Green synthesis of Au nanoparticles using an aqueous extract of Stachys lavandulifolia and their catalytic performance for alkyne/aldehyde/amine A3 coupling reactions

Article abstract of DOI:10.1039/c8ra06819d

High reaction rate and easy availability make green synthesis of metal nanoparticles noticeable. In the present study, gold nanoparticles with wide applications in different fields were synthesized by an ecofriendly method at room temperature using Stachy

Full text of DOI:10.1039/c8ra06819d

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Green synthesis of Au nanoparticles using an
aqueous extract of Stachys lavandulifolia and their
catalytic performance for alkyne/aldehyde/amine
A3 coupling reactions†
Cite this: RSC Adv., 2018, 8, 38186
a
Maliheh Farokhi,a Mona Hamelianb and Saba Hemmatia
*
Hojat Veisi,
High reaction rate and easy availability make green synthesis of metal nanoparticles noticeable. In the present
study, gold nanoparticles with wide applications in different fields were synthesized by an ecofriendly method
at room temperature using Stachys lavandulifolia extract as the reducing agent. Properties of the synthesized
gold nanoparticles (GNP) were identified by different analytical techniques including: UV-Vis absorption
spectroscopy verified presence of Au NPs in the solution while functional groups of its extract and
synthesized Au NPs were determined by FT-IR. Its crystalline analysis with a fcc plane was verified by X-ray
diffraction (XRD) and energy dispersive spectroscopy (EDS) determined elements in the sample. Surface
morphology, diverse shapes and sizes of the Au NPs were shown by scanning electron microscopy (SEM),
atomic force microscopy (AFM), and transmission electron microscopy (TEM). Beginning and end destruction
temperatures of the Au/S. lavandulifolia NPs were determined by thermal gravimetric analysis (TGA). The Au
nanoparticles were capped with extracts, preventing them from oxidation and agglomeration and were used
as an efficient heterogeneous nanocatalyst for a three-component reaction of amines, aldehydes, and alkynes
(A3 coupling). A diverse range of propargylamines were obtained in good yields. Furthermore, the separation
and recycling of Au/S. lavandulifolia NPs was very simple, effective, and economical.
Received 14th August 2018
Accepted 31st October 2018
DOI: 10.1039/c8ra06819d
rsc.li/rsc-advances
low cost, low toxicity, and high reactivity. Although the majority of
the catalytic systems were homogeneous, their loss at the end of
1. Introduction
a reaction reduces their utility especially for industrial applica-
tions. Nowadays, metal NPs are considered as heterogeneous
catalysts which possess a high surface-to-volume ratio. Because of
their enhanced activity and selectivity, they could be a competitive
alternative to classical catalysis.20,21 Diverse models of traditional
chemical22 and green chemistry23,24 approaches were applied to
produce metal NPs. Amongst all metallic NPs, Au NPs have been
widely used in different elds including medicine and gene
delivery,27 imaging,28 heating,29 labeling, sensing,30 and catalysis31
because of their unique optical features.25,26 Applications of green
chemistry comprising diverse parts of herbal extracts such as
leaves,32 fruit,33 roots,34 and seeds35 as a reducing agent for
synthesizing gold NPs makes them very useful because they have
no hazardous materials and are very cheap. Amongst 34 Stachys
spices, growing in many regions of Iran, Turkey, and Iraq,36,37
Stachys lavandulifolia (Fig. 1) is used as an herbal tea in Iran for
gastrointestinal disorders and extracts of this plant were intro-
duced to have an anxiolytic effect with a lower sedative activity than
diazepam.38 Stachys lavandulifolia extracts fractions including
avonoids, phenylpropanoids, polyphenols, and terpenoids from
the aerial parts of plants were considered to play an important role
in anxiolytic effects.39 Acteoside, as one of the secondary metabo-
lites isolated from S. lavandulifolia aerial part's extracts, is
In general, propargylamines are useful in organic chemistry as
precursors and versatile building blocks for preparing different
nitrogen-comprising heterocyclic compounds as well as main
intermediates for synthesizing biologically active medicines and
natural products.1 Additionally, several propargylamines have been
applied to treat neuropsychiatric diseases including Parkinson's
and Alzheimer's disorders.2 Due to their importance, many
synthetic methods have been developed.3 However, the most direct
and efficient method for preparation of propargylamines is
through transition metal-catalyzed three component coupling of
an aldehyde, an amine, and a terminal alkyne, which is known as
an A3 coupling reaction.4 In recent years, various homogeneous
and heterogeneous catalysts have been employed in the synthesis
of propargylamine via an A3-coupling reaction based on transition
metals including Zr,5 Mn,6 Re,7 Fe,8 Ru,9 Co,10 Ir,11 Ni,12 Pd,13 Cu,14
Ag,15 Au,16 Zn,17 Cd,18 and Hg.19 Among the different transition
metals, copper has been widely studied because of its abundance,
aDepartment of Chemistry, Payame Noor University, Tehran, Iran
bResearch Center of Oils and Fats, Kermanshah University of Medical Sciences,
Kermanshah, Iran. E-mail: hojatveisi@yahoo.com
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c8ra06819d
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Fig. 1 Stachys lavandulifolia image and acteoside structure.
