Sustainable Chemistry and Pharmacy
Sustainable Chemistry and Pharmacy
Sustainable Chemistry and Pharmacy
A R T I C L E I N F O A B S T R A C T
Keywords: The development of green nanotechnology is generating research interest in the ecological biosynthesis of
Nanoparticles nanoparticles (NPs). In this study, the biosynthesis of stable iron nanoparticles was carried out using Phoenix
Iron oxide dactylifera L. extract which is able to reduce iron ions to iron nanoparticles. The process comprises maceration
Green synthesis
extraction overnight and heat treatment of the extract with iron chloride (FeCl3) at 70 � C for 1 h. X-ray
Phoenix dactylifera L.
diffraction (XRD), scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) were
Antioxidant activity
used for nanoparticle characterization. The stability of the bioreduced iron nanoparticle was analyzed using UV-
VIS absorption spectra, and their antioxidant and anti-radical activities were measured against PhosPhoMo
lybdate (PPM) and 2,2-diphenyl-1-picryl-hydrazyl (DPPH), respectively. The results demonstrate that ecological
biosynthesis of 2–30 nm stable iron nanoparticles of size with antioxidant activity can be achieved suggesting
their possible applications.
1. Introduction 2008/08) and the conversion of energy (Kim et al., 2010/10). In fact,
Iron oxide nanoparticles (Fe-NPs) are particularly interesting in modern
Nanoscience is the study of materials with one or more dimensions in nanotechnology research because of their unique properties, which
the range of 1–100 nm. These materials are produced by atom/molecule make them fit a wide range of applications (Teja and Koh, 2009/03;
organization or by the destruction of a macroscopic material. Nowadays, Laurent et al., 2008).
the manufacturing technology of nanomaterials is growing interest in The synthesis of nanoparticles is usually carried out by various
view of their widespread use for a variety of applications in many in chemical methods such as pyrolysis, sol-gel transition, supercritical fluid
dustrial sectors (Darroudi et al., 2014/11; Chaudhuri and Malodia, synthesis and chemical deposit in steam phase or by a variety of physical
2017/11) Among nanomaterials, nanoparticles (NPs) are especially methods such as engraving, mechanical milling, ablation laser, thermal
interesting due to their capacity to act as a bridge between macroscopic decomposition and lithography (Muthuchamy et al., 2020; Justin et al.,
materials and atomic structures. Macroscopic materials exhibit constant 2017). Most of these methods are expensive and/or require the use of
properties, regardless of their size and mass. However, the properties of toxic solvents (Ahila et al., 2018; Sun et al., 2011). On the other hand,
NPs depend on their size due to the great relative proportion of super great efforts have recently been made to use environmentally friendly
ficial atoms with respect to their volume. Nanoparticles, because of their methods for the synthesis of noble metal nanoparticles (Toropov and
specific and unique properties, are currently being used in many Vartanyan, 2019). Such effort has produced the so-called green
high-tech fields, such as the medical sector for diagnostics, antimicrobial methods, aiming for providing highly pure nanoparticles through sim
purposes and drug delivery systems (Parveen et al., 2012/02; Gholami ple, economic and repetitive techniques.
et al., 2018/06), the electronics and optoelectronics industry (Phillips This is mainly achieved through the use of plant or fruit extracts
et al., 2011), the chemical sector for catalysis (Shiju and Guliants, (Ghodake et al., 2010) and bio-organisms (Sanghi and Verma, 2009)
2009/03), for the protection of the environment (Ju-Nam and Lead, along with polyphenols, which catalyze the synthesis of nanoparticles
* Corresponding author.
E-mail address: johabd@alum.us.es (J.A.A. Abdullah).
https://doi.org/10.1016/j.scp.2020.100280
Received 8 April 2020; Received in revised form 16 May 2020; Accepted 23 May 2020
Available online 9 June 2020
2352-5541/© 2020 Elsevier B.V. All rights reserved.
