Candida parapsilosis ATCC 7330 mediated oxidation of aromatic (activated) primary alcohols to aldehydes

Article abstract of DOI:10.1039/c5ra18532g

A green, simple and high yielding [up to 86% yield] procedure is developed for the oxidation of aromatic (activated) primary alcohols to aldehydes using whole cells of Candida parapsilosis ATCC 7330. The biotransformation is carried out under mild conditions at 25 °C, in hexane: water (48 : 2) (v/v).

Full text of DOI:10.1039/c5ra18532g

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Candida parapsilosis ATCC 7330 mediated
oxidation of aromatic (activated) primary alcohols
to aldehydes
Cite this: RSC Adv., 2015, 5, 91594
a
ab
Thakkellapati Sivakumari and Anju Chadha*
Received 10th September 2015
Accepted 19th October 2015
A green, simple and high yielding [up to 86% yield] procedure is developed for the oxidation of aromatic
DOI: 10.1039/c5ra18532g
(activated) primary alcohols to aldehydes using whole cells of Candida parapsilosis ATCC 7330. The
ꢀ
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biotransformation is carried out under mild conditions at 25 C, in hexane: water (48 : 2) (v/v).
benzaldehyde using different commercial oxidases and alcohol
Introduction
12
dehydrogenases,
and laccases with mediators is also
The laccase cross-linked enzyme aggregates are re-
–C10 aliphatic
antioxidants and anti-bacterials, anti-amoebics, drugs for the alcohols, to the corresponding aldehydes. Alditols to D-aldoses
17,18
Aldehydes are useful precursors in the synthesis of a variety of known.
1
2
pharmaceuticals e.g. anti-malarial drugs, anti-cancer drugs,
ported for the aerobic oxidation of linear C
5
3
4
18
5
19
treatment of iron overload and iron deciency and antipsy- using alditol oxidase and oxidation of primary alcohols hexan-
6
chotic drugs among others. Several chemical reagents have 1-ol, hexen-1-ols, epoxyhexan-1-ols and 3-phenylglycidol to their
been reported so far for the oxidation of primary alcohols to corresponding aldehydes catalysed by chloroperoxidase is
7
20,21
aldehydes. The limitations that are associated with the chem- reported.
ical reagents, (e.g. removal of metallic by-products, formation of
For oxidation of primary alcohols mainly two types of reac-
side products, difficulty in handling of hygroscopic reagents, tion media are reported. They are, water or buffer at different
8
9
12,14,16,17,19,21–28
requirements of low or high temperature which is an addi- pH
and biphasic systems i.e. use of water or buffer
tional setup to maintain the temperature) make it important to with an immiscible organic solvent (e.g. hexane, xylene, isooc-
1
5,20,29,30
develop alternate green methods for this oxidation. In the tane, ethyl acetate, toluene, octanol, octane, hexadecane).
search of green catalytic methods using chemical catalysts, In the case of biphasic systems, aqueous phase provides
10
different non-metal based oxidizing agents and ligands that a natural enzyme environment whereas the organic phase acts
11
can be used in catalytic amounts were developed. But this as a substrate reservoir and a product sink to avoid substrate or
31,32
involves the synthesis of ligands or reagents. In this context, product inhibition.
This can also overcome the problem of
biocatalysts offer attractive possibilities as oxidizing agents low productivity in aqueous media due to poor substrate solu-
33
because most living systems which require oxygen to survive bility. Moreover the use of biphasic systems in the case of
have the machinery for ‘oxidation’ and these biocatalysts are primary alcohol oxidation helps in the extraction of hydro-
34
easy to handle at room temperature in addition to the fact that phobic aldehydes in situ avoiding over oxidation to acids or
12
they are also selective.
reduction to alcohols that happens in aqueous media.
Biocatalysed alcohol oxidation is not as well explored as
It is well known that yeasts are rich in oxido-reductases
13
13,35
asymmetric reduction. Biocatalytic oxidation of substituted which are responsible for the oxidation of alcohols.