ꢀ
displayed in Fig. 1. Signicantly, green preparation of NPs has up- 100 mL of Milli-Q water and heated at 60 C for 15 min. Then,
surged as a new nanobiotechnology to produce eco-friendly and the extract was ltered through Whatman no. 1 lter paper and
inexpensive synthetic procedures for extremely stable NPs and it centrifuged at 6000 rpm for 5 min to remove unwanted aggre-
has emerged as a safer and best alternative to conventional gates. The ltered extract was stored in a refrigerator at 4 ꢀC for
approaches. Due to our ongoing interest on the biosynthesis of further use.
metal NPs and heterogeneous catalysts,40,41 in the current study Au
NPs were prepared for the rst time using Stachys lavandulifolia
through a green method and their morphological, structural, and
catalytic applications were studied in detail.
2.3. Green synthesis of Au NPs using Stachys lavandulifolia
extract
Different amounts of the Stachys lavandulifolia extract (5, 10, 15,
and 20 mL) were added to an aqueous solution of (1 mM)
2. Experimental
2.1. Materials and apparatus
HAuCl4 Â H2O (100 mL) at room temperature and stirred for the
purpose of studying time effects and extract concentrations on
synthesis of gold nanoparticles. The color of the solution turned
red during 2 h and the high concentration of extract created
a darker red (Fig. 1S†). Then, solutions containing the nano-
particles were centrifuged at 12 000 rpm for 15 min and the
upper phase was removed. Obtained nanoparticles were washed
for several ꢀtimes with deionized water and nally dried in an
oven at 50 C.
All the reagents were purchased from Aldrich and Merck and
were used without any purication. Crystalline structures of the
samples were evaluated by X-ray diffraction (XRD) analysis on
a Bruker D8 Advance Diffractometer with CuKa radiation at 40
kV and 20 mA. Fourier transform infrared (FT-IR) spectra were
recorded using KBr pellets with a PerkinElmer 65 spectropho-
tometer in the range of 400–4000 cmÀ1. TEM images at an
accelerating voltage of 80 KV were taken with a Zeiss-EM10C.
Morphology and particle dispersion was investigated by eld
emission scanning electron microscopy (FESEM) (Cam Scan
MV2300). Chemical composition of the prepared nano-
structures was measured by EDS (Energy Dispersive X-ray
Spectroscopy) performed in SEM. The UV-Vis absorbance
spectra were recorded using a double beam UV-visible spec-
trophotometer (PG Instrument, T80+), equipped with 10 mm
quartz cuvettes. The spectra were obtained using a Thermo-
Fisher Scientic K-Alpha XPS spectrometer. Survey spectra were
initially obtained at low energy resolution (pass energy À200 eV)
followed by the main regions of interest at higher resolution
(pass energy À25 eV). A monochromatic Al Ka X-ray was used,
with a nominal spot size of 400 mm.
2.4. General procedure for the synthesis of propargylamine
derivatives
The Au NPs catalyst (10 mol%) was added to a mixture of
aldehyde (1 mmol), phenylacetylene (1 mmol), and amine (1.2
mmol) in toluene (5 mL) and the mixture was stirred at 100 ꢀC.
