test organisms to monitor the con- a heterologous expression system for large-scale production.36
taminants' toxic levels. Since toxicity tests assess toxic substances' This last prerequisite is also used in the heterologous production
effect on biological systems, chemical analyses identify and quantify of recombinant enzymes that can maintain adequate folding of
these substances. Several aquatic biota representatives must evalu- proteins and increase their commercial production and applica-
ate toxicity tests, mostly when chosen from different trophic levels tion in enzyme engineering.155 Enzymes can also be isolated from
of the food chain.153 Thus, it is necessary to use more than one extremophiles obtained by classical protein engineering.156
aquatic biota species in toxicological tests so that the results Robust and highly efficient biocatalysts were designed for aug-
obtained with a more sensitive organism are compared and mented biocatalytic degradation of a range of different harmful
provide the toxicity levels of contaminants accumulated in the water pollutants. Molecular engineering approaches performed mainly
body.154
10

in the enzyme's catalytic regions can reduce redox limitations,

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Oxidoreductases as a versatile biocatalytic tool www.soci.org

Figure 8. The immobilization process of laccase on montmorillonite K10 and zeolite minerals. Reproduced from Ref. 145 with permission from Elsevier.
Copyright © 2020 Elsevier Ltd. License Number: 4992071323669.

Table 2. Application of bioassays in the evaluation of different chemical compounds treated with peroxidase enzymes

Enzyme Composite Response Reference

HRP Reactive Blue 19 and After enzymatic discoloration, they showed higher toxicity against D. magna 147
Reactive Black dyes (toxicity factor 16) and V. fischeri (toxicity factor 32)
TCS 95% reduction of both the growth of E. coli K12 cultures and TCS concentration. 100
Laccase BPA The initial toxicity expressed as inhibition of V. fischeri bioluminescence was 148
reduced from 85 to 4.65%.
DCF Biomass of D. salina was reduced by 63% and 72% using 100 and 200 mg/L of 133
DCF solution, respectively, before the laccase treatment.
MnP TCS Removal rate of 94% in 30 min and complete loss of growth inhibition of bacteria 99
(E. coli and B. subtilis) and algae (P. subcapitata)
Tween 8 24-h treatment the Tween 80 system resulted in a complete loss of B. subtilis 149
growth inhibition by MCZ and decreased 78% growth inhibition of the P.
subcapitata by SER.
CPO Sulfamethoxazole Enzymatic treatment increased the concentration of sulfamethoxazole (went 115
from 0.142 to 0.221 mg/L) at the end of the degradation, i.e., it increased about
56% of EC50 in 72 h with algae Chlorella Pyrenoidosis.
Norfloxacin Chlorella pyrenoidosa indicated that the measured 72-h EC50 value increased 121
from 0.0293 to 0.3668 mg/L with the increase of degradation efficiency of
norfloxacin.

Abbreviations: HRP - horseradish peroxidase, TCS - triclosan, BPA - bisphenol A, DCF - diclofenac, MnP - manganese peroxidase, CPO - chloroperox-
idase, MCZ - miconazole, SER - sertraline.

leading to increased varieties of substrates. The efficient regula- reaction conditions and are often inactivated in non-aqueous
tion of oxidoreductase enzymes can be achieved by optimizing solutions.159 Thus, it is necessary to improve protein stability
a culture medium's composition with the supplementation of and enzyme activity because this can increase the enzyme chyme
specific stimulating components of the strain, such as salts, low combinations of bio or inorganic catalysts. Thereafter, stabiliza-
molecular weight phenolic compounds, and nutrition sources.157 tion mutations occur based on the structure of the enzyme and
The inclusion of redox mediators can expand the substrates are produced through directed evolution. This engineering
range. These low molecular weight molecules are not regener- approach promotes the improvement of enzyme activity, stability,
ated and are non-recyclable during biocatalysis, resulting in toxic and specificity.160 Besides, the immobilization of enzymes
substances.158 Furthermore, compared to inorganic catalysts, bio- appears as an alternative to promote operational stability, ease
catalysts can be much more selective and be able to distinguish of storage, handling, reusability, recycling, and continuous pro-
cessing.161–167 Therefore, these new possibilities for catalyst
11

between functional groups. However, they require moderate

J Chem Technol Biotechnol 2021 © 2021 Society of Chemical Industry (SCI). wileyonlinelibrary.com/jctb
www.soci.org M Bilal et al.