C. par-
benzyl alcohols, aliphatic, allylic, and acetylenic alcohols to the apsilosis ATCC 7330, a yeast, is known to catalyse deracemiza-
3
6–39
corresponding aldehydes is reported using whole cells of Jan- tion of several secondary alcohols
and asymmetric
12,14
39–41
ibacter terrae DSM 13953.
Deracemization using C. parapsilosis
benzaldehyde using immobilized whole cells of Pichia pastoris is ATCC 7330 proceeds through stereoinversion. Based on this
Bio-oxidation of benzyl alcohol to reduction of ketones.
38
15
known. Oxidation of aliphatic and aromatic alcohols to the observation, C. parapsilosis ATCC 7330 mediated enantiose-
42
corresponding aldehydes using whole cells of Gluconobacter lective oxidation of secondary alcohols, regio- and enantiose-
16
43
oxydans DSM 2343 is reported. Benzyl alcohol oxidation to lective oxidation of diols were optimised. In the current study
the same yeast is used for the oxidation of primary alcohols.
a
Laboratory of Bioorganic Chemistry, Department of Biotechnology, IIT Madras,
Chennai 600 036, India. E-mail: anjuc@iitm.ac.in; Fax: +91 44 2257 4102; Tel: +91 Results and discussions
4
4 2257 4106
b
Cinnamyl alcohol 1 [Scheme 1, Table 2] was the model substrate
for the oxidation of primary alcohols using whole cells of
National Center for Catalysis Research, Indian Institute of Technology Madras,
Chennai 600 036, India
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Substrate concentration
Under the above optimized conditions, substrate concentration
was optimized to 0.05 mmol (6 mg) to give a conversion of 82%
for 2.6 g wet cell mass.
Biomass
Scheme 1 Oxidation of cinnamyl alcohol by C. parapsilosis ATCC
7330.
For this biocatalysed reaction, which uses whole cells, biomass
concentration has signicant effects on a biotransformation,
45
therefore in order to maximise the conversion, biomass
concentration (dry cell weight) was also optimized. Maximum
conversion 91% was observed at 2 g of wet biomass. Finally at
optimum reaction conditions as discussed above oxidation of
cinnamyl alcohol 1 to cinnamaldehyde showed 91% conversion
with yield 86% (51 mg). The same reaction conditions were used
for the oxidation of the other primary alcohols with change in
the reaction times.
C. parapsilosis ATCC 7330. The reaction was monitored by HPLC
using reverse phase C18 column. Several parameters like reac-
tion medium, reaction time, substrate concentration and
proportion of solvents for reaction were optimized in order to
get maximum conversion.
Optimization of reaction conditions
The 14 h culture of C. parapsilosis ATCC 7330 as reported for the
Cosolvent optimization
enantioselective oxidation of secondary alcohols, was used for
42
For solid substrates, cosolvent screening was done using 4-
methyl benzyl alcohol 4 [Table 3] as model substrate. Different
cosolvents acetone, acetonitrile, dimethyl sulfoxide, dime-
thylformamide, ethanol, 1,4-dioxane and diisopropyl ether were
screened. Among the cosolvents screened, acetonitrile (0.4% of
the total volume 50 ml) showed maximum conversion 60% at 22
h with a yield of 54% (29 mg). Biocatalytic oxidation of 4
the oxidation of primary alcohols.
Reaction medium
Initially, oxidation of cinnamyl alcohol 1 (0.06 mmol) was
carried out in water (5 ml) using acetone (4%, 200 ml) as co-
ꢀ
solvent for 2.6 g wet cells (dry cell mass 696 mg) at 25 C, 150
[Table 3] i.e. with p-Me substituent resulted in average conver-
rpm. Maximum conversion (21%) was observed at 15 min. In
order to increase the conversion, a buffer at different values of
pH, ranging from 6–8 was used. Decrease in conversion was
observed. Water was therefore used for further studies.
