Syntheses of aromatic aldehydes by laccase of pleurotus ostreatus MTCC-1801

Article abstract of DOI:10.1080/00397911.2014.904879

GRAPHICAL ABSTRACT Selective bioconversion of the aromatic methyl group to its aldehyde group is one of the best applications of the laccases. In the present communication, crude laccase, obtained from the liquid culture medium of the fungal strain Pleurotus ostreatus MTCC-1801, has been used for the selective bioconversion of toluene, 3-nitrotoluene, 4-nitrotoluene, 2-fluorotoluene, 4-fluorotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, and 3,4-dimethoxytoluene to benzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, and 3,4-dimethoxybenzaldehyde, respectively, in the presence of 2,2′-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt (ABTS) as a mediator molecule. Time taken by these conversions was 1-2 h, and average yield of products was more than 93%.

Full text of DOI:10.1080/00397911.2014.904879

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Syntheses of Aromatic Aldehydes
by Laccase of Pleurotus ostreatus
MTCC-1801
Pankaj Kumar Chaurasia a , Sudha Yadava a , Shashi Lata Bharati a &
Sunil Kumar Singh a
a Department of Chemistry , D.D.U. Gorakhpur University ,
Gorakhpur , Uttar Pradesh , India
Accepted author version posted online: 05 May 2014.Published
online: 02 Jul 2014.
To cite this article: Pankaj Kumar Chaurasia , Sudha Yadava , Shashi Lata Bharati & Sunil Kumar Singh
(2014) Syntheses of Aromatic Aldehydes by Laccase of Pleurotus ostreatus MTCC-1801, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
44:17, 2535-2544, DOI: 10.1080/00397911.2014.904879
To link to this article: http://dx.doi.org/10.1080/00397911.2014.904879
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Synthetic Communications1, 44: 2535–2544, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2014.904879
SYNTHESES OF AROMATIC ALDEHYDES BY LACCASE
OF PLEUROTUS OSTREATUS MTCC-1801
Pankaj Kumar Chaurasia, Sudha Yadava, Shashi Lata Bharati,
and Sunil Kumar Singh
Department of Chemistry, D.D.U. Gorakhpur University, Gorakhpur,
Uttar Pradesh, India
GRAPHICAL ABSTRACT
Abstract Selective bioconversion of the aromatic methyl group to its aldehyde group is one
of the best applications of the laccases. In the present communication, crude laccase,
obtained from the liquid culture medium of the fungal strain Pleurotus ostreatus MTCC-
1801, has been used for the selective bioconversion of toluene, 3-nitrotoluene, 4-nitrotolu-
ene, 2-fluorotoluene, 4-fluorotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene,
and 3,4-dimethoxytoluene to benzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2-
fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde,
4-chlorobenzaldehyde, and 3,4-dimethoxybenzaldehyde, respectively, in the presence of 2,20-
azino-bis (3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt (ABTS) as a mediator
molecule. Time taken by these conversions was 1–2 h, and average yield of products was
more than 93%.
Keywords ABTS; HPLC; laccase; Pleurotus ostreatus; selective oxidation
Received December 9, 2013.
Address correspondence to S. L. Bharati, Department of Chemistry, D.D.U. Gorakhpur
University, Gorakhpur 273009, Uttar Pradesh, India. E-mail: shashilatachem@gmail.com
2535

