Production of dicarboxylic acids from novel unsaturated fatty acids by laccase-catalyzed oxidative cleavage

Article abstract of DOI:10.1080/09168451.2016.1200457

The establishment of renewable biofuel and chemical production is desirable because of global warming and the exhaustion of petroleum reserves. Sebacic acid (decanedioic acid), the material of 6,10-nylon, is produced from ricinoleic acid, a carbonneutral material, but the process is not eco-friendly because of its energy requirements. Laccase-catalyzing oxidative cleavage of fatty acid was applied to the production of dicarboxylic acids using hydroxy and oxo fatty acids involved in the saturation metabolism of unsaturated fatty acids in Lactobacillus plantarum as substrates. Hydroxy or oxo fatty acids with a functional group near the carbon-carbon double bond were cleaved at the carbon-carbon double bond, hydroxy group, or carbonyl group by laccase and transformed into dicarboxylic acids. After 8 h, 0.58 mM of sebacic acid was produced from 1.6 mM of 10-oxo-cis-12,cis-15-octadecadienoic acid (αKetoA) with a conversion rate of 35% (mol/mol). This laccase-catalyzed enzymatic process is a promising method to produce dicarboxylic acids from biomass-derived fatty acids.

Full text of DOI:10.1080/09168451.2016.1200457

Bioscience, Biotechnology, and Biochemistry
ISSN: 0916-8451 (Print) 1347-6947 (Online) Journal homepage: http://www.tandfonline.com/loi/tbbb20
Production of dicarboxylic acids from novel
unsaturated fatty acids by laccase-catalyzed
oxidative cleavage
Michiki Takeuchi, Shigenobu Kishino, Si-Bum Park, Nahoko Kitamura, Hiroko
Watanabe, Azusa Saika, Makoto Hibi, Kenzo Yokozeki & Jun Ogawa
To cite this article: Michiki Takeuchi, Shigenobu Kishino, Si-Bum Park, Nahoko Kitamura,
Hiroko Watanabe, Azusa Saika, Makoto Hibi, Kenzo Yokozeki & Jun Ogawa (2016): Production of
dicarboxylic acids from novel unsaturated fatty acids by laccase-catalyzed oxidative cleavage,
Bioscience, Biotechnology, and Biochemistry, DOI: 10.1080/09168451.2016.1200457
To link to this article: http://dx.doi.org/10.1080/09168451.2016.1200457
Published online: 27 Jun 2016.
Submit your article to this journal
View related articles
View Crossmark data
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=tbbb20
Download by: [Florida State University]
Date: 28 June 2016, At: 18:46

Bioscience, Biotechnology, and Biochemistry, 2016
Production of dicarboxylic acids from novel unsaturated fatty acids by
laccase-catalyzed oxidative cleavage
1
1
2
1
1
Michiki Takeuchi , Shigenobu Kishino , Si-Bum Park , Nahoko Kitamura , Hiroko Watanabe ,
1
2
2
1,3,
Azusa Saika , Makoto Hibi , Kenzo Yokozeki and Jun Ogawa
*
1
2
Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kyoto, Japan; Industrial
3
Microbiology, Graduate School of Agriculture, Kyoto University, Kyoto, Japan; Research Unit for Physiological
Chemistry, Kyoto University, Kyoto, Japan
Received April 1, 2016; accepted May 31, 2016
http://dx.doi.org/10.1080/09168451.2016.1200457
The establishment of renewable biofuel and chem-
ical production is desirable because of global warm-
ing and the exhaustion of petroleum reserves.
Sebacic acid (decanedioic acid), the material of 6,10-
nylon, is produced from ricinoleic acid, a carbon-
neutral material, but the process is not eco-friendly
because of its energy requirements. Laccase-catalyz-
ing oxidative cleavage of fatty acid was applied to
the production of dicarboxylic acids using hydroxy
and oxo fatty acids involved in the saturation meta-
bolism of unsaturated fatty acids in Lactobacillus
plantarum as substrates. Hydroxy or oxo fatty acids
with a functional group near the carbon–carbon
double bond were cleaved at the carbon–carbon
double bond, hydroxy group, or carbonyl group by
laccase and transformed into dicarboxylic acids.