Different cosolvents viz. 1,4-dioxane (conversion 17%), aceto-
nitrile (conversion 18%) and dimethylsulfoxide (conversion
sion of 60% with an isolated yield of 54%, which was also re-
ported using lyophilized cells of Janibacter terrae [conversion
12
1
6%] in 24 h. For other solid substrates acetonitrile was used
as cosolvent (Table 1).
Substrate scope [Table 2]
15%) were screened for maximum conversion instead of
acetone. Cosolvents can affect the rate of enzymatic reactions by
To increase the substrate spectrum, different primary alcohols
were subjected to oxidation. Under the above optimized
conditions thiophen-2-ylmethanol 2 [Table 2] showed a conver-
sion of 81% in 16.5 h with a yield 73% (37 mg). Substitution to 5-
Br in the case of (5-bromothiophen-2-yl)methanol 3 [Table 2]
with an increased reaction time of 24 h, gave a conversion of
altering the free energy gap between ground and transition
44
states and also the conformational motility of the enzyme.
A
biphasic system of hexane : water (48 : 2) (v/v) was tried based
on an earlier report for the hexanol oxidation where the yield
29
was 96%.
8
6%, yield 77% (66 mg) to the corresponding 5-bromothio-
phene-2-carbaldehyde.
Substitution to a Me group at 5 position instead of 5-Br, i.e.
Reaction time
th
Using hexane : water (48 : 2) (v/v) as reaction medium, the of (5-methylthiophen-2-yl) methanol 4 [Table 2] gave a reduced
reaction time was optimized. Maximum conversion of 75% was conversion of 76% with a of yield 67% (38 mg) to 5-
observed at 1.5 h. Cinnamyl alcohol 1 was added to the reaction methylthiophene-2-carbaldehyde. Attachment of benzene ring
medium using hexane.
in benzo[b]thiophen-3-ylmethanol 5 [Table 2] did not show
conversion aer 24 h. Similar observation, i.e. increase in size of
the alcohol with a decrease in catalytic efficiency was reported
Hexane volume
46,47
for Saccharomyces cerevisiae ADH1.
Starting from cinnamyl
In order to optimise the volume of hexane required, the water alcohol 1 considering the other alcohols 2–4, [Table 2] the
volume was kept constant and the following biphasic systems reaction time increased and a decrease in conversion was
were tried: Hexane : water (3 : 2) (v/v), (8 : 2) (v/v), (28 : 2) (v/v) observed which may be due to steric hindrance at the alcoholic
46
and (68 : 2) (v/v) and the conversions were 17%, 26%, 45%, carbon for hydride ion transfer. In the case of cinnamyl
5% and 62% respectively. The hexane : water ratio of 48 : 2 alcohol 1, the –OH group is 3 carbons away from the aromatic
v/v) was used for further studies as it gave the best conversion ring, while for the rest of the alcohols the aromatic ring is
7
(
(
75%).
attached to the same carbon as the –OH group.
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ꢀ
50
Table 1 Optimum conditions for the oxidation of primary alcohols by using Ru/C at 50 C in 24 h, giving yield of 87%. Hence the
Candida parapsilosis ATCC 7330 (cinnamyl alcohol as model substrate)
present method is more efficient: faster for the oxidation of 1 i.e.
in less reaction time and for 2 it is neat i.e. without side prod-
Reaction parameters
Optimum
Conversion (%)
ucts. Oxidation of 3 and 4 to their corresponding aldehydes is
not reported so far either by chemical or biological methods.