2536
P. K. CHAURASIA ET AL.
INTRODUCTION
Laccase [benzenediol: oxygen oxidoreductase; E.C. 1.10.3.2] is a polyphenol
oxidase, which belongs to the superfamily of multicopper oxidases[1–3] and
catalyzes[4–6] the four-electron reduction of molecular oxygen to water. Laccases
are dimeric or tetrameric glycoproteins. To perform their catalytic functions, lac-
cases depend on Cu atoms that are distributed at the three different copper centers
(viz., type-1 or blue copper center, type-2 or normal copper center, and type-3 or
coupled binuclear copper centers), differing in their characteristic electronic para-
magnetic resonance (EPR) signals. The organic substrate is oxidized by one electron
at the active site of the laccase, generating a reaction radical that further reacts none-
nzymatically. The electron is received at type-1 Cu and is shuttled to the trinuclear
cluster where oxygen is reduced to water.
Laccase is one of the few enzymes that have been studied since the end of the
nineteenth century. It was first demonstrated in the exudates of Rhus vernicifera, the
Japanese lacquer tree,[7] and subsequently was demonstrated as a fungal enzyme
as well.[8] At present, there is only one bacterium, Azospirillum lipoferum, in which
a laccase-type phenol oxidase has been demonstrated.[9]
Laccases are the lignolytic enzymes and abundantly occur in the fungal sys-
tems,[5] mainly in ascomycetes, deuteromycetes, and basidiomycetes. White rot fungi
are the greatest producers of the laccases but also litter decomposing and ectomicor-
rhizal fungi secrete laccases.[5] However, it should not be generalized that only the
fungal system has ability to produce the laccases. Laccase production has never been
demonstrated in lower fungi, that is, Zygomycetes and Chytridiomycetes.[10] Several
reports can be found in the literature on production of laccase in ascomycetes such
as Gaeumannomyces graminis,[11] Magnaporthe grisea,[12] Ophiostoma novo-ulmi,[13]
Mauginella,[14] Melanocarpus albomyces,[15] Monocillium indicum,[16] Neurospora
crassa,[17] and Podospora anserine.[18] In addition to plant pathogenic species, laccase
production was also reported for some soil ascomycete species from the genera
Aspergillus, Curvularia, and Penicillium[19–21] and in some freshwater ascomycetes.[22]
Ortho and para diphenols, aminophenols, polyphenols, polyamines, lignins,
arylamines, and some of the inorganic ions are the substrates for laccases. The
ability of laccases to catalyze the oxidation of various phenolic as well as nonpheno-
lic compounds, coupled to the reduction of molecular oxygen to water, makes it
valuable from the point of view of their commercial applications.[5,23–25] The biotech-
nological importance of laccases have increased after the discovery that oxidizable
reaction substrate range could be further extended in the presence of small readily
oxidizable molecules called mediators.[26,27] During the past two decades, laccases
have turned out to be the most promising enzymes for industrial uses,[24,25] having
applications in food, pulps, paper, textile, cosmetics industries, and synthetic organic
chemistry.[28–35]
The objective of this communication was to obtain the crude laccase from
the liquid culture growth medium containing natural lignin substrate wheat
straw particles of Pleurotus ostreatus MTCC-1801 and to demonstrate the selective
bioconversions of toluene, and different substituted toluenes as 3-nitrotoluene,
4-nitrotoluene, 2-fluorotoluene, 4-fluorotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-
chlorotoluene, and 3,4-dimethoxytoluene to benzaldehyde, 3-nitrobenzaldehyde,

SYNTHESES OF AROMATIC ALDEHYDES BY CRUDE LACCASE
2537
4-nitrobenzaldehyde, 2-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzalde-
hyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, and 3,4-dimethoxybenzaldehyde,
respectively, in the presence of 2,20-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid)
diammonium salt (ABTS) as mediator molecule at room temperature. P. ostreatus
MTCC-1801 is an edible and wood-degrading fungus and shows good secretion of
lignolytic enzymes. Authors have found it as a hyperlaccase secreting lygnolytic
fungus. This was the main reason to use crude laccase from this source for such
bioconversions. The novelty of this research is in the use of crude laccase as an
effective biocatalyst for theses bioconversions instead of purified laccase because
purification of an enzyme needs very expensive materials and long reaction times.
DISCUSSION
Selective bioconversion of aromatic methyl group to the aldehyde group is one
of the best reactions of laccases in organic syntheses. The chemical routes of these
conversions are inconvenient because methyl groups are preferably converted into
carboxylic acids and it is very difficult to stop the reaction at the aldehyde stage.
Moreover, they require drastic reaction conditions which pollute the environment.
The conversion done with crude laccase occurs under milder conditions, yield
is >90%, and the process is ecofriendly. The use of laccases for this purpose has
been studied[32,33] in the presence of mediator molecules such as ABTS.[32] These
enzymatic syntheses are much more valuable in comparison to other methods known
for the syntheses of benzaldehydes and substituted benzaldehydes. Keeping
the importance of laccase-catalyzed oxidations in mind, the potential of the crude
laccase as a biocatalyst for the conversion of aromatic methyl group to the
corresponding aldehyde group in the presence of mediator molecule was tested using
toluene and different substituted toluenes as the substrates shown in Scheme 1.
In above selective enzyme catalyzed bioconversaions, all products formed are
easily available and simple. So, authors have used high performance liquid chroma-
tography (HPLC) technique to confirm the actual product formation by comparing
the HPLC chromatograms of standard aldehyde compounds with the enzymatically
transformed aldehyde compounds. A comparison of retention time of standard
Scheme 1. Reactions of toluene and different substituted toluenes with crude laccase of Pleurotus ostreatus
MTCC-1801 in presence of ABTS as mediator at room temperature.

