Self-assembled nanoporphyrins in the presence of gold bio-nanoparticles as heterogeneous nano-biocatalyst for green production of aldehydes and ketones

Article abstract of DOI:10.1002/aoc.5286

We report a simple and facile self-assembly method for the successful fabrication of a biological macromolecule, MnTPPCl (manganese(III) chloride 5,10,15,20-tetraphenylporphyrin), intercalated into gold nanoparticles using the cooperative effects of Sesbania sesban plant. This biohybrid was characterized using various techniques for further investigation. The catalytic activity of this biological hybrid was considered in the production of aldehydes and ketones from primary and secondary alcohols, respectively. Excellent conversions and selectivties were obtained applying Au@MnTPPCl colloidal nanocomposite and NaIO₄ as an oxygen donor in ethanol.

Full text of DOI:10.1002/aoc.5286

Received: 13 June 2019
DOI: 10.1002/aoc.5286
Revised: 3 September 2019
Accepted: 14 September 2019
F U L L P A P E R
Self‐assembled nanoporphyrins in the presence of gold bio‐
nanoparticles as heterogeneous nano‐biocatalyst for green
production of aldehydes and ketones
1
2
1
Mahmoud Taheri Bazmi | Atena Naeimi
| Samira Saeednia |
1
Mehdi Hatefi Ardakani
1
Department of Chemistry, Faculty of
We report a simple and facile self‐assembly method for the successful fabrica-
Science, Vali‐e‐Asr University of
Rafsanjan, Rafsanjan, Iran
tion of a biological macromolecule, MnTPPCl (manganese(III) chloride
2
Department of Chemistry, Faculty of
5,10,15,20‐tetraphenylporphyrin), intercalated into gold nanoparticles using
Science, University of Jiroft, Jiroft, Iran
the cooperative effects of Sesbania sesban plant. This biohybrid was character-
ized using various techniques for further investigation. The catalytic activity of
this biological hybrid was considered in the production of aldehydes and
ketones from primary and secondary alcohols, respectively. Excellent conver-
sions and selectivties were obtained applying Au@MnTPPCl colloidal nano-
Correspondence
Atena Naeimi, Department of Chemistry,
Faculty of Science, University of Jiroft,
Jiroft, Iran.
Email: a.naeimi@ujiroft.ac.ir
Samira Saeednia, Department of
Chemistry, Faculty of Science, Vali‐e‐Asr
University of Rafsanjan, Rafsanjan, Iran.
E‐mail: s.saeednia@vru.ac.ir
composite and NaIO as an oxygen donor in ethanol.
4
KEYWORDS
biological catalyst, macromolecules, porphyrin
1
| INTRODUCTION
the strategy of the intimate packing of these aromatic
macrocycles which can result in rich photophysical and
Cytochromes P‐450 with iron porphyrin, heme, active
site can catalyze oxidation reactions of aliphatic C─H
hydroxylation, aromatic C─H hydroxylation, C═C bond
epoxidation, sulfoxidation, N‐dealkylation and dehydroge-
photochemical properties that are important in many
technological applications. Covalent or noncovalent
porphyrinic assemblies have been applied for solar cells,
photosynthesis and artificial photoactive molecular
devices. Combination of porphyrins with metallic or
metal oxide nanoparticles can add a high surface area‐to‐
[1]
[9]
nation. Applications of porphyrin macromolecules in
optical and electronics devices have attracted considerable
attention, because these aromatic macromolecules are rich
in photophysical and photochemical properties which
volume ratio to systems for higher activity in many chem-
[
10–12]
ical reactions.
In addition to the high ratio of surface
[
2]
are important in these technological applications.
atoms with free valences to the cluster of total atoms for
metal nanoparticles, the size controllability, chemical sta-
bility and surface tenability provide an ideal platform for
their use in sensing/biosensing and catalytic applica-
Much effort has been devoted to the incorporation of
metal/metal oxide nanoparticles into conducting porphy-
[
3,4]
rins.
In fact, the design of nanocomposites including
[
13]
transition metal–porphyrin macromolecules and metal
tions.
Very recently, self‐assembly of porphyrins along
nanoparticles provides enhanced performance for both
the ‘host’ and the ‘guest’. These kinds of nanocomposites
with metal nanoparticles has been performed using natu-
ral plants from a biological and environmentally friendly
point of view. In fact, green synthesis of these kinds of
composite materials lead to simplicity, time saving, eco‐
friendliness, high rate and the possibility of obtaining
[5]
can lead to interesting physical properties and important
[6–8]
potential applications.
The self‐assembly approach
has been widely adopted in the effort to prepare composite
materials including porphyrins as the building blocks for
[
14]
nanohybrids with various properties.
Appl Organometal Chem. 2019;e5286.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5286