The progress of the reaction was monitored by TLC. Aer
complete conversion of the aldehyde, the mixture was le to
cool down to room temperature and then centrifuged. Aer
evaporation of the solvent, the crude product was obtained.
Purication was performed by silica gel column chromatog-
raphy (70 : 30, hexane/EtOAc). All compounds were known and
were characterized by spectral analysis or melting points.48–61
3. Results and discussion
2.2. Preparation of Stachys lavandulifolia extract
Freshly collected herbal tea (10 g) from the Kermanshah, A UV-Vis spectroscopy (PerkinElmer, Lambda 25) instrument at
Zagrous region, was washed, dried, and used for preparation of wavelengths of 300–700 nm was used to conrm dimensions
the Stachys lavandulifolia extract. The tea (10 g) was added to and effective preparation of gold NPs. Fig. 2 shows the results
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Fig. 2 Extract concentrations and time effect on UV-Vis spectroscopy of synthesized gold nanoparticles.
from comparison of UV-Vis spectra of green synthesized of Au groups creating hydrogen bonds, saturated hydrocarbons (Csp3-
NPs using Stachys lavandulifolia extract with diverse levels of H), carbonyl group (C]O), and stretching C]C aromatic ring,
extracts at 5, 10, 15, and 20 mL. These results conrm the faster respectively. Due to existence of these functional groups in the
formation of Au NPs in the solution by enhancing contents of structure of antioxidant polyphenolics, the spectrum proves the
the extract. As observed, the amounts of NPs prepared were existence of phenolics in the herbal extract and supports the
enhanced over time with all levels of extract.
outcomes of relevant research.42 Moreover, an FT-IR spectrum
FT-IR measurements ranging from 400 to 4000 cmÀ1 were corresponding to Au NPs is presented in Fig. 2Sb.† The peaks
applied to identify the responsible phytochemicals during green from Au/S. lavandulifolia NPs are nearly identical to Fig. 2Sa†
synthesis of the Au NPs. The FT-IR spectrum of the pure extract, and its representation of the functional groups of biomolecules
(Fig. 2Sa†) showed several peaks at 3369 cmÀ1, 2923 cmÀ1
,
adsorbed on NPs. The broad band at 3418 cmÀ1 can be attrib-
1618 cmÀ1, and 1400 cmÀ1 corresponding to free OH and OH uted to a stretching bond of the hydroxyl functional group and
Fig. 3 XRD spectrum of Au/S. lavandulifolia NPs.
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Fig. 4 EDS image of Au/S. lavandulifolia NPs.
the band near 1447 cmÀ1 is normally assigned to the bending
vibration corresponding to sp2-carbon groups of aromatics and
1628 cmÀ1 for a carbonyl functional group.
The structure of prepared Au NPs also was analyzed with
XRD by means pf a Bruker AXS-D8 Advance instrument working
at a voltage of 40 kV and current of 30 mA with CuK radiation.
The crystalline feature of Au NPs was conrmed with an X-ray
intensity which reected from crystals which are highest at
certain angles. Diffraction peaks appeared at 38.067, 44.215,
64.291, and 77.592 in a 2q range 100–80ꢀ relating to (111), (200),
(220), and (311) facets of a face centered cubic crystal structure
(JCPDS. no. 004-0784) and showed the crystalline structure of
prepared Au NPs with Stachys lavandulifolia extract (Fig. 3).
Energy Dispersive X-ray Spectroscopy (TESCAN Vega, USA)
veried the existence and purity of particles in the specimens.
Fig. 4's EDX spectrum of prepared Au NPs shows a strong signal
that reveals presence of pure metallic gold NPs.
A scanning electron microscope (TESCAN Vega Model) was
applied for identifying morphology and aggregates of NPs.
According to SEM images of Au/S. lavandulifolia NPs presented
in Fig. 3S,† nanoparticles were formed and their shape was
somewhat spherical in nature.
Fig. 6 HR-TEM images of Au/S. lavandulifolia NPs and FFT image
corresponding to Au NPs (inset).