After 8 h, 0.58 mM of sebacic acid was produced
from 1.6 mM of 10-oxo-cis-12,cis-15-octadecadienoic
acid (αKetoA) with a conversion rate of 35%
processes for the synthesis of succinic acid, 1,4-butane-
diol, 1,3-propanediol and biodiesel were developed
1
–4)
and won Green Chemistry Challenge Awards. How-
ever, it is difficult to produce oxygenated long-chain
carboxylic acids because of stringent regulation of the
carbon chain length and the thermodynamically unfa-
3
,5)
vorable nature of ω-hydroxylation.
Long-chain dicar-
boxylic acids and hydroxy fatty acids are used for
several polymers (e.g. polyamides and polyesters), plas-
ticizers, lubricants, and perfumes. For instance, sebacic
acid (1,10-decanedioic acid) is the material of 6,10-ny-
lon, a polyamide representative, and is derived from
biomass. Several ten thousand tons of sebacic acid are
transferred from ricinoleic acid (12-hydroxy-cis-9-oc-
tadecenoic acid), which is abundant in castor oil, a
well-known carbon-neutral compound. However, the
chemical process for producing sebacic acid requires a
huge amount of energy, involving alkaline conditions
6
)
with high temperature and pressure. Therefore, it is
desirable to establish an eco-friendly process for pro-
ducing dicarboxylic acids such as sebacic acid.
(
mol/mol). This laccase-catalyzed enzymatic process
is a promising method to produce dicarboxylic acids
from biomass-derived fatty acids.
In a previous study, we revealed the polyunsaturated
fatty acid saturation metabolism in Lactobacillus plan-
7)
Key words: dicarboxylic acid; laccase; unsaturated
fatty acid; hydroxy fatty acid; oxo fatty
acid
tarum AKU 1009a. The saturation metabolism con-
sists of four enzymes: CLA-HY (unsaturated fatty acid
hydratase), CLA-DH (hydroxy fatty acid dehydroge-
nase), CLA-DC (isomerase), and CLA-ER (enone
8
–11)
reductase).
This strain produces cis-9,trans-11-con-
Global warming and the exhaustion of petroleum
reserves necessitate the establishment of an environ-
mentally friendly way of producing renewable biofuels
and chemicals. Over the past 10 years, scientific and
technological advances have established biocatalysis as
a practical and environmentally friendly alternative to
traditional chemical synthesis, both in the laboratory
and on an industrial scale. For instance, biocatalytic
jugated linoleic acid (CLA) and trans-9,trans-11-CLA
as byproducts during the saturation of linoleic acid
1
2–14)
(LA) to oleic acid (OA).
The application of these
enzymes enables us to produce intermediate fatty acids
such as 10-hydroxy-cis-12-octadecenoic acid (HYA),
10-hydroxyoctadecanoic acid (HYB), 10-oxo-cis-12-oc-
tadecenoic acid (KetoA), and 10-oxooctadecanoic acid
(KetoB) from LA. In addition to LA, α-linolenic acid
*Corresponding author. Email: ogawa@kais.kyoto-u.ac.jp
Abbreviations: LA, linoleic acid; OA, oleic acid; CLA, conjugated linoleic acid; NADH, nicotinamide adenine dinucleotide; FAD, flavin adenine
dinucleotide; BSA, bovine serum albumin; HBT, 1-hydroxybenzotriazole; TEMPO, 2,2,6,6-tetramethylpiperidine 1-oxyl; ABTS, 2,2′-azinobis
(
3-ethylbenzothiazoline-6-sulfonic acid ammonium salt); GC, gas–liquid chromatography; MS, mass spectrometry; HYA, 10-hydroxy-cis-12-octade-
cenoic acid; HYB, 10-hydroxyoctadecanoic acid; KetoA, 10-oxo-cis-12-octadecenoic acid; KetoB, 10-oxooctadecanoic acid; αHYA, 10-hydroxy-
cis-12,cis-15-octadecenoic acid; αKetoA, 10-oxo-cis-12,cis-15-octadecadienoic acid; γHYA, 10-hydroxy-cis-6,cis-12-octadecenoic acid; γKetoA,
10-oxo-cis-6,cis-12-octadecenoic acid.