Under these experimental conditions aliphatic alcohols n-
butyl alcohol 7 [Table 2], hexan-1-ol 8 [Table 2] and cyclohexyl
methanol 9 [Table 2] did not show any oxidation products. The
fact that deracemization of aliphatic b-hydroxy esters occurs
using the same biocatalyst and deracemization proceeds via
stereo inversion, there is a good possibility that this biocatalyst
can be used for the oxidation of aliphatic substrates, but
Medium
Hexane : water ratio
Substrate concentration
Hexane : water (1.5 h)
(48 : 2) (v/v)
0.05 mmol
2 g wet cells
Acetonitrile [200 mL,
75
75
82
91
60
Biomass a
Cosolvent (for solids)
(
0.4% of the total
volume 50 ml)]
a
Cosolvent optimization was done for p-Me benzyl alcohol 4 [Table 3].
51,52
conditions need to be optimized.
Biotransformation of (6-methoxynaphthalen-2-yl) methanol 6 Effect of substitution [Scheme 2 Table 3]
[
Table 2] did not show any oxidized product even aer 24 h.
In order to check the effect of substitution on the aromatic ring
in the case of benzyl alcohols different substituents were tried
under the above optimized conditions (Scheme 2, Table 3).
Oxidation of p-OMe benzyl alcohol 1 [Table 3] to p-OMe
benzaldehyde showed 68% conversion with the yield of 59% (36
mg). Biocatalytic oxidation of p-OMe benzyl alcohol to p-OMe
benzaldehyde was reported by laccase-with the aid of AZADO (2-
Oxidation of 1 [Table 2] was reported by lyophilized cells of
ꢀ
14
Janibacter terrae with conversion 36% in 24 h at 30 C.
Oxidation of 1 was also reported by Pd(OAc) as catalyst and
] as ligand in 24 h
2
tertiary n-butyl phosphine oxide [O]P(n-Bu)
3
ꢀ
at 80 C with a yield of 98% and additionally, [O]P(n-Bu)
needs to be synthesized. Oxidation of thiophen-2-ylmethanol 2
was also reported by tert-butyl nitrite (t-BuONO) as an oxidant in
1
thiophenecarboxylic acid was also formed in 17% yield (calcu-
lated by GC). Another report for thiophen-2-ylmethanol 2 is
3
]
48
53
azaadamantane N-oxyl) as mediator in 4 h with a yield of 98%,
ꢀ
3 h at 100 C with a yield of 82% (calculated by GC) and 2-
and by lyophilized cells of Janibacter terrae [conversion 46% in
ꢀ
14
2
4 h, at 30 C]. Oxidation of 1 [Table 3] was also reported by
49
ꢀ
vanadium catalyst with yield of 35% at 90 C in 22 h, but here,
b
Table 2 Oxidation of primary alcohols to aldehydes by C. parapsilosis ATCC 7330
a
Substrate
Reaction time (h)
Conversion to aldehyde (%)
Yield of aldehyde (%)
1
1
.5
91 ꢁ 3
86 ꢁ 3
73 ꢁ 4
6.5
81 ꢁ 4
86 ꢁ 2
76 ꢁ 3
2
2
4
4
77 ꢁ 1
67 ꢁ 2
24
—
—
24
—
—
2
2
4
4
—
—
—
—
24
—
—
a
b
Yield experiments were done for 0.45 mmol substrate. (—) no conversion.
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benzyl alcohol 6 [Table 3] gave a considerably low conversion
(14%) and yield (7%; 6 mg) at 22 h. The electron withdrawing
substituent p-CN in 7 [Table 3] showed low conversion 24%,
with a yield of 16% (9 mg). The 2,4-dichloro substituent in 8
[Table 3] did not show the oxidation product in 24 h. Poor yields
were reported for the electron withdrawing substituent p-NO
2
5
0
(4.9%)
using
[Cu(3,3 -disulfanediyl-bis(N-((1H-benzo[d]
imidazol-2-yl)ethyl)propan amide))(NO
3 3
)]$NO (ref. 55) and for
Scheme 2 Oxidation of substituted benzyl alcohols [Table 3] by
C. parapsilosis ATCC 7330.
the p-CN 7 (15%), using a (nitrosyl)Ru(salen) complex as cata-
56
lyst. Similarly, for 6 with a p-Br substituent, reduced yield 40%
57
was reported using 2-butanone catalyzed by iridium complex.