2538
P. K. CHAURASIA ET AL.
sample of expected products were done with their corresponding enzyme-catalyzed
products.
The retention times of the standard samples of toluene, 3-nitrotoluene,
4-nitrotoluene, 2-fluorotoluene, 4-fluorotoluene, 2-chlorotoluene, 3-chlorotoluene,
Figure 1. HPLC profiles of synthesized products: Benzaldehyde (a), 3-nitrobenzaldehyde (b),
4-nitrobenzaldehyde (c), 2-fluorobenzaldehyde (d), 4-fluorobenzaldehyde (e), 2-chlorobenzaldehyde (f),
3-chlorobenzaldehyde (g), 4-chlorobenzalaldehyde (h), and 3,4-dimethoxybenzaldehyde (i).

SYNTHESES OF AROMATIC ALDEHYDES BY CRUDE LACCASE
2539
Figure 1 Continued.
4-chlorotoluene, 3,4-dimethoxytoluene, benzaldehyde, 3-nitrobenzaldehyde, 4-nitro-
benzaldehyde, 2-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde,
3-chlorobenzaldehyde, 4-chlorobenzaldehyde, and 3,4-dimethoxybenzaldehyde were
4.25, 6.58, 6.49, 6.89, 7.23, 6.93, 7.16, 7.33, 7.19, 3.11, 5.91, 5.75, 5.98, 6.05, 6.21,
6.13, 6.25, and 6.35 min, respectively. Thus, the retention time of the products of
the enzyme-catalyzed reactions (3.16, 5.93, 5.72, 6.01, 6.11, 6.18, 6.10, 6.27, and
6.37 min) revealed that the products of the enzyme-catalyzed reactions were
benzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2-fluorobenzaldehyde,
4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chloroben-
zaldehyde, and 3,4-dimethoxybenzaldehyde. High-performance liquid chromato-
graphy (HPLC) chromatograms of all the synthesized products are given in Fig. 1.
Yields of the extracted products are given in Table 1.
Tests of this laccase for the selective oxidation of aromatic methyl group of
xylenes, 7-methylquinoline, 2-methylfuran, etc., have also been done but these reac-
tions were either not successful or gives very poor product yield (<18%). Only HPLC
chromatogram of the 7-methylquinoline and its product has been given as Fig. 2
because in this case yield was about 18%, also too poor to be characterized. During

2540
P. K. CHAURASIA ET AL.
Table 1. Enzymatically synthesized different benzaldehydes from their respective
toluenes with percentage yields
Reactant
Product
Benzaldehyde
Yield (%)
Toluene
96
98
94
90
93
89
92
92
98
3-Nitrotoluene
4-Nitrotoluene
2-Fluorotoluene
4-Fluorotoluene
2-Chlorotoluene
3-Chlorotoluene
4-Chlorotoluene
3,4-Dimethoxytoluene
3-Nitrobenzaldehyde
4-Nitrobenzaldehyde
2-Fluorobenzaldehyde
4-Fluorobenzaldehyde
2-Chlorobenzaldehyde
3-Chlorobenzaldehyde
4-Chlorobenzaldehyde
3,4-Dimethoxybenzaldehyde
the study of reaction of methyl-substituted alkenes with laccase the authors found
that no reaction occurred at all even after several days of reaction.
Identification and characterization of products obtained during enzymatic
1
reaction were analyzed on the basis of IR and H NMR results (for detailed data,
see the experimental section). In an infrared (IR) study, aldehydic C-H stretching
bands for all the biotransformed products were in range of 2825–2834 cmꢀ1 while
conjugated aldehydic C O stretching bands were in range of 1695–1705 cmꢀ1. These
=
analyses confirm the desired aromatic aldehydes formation. In proton NMR study,
chemical shift for aldehydic protons for all the synthesized aldehydes were d > 9.30
(singlet), which confirms the aldehydic products formation.
1
In this way, all these described results of HPLC, IR, and H NMR, clearly
demonstrate the successful syntheses of desired aldehydic products. The advantage
of these enzymatically catalyzed oxidation reactions are substantial in comparison
to existing methods for the oxidation of aromatic methyl group. The reactions
proceed under milder condition at atmospheric pressure and room temperature.
No side reactions occur because of the high specificity of this biocatalyst.
This article shows the selective bioconversions of aromatic methyl group of
toluene as well as differently substituted toluenes to corresponding aldehyde groups
in the presence of ABTS as mediator molecule by crude laccase of P. ostreatus in
Figure 2. HPLC chromatograms of 7-methylquinoline (a) and its reaction products (b).