©
2016 Japan Society for Bioscience, Biotechnology, and Agrochemistry

2
M. Takeuchi et al.
and γ-linolenic acid are also converted into 10-hy-
droxy-cis-12,cis-15-octadecadienoic acid (αHYA) and
Reaction conditions.
As standard reaction condi-
tion, the reaction with laccase was conducted with
shaking (300 strokes/min) at 37 °C for 8 h in a test
tube (16.5 × 105 mm) that contained 1 mL of reaction
mixture (20 mM of sodium acetate buffer, pH 4.0) with
11.3 U/mL laccase, 1.5 mM of αKetoA, and 1 mM of
HBT. One unit was defined as the amount of enzyme
that catalyzes the oxidation of 1 μmol of 2,2′-azinobis
(3-ethylbenzothiazoline-6-sulfonic acid ammonium salt)
(ABTS) per minute. All experiments were performed in
triplicate. For substrate specificity experiments, we pre-
pared 23 kinds fatty acids including hydroxy and oxo
fatty acids. Twenty-three different fatty acids were
tested under the standard reaction condition except for
the substrate and reaction time. Reaction time was
24 h. The concentration of dicarboxylic acids from
reaction mixture with αKetoA was defined as 100%.
For experiments of mediators effects, 1 mM of six
mediators [HBT, benzotriazole, veratryl alcohol, vio-
luric acid, ABTS, 2,2,6,6-tetramethylpiperidine 1-oxyl
(TEMPO)] were used. For experiments of mediator
concentration effects, HBT was used with a range of
0–5 mM. For experiments of reaction temperature
effects, reaction temperature was 18–52 °C. For experi-
ments of reaction pH effects, sodium acetate buffer,
HEPES buffer, and Tris-HCl buffer were used for
pH 3–5, 6–7.5, and 7–9, respectively. For time course
of sebacic acid production, reaction was conducted
with 20 mM of sodium acetate buffer (pH 5.0) at 40 °C
for 0–8 h.
1
0-hydroxy-cis-6,cis-12-octadecadienoic acid (γHYA)
1
5)
by CLA-HY.
These novel fatty acids are potential
materials for the production of biopolymers because
they are produced from LA, α-linolenic acid, or γ-li-
nolenic acid in biomass-derived oils, and have func-
tional groups such as a hydroxy group or an oxo
group.
Laccase belongs to the multi-copper oxidase family
and catalyzes four-electron oxidation by reducing oxy-
1
6,17)
gen to water.
Trametes sp. Ha-1, the white-rot fun-
gus, shows lignolytic oxidation activity and produces
commercial laccase, which has high oxidation activity
1
8)
and thermostability.
Laccase can directly oxidize
phenolic lignin structures and also non-phenolic lignin
1
9)
compounds in the presence of suitable mediators.
For example, the laccase-mediator system is applied to
2
0)
dye-decolorization
and rice straw treatment for
2
1)
bioethanol production. In addition, it is reported that
azelaic acid (nonanedioic acid) was produced from
linoleic acid and oleic acid using laccase mediator sys-
2
2)
tem. However the substrates investigated were only
common unsaturated fatty acids and there is no report
to produce C10 dicarboxylic acid enzymatically. There-
fore, in this study, we attempted to establish microbial
processes to produce dicarboxylic acids especially for
C10 dicarboxylic acid, e.g. sebacic acid from biomass-
derived fatty acids, for example, ricinoleic acid and
intermediate fatty acids, during the saturation of
linoleic acid to oleic acid.