Over all, the electron withdrawing groups p-NO and p-CN
did not show any conversion or less conversion respectively.
54
the corresponding acid was also formed in 26% yield. Hence
the present developed method is better for the preparation of p-
OMe benzaldehyde with respect to time and without the
formation of the acid.
2
Electron donating substituents p-OMe 1, 3,4-diOMe 2 and p-Me
4
showed better conversion. Similarly p-Br 6 showed poor
conversion and 2,4-dichloro 8 did not show any conversion
chlorine is more electronegative than bromine). Similar types
of observations were reported for p-OMe (conversion 46%), p-Cl
For 3,4-diOMe benzyl alcohol 2, [Table 3] the reaction time
was increased to 5 h and the conversion reduced to 43% with
yield of 35% (26 mg). Very low conversion was reported for the
(
oxidation of 2 [Table 3] mediated by Gluconobacter oxydans DSM
(conversion 11%), p-Br (conversion 6%) and p-NO (conversion
2
ꢀ
2
343 in 24 h with conversion <5% at 28 C due to steric
14
8%) benzyl alcohols using Janibacter terrae whole cells.
16
hindrance. For o-OMe 3, [Table 3] when the reaction time was
increased to 16 h, the conversion was reduced to 26%, giving
a yield of 19% (12 mg).
Cell viability [Table 4]
An electron withdrawing p-NO group 5 [Table 3] did not
show any oxidized product even aer 24 h. The p-Br substituted
2
A reaction time of 24 h warrants a check on cell viability.
Viability of C. parapsilosis ATCC 7330 cells in the hexane: water
b
Table 3 Oxidation of substituted benzyl alcohols to aldehydes by C. parapsilosis ATCC 7330
a
Substrate
Reaction time (h)
2
Conversion to aldehyde (%) 1a–8a
68 ꢁ 2
Yield of aldehyde 1a–8a (%)
59 ꢁ 3
35 ꢁ 1
5
43 ꢁ 2
1
2
2
6
2
2
26 ꢁ 1
60 ꢁ 1
—
19 ꢁ 1
54 ꢁ 1
—
2
2
2
2
14
7 ꢁ 2
24 ꢁ 2
16 ꢁ 2
22
—
—
a
b
Yield experiments were done for 0.45 mmol substrate. (—) no conversion.
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Table 4 Cell viability of Candida parapsilosis ATCC 7330 cells in column (Table 2). Isolated yield for the products was deter-
a
hexane : water (48 : 2) (v/v) reaction medium
mined aer column chromatography using hexane : ethyl
acetate (98 : 2) (v/v) as an eluent.
Reaction time (h)
Cell viability (%)
The same procedure was followed for the other primary
alcohols 2–9 in [Table 2] and 1–8 in [Table 3] using C. para-
psilosis ATCC 7330. Reaction time was optimized for every
substrate. For the substrates HPLC was used to check the
conversion by acetonitrile : water (85 : 15) (v/v) was the mobile
phase. The reactions were repeated in triplicate for consistent
results and control experiments were done in parallel without
1
2
4
4
48
4
a
Experiments were performed in triplicate and average values are given.
(
48 : 2) (v/v) reaction medium was checked up to 24 h using the the whole cells and also using heat killed cells under identical
58
agar plate method.
conditions.