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TAHERI BAZMI ET AL.
[
15–17]
In continuation of our works,
in the study
progress of the reactions were monitored using TLC on
silica gel Polygram SILG/UV254 plates.
reported herein, a simple manganese porphyrin was
assembled in the presence of gold nanoparticles using
Sesbania sesban plant. It was then applied as a heteroge-
neous catalyst for green oxidation of alcohols in biomi-
metic and industrial reactions. In this clean catalytic
system, oxidation of primary and secondary alcohols
was performed in ethanol as a green media and sodium
periodate as an oxidant.
2.1 | Synthesis of colloidal gold
nanoparticles
An amount of 0.1 mmol of KAuCl (0.0038 g) was added
4
to extracted Sesbania sesban solution. The gold nanopar-
ticles were obtained after 5 hours at room temperature.
The color changed from gray to pink during the reaction.
2
| MATERIALS AND METHODS
2
.2 | Synthesis of Au@MnTPPCl
Sesbania sesban was collected from the University of
Jiroft, Jiroft, Iran. Potassium gold(III) chloride (98%) and
ethanol were purchased from Aldrich and Merck, respec-
tively. Transmission electron microscopy (TEM) analysis
was performed using a Zeiss TEM‐em10 microscope. Mor-
phology and elemental composition were determined
using scanning electron microscopy (SEM; Philips
XL30ESE) and energy‐dispersive X‐ray analysis. Fourier
transform infrared (FT‐IR) spectra in the range 400–
bio‐nanocomposite
An amount of 400 μl of a 1 mM solution of manganese
porphyrin was added to 20 ml of colloidal gold nanopar-
ticles. The reaction was performed under vigorous
stirring at room temperature. Au@MnTPPCl bio‐
nanocomposite was obtained after 30 minutes.
−
1
4
000 cm as KBr disks were recorded with a Thermo Sci-
2.3 | Oxidation of alcohols using NaIO4
catalyzed by Au@MnTPPCl
bio‐nanocomposite
entific model Nicolet iS10 spectrophotometer. UV–visible
spectra were recorded with a PerkinElmer spectropho-
tometer. Manganese(III) meso‐tetraphenylporphyrin
complex (MnTPPCl) was synthesized using the methods
In a typical procedure, to a solution of benzyl alcohol
(1 mmol) in ethanol (1 ml), Au@MnTPPCl bio‐
[18–20]
reported previously.
GC experiments were per-
formed with a Shimadzu 16A chromatograph (flame ion-
ization detection). The purity of the products and the
nanocomposite (1 ml) and NaIO (1 mmol) were added.
The reaction mixture was stirred for 7 hours at 70°C,
4
SCHEME 1 Synthesis procedure of biological Au@MnTPPCl macromolecule

TAHERI BAZMI ET AL.
3 of 8
FIGURE 1 FT‐IR spectra (top), and
UV–visible spectra of Au nanoparticles
(
center) and Au@MnTPPCl bio‐
nanocomposite (bottom)

4
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TAHERI BAZMI ET AL.
FIGURE 2 SEM (top left) and TEM (top right) images, and distribution of particle size (bottom) of Au@MnTPPCl bio‐nanocomposite
SCHEME 2 Oxidation of alcohols
catalyzed by Au@MnTPPCl bio‐
nanocomposite