Fatty acid analysis.
Lipids were extracted from
the reaction mixture with ethyl acetate (containing 10%
methanol) and then concentrated by evaporation under
reduced pressure. The resulting lipids were dissolved in
Materials and methods
Materials. Laccase (from Trametes sp. Ha-1) was
purchased from Daiwa Fine Chemicals Co., Ltd.
5
mL of benzene/methanol (3:2, by volume) and
(
Kobe, Japan). OA, nicotinamide adenine dinucleotide,
methylated with 300 μL of 1% trimethylsilyldia-
zomethane (in hexane) at 28 °C for 30 min. The result-
ing fatty acid methyl esters were concentrated by
evaporation under reduced pressure and analyzed by
gas–liquid chromatography (GC) using a Shimadzu
flavin adenine dinucleotide, and 1-hydroxybenzotriazole
were purchased from Wako Pure Chemical Industries,
Ltd. (Osaka, Japan). LA and fatty acid-free (<0.02%)
bovine serum albumin were purchased from Sigma (St.
Louis, MI, USA). α-Linolenic acid and γ-linolenic acid
were purchased from Nu-Chek-Prep, Inc. (Elysian,
MN, USA). HYA, HYB, αHYA, and γHYA were pro-
duced from OA, LA, α-linolenic acid, and γ-linolenic
acid, respectively, by Escherichia coli Rosetta2/pCLA-
(
Kyoto, Japan) gas chromatograph equipped with a
flame ionization detector and a split injection system
and fitted with capillary column (SPB-1,
0 m × 0.25 mm I.D.; Supelco, Bellefonte, PA, USA).
The column temperature was initially 180 °C for
0 min, was raised to 220 °C at a rate of 40 °C/min,
a
3
1
5)
HY. 10-Hydroxy-trans-11-octadecenoic acid and 10-
oxo-trans-11-octadecenoic acid were produced from
3
and was then maintained at that temperature for 9 min.
The injector and detector were operated at 250 °C.
Helium was used as a carrier gas at a flow rate of
7
)
LA as described previously. 10-Hydroxy-cis-15-oc-
tadecenoic acid, 10-hydroxy-trans-11,cis-15-octadeca-
dienoic acid, 10-oxo-cis-15-octadecenoic acid, and 10-
oxo-trans-11,cis-15-octadecadienoic acid were pro-
1.9 mL/min in the column. Heptadecanoic acid (17:0)
was used as an internal standard for quantification.
7
)
duced from α-linolenic acid as described previously.
0-Hydroxy-cis-6-octadecenoic acid, 10-hydroxy-cis-6,
1
trans-11-octadecadienoic acid, 10-oxo-cis-6-octade-
cenoic acid, and 10-oxo-cis-6,trans-11-octadecadienoic
acid were produced from γ-linolenic acid as described
GC-MS analysis. Methyl esters of fatty acids were
subjected to GC-MS analysis using GCMS-QP2010
Plus (Shimadzu) with a GC-2010 gas chromatograph.
The GC separation of fatty acid methyl esters was per-
formed on an SPB-1 column as described above. The
column temperature was initially 180 °C for 30 min,
was raised to 220 °C at a rate of 30 °C/min, and was
then maintained at that temperature for 40 min. The
injector and MS interface were operated at 220 °C.
7
)
previously. 10-Oxo-cis-12-octadecenoic acid (KetoA),
0-oxooctadecanoic acid (KetoB), 10-oxo-cis-12,cis-15-
octadecadienoic acid (αKetoA), and 10-oxo-cis-6,cis-
2-octadecadienoic acid (γKetoA) were produced from
the above hydroxy fatty acids by Jones oxidation,
1
1
2
3)
which is oxidation of a hydroxy group with CrO3.