SYNTHESES OF AROMATIC ALDEHYDES BY CRUDE LACCASE
2541
good yields. This work strongly shows that crude laccase obtained from this edible
fungus P. ostreatus MTCC-1801 can be utilized for such bioconversions as an effec-
tive biocatalyst instead of purified laccase, which will save time and unnecessary use
of high cost materials during purification of an enzyme.
EXPERIMENTAL
4-Fluorotoluene and 4-chlorotoluene were from Sigma Chemical Company,
St. Louis (USA). 2-Fluorotoluene, 2-chlorotoluene, 2,20-azino-bis (3-ethylbenzthia-
zoline-6-sulphonic acid) diammonium salt (ABTS), and 2,6-dimethoxy phenol
(DMP) were from Fluka, Chemi new Ulm (Switzerland). All other chemicals used
in these investigations were either from Himedia Laboratory Ltd. Mumbai (India)
or from E. Merck Ltd. Mumbai (India) and were used without further purifications.
Enzyme Assay
1.0 mL of the assay solution for DMP as the substrate contained 1.0 mM DMP
in 50 mM sodium malonate buffer pH 4.5 at 37 ꢁC. The reaction was monitored by
measuring the absorbance change at k ¼ 468 nm, using the molar extinction
coefficient value of 49.6 ꢂ 103 Mꢀ1 cmꢀ1 [36]
.
The ultraviolet=visible (UV=vis)
spectrophotometer Hitachi (Japan) model U-2900 fitted with electronic temperature
control unit was used for absorbance measurement. The least count of absorbance
measurement was 0.001 absorbance unit. One enzyme unit produced 1 mmol of the
product per minute under the specified assay conditions.
Fungal Strain and Its Growth
The fungal strain was procured from the Microbial Type Culture Collection
Center and Gene Bank, Institute of Microbial Technology, Chandigarh, India, and
was maintained on agar slant as reported in MTCC Catalogue of Strains 2000.[37]
To detect the extracellular secretion of the laccase by Pleurotus ostreatus
MTCC-1801, the liquid culture growth medium[37] containing glucose 10.0 g, aspara-
gine 1.0 g, yeast extract 0.5 g, MgSO4 ꢃ 7H2O and FeSO4 ꢃ 7H2O, 0.01 g in 1.0 L of
Milli-Q water was used. The medium containing natural lignin substrates such as
coir dust, corn cob, wheat straw, sawdust, and bagasse particles were separately pre-
pared by adding 0.5 g of one of the natural lignin substrates to 25 mL of growth
medium in 100-mL culture flasks, which were sterilized. The sterilized growth media
were inoculated with small pieces of mycelia (0.5 cm ꢂ 0.5 cm) under aseptic con-
ditions and the fungal cultures were grown under stationary culture conditions at
25 ꢁC in a biological oxygen demand (BOD) incubator. To monitor the production
of the laccase in the liquid culture medium, 0.5-mL aliquots of the growth medium
were withdrawn at the regular intervals of 24 h and filtered through sterilized Milli-
pore filters, 0.22 mm. The filtered extract was analyzed for the activity of the laccase
using DMP as the substrate by the method given in assay section. Extracellular
secretion of the laccase in the liquid culture medium by P. ostreatus MTCC-1801
was determined by plotting the enzyme unit=mL of the growth medium against
the number of days after inoculation of the fungal mycelia. Each point on the curve