combinations open promising prospects for new technologies in remediation of emerging environmental pollutants, in Emerging
the field of green chemistry and should become the focus of Technologies in Environmental Bioremediation. Amsterdam,
Netherlands: Elsevier, pp. 165–196 (2020).
future research and advances in protein engineering. 9 Richardson SD, Water analysis: emerging contaminants and current
issues. Anal Chem 81:4645–4677 (2009).
10 Khan NA, Khan SU, Ahmed S, Farooqi IH, Yousefi M, Mohammadi AA
CONCLUDING REMARKS et al., Recent trends in disposal and treatment technologies of
The enzymatic process based on laccases and peroxidases was emerging-pollutants- a critical review. TrAC Trends Anal Chem 122:
considered a promising technology in the treatment of EPs due 115744 (2020).
11 Rajala K, Grönfors O, Hesampour M and Mikola A, Removal of micro-
to its high specificity, allowing a higher yield of the process and plastics from secondary wastewater treatment plant effluent by coa-
biodegradable products while reducing the amount of waste gen- gulation/flocculation with iron, aluminum and polyamine-based
erated. Immobilized enzymatic materials have also received chemicals. Water Res 183:116045 (2020).
increasing attention as a strategy to improve the enzyme's stabil- 12 Hou L, Kumar D, Yoo CG, Gitsov I and Majumder EL-W, Conversion
and removal strategies for microplastics in wastewater treatment
ity and reuse. In addition to this, advances in protein engineering plants and landfills. Chem Eng J 406:126715 (2021).
remarkably allow the development of biocatalytic materials with 13 Chen G, Fu Z, Yang H and Wang J, An overview of analytical methods
unique properties and better performance to treat recalcitrant for detecting microplastics in the atmosphere. TrAC Trends Anal
contaminants. However, immobilized enzymatic materials still Chem 130:115981 (2020).
needs to be studied in more depth to elucidate its reaction mech- 14 Veerasingam S, Ranjani M, Venkatachalapathy R, Bagaev A,
Mukhanov V, Litvinyuk D et al., Microplastics in different environ-
anisms and operational optimization. Therefore, it is essential to mental compartments in India: analytical methods, distribution,
expand the applications of these oxidoreductase enzymes for associated contaminants and research needs. TrAC Trends Anal
synthesizing biodegradable products to reduce or eliminate Chem 133:116071 (2020).
organic contaminants. In future, biocatalysis engineering will play 15 He D, Luo Y, Lu S, Liu M, Song Y and Lei L, Microplastics in soils: ana-
lytical methods, pollution characteristics and ecological risks. TrAC
an essential role in developing new biocatalysts for the efficient Trends Anal Chem 109:163–172 (2018).
degradation of persistent organic pollutants. 16 Patel M, Kumar R, Kishor K, Mlsna T, Pittman CU and Mohan D, Phar-
maceuticals of emerging concern in aquatic systems: chemistry,
occurrence, effects, and removal methods. Chem Rev 119:3510–
ACKNOWLEDGEMENTS 3673 (2019).
The listed authors are highly obliged to their institutes and univer- 17 Choi Y, Lee J-H, Kim K, Mun H, Park N and Jeon J, Identification, quan-
tification, and prioritization of new emerging pollutants in domestic
sities for the literature services. Generous support from Khalifa and industrial effluents, Korea: application of LC-HRMS based sus-
University (CIRA-2020-046) is also graciously acknowledged. Con- pect and non-target screening. J Hazard Mater 402:123706 (2021).
sejo Nacional de Ciencia y Tecnología (CONACYT) is thankfully 18 Jiang J, Wang X, Liu Y, Ma Y, Li T, Lin Y et al., Photo-Fenton degrada-
acknowledged for partially supporting this work under Sistema tion of emerging pollutants over Fe-POM nanoparticle/porous and
ultrathin g-C3N4 nanosheet with rich nitrogen defect: degradation
Nacional de Investigadores (SNI) program awarded to Hafiz mechanism, pathways, and products toxicity assessment. Appl Catal
M.N. Iqbal (CVU: 735340). Environ 278:119349 (2020).
19 Teodosiu C, Gilca A-F, Barjoveanu G and Fiore S, Emerging pollutants
removal through advanced drinking water treatment: a review on
CONFLICT OF INTEREST processes and environmental performances assessment. J Clean
The listed authors declare no conflict of interest. Prod 197:1210–1221 (2018).
20 Sauvé S and Desrosiers M, A review of what is an emerging contam-
inant. Chem Cent J 8:1–7 (2014).
21 Bilal M and Iqbal HM, Persistence and impact of steroidal estrogens
REFERENCES on the environment and their laccase-assisted removal. Sci Total
1 Peña-Guzmán C, Ulloa-Sánchez S, Mora K, Helena-Bustos R, Lopez- Environ 690:447–459 (2019).
Barrera E, Alvarez J et al., Emerging pollutants in the urban water 22 Lapworth D, Baran N, Stuart M and Ward R, Emerging organic con-
cycle in Latin America: a review of the current literature. J Environ taminants in groundwater: a review of sources, fate and occurrence.
Manage 237:408–423 (2019). Environ Pollut 163:287–303 (2012).
2 Deblonde T, Cossu-Leguille C and Hartemann P, Emerging pollutants 23 Deegan A, Shaik B, Nolan K, Urell K, Oelgemöller M, Tobin J et al.,
in wastewater: a review of the literature. Int J Hyg Environ Health 214: Treatment options for wastewater effluents from pharmaceutical
442–448 (2011). companies. Int J Environ Sci Technol 8:649–666 (2011).
3 Vanderford BJ and Snyder SA, Analysis of pharmaceuticals in water by 24 Ahmed MB, Zhou JL, Ngo HH, Guo W, Thomaidis NS and Xu J, Pro-
isotope dilution liquid chromatography/tandem mass spectrome- gress in the biological and chemical treatment technologies for
try. Environ Sci Technol 40:7312–7320 (2006). emerging contaminant removal from wastewater: a critical review.
4 Petrie B, Barden R and Kasprzyk-Hordern B, A review on emerging J Hazard Mater 323:274–298 (2017).
contaminants in wastewaters and the environment: current knowl- 25 Borrull J, Colom A, Fabregas J, Borrull F and Pocurull E, Liquid chroma-
edge, understudied areas and recommendations for future monitor- tography tandem mass spectrometry determination of 34 priority
ing. Water Res 72:3–27 (2015). and emerging pollutants in water from the influent and effluent of
5 Bilal M, Adeel M, Rasheed T, Zhao Y and Iqbal HM, Emerging contam- a drinking water treatment plant. J Chromatogr A 1621:461090
inants of high concern and their enzyme-assisted biodegradation–a (2020).
review. Environ Int 124:336–353 (2019). 26 Robichaud A, An overview of selected emerging outdoor airborne
6 Kumar M, Borah P and Devi P, Chapter 3 - Priority and emerging pol- pollutants and air quality issues: the need to reduce uncertainty
lutants in water, in Inorganic Pollutants in Water, ed. by Devi P, about environmental and human impacts. J Air Waste Manage Assoc
Singh P and Kansal SK. Amsterdam, Netherlands: Elsevier, pp. 33– 70:341–378 (2020).
49 (2020). 27 Tran NH, Urase T, Ngo HH, Hu J and Ong SL, Insight into metabolic
7 Roy N, Alex SA, Chandrasekaran N, Mukherjee A and Kannabiran K, A and cometabolic activities of autotrophic and heterotrophic micro-
comprehensive update on antibiotics as an emerging water pollut- organisms in the biodegradation of emerging trace organic contam-
ant and their removal using nano-structured photocatalysts. J Envi- inants. Bioresource Technol 146:721–731 (2013).
ron Chem Eng 9(2):104796 (2020). 28 Belhaj D, Baccar R, Jaabiri I, Bouzid J, Kallel M, Ayadi H et al., Fate of
8 Agrawal K, Bhatt A, Chaturvedi V and Verma P, Bioremediation: an selected estrogenic hormones in an urban sewage treatment plant
effective technology toward a sustainable environment via the in Tunisia (North Africa). Sci Total Environ 505:154–160 (2015).
12