J.A.A. Abdullah et al. Sustainable Chemistry and Pharmacy 17 (2020) 100280
thanks to their unique properties (nucleophilia, reducing character, necessary. This section describes the conditions under which the char
polarizability, ability to form hydrogen bond, acidity and ability to acterizations were performed.
chelate metal ions) (Zayed and Eisa, 2014). These green methods are
inexpensive, fast, effective and generally lead to the formation of crys 2.3.1. X-Ray diffraction (XRD)
talline nanoparticles with a variety of shapes (spheres, stems, prisms, The different sized nanoparticles were characterized by XRD in order
plates, needles, leaves or dendrites) and sizes. These characteristics to determine more precisely which crystalline phase was present in the
depend mainly on the parameters used in the process, such as the nature nanoparticles. The XRD also provides information about the mesh
of the plant extract, the relative concentrations of the extract and the parameter of the formed Fe2O3, as well as the average size of the dif
metal salts, the pH, the temperature and the reaction time, as well as the fracting domains. To perform this test, they were mixed with silicon
mixing rate of vegetable extract and metallic salts (Noruzi et al., 2011). powder. The silicon diffraction peaks serve as an internal standard to
Phoenix dactylifera L. is one of the plants with higher polyphenol determine the zero shift of the zero diffractograms. The data was refined
content. They are considered bioactive molecules and act both as a with the Full prof software (Rodríguez-Carvajal, 1993),which uses the
reducing and capping agent. For this reason, it has gained immense Le Bail method (Le Bail et al., 1988).
popularity in various fields from therapeutics to food additives. The size of the diffracting domains was also measured on the most
Although its use as an antioxidant additive is restricted, these properties intense peak (311) using the Debye-Scherrer formula (Equation (4)), a
could lead to the synthesis of nanoparticles with different and unique method often used in the literature.
properties (Bayraktar et al., 2017; Gajanan et al., 2011).
kλ
The overall objective of this work was to study the synthesis of Fe- t ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi (4)
H 2 S2 ⋅cosθ
NPs using Phoenix dactylifera L. extract and to characterize these nano
particles using XRD, SEM, UV visible and FTIR to demonstrate that the with t being the size of the diffracting domain, k a correction factor (¼
iron oxide nanoparticles synthesized by this procedure contain certain 0.9), λ the wavelength used, H the width at half-height of the principal
compounds with antioxidant activity and that, therefore, they could be peak of the sample, S the width at half-height of the main peak from the
used as natural antioxidant additives in pharmaceutical and food reference (for monocrystalline Si, S ¼ 0.289) and θ the position of the
products. main peak.
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J.A.A. Abdullah et al. Sustainable Chemistry and Pharmacy 17 (2020) 100280
where h is Planck’s constant, v the frequency and B is a constant. The The evaluation of the antioxidant capacity was carried out as follows:
UV–vis analysis allows us to indirectly measure the absorbance of our 0.5 mL of a methanolic solution of DPPH (7.8 mg of DPPH in 100 mL of
samples and to calculate their optical gap. DMSO) was mixed with 0.3 mL of the nanoparticles dissolved in DMSO
(0.5 mg/mL). Then, the resulting mixture was kept away from light at
room temperature for 30 min. After that, the absorbance was measured
2.4. Determination of the antioxidant activity at 517 nm against a control consisting of 0.5 mL of the DPPH solution
and 0.3 mL of methanol (Basavegowda et al., 2014b). The value for the
The antioxidant potential was carried out by determining the prod control was A0 ¼ 0.382.
ucts resulting from the oxidation or by evaluating the ability to trap By varying the concentration of the extracts and calculating the
radicals of reaction models. Two methods were used to evaluate the corresponding IC (%) for each concentration, it is possible to establish a
antioxidant activity of NPs: Total antioxidant activity (TAC) and DPPH linear regression between the different concentrations and the IC (%).
antioxidant activity. The inhibition of the DPPH radical is a function of the concentration of
The first, older method requires prior knowledge of oxidation com the different NPs synthesized (antioxidant). The anti-radical activity
pounds. Indeed, this method looks for certain functional groups (alde may be expressed in terms of the IC50 (mg/mL), that is, the anti-radical
hydes, ketones, dicarbonyls, etc.) in the derivatives of the original dose necessary to cause 50% inhibition. All the results presented are
constituents. The second method relates the number of radicals trapped average values from three replicates. From this regression, the corre
to that of antioxidants used. sponding value of IC50 is calculated.