Dicarboxylic acid production by laccase
3
Table 1. Substrate specificity.
Substrate
Product
Relative activity [%]
1
9
1
2
1
1
7
3
b
tr
1
1
3
4
8
8
a
1
00
4
2
tr.
7
.1
6
6
4
4
1
7
(
Continued)

4
M. Takeuchi et al.
Table 1. (Continued).
Substrate
Product
Relative activity [%]
1
.0
7
.6
a
The mole amount of products from 10-Oxo-cis-12,cis-15-octadecadienoic acid under the condition (1 mM of HBT, 37 °C, pH 4.0, 24 h) was defined as 100%.
tr., trace, ˂0.001%.
not detected.
b
c
Cleavage positions were indicated by arrows.
Helium was used as a carrier gas at a flow rate of
indicated by arrows in Table 1. αKetoA was used in
the following experiments because the amount of prod-
ucts was the highest among these various fatty acids.
1
.7 mL/min in the column.
Results and discussion
Substrate specificity
Effect of mediators for dicarboxylic acid production
Six mediators were examined for their ability to
mediate laccase-catalyzed oxidation of fatty acids
Twenty-three different fatty acids were applied to the
oxidative reaction by laccase, and shorter products were
observed by GC analysis (Table 1). As a representative
result, the GC chromatogram and mass spectrum of
products from 10-oxo-cis-12,cis-15-octadecadienoic
acid (αKetoA) are shown in Fig. 1. In terms of the
results of GC-MS analysis, the product was identified
as sebacic acid because the retention time and MS frag-
ments of the methyl-esterified product corresponded to
those of the methyl-esterified sebacic acid standard
(Table 2). Among these six, HBT and TEMPO gave
highest production of sebacic acid (0.40 mM). Among
six mediators, TEMPO, HBT, and violuric acid belong
2
0)
to N–OH-type mediator. N–OH is necessary but not
sufficient for efficient production of dicarboxylic acid.
The productivity is determined by combination of enzy-
matic activity for mediator oxidation and reactivity of
oxidized mediator toward substrate. Mediator concen-
tration was varied from 0 to 5 mM. The production of
sebacic acid depended on mediator concentration
(
Fig. 1(b)). The byproduct was expected to be C8 com-
pounds, but was not detected under these conditions.
Dicarboxylic acids were produced from almost all of
the fatty acids, except for six hydroxy and oxo fatty
acids that have no carbon–carbon double bond near a
hydroxy or oxo group, such as HYB, 10-hydroxy-cis-
(Fig. 2). Sebacic acid production increased depending
on HBT concentration under 1 mM, but was constant
over 1 mM.
6
-octadecenoic acid, 10-hydroxy-cis-15-octadecenoic
Effects of reaction pH and temperature
The effects of reaction pH and temperature were
examined. The optimal reaction pH was found to be
acid, KetoB, 10-oxo-cis-6-octadecenoic acid, and 10-
oxo-cis-15-octadecenoic acid (Table 1). The oxidative
cleavage of fatty acids by laccase occurred in the unsat-
urated fatty acids which have carbon–carbon double
bond, hydroxy group, or carbonyl group at allylic or
homoallylic position. The cleavage positions were
5
.0 (Fig. 3), although the optimum pH of laccase for
ABTS oxidation was 3.0 (data not shown). The differ-
ence of optimum pH between the cleavage of αKetoA
and the oxidation of ABTS was probably caused by
the difference in the stability of αKetoA and laccase at
each pH. The optimal reaction temperature was found
to be 40 °C (Fig. 4). The time course of oxidative
cleavage of αKetoA by laccase is shown in Fig. 5.
After 8 h, 0.58 mM of sebacic acid was produced from
Table 2. Effect of mediator on sebacic acid production.