wileyonlinelibrary.com/jctb © 2021 Society of Chemical Industry (SCI). J Chem Technol Biotechnol 2021
Oxidoreductases as a versatile biocatalytic tool www.soci.org

29 Bonefeld-Jorgensen EC, Long M, Bossi R, Ayotte P, Asmund G, 51 Rauf MA and Salman Ashraf S, Survey of recent trends in biochemi-
Krüger T et al., Perfluorinated compounds are related to breast can- cally assisted degradation of dyes. Chem Eng J 209:520–530 (2012).
cer risk in Greenlandic Inuit: a case control study. Environ Health 10: 52 Bilal M, Iqbal HMN and Barceló D, Persistence of pesticides-based
88 (2011). contaminants in the environment and their effective degradation
30 Vélez M, Arbuckle T and Fraser W, Maternal exposure to perfluori- using laccase-assisted biocatalytic systems. Sci Total Environ 695:
nated chemicals and reduced fecundity: the MIREC study. Hum 133896 (2019).
Reprod 30:701–709 (2015). 53 Bilal M, Zhao Y, Noreen S, Shah SZH, Bharagava RN and Iqbal HMN,
31 Kelly KR and Brooks BW, Global aquatic hazard assessment of cipro- Modifying bio-catalytic properties of enzymes for efficient biocatal-
floxacin: exceedances of antibiotic resistance development and eco- ysis: a review from immobilization strategies viewpoint. Biocatal Bio-
toxicological thresholds, in Progress in Molecular Biology and transformation 37:159–182 (2019).
Translational Science. Cambridge, United States: Elsevier, pp. 59–77 54 Sheldon RA, Cross-linked enzyme aggregates as industrial biocata-
(2018). lysts. Org Process Res Dev 15:213–223 (2011).
32 Nakayama SF, Yoshikane M, Onoda Y, Nishihama Y, Iwai-Shimada M, 55 Zdarta J, Meyer AS, Jesionowski T and Pinelo M, Developments in sup-
Takagi M et al., Worldwide trends in tracing poly-and perfluoroalkyl port materials for immobilization of oxidoreductases: a comprehen-
substances (PFAS) in the environment. TrAC Trends Anal Chem 121: sive review. Adv Colloid Interface Sci 258:1–20 (2018).
115410 (2019). 56 Zdarta J, Meyer AS, Jesionowski T and Pinelo M, Multi-faceted strat-
33 Corbel V, Stankiewicz M, Pennetier C, Fournier D, Stojan J, Girard E egy based on enzyme immobilization with reactant adsorption
et al., Evidence for inhibition of cholinesterases in insect and mam- and membrane technology for biocatalytic removal of pollutants: a
malian nervous systems by the insect repellent deet. BMC Biol 7:1– critical review. Biotechnol Adv 37:107401 (2019).
11 (2009). 57 Bilal M, Rasheed T, Nabeel F, Iqbal HMN and Zhao Y, Hazardous con-
34 Geissen V, Mol H, Klumpp E, Umlauf G, Nadal M, van der Ploeg M et al., taminants in the environment and their laccase-assisted degrada-
Emerging pollutants in the environment: a challenge for water tion – a review. J Environ Manage 234:253–264 (2019).
resource management. Int Soil Water Conserv Res 3:57–65 (2015). 58 Alneyadi AH, Rauf MA and Ashraf SS, Oxidoreductases for the remedi-
35 Morsi R, Bilal M, Iqbal HM and Ashraf SS, Laccases and peroxidases: ation of organic pollutants in water – a critical review. Crit Rev Bio-
the smart, greener and futuristic biocatalytic tools to mitigate recal- technol 38:971–988 (2018).
citrant emerging pollutants. Sci Total Environ 714:136572 (2020). 59 Falade A, Nwodo U, Iweriebor B, Green E, Mabinya L and Okoh A, Lig-
36 Bilal M and Iqbal HM, Tailoring multipurpose biocatalysts via nin peroxidase functionalities and prospective applications. Micro-
protein engineering approaches: a review. Catal Lett 149:2204– biologyOpen 6:e00394 (2017).
2217 (2019). 60 Zhuo R, Yuan P, Yang Y, Zhang S, Ma F and Zhang X, Induction of lac-
37 Rasheed T, Bilal M, Nabeel F, Adeel M and Iqbal HM, Environmentally- case by metal ions and aromatic compounds in Pleurotus ostreatus
related contaminants of high concern: potential sources and analyt- HAUCC 162 and decolorization of different synthetic dyes by the
ical modalities for detection, quantification, and treatment. Environ extracellular laccase. Biochem Eng J 117:62–72 (2017).
Int 122:52–66 (2019). 61 Chio C, Sain M and Qin W, Lignin utilization: a review of lignin depo-
38 Bilal M and Iqbal HM, Chemical, physical, and biological coordination: lymerization from various aspects. Renew Sustain Energy Rev 107:
an interplay between materials and enzymes as potential platforms 232–249 (2019).
for immobilization. Coord Chem Rev 388:1–23 (2019). 62 Datta R, Kelkar A, Baraniya D, Molaei A, Moulick A, Meena R et al., Enzy-
39 Petrović M, Gonzalez S and Barceló D, Analysis and removal of emerg- matic degradation of lignin in soil: a review. Sustain MDPI 9:1163
ing contaminants in wastewater and drinking water. TrAC Trends (2017).
Anal Chem 22:685–696 (2003). 63 Furukawa T, Bello FO and Horsfall L, Microbial enzyme systems for lig-
40 Ikehata K, Jodeiri Naghashkar N and Gamal El-Din M, Degradation of nin degradation and their transcriptional regulation. Front Biol 9:
aqueous pharmaceuticals by ozonation and advanced oxidation 448–471 (2014).
processes: a review. Ozone Sci Eng 28:353–414 (2006). 64 Pinto PI, Estêvão MD and Power DM, Effects of estrogens and estro-
41 Comninellis C, Kapalka A, Malato S, Parsons SA, Poulios I and genic disrupting compounds on fish mineralized tissues. Mar Drugs
Mantzavinos D, Advanced oxidation processes for water treatment: 12:4474–4494 (2014).
advances and trends for R&D. J Chem Technol Biotechnol 83:769–776 65 Caliman FA and Gavrilescu M, Pharmaceuticals, personal care prod-
(2008). ucts and endocrine disrupting agents in the environment–a review.
42 Unuofin JO, Okoh AI and Nwodo UU, Aptitude of oxidative enzymes CLEAN Soil Air Water 37:277–303 (2009).
for treatment of wastewater pollutants: a laccase perspective. Mole- 66 Samavat H and Kurzer MS, Estrogen metabolism and breast cancer.
cules 24:2064 (2019). Cancer Lett 356:231–243 (2015).
43 Pirsaheb M, Mohamadisorkali H, Hossaini H, Hossini H and 67 Chatterjee A and Abraham J, Mycoremediation of 17 ⊎-estradiol using
Makhdoumi P, The hybrid system successfully to consisting of acti- trichoderma citrinoviride strain AJAC3 along with enzyme studies.
vated sludge and biofilter process from hospital wastewater: ecotox- Environ Prog Sustain Energy 38:13142 (2019).
icological study. J Environ Manage 276:111098 (2020). 68 Mao L, Lu J, Gao S and Huang Q, Transformation of 17ß-estradiol
44 Calza P, Pazzi M, Medana C, Baiocchi C and Pelizzetti E, The photoca- mediated by lignin peroxidase: the role of veratryl alcohol. Arch Envi-
talytic process as a tool to identify metabolitic products formed from ron Contam Toxicol 59:13–19 (2010).
dopant substances: the case of buspirone. J Pharm Biomed Anal 35: 69 Singh AK, Bilal M, Iqbal HM and Raj A, Lignin peroxidase in focus
9–19 (2004). for catalytic elimination of contaminants—a critical review on
45 Ternes TA, Stüber J, Herrmann N, McDowell D, Ried A, Kampmann M recent progress and perspectives. Int J Biol Macromol 177:58–
et al., Ozonation: a tool for removal of pharmaceuticals, contrast media 82 (2021).
and musk fragrances from wastewater? Water Res 37:1976–1982 (2003). 70 Bankole PO, Adekunle AA, Jeon B-H and Govindwar SP, Novel cobio-
46 Ali I, New generation adsorbents for water treatment. Chem Rev 112: mass degradation of NSAIDs by two wood rot fungi, Ganoderma
5073–5091 (2012). applanatum and Laetiporus sulphureus: Ligninolytic enzymes
47 Al-Maqdi KA, Hisaindee S, Rauf MA and Ashraf SS, Detoxification and induction, isotherm and kinetic studies. Ecotoxicol Environ Saf 203:
degradation of sulfamethoxazole by soybean peroxidase and UV + 110997 (2020).
H2O2 remediation approaches. Chem Eng J 352:450–458 (2018). 71 Zhang Y and Geißen S-U, In vitro degradation of carbamazepine and
48 Stadlmair LF, Letzel T, Drewes JE and Grassmann J, Enzymes in diclofenac by crude lignin peroxidase. J Hazard Mater 176:1089–
removal of pharmaceuticals from wastewater: a critical review of 1092 (2010).
challenges, applications and screening methods for their selection. 72 Shaheen R, Asgher M, Hussain F and Bhatti HN, Immobilized lignin
Chemosphere 205:649–661 (2018). peroxidase from Ganoderma lucidum IBL-05 with improved dye
49 Routoula E and Patwardhan SV, Degradation of anthraquinone dyes decolorization and cytotoxicity reduction properties. Int J Biol
from effluents: a review focusing on enzymatic dye degradation Macromol 103:57–64 (2017).
with industrial potential. Environ Sci Technol 54:647–664 (2020). 73 Bilal M, Asgher M, Parra-Saldivar R, Hu H, Wang W, Zhang X et al.,
50 Barber EA, Liu Z and Smith SR, Organic contaminant biodegradation Immobilized ligninolytic enzymes: an innovative and environmental
by oxidoreductase enzymes in wastewater treatment. Microorgan- responsive technology to tackle dye-based industrial pollutants–a
isms 8:122 (2020). review. Sci Total Environ 576:646–659 (2017).
13

J Chem Technol Biotechnol 2021 © 2021 Society of Chemical Industry (SCI). wileyonlinelibrary.com/jctb
www.soci.org M Bilal et al.