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J.A.A. Abdullah et al. Sustainable Chemistry and Pharmacy 17 (2020) 100280
Fig. 2. Scanning electron microscopy (SEM) images of Fe-NPs synthesized by Phoenix dactylifera. L. extract at 70 � C treated at 400 � C for 1h, 0.01 M (a), 0.02 M (b),
0.03 M (c), the diameter distribution average for the three samples (d).
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J.A.A. Abdullah et al. Sustainable Chemistry and Pharmacy 17 (2020) 100280
Fig. 3. FTIR spectrum of the Fe-NPs synthesized by Phoenix dactylifera. L. extract at 70 � C treated at 400 � C for 1h compared with the extract.
peaks are attributed to Fe–O bonds in iron stearate, which shows the 3.4. Characterization by UV–visible spectroscopy
difficulty and importance of the washing stage (Ayachi et al., 2015).
There can also remain a fraction of the synthesis precursor in the The optical properties (absorbance) of the nanoparticles synthesized
nanoparticle suspensions. As a result, the nanoparticles had an inter by the Phoenix extract as well as the NPs (0.01 M, 0.02 and 0.03 M)
mediate composition between magnetite and maghemite, and as the size treated at 400 � C are shown in Fig. 4, which. represents the diffuse
of the nanoparticles increased, the proportion of magnetite also reflectance of the nanoparticles in the UV–visible spectra. In addition to
increased. 225 and 275 nm, a broad absorption band was observed throughout the
spectral range, especially between 350 and 500 nm for the three spectra.
Fig. 4. UV–visible spectrum of the absorbance of Fe-NPs synthesized by Phoenix dactylifera. L. extract at 70 � C treated at 400 � C for 1h compared with the extract.
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J.A.A. Abdullah et al. Sustainable Chemistry and Pharmacy 17 (2020) 100280
The absorption band around 350 nm corresponds to the gap of magnetite Table 1
(Tartaj et al., 2003). However, the synthesized Fe3O4-NPs show a Results for the total antioxidant activity and IC50 DPPH values for the different
continuous absorption in the visible range of 300–800 nm without any NPs (0.01, 0.02 and 0.03 M).
strong absorption peak (Ghodake et al., 2010; Sanghi and Verma, 2009). NPs IC50 DPPH (mg/ml) Total antioxidant activity PPM NPs (mg/g)
The gap energies calculated by the Kabulka-Munk law are 2.39, 2.27 0.03 2.0 77
and 2.49 eV for Fe3O4 corresponding to the NPs obtained at different 0.02 4.0 170
concentrations (0.01, 0.02 and 0.03 M), which is probably due to the 0.01 26.4 180
effect of the quantum confinement related to their nanometric size. In
fact, the position of the resonance bands varies significantly with the size
interests or personal relationships that could have appeared to influence
(Ayachi et al., 2015).
the work reported in this paper.
3.5. Evaluation of the antioxidant activity
CRediT authorship contribution statement
The antioxidant activity of NPs synthesized by the extract of Phoenix
J. Amin Ahmed Abdullah: Writing - original draft, Formal analysis.
dactylifera L. reflects their ability to trap free radicals in the body.
Laouini Salah Eddine: Writing - original draft, Formal analysis.
The anti-free radical activity is achieved by the DPPH method, which
Bouafia Abderrhmane: Writing - original draft, Formal analysis. M.
is frequently used due to its simplicity. Table 1 shows IC50 DPPH values
Alonso-Gonza �lez: Writing - original draft, Formal analysis. A. Guer
for the NPs. From the results obtained, the synthesized NPs at 0.03 M
rero: Writing - original draft, Formal analysis. A. Romero: Writing -
FeCl3 gives the most significant antioxidant activity, with a value of 2.0
original draft, Formal analysis.
mg/ml.
Table 1 also shows the high values for the total antioxidant activity of
Acknowledgments
Fe2O3, Fe3O4-NPs green synthetic nanoparticles (TAC). The highest and
lowest total antioxidant activity of the different nanoparticle concen
This work is part of a project funded by the Spanish Ministry of
trations were 180 mg EAG/g NPs (0.01 M NPs) and 77 mg EAG/g NPs
“Ciencia, Innovacio�n y Universidades” (RTI2018-097100-B-C21). The
(0.03 M). This could illustrate the relationship between concentration
authors gratefully acknowledge their financial support. The authors also
and antioxidant activity, suggesting that, at low concentration, the de
acknowledge the “Cooperacio �n al Desarrollo, Universidad de Sevilla” for
gree of inhibition of both DPPH and TAC is much higher than at high
the pre-doctoral grant from Johar Amin Ahmed Abdullah (CODE).
concentration.
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