TAHERI BAZMI ET AL.
5 of 8
and the products were monitored using TLC or GC. After
completion of the reaction, the catalyst was centrifuged
and separated for reuse.
particles were observed in both TEM and SEM images.
The sizes of particles are between 5 and 25 nm according
to the TEM image. The aggregation of particles was
observed in the SEM image. According to the TEM and
SEM images (Figure 2, top) and distribution of size
2.4 | General procedure for recycling of
(
Figure 2, bottom), spherical Au@MnTPPCl nanoparti-
catalyst
cles with a mean particle size of 11 nm are formed.
An amount of 1 mmol of benzyl alcohol (0.1 ml) was
added to 1 ml of colloidal nanocomposite catalyst and
1
mmol (0.2 g) of NaIO in ethanol at 70°C within 7 hours.
3.1 | Oxidation of alcohols catalyzed by
Au@MnTPPCl bio‐nanohybrid
4
After completion of the reaction, the catalyst was filtered
and used for the next run without any purification.
The catalytic activity of the Au@MnTPPCl bio‐
nanocomposite was investigated in the oxidation of alco-
hols (Scheme 2). For this, oxidation of benzyl alcohol was
3
| RESULTS AND DISCUSSION
Gold nanoparticles were prepared using Sesbania sesban
plant. Self‐organization of a simple porphyrin was real-
ized by injecting manganese porphyrin in the presence
of the colloidal gold nanoparticles (Scheme 1).
FT‐IR spectra of bio‐synthesized gold nanoparticles
and Au@MnTPPCl bio‐nanocomposite in the region
−
1
3
00–800 cm confirmed the structure and functional
groups (Figure 1). FT‐IR analysis was performed to iden-
tify the possible biomolecules responsible for the reduc-
+
tion of Au ions and capping of the reduced gold
nanoparticles synthesizing using Sesbania sesban extract.
−
1
The band at 1341 cm corresponds to C─O stretching
[21]
−1
vibration of phenyl.
The band at 1605 cm corre-
sponds to polysaccharides and pectin. The bands at 2207
−
1
and 3824 cm are related to water molecules and OH
[
22]
−1
groups.
The band at 1632 cm corresponds to amide
−
1
and phenyl. The band at 2042 cm corresponds to lipids
and fatty acid and the band at 3465 cm corresponds to
OH bond.
vibration bands of the TPP porphyrinato moiety.
C─H stretching frequencies of the porphyrin molecules
−
1
[
23]
The spectrum presents the characteristic
[
24]
The
−
1
are in the range 3060 to 2860 cm
and the C═N
stretching frequencies are assigned to the band at
−
1
1
654 cm . A band attributed to the bending vibration
of the CCH moieties of the porphyrin core is centered at
−
1 [25]
about 1010 cm .
The syntheses of gold nanoparticles
and Au@MnTPPCl bio‐nanocomposite were monitored
using their UV–visible spectra (Figure 1). The peak at
5
30 nm is related to gold nanoparticles and confirmed
[26]
the synthesis of these bio‐nanoparticles.
A red shift
of Q band, 470 nm, and Soret band of manganese porphy-
rin in the UV–visible spectrum of Au@MnTPPCl was
observed clearly showing the self‐assembly of porphyrins
[11]
in this nanocomposite.
TEM and SEM of the Au@MnTPPCl bio‐
nanocomposite were conducted to investigate the size
and morphology of this hybrid. The spherical shapes of
FIGURE 3 Effect of amount of catalyst (top), time (center) and
amount of NaIO (bottom) on the oxidation of benzyl alcohol
4