74 Ferreira-Leitão VS, de Carvalho MEA and Bon EP, Lignin peroxidase 96 da Silva CJ, de Souza CGM, de Oliveira AL, Bracht A, Costa MAF and
efficiency for methylene blue decolouration: comparison to Peralta RM, Comparative removal of bentazon by Ganoderma luci-
reported methods. Dyes Pigm 74:230–236 (2007). dum in liquid and solid state cultures. Curr Microbiol 60:350–355
75 Parshetti GK, Parshetti S, Kalyani DC, Doong R-A and Govindwar SP, (2010).
Industrial dye decolorizing lignin peroxidase from Kocuria rosea 97 Ansari Z, Karimi A, Sedghi S, Razzaghi M and Ebrahimi S, Glucose oxi-
MTCC 1532. Ann Microbiol 62:217–223 (2012). dase effect on treatment of textile effluent containing reactive azo
76 Christenson A, Dimcheva N, Ferapontova EE, Gorton L, Ruzgas T, dyes by Phanerochaete chrysosporium. J Chem Technol Biotechnol
Stoica L et al., Direct electron transfer between ligninolytic redox 92:1721–1726 (2017).
enzymes and electrodes. Electroanalysis 16:1074–1092 (2004). 98 Bilal M, Iqbal HM, Shah SZH, Hu H, Wang W and Zhang X, Horseradish
77 Veitch NC, Horseradish peroxidase: a modern view of a classic peroxidase-assisted approach to decolorize and detoxify dye pollut-
enzyme. Phytochemistry 65:249–259 (2004). ants in a packed bed bioreactor. J Environ Manag 183:836–842
78 Stiborova M and Anzenbacher P, What are the principal enzymes oxi- (2016).
dizing the xenobiotics in plants: cytochromes P-450 or peroxidases? 99 Inoue Y, Hata T, Kawai S, Okamura H and Nishida T, Elimination and
(A hypothesis). Gen Physiol Biophys 10:209–216 (1991). detoxification of triclosan by manganese peroxidase from white
79 Agostini E, Coniglio MS, Milrad SR, Tigier HA and Giulietti AM, Phytor- rot fungus. J Hazard Mater 180:764–767 (2010).
emediation of 2, 4-dichlorophenol by Brassica napus hairy root cul- 100 Melo CF and Dezotti M, Evaluation of a horseradish peroxidase-
tures. Biotechnol Appl Biochem 37:139–144 (2003). catalyzed process for triclosan removal and antibacterial activity
80 Huber C, Preis M, Harvey PJ, Grosse S, Letzel T and Schröder P, Emerg- reduction. J Chem Technol Biotechnol 88:930–936 (2013).
ing pollutants and plants–metabolic activation of diclofenac by per- 101 Tsutsumi Y, Haneda T and Nishida T, Removal of estrogenic activities
oxidases. Chemosphere 146:435–441 (2016). of bisphenol A and nonylphenol by oxidative enzymes from lignin-
81 Li J, Chen X, Xu D and Pan K, Immobilization of horseradish peroxi- degrading basidiomycetes. Chemosphere 42:271–276 (2001).
dase on electrospun magnetic nanofibers for phenol removal. Eco- 102 Gassara F, Brar SK, Verma M and Tyagi RD, Bisphenol A degradation in
toxicol Environ Saf 170:716–721 (2019). water by ligninolytic enzymes. Chemosphere 92:1356–1360 (2013).
82 Zhou F, Luo J, Qi B, Chen X and Wan Y, Horseradish peroxidase immo- 103 Tran NH, Urase T and Kusakabe O, Biodegradation characteristics of
bilized on multifunctional hybrid microspheres for aflatoxin B1 pharmaceutical substances by whole fungal culture Trametes versi-
removal: will enzymatic reaction be enhanced by adsorption? Ind color and its laccase. J Water Environ Technol 8:125–140 (2010).
Eng Chem Res 58:11710–11719 (2019). 104 Ali L, Algaithi R, Habib HM, Souka U, Rauf MA and Ashraf SS, Soybean
83 Liu S, Huang B, Zheng G, Zhang P, Li J, Yang B et al., Nanocapsulation peroxidase-mediated degradation of an azo dye–a detailed mecha-
of horseradish peroxidase (HRP) enhances enzymatic performance nistic study. BMC Biochem 14:1–14 (2013).
in removing phenolic compounds. Int J Biol Macromol 150:814– 105 Mashhadi N, Taylor KE, Biswas N, Meister P and Gauld JW, Oligomer-
822 (2020). ization of 3-substituted quinolines by catalytic activity of soybean
84 Chowdhary P, Shukla G, Raj G, Ferreira LFR and Bharagava RN, Micro- peroxidase as a wastewater treatment. Product formation and com-
bial manganese peroxidase: a ligninolytic enzyme and its ample putational studies. Chem Eng J 364:340–348 (2019).
opportunities in research. SN Appl Sci 1:45 (2019). 106 Li J, Peng J, Zhang Y, Ji Y, Shi H, Mao L et al., Removal of triclosan via
85 Zhang H, Zhang J, Zhang X and Geng A, Purification and characteriza- peroxidases-mediated reactions in water: reaction kinetics, products
tion of a novel manganese peroxidase from white-rot fungus Cer- and detoxification. J Hazard Mater 310:152–160 (2016).
rena unicolor BBP6 and its application in dye decolorization and 107 Steevensz A, Al-Ansari MM, Taylor KE, Bewtra JK and Biswas N, Com-