Mediator
TEMPO
Sebacic acid production (mM)
0.40
0.39
0.22
0.22
0.22
0.19
1
-Hydroxybenzotriazole (HBT)
Veratryl alcohol
Violuric acid
ABTS
Benzotriazole
TEMPO: 2,2,6,6-tetramethylpiperidine 1-oxyl, HBT: 1-hydroxybenzotriazole,
ABTS: 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) ammonium salt.
The reaction mixture contained 1.5 mM of 10-oxo-cis-12,cis-15-octadeca-
dienoic acid, laccase, and 1 mM of each mediator. Experimental conditions:
temperature, 37 °C; shaking frequency, 300 rpm; reaction time; 8 h.
Fig. 1. Gas-chromatography chromatogram (a) and mass spectrum
(
b) of the product from αKetoA.

Dicarboxylic acid production by laccase
5
Fig. 4. Effect of reaction temperature on sebacic acid production.
Fig. 2. Effect of mediator concentration on sebacic acid production.
Note: The reaction mixture containing 1.5 mM of αKetoA, 11.3 U/
mL laccase, and 1-hydroxybenzotriazole (HBT) (0–5 mM). Reaction
conditions: temperature, 37 °C; shaking frequency, 300 strokes/min;
reaction time, 8 h.
Note: The reaction mixture contained 1.5 mM of αKetoA, 11.3 U/
mL laccase, 1 mM of HBT, and 20 mM of sodium acetate buffer
(pH 4.0). Reaction conditions: temperature, 18–52 °C; shaking fre-
quency, 300 strokes/min; reaction time, 8 h.
1
.6 mM of αKetoA with a conversion rate of 35%
into dicarboxylic acid by the same mechanism as aze-
laic acid (nonanedioic acid) generation as an end pro-
(
mol/mol).
2
6)
In a previous study, we established a process for pro-
duct of LA peroxidation.
The rate of conversion
ducing hydroxy fatty acids using linoleic acid hydratase
from αKetoA to sebacic acid was low level [about 35%
(mol/mol)] because of the difficulty of controlling the
radical reaction (Fig. 5). However, the laccase-catalyzed
enzymatic process appears to be promising for eco-
friendly production of dicarboxylic acid from biomass-
derived fatty acids because this process does not
require high energy and highly alkaline condition
compared with chemical process. Innovation Commer-
cialization Venture Support Project from the New
Energy and Industrial Technology Development Orga-
nization (NEDO) of Japan (to collaboration of NITTO
PHARMA and J. O.) Science and Technology
Promotion Program for Agriculture Forestry, Fisheries,
and Food Industry from the Ministry of Agriculture,
1
5)
from L. plantarum AKU 1009a. These hydroxy fatty
acids have health-supporting activities such as anti-in-
flammatory, anti-obesity, and immunomodulatory
2
4,25)
effects.
In this study, these hydroxy fatty acids
were also shown to be promising starting materials for
bioplastic production because dicarboxylic acids were
produced from hydroxy and oxo fatty acids by laccase.
Hydroxy and oxo unsaturated fatty acids are favorable
compounds to control the chain length of products of
oxidative reactions for dicarboxylic acid production
(
Table 1). The mechanism is expected that dihydroxy
fatty acid generated by epoxidation and hydration of
carbon–carbon double bond is cleaved and converted
Fig. 3. Effect of reaction pH on sebacic acid production.
Note: The reaction mixture contained 1.5 mM of αKetoA, 11.3 U/
mL laccase, 1 mM of HBT, and 20 mM of buffer. Reaction condi-
tions: temperature, 37 °C; shaking frequency, 300 strokes/min; reac-
tion time, 8 h; circle, sodium acetate buffer; triangle, HEPES buffer;
square, Tris-HCl buffer.
Fig. 5. Time course of sebacic acid production from αKetoA.
Note: The reaction mixture contained 1.6 mM of αKetoA, 11.3 U/
mL laccase, 1 mM of HBT, and 20 mM of sodium acetate buffer
(pH 5.0). Reaction conditions: temperature, 40 °C; shaking frequency,
300 strokes/min; triangle, αKetoA; circle, sebacic acid.