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TAHERI BAZMI ET AL.
performed in the absence of catalyst and in the presence
be noted that the oxidation of benzyl alcohol was also
performed in the presence of gold nanoparticles,
MnTPPCl nanoparticles and MnTPPCl bulk using NaIO4
as an oxygen donor and trace, 45 and 20% of benzalde-
hyde were obtained.
Various primary and secondary alcohols were oxidized
using this green system catalyzed by Au@MnTPPCl bio‐
nanocomposite using NaIO4 at 70°C during 7 hours
(Table 2). It seems that electronic and steric demands of
the substrate could have a significant effect on the conver-
sion of reactants. Electron‐withdrawing moieties such as
chlorine could reduce the conversion. In contrast, the con-
version could be enhanced in the presence of electron‐
donating substituents of benzyl alcohols. It should be
of NaIO as a blank reaction. The oxidation process was
4
very sluggish (5% after 24 hours) at room temperature
in ethanol. Yields of 25, 50, 80 and 85% benzaldehyde
were obtained at room temperature within 24 hours with
amounts of catalyst of 0.1, 0.2, 0.5 and 1 ml, respectively
(Figure 3a). The effect of temperature was evaluated in
this green oxidation system. The yields of reactions were
increased significantly on enhancement of the tempera-
ture. Temperatures of 25, 50, 60 and 70°C were applied
and 20, 50, 60 and 85% benzaldehyde was obtained,
respectively (Table 1, entries 1–4). By reducing the time
of reaction from 24 to 7, 4, 2, 1 and 0.5 hours at 70°C,
yields of 85, 85, 45, 30, 20 and 10% aldehyde product were
obtained, respectively (Figure 3b). Therefore, 7 hours and
7
0°C were selected for further studies. The nature of the
TABLE 2 Oxidation of alcohols catalyzed by Au@MnTPPCl bio‐
nanocomposite using NaIO4
a
reaction media, such as ethanol, tetrahydrofuran (THF),
water and n‐hexane, and solvent‐free condition were con-
sidered and 85, 80, 5 and 0% and a trace of benzaldehyde
were obtained, respectively (Table 1, entries 4–8). TBHP,
H O , UHP and NaIO were used as different oxidants
b
Entry Alcohol
Product
Conversion (%)
1
90
2
2
4
2
3
4
5
30
70
60
50
in the oxidation of benzyl alcohol in the presence of the
Au@MnTPPCl bio‐nanocomposite at 70°C and yields of
5
, 40, 65 and 85% benzaldehyde were obtained as sole
product after 7 hours, respectively (Table 1, entries 9–
2). It seems that NaIO is the best oxygen donor in this
1
4
green strategy. In the next step, different amounts of
NaIO (0.5, 1 and 2 mmol) were investigated, and it
4
seems that 1 mmol of NaIO is sufficient for oxidation
4
of alcohols in this green strategy (Figure 3c). It should
6
7
90
70
TABLE 1 Effect of various factors on the oxidation of benzyl
alcohol catalyzed by Au@MnTPPCl bio‐nanocomposite
a
Oxidant
Entry (mmol)
Temperature
(°C)
Conversion
(%)
b
Solvent
1
2
3
4
5
6
7
8
9
1
1
1
NaIO
NaIO
NaIO
NaIO
NaIO
NaIO
NaIO
NaIO
4
4
4
4
4
4
4
4
EtOH
EtOH
EtOH
EtOH
THF
25
50
60
70
70
70
20
50
60
85
80
0
8
9
90
85
1
1
55
90
70
Water
n‐Hexane 70
5
12
—
70
70
70
70
70
Trace
5
1
3
TBHP
UHP
EtOH
EtOH
EtOH
EtOH
0
1
2
40
65
85
H
2
O
2
14
60
NaIO
4
a
a
All reactions were run in the presence of Au@MnTPPCl bio‐nanocomposite
1 ml) within 7 hours using 1 mmol of oxidant.
All reactions were run under air for 7 hours in ethanol (1 ml), NaIO
4
(
(1 mmol) and alcohol (0.2 mmol) at 70°C.
b
b
Determined by GC.
Determined by GC.