denim bleaching. Process Biochem 66:222–229 (2018). parison of soybean peroxidase with laccase in the removal of phenol
86 Yee KL, Jansen LE, Lajoie CA, Penner MH, Morse L and Kelly CJ, Furfu- from synthetic and refinery wastewater samples. J Chem Technol Bio-
ral and 5-hydroxymethyl-furfural degradation using technol 84:761–769 (2009).
recombinant manganese peroxidase. Enzyme Microb Technol 108: 108 Al-Ansari MM, Modaressi K, Taylor KE, Bewtra JK and Biswas N, Soy-
59–65 (2018). bean peroxidase-catalyzed oxidative polymerization of phenols in
87 Oliveira PLD, Duarte MCT, Ponezi AN and Durrant LR, Purification and coal-tar wastewater: comparison of additives. Environ Eng Sci 27:
partial characterization of manganese peroxidase from Bacillus 967–975 (2010).
pumilus and Paenibacillus sp. Braz J Microbiol 40:818–826 (2009). 109 Li X, He Q, Li H, Gao X, Hu M, Li S et al., Bioconversion of non-steroidal
88 Kulikova N, Klein O, Stepanova E and Koroleva O, Use of basidiomy- anti-inflammatory drugs diclofenac and naproxen by chloroperoxi-
cetes in industrial waste processing and utilization technologies: dase. Biochem Eng J 120:7–16 (2017).
fundamental and applied aspects. Appl Biochem Microbiol 47:565– 110 Alneyadi AH and Ashraf SS, Differential enzymatic degradation of thi-
579 (2011). azole pollutants by two different peroxidases–a comparative study.
89 Peralta RM, da Silva BP, Côrrea RCG, Kato CG, Seixas FAV and Bracht A, Chem Eng J 303:529–538 (2016).
Enzymes from basidiomycetes—peculiar and efficient tools for bio- 111 Fernandes M, Souza DH, Henriques RO, Alves MV, Skoronski E and
technology, in Biotechnology of Microbial Enzymes. Cambridge, Junior AF, Obtaining soybean peroxidase from soybean hulls and
United States: Elsevier, pp. 119–149 (2017). its application for detoxification of 2,4-dichlorophenol contami-
90 Xie Q, Xue C, Chen A, Shang C and Luo S, Phanerochaete nated water. J Environ Chem Eng 8:103786 (2020).
chrysosporium-driven quinone redox cycling promotes degradation 112 Tolardo V, García-Ballesteros S, Santos-Juanes L, Vercher R, Amat AM,
of imidacloprid. Int Biodeter Biodegr 151:104965 (2020). Arques A et al., Pentachlorophenol removal from water by soybean
91 dos Santos Bazanella GC, de Souza DF, Castoldi R, Oliveira RF, Bracht A peroxidase and iron (II) salts concerted action. Water Air Soil Pollut
and Peralta RM, Production of laccase and manganese peroxidase 230:140 (2019).
by pleurotus pulmonarius in solid-state cultures and application in 113 He J, Zhang Y, Yuan Q and Liang H, Catalytic activity and application
dye decolorization. Folia Microbiol 58:641–647 (2013). of immobilized chloroperoxidase by biometric magnetic nanoparti-
92 Qin X, Zhang J, Zhang X and Yang Y, Induction, purification and char- cles. Ind Eng Chem Res 58:3555–3560 (2019).
acterization of a novel manganese peroxidase from Irpex lacteus 114 García-Zamora JL, León-Aguirre K, Quiroz-Morales R, Parra-Saldívar R,
CD2 and its application in the decolorization of different types of Gómez-Patiño MB, Arrieta-Baez D et al., Chloroperoxidase-mediated
dye. PLoS One 9:e113282 (2014). halogenation of selected pharmaceutical micropollutants. Catalysts
93 Zhang H, Zhang S, He F, Qin X, Zhang X and Yang Y, Characterization 8:32 (2018).
of a manganese peroxidase from white-rot fungus Trametes 115 Zhang X, Li X, Jiang Y, Hu M, Li S and Zhai Q, Combination of enzy-
sp. 48424 with strong ability of degrading different types of dyes matic degradation by chloroperoxidase with activated sludge treat-
and polycyclic aromatic hydrocarbons. J Hazard Mater 320:265– ment to remove sulfamethoxazole: performance, and eco-toxicity
277 (2016). assessment. J Chem Technol Biotechnol 91:2802–2809 (2016).
94 Pizzul L, del Pilar CM and Stenström J, Degradation of glyphosate and 116 But A, Van Noord A, Poletto F, Sanders JP, Franssen MC and Scott EL,
other pesticides by ligninolytic enzymes. Biodegradation 20:751– Enzymatic halogenation and oxidation using an alcohol
759 (2009). oxidase-vanadium chloroperoxidase cascade. Mol Catal 443:92–
95 Lee H, Choi Y-S, Kim M-J, Huh N-Y, Kim G-H, Lim Y et al., Degrading 100 (2017).
ability of oligocyclic aromates by phanerochaete sordida selected 117 Ayala M, Hernandez-Lopez EL, Perezgasga L and Vazquez-Duhalt R,
via screening of white rot fungi. Folia Microbiol 55:447–453 (2010). Reduced coke formation and aromaticity due to chloroperoxidase-
14