2542
P. K. CHAURASIA ET AL.
is an average of three measurements. The growth medium for the control experiment
has the same composition except that no natural lignolytic substrate has been added.
It has been found that secretion of crude laccase by Pleurotus ostreatus MTCC-1801
is better in wheat straw particles with 500 mg of its concentration. The filtrate of
liquid culture growth medium containing wheat straw particles has been used for
selective oxidation reactions.
Bioconversions in the Presence of ABTS
The biotransformation of toluene to benzaldehyde [32-34] was done in 15 mL
of 100 mM sodium acetate buffer pH 4.5 containing 20 mM toluene in dioxane,
0.1 mM ABTS, and 500 mL of twice-diluted crude laccase (activity of concentrated
laccase was 1.91 IU=mL) kept in a 100-mL conical flask, which was stirred vigor-
ously for 60 min (completion of the reaction was confirmed by the UV=vis spectro-
photometer (Hitachi, Japan, model U-2900). The reaction solution was extracted
three times with 40 mL of ethyl acetate, and 20 mL of the n-ethyl acetate extract
was injected in Waters HPLC model 600E using spherisorb C18 5 UV, 4.5 ꢂ 250 mm
mm column. The mobile phase was methanol at the flow rate of 0.5 mL=min. The
detection was made using Waters UV detector model 2487 at k ¼ 254 nm.
The biotransformations of 3-nitrotoluene to 3-nitrobenzaldehyde, 4-nitrotolu-
ene to 4-nitrobenzaldehyde, 2-fluorotoluene to 2-fluorobenzaldehyde, 4-fluorotoluene
to 4-fluorobenzaldehyde, 2-chlorotoluene to 2-chlorobenzaldehyde, 3-chlorotoluene
to 3-chlorobenzaldehyde, 4-chlorotoluene to 4-chlorobenzaldehyde, and 3,4-
dimethoxytoluene to 3,4-dimethoxybenzaldehyde were also studied using the same
method except the times of stirring the reaction solutions were 75, 90, 120, 120, 120,
120, 120, and 90 min, respectively.
Isolation
Because only small amounts of chemical auxiliaries are applied which remain
in the aqueous phase after extraction of the aldehydes with an organic solvent (ethyl
acetate), very pure compounds are obtained that require no further purification.
During these oxidations, no side reactions occur because of the high specificity of
laccase as biocatalyst. Thus, authors have used ethyl acetate as organic solvent for
the extraction of products and found the almost pure benzaldehydes and substituted
benzaldehydes in excellent yields (average yield was 93%).
Characterization
Infrared (IR) spectroscopy (KBr, n, cmꢀ1). For 3-nitrobenzaldehyde and
4-nitrobenzaldehyde: 3056–3061, 2822–2827, 1696–1699, 1515–1523, 1325–1332, and
1368–1371 cmꢀ1. For benzaldehyde, 2-fluorobenzaldehyde, 4-fluorobenzaldehyde,
2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, and 3,4-
dimethoxybenzaldehyde: 3053–3062, 2825–2834, 1695–1705, and 1355–1363 cmꢀ1
.
1H NMR (CDCl3, 300 MHz, ppm). For benzaldehyde: 9.39 (s, 1H), 7.80 (d,
2H), 7.26 (t, 2H), 7.49 (t, 1H). For 3-chlorobenzaldehyde and 3-nitrobenzaldehyde:
ꢄ9.51 (s, 1H), ꢄ8.32 (s, 1H), ꢄ8.27 (db, 1H), ꢄ7.96 (t, 1H), and ꢄ8.16 (db, 1H). For

SYNTHESES OF AROMATIC ALDEHYDES BY CRUDE LACCASE
2543
2-fluorobenzaldehyde and 2-chlorobenzaldehyde: ꢄ9.45 (s, 1H), ꢄ7.81 (db, 1H),
ꢄ7.75 (db, 1H), ꢄ7.16 (t, 1H), and ꢄ6.88 (t, 1H). For 4-nitrobenzaldehyde, 4-
fluorobenzaldehyde, and 4-chlorobenzaldehyde: ꢄ9.42 (s, 1H), ꢄ7.79 (db, 2H),
and ꢄ7.39 (db, 2H). For 3,4-dimethoxybenzaldehyde: 9.49 (s, 1H), 8.12 (s, 1H),
7.89 (db, 1H), 7.93 (db, 1H) and 3.78 (s).
FUNDING
The authors acknowledge the financial support of CSIR-HRDG, New Delhi,
for the award of junior and senior research fellowships (NET), Award No.
09=057(0201)2010-EMR-I, to P. K. Chaurasia. Authors are also thankful to
UGC-New Delhi for the award of UGC-Post Doctoral Fellowship (women) to
Dr. S. L. Bharati.
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