Spectral data of products
Experimental
4
8
59
60
61
Spectral data for the compounds 1a, 2a, 3a, 4a from
C. parapsilosis ATCC 7330 was bought from ATCC Manassas, A
48
62
11
48
11
62
Table 2 and 1a, 2a, 3a, 4a, 6a, 7a from Table 3 were in
ꢀ
201018, USA and maintained at 4 C in yeast malt agar (Hime-
coincidence with the earlier reported values.
dia). All yeast malt broth media components (glucose, soya-
peptone, yeast extract and malt extract) were purchased from
Himedia. All substituted benzaldehydes were purchased from Conclusion
Spectrochem, hexan-1-ol from S.D.Fine Chemicals n-butyl
Oxidation of primary alcohols to aldehydes is reported for the
rst time using whole cells of C. parapsilosis ATCC 7330. Cin-
namyl alcohol showed good conversion [91%] with a yield of
6%. Thiophen-2-ylmethanol and its substituents showed good
alcohol from Rankem, butyraldehyde and cyclohexane carbox-
aldehyde from Sigma Aldrich, hexanal and cyclohexyl methanol
from Lancaster, sodium borohydride from Merck were
purchased. p-OMe benzyl alcohol, 1-butanol, 1-hexanol and
cyclohexylmethanol were analyzed by GC using DB Wax
column. GC conditions are as follows: injector temperature: 240

8
conversions [76–86%] with yields of [67–77%]. Benzo[b]
thiophen-3-ylmethanol, (6-methoxynaphthalen-2-yl) methanol,
n-butyl alcohol, 1-hexanol and cyclohexyl methanol did not
show oxidized products aer 24 h. p-OMe Benzyl alcohol
showed highest conversion 68% with a yield of 59% among
differently substituted benzyl alcohols. 3,4-Dimethoxy and p-Me
benzyl alcohols showed average conversion while o-OMe, p-Br
and p-CN benzyl alcohols showed very less conversion. p-NO2
and 2,4-dichloro benzyl alcohols did not show any oxidized
product even aer 24 h. Addition of cosolvent (ACN) in the case
of solids, increased the reaction time to 22 h compared to the
liquid substrates. Over all substituted thiophenyl alcohols
showed good conversion [76 to 86%] compared to the
substituted benzyl alcohols [14 to 68%] thus emphasising the
usefulness of the developed biocatalyst mediated ‘green’
method.
ꢀ
ꢀ
C, oven temperature: 250 C, split: 1 : 10, carrier gas : helium,
ꢂ1
ꢀ

ow: 3 ml min . GC programmed: 90 C hold for 1 min, at the
ꢀ
ꢂ1
ꢀ
rate 3 C min to 200 C, hold for 15 min. Remaining alcohols
were analyzed by HPLC (Jasco PU-1580 liquid chromatography
with a PDA detector) using (100 RP 18e (Hibar® RT), 250 ꢃ 4.6
mm, 5 mm from Merck) C18 column, acetonitrile : water
(
85 : 15) (v/v) as mobile phase. Products were characterized by
1
13
H and C NMR, spectra were recorded in CDCl on Bruker
3
AVANCE III 500 MHz spectrometer operating at 500 and 125
MHz respectively.
Cultivation of C. parapsilosis ATCC 7330
C. parapsilosis ATCC 7330 was grown and harvested according
45
to the earlier report and used for biotransformation.
Acknowledgements
General procedure for biocatalytic oxidation
Sivakumari T. thanks Council of Scientic and Industrial
research (CSIR, India) for fellowship. We thank the Sophisti-
cated Analytical Instrumentation Facility (SAIF), IIT Madras,
India for the spectral analysis.
Hexane : water (48 : 1) (v/v) was sonicated for 5 min using Ultra
sonicator (pulse 5 s on, 5 s off, amplitude 38) prior to the
reaction, to make the reaction medium homogeneous. Wet cells
2
g (dry cell weight 535 mg) of C. parapsilosis ATCC 7330 were
suspended in hexane : water (48 : 1) (v/v) with 1 ml water, now
total reaction volume is 50 ml. Cinnamyl alcohol 1 0.05 mmol (6
mg) was added to the cell suspension, incubated at 25 C, 150
Notes and references
ꢀ
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