wileyonlinelibrary.com/jctb © 2021 Society of Chemical Industry (SCI). J Chem Technol Biotechnol 2021
Oxidoreductases as a versatile biocatalytic tool www.soci.org

catalyzed transformation of asphaltenes from Maya crude oil. Fuel 140 Cabana H, Jiwan J-LH, Rozenberg R, Elisashvili V, Penninckx M,
92:245–249 (2012). Agathos SN et al., Elimination of endocrine disrupting chemicals
118 Piantini U, Schrader J, Wawrzun A and Wüst M, A biocatalytic route nonylphenol and bisphenol A and personal care product ingredient
towards rose oxide using chloroperoxidase. Food Chem 129:1025– triclosan using enzyme preparation from the white rot fungus Corio-
1029 (2011). lopsis polyzona. Chemosphere 67:770–778 (2007).
119 Longoria AM, Hu H and Vazquez-Duhalt R, Enzymatic synthesis of 141 Ramírez-Cavazos LI, Junghanns C, Ornelas-Soto N, Cárdenas-
semiconductor polymers by chloroperoxidase of caldariomyces Chávez DL, Hernández-Luna C, Demarche P et al., Purification and
fumago. Appl Biochem Biotechnol 162:927–934 (2010). characterization of two thermostable laccases from pycnoporus san-
120 Guerrero E, Aburto P, Terrés E, Villegas O, González E, Zayas T et al., guineus and potential role in degradation of endocrine disrupting
Improvement of catalytic efficiency of chloroperoxidase by its cova- chemicals. J Mol Catal B Enzym 108:32–42 (2014).
lent immobilization on SBA-15 for azo dye oxidation. J Porous Mater 142 Saito T, Kato K, Yokogawa Y, Nishida M and Yamashita N, Detoxifica-
20:387–396 (2013). tion of bisphenol A and nonylphenol by purified extracellular lac-
121 Zhao R, Li X, Hu M, Li S, Zhai Q and Jiang Y, Efficient enzymatic degra- case from a fungus isolated from soil. J Biosci Bioeng 98:64–66
dation used as pre-stage treatment for norfloxacin removal by acti- (2004).
vated sludge. Bioprocess Biosyst Eng 40:1261–1270 (2017). 143 Kim YJ and Nicell JA, Laccase-catalysed oxidation of aqueous triclo-
122 Gao F, Guo Y, Fan X, Hu M, Li S, Zhai Q et al., Enhancing the catalytic san. J Chem Technol Biotechnol 81:1344–1352 (2006).
performance of chloroperoxidase by co-immobilization with glu- 144 Dubroca J, Brault A, Kollmann A, Touton I, Jolivalt C, Kerhoas L et al.,
cose oxidase on magnetic graphene oxide. Biochem Eng J 143: Biotransformation of nonylphenol surfactants in soils amended with
101–109 (2019). contaminated sewage sludges, in Environmental Chemistry.
123 Hoffmann N, Benske A, Betz H, Schuetz M and Samuels AL, Laccases Springer-Verlag Berlin, Germany: Springer, pp. 305–315 (2005).
and peroxidases co-localize in lignified secondary cell walls through- 145 Rahmani H, Lakzian A, Karimi A and Halajnia A, Efficient removal of
out stem development. Plant Physiol 184:806–822 (2020). 2,4-dinitrophenol from synthetic wastewater and contaminated soil
124 Albarrán-Velo J, Gotor-Fernández V and Lavandera I, One-pot two- samples using free and immobilized laccases. J Environ Manage 256:
step chemoenzymatic deracemization of allylic alcohols using lac- 109740 (2020).
cases and alcohol dehydrogenases. Mol Catal 493:111087 (2020). 146 Mo D, Zeng G, Yuan X, Chen M, Hu L, Li H et al., Molecular docking sim-
125 Gasser CA, Ammann EM, Shahgaldian P and Corvini PFX, Laccases to ulation on the interactions of laccase from trametes versicolor with
take on the challenge of emerging organic contaminants in waste- nonylphenol and octylphenol isomers. Bioprocess Biosyst Eng 41:
water. Appl Microbiol Biotechnol 98:9931–9952 (2014). 331–343 (2018).
126 Ouzounis C and Sander C, A structure-derived sequence pattern for 147 Duarte Baumer J, Valério A, de Souza SMAGU, Erzinger GS, Furigo A
the detection of type I copper binding domains in distantly related and de Souza AAU, Toxicity of enzymatically decolored textile dyes
proteins. FEBS Lett 279:73–78 (1991). solution by horseradish peroxidase. J Hazard Mater 360:82–88
127 Falade AO, Mabinya LV, Okoh AI and Nwodo UU, Ligninolytic (2018).
enzymes: versatile biocatalysts for the elimination of endocrine- 148 de Freitas EN, Bubna GA, Brugnari T, Kato CG, Nolli M, Rauen TG et al.,
disrupting chemicals in wastewater. MicrobiologyOpen 7:e00722 Removal of bisphenol A by laccases from pleurotus ostreatus and
(2018). pleurotus pulmonarius and evaluation of ecotoxicity of degradation
128 Lloret L, Eibes G, Lú-Chau TA, Moreira MT, Feijoo G and Lema JM, Lac- products. Chem Eng J 330:1361–1369 (2017).