Fig. 5 AFM images of Au/S. lavandulifolia NPs.
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Fig. 7 TGA analysis of Au/S. lavandulifolia NPs.
Atomic force microscopy (AFM) (DME-95-50 E) was used to
Thermal gravimetric analysis (Netzsch-TGA 209 F1) is an
recognize topological appearance and sizes of NPs. Fig. 5 is an important method to determine beginning and end destruction
AFM image corresponding to GNP where height measurement temperatures of nanoparticles (heat-resistance) and amounts of
indicates sizes ranging from 22 to 30 nm and also represents weight loss during heating at different temperatures. The
rough surface of NPs.
beginning part of the graph that is straight (Fig. 7) shows that
High resolution transmission electron microscopy (HR-TEM) biosynthesized Au NPs are pure (free of impurities and mois-
was applied to determine the dimension and shape of NPs. ture). The earliest weight loss for the synthesized gold nano-
ꢀ
Usual TEM images achieved for colloids are presented in Fig. 6. particles occurred at 190 C and shows a steady weight loss in
According to the image, it is obvious that gold NPs have a nearly the temperature range from 180–620 ꢀC with a total weight loss
spherical and triangular morphology with an excellent distribu- up to 700 ꢀCꢀ which is about 52.62ꢀ% and occurred at 190 ꢀC
tion of particles with sizes between 20 and 30 nm. Moreover, (4.01%), 390 C, (16.89%), and 640 C (31.71%).
Fig. 6 shows a HR-TEM image corresponding to the Au NPs at
Polyphenolic compounds have been revealed as a reducing
5 nm magnication. Based on this image, the Au NPs contained agent during the biological extract mediated synthesis of
lattice fringes, which conrmed their great crystallinity. Mean- nanomaterials.44 Moreover, a rich source for polyphenolic
time, a Fast Fourier Transform (FFT) image corresponding to the compounds and avonoid groups is the Stachys lavandulifolia
Au NPs (inset) shows bright diffraction spots and ring patterns extract.45–47 These polyphenolic compounds (such as acteoside)
that prove the crystalline nature of the Au atoms.
may play a role as reducing agents to reduce Au3+ ions. Scheme
Scheme 1 Probable mechanism for formation of Au NPs using Stachys lavandulifolia extract.
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Table 1 Optimization of various conditions in the model reaction using Au/S. lavandulifolia NPs catalysta
Entry
Catalyst (mol%)
Solvent
T (ꢀC)
Yieldb (%)
1
2
3
4
5
6
7
8
—
10
10
7
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
CH2Cl2
DMF
EtOH
H2O
CH3CN
—
60
60
—
75
92
65
50
92
30
70
65
40
65
30
100
100
100
100
70
100
80
100
70
5
12
10
10
10
10
10
10
9
10
11
12
100
a
Reaction conditions: benzaldehyde (1.0 mmol), morpholine (1 mmol), phenylacetylene (1.2 mmol), Au/S. lavandulifolia NPs, solvent (5.0 mL) for
8 h. b Yields are based on H NMR.
1
1 is a schematic representation of possible pathways. In the rst
Under the optimal reaction conditions, other aldehydes were
phase, as the extract combines with the metal salt solution, reacted with different aliphatic amines and phenylacetylene
hydroxyl groups of the polyphenolic compounds could be and resulted A3 coupling products with good yields (Table 2). In
reduced into Au atoms. Then, synthesized Au atoms nucleate the primary study of the aldehyde substrate's scope, morpho-
followed by more growth which causes the NPs formation.
line, and phenylacetylene were utilized as model substrates and
The catalytic behaviour of Au/S. lavandulifolia NPs was different aldehydes were studied for the A3-coupling reactions
studied for the A3-coupling reaction of aldehydes, amines, and (Table 2, entries 1–20). Results showed that aromatic aldehyde's
alkynes to produce propargylamines. Initially, we employed behaviors with functional groups like –Cl, –Br, –OH, –Me, or
benzaldehyde (1.0 mmol), morpholine (1.0 mmol), and phe- –OMe could impact the A3-coupling. Moreover, a minor elec-
nylacetylene (1.2 mmol) as model substrates for optimizing tronic effect was found which is related to reaction of aryl
different factors including time, temperature, solvents, and aldehydes with electron-withdrawing groups (Table 2, entries 2–
catalyst loading. The results are presented in Table 1. First, 4) and generation of relevant products in excellent yields, while
inuence of the catalyst was studied, and as expected, the replacement of electron rich groups (Table 2, entries 5–7) on the
desired product was not achieved without the catalyst, repre- benzene ring reduced performance and caused lesser yields.