6
M. Takeuchi et al.
Forestry, and Fisheries of Japan [grant number 26002A
and 26002AB] (to J.O.)
[9] Takeuchi M, Kishino S, Park S-B, et al. Characterization of
hydroxy fatty acid dehydrogenase involved in polyunsaturated
fatty acid saturation metabolism in Lactobacillus plantarum
AKU 1009a. J. Mol. Catal. B Enzym. 2015;117:7–12.
10] Kishino S, Park SB, Takeuchi M, et al. Novel multi-component
enzyme machinery in lactic acid bacteria catalyzing C=C double
bond migration useful for conjugated fatty acid synthesis.
Biochem. Biophys. Res. Commun. 2011;416:188–193.
11] Hou F, Miyakawa T, Kitamura N, et al. Structure and reaction
mechanism of a novel enone reductase. FEBS J. 2015;282:
1526–1537.
[
[
Author contributions
All members conceived and designed the experi-
ments, and discussed the results for the completion of
the manuscript. MT, SK, SBP, NK, HW, and AS per-
formed the experiments. MT analyzed the data and
wrote the manuscript in consultation with SK, MH,
KY, and JO.
[12] Kishino S, Ogawa J, Omura Y, et al. Conjugated linoleic acid
production from linoleic acid by lactic acid bacteria. J. Am. Oil
Chem. Soc. 2002;79:159–163.
[
[
[
13] Ogawa J, Matsumura K, Kishino S, et al. Conjugated linoleic
acid accumulation via 10-hydroxy-12-octadecaenoic acid during
microaerobic transformation of linoleic acid by Lactobacillus
acidophilus. Appl. Environ. Microbiol. 2001;67:1246–1252.
14] Kishino S, Ogawa J, Ando A, et al. Structural analysis of
conjugated linoleic acid produced by Lactobacillus plantarum,
and factors affecting isomer production. Biosci. Biotechnol.
Biochem. 2003;67:179–182.
15] Takeuchi M, Kishino S, Park SB, et al. Efficient enzymatic pro-
duction of hydroxy fatty acids by linoleic acid Δ9 hydratase
from Lactobacillus plantarum AKU 1009a. J. Appl. Microbiol.
2016;120:1282–1288.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported, in part, by the Industrial Technology
Research Grant Program in 2007 [grant number 07A08005a] (to S.K.);
Innovation Commercialization Venture Support Project from the New
Energy and Industrial Technology Development Organization (NEDO)
of Japan (to collaboration of NITTO PHARMA and J. O.); Scientific
Research Grants in Aid [grant number 19780056] (to S.K.), [grant
number 16688004] (to J.O.); the Bio-Oriented Technology Research
Advancement Institution of Japan (J.O.); the Advanced Low Carbon
Technology Research and Development Program of Japan (S.K.);
Science and Technology Promotion Program for Agriculture Forestry,
Fisheries, and Food Industry from the Ministry of Agriculture, For-
estry, and Fisheries of Japan [grant number 26002A and 26002AB] (to
J.O.). M.T. and S.K. received Research Fellowship from the Japan
Society for the Promotion of Science for Young Scientists.
[16] Baldrian P. Fungal laccases - occurrence and properties. FEMS
Microbiol. Rev. 2006;30:215–242.
[17] Sulistyaningdyah WT, Ogawa J, Tanaka H, et al. Characteriza-
tion of alkaliphilic laccase activity in the culture supernatant of
Myrothecium verrucaria 24G-4 in comparison with bilirubin oxi-
dase. FEMS Microbiol. Lett. 2004;230:209–214.
[18] Nakatani M, Hibi M, Minoda M, et al. Two laccase isoenzymes
and a peroxidase of a commercial laccase-producing basid-
iomycete, Trametes sp. Ha1. N. Biotechnol. 2010;27:317–323.