case-catalyzed degradation of anti-inflammatories and estrogens. 149 Inoue S, Igarashi Y, Yoneda Y, Kawai S, Okamura H and Nishida T, Elim-
Biochem Eng J 51:124–131 (2010). ination and detoxification of fungicide miconazole and antidepres-
129 Shao B, Liu Z, Zeng G, Liu Y, Yang X, Zhou C et al., Immobilization of sant sertraline by manganese peroxidase-dependent lipid
laccase on hollow mesoporous carbon nanospheres: noteworthy peroxidation system. Int Biodeter Biodegr 100:79–84 (2015).
immobilization, excellent stability and efficacious for antibiotic con- 150 Costa CZ, Albuquerque MDCCD, Brum MC and Castro AMD, Degrada-
taminants removal. J Hazard Mater 362:318–326 (2019). ção Microbiológica E Enzimática De Polímeros: Uma Revisão. Quím
130 Xu P, Du H, Peng X, Tang Y, Zhou Y, Chen X et al., Degradation of sev- Nova 38:259–267 (2015).
eral polycyclic aromatic hydrocarbons by laccase in reverse micelle 151 Rodarte-Morales A, Feijoo G, Moreira M and Lema J, Biotransforma-
system. Sci Total Environ 708:134970 (2020). tion of three pharmaceutical active compounds by the fungus Pha-
131 Ferrari B, Paxéus N, Giudice RL, Pollio A and Garric J, Ecotoxicological nerochaete chrysosporium in a fed batch stirred reactor under air
impact of pharmaceuticals found in treated wastewaters: study of and oxygen supply. Biodegradation 23:145–156 (2012).
carbamazepine, clofibric acid, and diclofenac. Ecotoxicol Environ 152 Hata T, Kawai S, Okamura H and Nishida T, Removal of diclofenac and
Saf 55:359–370 (2003). mefenamic acid by the white rot fungus Phanerochaete sordida YK-
132 Naghdi M, Taheran M, Brar SK, Kermanshahi-pour A, Verma M and 624 and identification of their metabolites after fungal transforma-
Surampalli RY, Biotransformation of carbamazepine by laccase- tion. Biodegradation 21:681–689 (2010).
mediator system: kinetics, by-products and toxicity assessment. Pro- 153 Nowell LH, Norman JE, Moran PW, Martin JD and Stone WW, Pesticide
cess Biochem 67:147–154 (2018). toxicity index—a tool for assessing potential toxicity of pesticide
133 Ben Younes S, Ben Khedher S, Zhang Y, Geissen S-U and Sayadi S, Lac- mixtures to freshwater aquatic organisms. Sci Total Environ 476:
case from scytalidium thermophilum: production improvement, cat- 144–157 (2014).
alytic behavior and detoxifying ability of diclofenac. Catal Lett 149: 154 Varga B, Somogyi V, Meiczinger M, Kováts N and Domokos E, Enzy-
1833–1844 (2019). matic treatment and subsequent toxicity of organic micropollu-
134 Halden RU, On the need and speed of regulating triclosan and triclo- tants using oxidoreductases - a review. J Clean Prod 221:306–322
carban in the United States. Environ Sci Technol 48:3603–3611 (2019).
(2014). 155 Conesa A, Punt PJ and van den Hondel CAMJJ, Fungal peroxidases:
135 Thompson A, Griffin P, Stuetz R and Cartmell E, The fate and removal molecular aspects and applications. J Biotechnol 93:143–158 (2002).
of triclosan during wastewater treatment. Water Environ Res 77:63– 156 Gasser CA, Hommes G, Schäffer A and Corvini PF-X, Multi-catalysis
67 (2005). reactions: new prospects and challenges of biotechnology to valo-
136 Malchi T, Maor Y, Tadmor G, Shenker M and Chefetz B, Irrigation of rize lignin. Appl Microbiol Biotechnol 95:1115–1134 (2012).
root vegetables with treated wastewater: evaluating uptake of phar- 157 Asina F, Brzonova I, Kozliak E, Kubátová A and Ji Y, Microbial treat-
maceuticals and the associated human health risks. Environ Sci Tech- ment of industrial lignin: successes, problems and challenges. Renew
nol 48:9325–9333 (2014). Sustain Energy Rev 77:1179–1205 (2017).
137 Dann AB and Hontela A, Triclosan: environmental exposure, toxicity 158 Ayala M, Pickard MA and Vazquez-Duhalt R, Fungal enzymes for envi-
and mechanisms of action. J Appl Toxicol 31:285–311 (2011). ronmental purposes, a molecular biology challenge. Microb Physiol
138 Sajiki J and Yonekubo J, Leaching of bisphenol A (BPA) to seawater 15:172–180 (2008).
from polycarbonate plastic and its degradation by reactive oxygen 159 Sheldon RA and Pereira PC, Biocatalysis engineering: the big picture.
species. Chemosphere 51:55–62 (2003). Chem Soc Rev 46:2678–2691 (2017).
139 Asakura H, Matsuto T and Tanaka N, Behavior of endocrine-disrupting 160 Zhu B, Chen Y and Wei N, Engineering biocatalytic and biosorptive
chemicals in leachate from MSW landfill sites in Japan. Waste Manag materials for environmental applications. Trends Biotechnol 37:
24:613–622 (2004). 661–676 (2019).
15