senting the essential role of Au/S. lavandulifolia NPs in the Additionally, reactions with challenging heterocyclic
reaction mechanism (Table 1, entry 1). The reaction yield ach- compounds such as thiophene-2-carbaldehyde or furan-2-
ieved 75% by utilizing a 10 mol% catalyst loading in toluene at carboxaldehyde with morpholine and phenylacetylene pro-
60 ꢀC (Table 1, entry 2). Furthermore, the reaction occurred ceeded efficiently and the corresponding propargylamines were
quantitatively when applying 10 mol% of catalyst at 100 ꢀC obtained in good yields (Table 2, entries 8 and 9). On the other
(Table 1, entry 3). Lower yields were obtained by decreasing the hand, an aliphatic aldehyde (i.e., cyclohexanecarbaldehyde or
catalyst level to 7 and 5 mol%, respectively (Table 1, entries 4 butyraldehyde) also showed good yields under this optimum
and 5). Increasing the catalyst level to 12 mol% did not improve condition (Table 2, entries 10 and 11). To expand the scope of
the reaction yield or time (Table 1, entry 6). Applying 10 mol% of amine substrates a mixture of benzaldehyde–phenylacetylene–
catalyst in other solvents including CH2Cl2, DMF, EtOH, H2O, amine was selected and different amines were studied (Table 2,
CH3CN, and neat, resulted in lower reaction yields (Table 1, entries 1 and 12–16). The results indicate that cyclic, heterocy-
entries 7–12). Consequently, we chose toluene as the optimum clic (i.e., piperidine, pyrrolidine, or morpholine), and acyclic
ꢀ
solvent, 10 mol% catalyst loading and 100 C reaction temper- (i.e., diethyl or dibenzyl) secondary amines also provided high
ature as the most effective and optimum reaction conditions for yields of products under the optimal reaction conditions (Table
studying the scope of this A3 coupling.
2, entries 1 and 12–15). However, no product was found when
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Table 2 The reactions of aldehydes, amines, and alkynes in the presence of Au/S. lavandulifolia NPs catalysta
Entry
R1
Amine
R3
Yieldb (%)
Ref.c
1
2
3
4
5
6
7
8
Ph
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Piperidine
Pyrrolidine
Diethyl
Dibenzyl
Aniline
Morpholine
Piperidine
Morpholine
Morpholine
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
95
96
95
96
90
88
85
92
90
90
85
95
95
90
90
0
48
59
61
51
59
48
59
43
48
59
59
59
60
59
59
59
49
59
59
59
4-ClC6H4
3-ClC6H4
4-BrC6H4
4-OHC6H4
4-MeC6H4
4-OMeC6H4
2-Thiophenyl
2-Furfuryl
Cyclohexyl
C3H7
Ph
Ph
Ph
Ph
Ph
Ph
Ph
9
10
11
12
13
14
15
16
17
18
19
20
n-C6H13
n-C6H13
n-C6H13
n-C6H13
82
80
85
70
4-ClC6H4
4-OMeC6H4
a
Reaction conditions: aldehyde (1.0 mmol), amine (1 mmol), alkyne (1.2 mmol), and Au/S. lavandulifolia NPs (10 mol%) were stirred in toluene (5.0
mL) at 100 ꢀC for 8 h. b Yields are based on H NMR. c Earlier reference of the corresponding product.