TAHERI BAZMI ET AL.
7 of 8
FIGURE 4 Reusability of
Au@MnTPPCl bio‐nanocomposite for the
oxidation of benzyl alcohol and 4‐
chlorobenzyl alcohol using NaIO
ethanol as a green medium at 70°C within
hours
4
and
7
TABLE 3 Comparison of benzyl alcohol oxidation using NaIO
4
catalyzed by various heterogeneous catalysts
Conversion (%)
Entry
Solvent
Time
Conditions
Ref.
+
1
2
3
4
5
6
7
Water
7 h
NaIO
4
/H /LiBr
79
80
27
28
29
30
31
32
CH
CH
CH
2
3
3
Cl
2
60 s
Iodic acid/wet montmorillonite K 10 or silica gel
MnTPyP‐CMP/without axial ligand
CN/H
CN
2
O
45 min
30 min
10 h
7 (90)
19
Mn(salen)OAc/NaIO4/without axial ligand
H
2
O/CH
CH Cl
EtOH
2
Cl
2
1.2 equiv. NaIO
NH OH/NaIO
NaIO , Au@MnTPPCl, EtOH
4
, 1 mol% TEMPO, 10 mol% NaBr, reflux
96
2
2
30 min
7 h
2
4
80
4
85
This work
noted no ester and acid byproduct was observed in any of
the reactions. In addition, the chemoselectivity of this
clean system is worth mentioning (Table 2, entry 12). In
the presence of double bond, the primary alcohol was
changed to the corresponding aldehyde product under
the influence of this catalyst. However, excellent selectiv-
ity and good conversion were obtained in the oxidation
of various alcohols without any byproducts.
The recoverability of the catalyst was considered from
an economic and environmental point of view. After
finishing the reaction, the catalyst was filtered, washed
with ethanol and dried. The dried catalyst could be
reused for seven runs. The obtained results showed the
high activity and durability of this heterogeneous catalyst.
The novel bio‐nanocatalyst as a very stable catalyst could
tolerate the reaction conditions and be reused at least
seven times without marked loss of activity (Figure 4).
It seems that the presence of Sesbania sesban as an
inexpensive and natural plant not only prevented the
aggregation of the bio‐nanocomposite but also improved
the catalytic activity of the catalyst for efficient oxidation
of alcohols.
Finally, we compared the conditions of oxidation of
benzyl alcohol in this clean and cheap system with the
results of other reports using NaIO as oxidant (Table 3).
4
The results showed that this Au@MnTPPCl bio‐
nanocomposite can be used as a robust, reusable and
active heterogeneous catalyst in the oxidation of primary
and secondary alcohols with sodium periodate.
4 | CONCLUSIONS
Bio‐fabrication of gold nanoparticles was performed in the
presence of Sesbania sesban plant. Also, Au@MnTPPCl
bio‐nanocomposite was synthesized via a simple and safe
procedure. In this green process, no expensive or toxic
reagent or solvent was used and only natural and environ-
mentally friendly materials were employed. The prepara-
tion of this biohybrid, with spherical particles of size of

8
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TAHERI BAZMI ET AL.
between 5 and 30 nm, was confirmed using SEM, TEM
and UV–visible and FT‐IR spectroscopies. The activity of
this hybrid was investigated as a heterogeneous catalyst
in the oxidation of alcohols to afford aldehyde and ketone
products. Excellent conversion and selectivity were fea-
tures of this system. The easy recoverability and reusabil-
ity of the catalyst are some of the advantages of this
strategy.
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Atena Naeimi https://orcid.org/0000-0001-6328-7342
[
[
[
[
Mehdi Hatefi Ardakani
840
https://orcid.org/0000-0002-2216-
1
6
2
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How to cite this article: Taheri Bazmi M,
Naeimi A, Saeednia S, Hatefi Ardakani M. Self‐
assembled nanoporphyrins in the presence of gold
bio‐nanoparticles as heterogeneous nano‐
biocatalyst for green production of aldehydes and
ketones. Appl Organometal Chem. 2019;e5286.
https://doi.org/10.1002/aoc.5286
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