J Chem Technol Biotechnol 2021 © 2021 Society of Chemical Industry (SCI). wileyonlinelibrary.com/jctb
www.soci.org M Bilal et al.

161 Liese A and Hilterhaus L, Evaluation of immobilized enzymes for magnetically recyclable biocatalyst for removal of ferulic acid. Bio-
industrial applications. Chem Soc Rev 42:6236–6249 (2013). process Biosyst Eng 41:97–106 (2018).
162 Bettin F, Cousseau F, Martins K, Boff NA, Zaccaria S, Moura da 165 Lau YJ, Karri RR, Mubarak NM, Lau SY, Chua HB, Khalid M et al.,
Silveira M et al., Phenol removal by laccases and other phenol Removal of dye using peroxidase-immobilized Buckypaper/polyvi-
oxidases of Pleurotus sajor-caju PS-2001 in submerged cultiva- nyl alcohol membrane in a multi-stage filtration column via RSM
tions and aqueous mixtures. J Environ Manage 236:581–590 and ANFIS. Environ Sci Pollut Res 27:40121–40134 (2020).
(2019). 166 Altikatoglu Yapaoz M and Attar A, An accomplished procedure of
163 Becker D, Rodriguez-Mozaz S, Insa S, Schoevaart R, Barceló D, de horseradish peroxidase immobilization for removal of acid yellow
Cazes M et al., Removal of endocrine disrupting chemicals in waste- 11 in aqueous solutions. Water Sci Technol 81:2664–2673 (2020).
water by enzymatic treatment with fungal laccases. Org Process Res 167 Farias S, Mayer DA, de Oliveira D, de Souza SMAGU and de
Dev 21:480–491 (2017). Souza AAU, Free and Ca-alginate beads immobilized horseradish
164 Tavares TS, Torres JA, Silva MC, Nogueira FGE, da Silva AC and peroxidase for the removal of reactive dyes: an experimental and
Ramalho TC, Soybean peroxidase immobilized on ⊐-FeOOH as new modeling study. Appl Biochem Biotechnol 182:1290–1306 (2017).
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