1
using aniline as a substrate (Table 2, entry 16). Remarkably, lavandulifolia NPs under heating conditions is presented in
reaction of the aliphatic alkyne 1-octyne, a substrate which is Scheme 2. The rst phase involves activating the terminal
usually hard to activate, also worked well and resulted in alkyne using the Au NPs catalyst under heating to result in the
a product with a good yield under optimal conditions (Table 2, related Au–alkylidine complex on the surface of NPs. Next, the
entries 17–20).
reaction between an Au–acetylide intermediate with iminium
According to the above outcomes, a suggested reaction ion (formed in situ from the related aldehyde and amine) occurs
pathway for the A3 coupling reaction catalyzed by Au/S. to result in the desired propargylamine, with the Au/S. lav-
andulifolia NPs catalyst being reformed for a further cycle of
reactions.48
Recovering heterogeneous new catalysts is extremely vital in
terms of economic and sustainable chemistry views.
Scheme 2 Proposed mechanism for the A3 coupling reaction cata- Fig. 8 Recycling of catalyst for the reaction of benzaldehyde, mor-
lyzed by Au/S. lavandulifolia NPs.
pholine, and phenylacetylene.
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Table 3 Comparison efficiency of Au/S. lavandulifolia NPs with some reported methods for the A3 coupling reaction between benzaldehyde and
piperidine with phenylacetylene
Entry
Reaction conditions
Time (h)
Yield %
Ref.
1
2
3
4
5
6
7
8
Au/S. lavandulifolia NPs, toluene, 100 ꢀ
C
8
14
6
12
14
20
15
16
8
95
70
80
87
34
77
87
75
76
87
73
83
90
92
80
This work
AgI, H2O, 100 ꢀC, N2
49
50
51
52
53
54
55
56
57
58
24
59
60
61
CuSBA-15, toluene, 90 ꢀ
C
Au@PMO-IL, CHCl3, 60 ꢀ
FeCl3, 70 ꢀC
C
Ag NPs, PEG, 100 ꢀ
C
Nano Co3O4, 130 ꢀ
C
Fe3O4, toluene, 80 ꢀ
C
9
Fe3O4@SBA-15, toluene, 110 ꢀC
NiCl2, toluene, 111 ꢀC
10
11
12
13
14
15
9
Ag–NaY, neat, 100 ꢀC
15
18
7
5
6
Ag NPs/plant extract, PEG, 90 ꢀ
MNP@Au/NNN-pincer, H2O, 85 ꢀ
C
C
[CuCl{2,5-bis(2-thienyl)-1-phenylphosphole}2], 100 ꢀ
InBr3, toluene, 80 ꢀC
C
Consequently, we investigated recovery of the Au/S. lav-
andulifolia NPs catalyst for the reaction of benzaldehyde, mor-
pholine, and phenylacetylene under optimum reaction
conditions. For this goal, at the end of the reaction, the catalyst
was isolated from the reaction solution through centrifugation
and rinsed with water and ethanol twice, and then was recycled
for seven times with no signicant change in catalytic perfor-
mance (Fig. 8). This reusability proves the excellent stability and
turnover of the catalyst under working conditions.
Several chosen procedures in the literature and current
procedures were compared in Table 3, which indicates that Au/
S. lavandulifolia NPs are a similar or a more effective catalyst in
terms of reaction time and yield than earlier reported ones.
Acknowledgements
We are thankful to Payame Noor University (PNU) for nancial
supports.
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4. Conclusion
In conclusion, a green, effective, simple, and cost-effective
technique has been developed for synthesizing Au NPs with
Stachys lavandulifolia extract as a reducer and stabilizer. Char-
acterization of the prepared Au/S. lavandulifolia NPs was carried
out using SEM, HR-TEM, FFT, XRD, EDS, TGA, FT-IR, and UV-
visible methods. It was found that Au/S. lavandulifolia NPs are
cost-effective, air stable, and an effective catalyst for synthesis of
propargylamines through
a
one-pot three-component A3-
coupling reaction of aldehydes, amines, and alkynes. The
products were achieved in good to high yields and the catalyst
can be reused up to seven cycles with nearly no change in its
performance. The important properties of the presented
approach are: (i) high catalytic activity; (ii) excellent yield of the
products; (iii) application of the plant extract as a fast and clean
synthetic pathway for synthesis of Au NPs; (iv) no surfactant,
capping agent, and/or template were utilized in the process; and
(v) the Au NPs can be simply retained and reused.
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Conflicts of interest
There are no conicts to declare.
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