[19] ten Have R, Teunissen PJ. Oxidative mechanisms involved in
lignin degradation by white-rot fungi. Chem. Rev.
2
001;101:3397–3414.
[
20] Morozova OV, Shumakovich GP, Shleev SV, et al. Laccase-me-
diator systems and their applications: a review. Appl. Biochem.
Microbiol. 2007;43:523–535.
References
[
1] Nakamura CE, Whited GM. Metabolic engineering for the
microbial production of 1,3-propanediol. Curr. Opin. Biotech.
[21] Nakanishi A, Bae JG, Fukai K, et al. Effect of pretreatment of
hydrothermally processed rice straw with laccase-displaying
yeast on ethanol fermentation. Appl. Microbiol. Biotechnol.
2012;94:939–948.
[22] Kimura T. Toyota Motor Corporation. Production method of
dicarboxylic acids. Japan Kokai Tokkyo Koho, P2006-262728A
(2006. Oct. 5).
[23] Curtis RG, Heilbron I, Jones ERH, et al. 92. The chemistry of
the triterpenes. Part XIII. The further characterisation of poly-
porenic acid A. J. Chem. Soc. 1953;457–464.
[24] Bergamo P, Luongo D, Miyamoto J, et al. Immunomodulatory
activity of a gut microbial metabolite of dietary linoleic acid, 10-
hydroxy-cis-12-octadecenoic acid, associated with improved antiox-
idant/detoxifying defences. J. Funct. Foods. 2014;11:192–202.
[25] Miyamoto J, Mizukure T, Park SB, et al. A gut microbial
metabolite of linoleic acid, 10-hydroxy-cis-12-octadecenoic acid,
ameliorates intestinal epithelial barrier impairment partially via
GPR40-MEK-ERK pathway. J. Biol. Chem. 2015;290:
2902–2918.
[26] Raghavamenon A, Garelnabi M, Babu S, et al. α-Tocopherol is
ineffective in preventing the decomposition of preformed lipid
peroxides and may promote the accumulation of toxic aldehydes:
a potential explanation for the failure of antioxidants to affect
human atherosclerosis. Antioxid. Redox Signal. 2009;11:
1237–1248.
2003;14:454–459.
[
2] Yim H, Haselbeck R, Niu W, et al. Metabolic engineering of
Escherichia coli for direct production of 1,4-butanediol. Nat.
Chem. Biol. 2011;7:445–452.
[
3] Bornscheuer UT, Huisman GW, Kazlauskas RJ, et al. Engineer-
ing the third wave of biocatalysis. Nature. 2012;485:185–194.
4] Steen EJ, Kang Y, Bokinsky G, et al. Microbial production of
fatty-acid-derived fuels and chemicals from plant biomass.
Nature. 2010;463:559–562.
[
[
5] Song JW, Jeon EY, Song DH, et al. Multistep enzymatic synthe-
sis of long-chain alpha, omega-dicarboxylic and omega-hydroxy-
carboxylic acids from renewable fatty acids and plant oils.
Angew. Chem. Int. Ed. 2013;52:2534–2537.
[
[
[
6] Bouis MJ. Sur l’huile de ricin et sur l’alcool caprylique qui en
resulte [About castor oil and resulting octanol]. Annales de
chimie et de physique. 1855;44:77–151.
7] Kishino S, Takeuchi M, Park SB, et al. Polyunsaturated fatty acid
saturation by gut lactic acid bacteria affecting host lipid composi-
tion. Proc. Natl. Acad. Sci. USA. 2013;110:17808–17813.
8] Takeuchi M, Kishino S, Hirata A, et al. Characterization of the
linoleic acid Δ9 hydratase catalyzing the first step of polyunsatu-
rated fatty acid saturation metabolism in Lactobacillus plantarum
AKU 1009a. J. Biosci. Bioeng. 2015;119:636–641.