Chemistry Africa
https://doi.org/10.1007/s42250-019-00102-w
ORIGINAL ARTICLE
Synthesis, Characterization and Antifungal Activity of Fe(III)
Metal–Organic Framework and its Nano‑composite
Adedibu C. Tella1 · Hussein K. Okoro2 · Samuel O. Sokoya1 · Vincent O. Adimula1,2
Caliphs Zvinowanda3 · Jane C. Ngila3 · Rafiu O. Shaibu4 · Olalere G. Adeyemi5
· Sunday O. Olatunji1 ·
Received: 22 July 2019 / Accepted: 30 October 2019
© The Tunisian Chemical Society and Springer Nature Switzerland AG 2019
Abstract
Metal–organic frameworks (MOFs) have gained developing interest due to their high specific surface area and pore volume,
which has been exploited for gas storage, sensors and, drug delivery. This study presents the synthesis of a non-toxic, biocompatible and thermally stable MIL-53(Fe) and the preparation of its silver(I) nitrate nano-composite. This MIL-53(Fe) is
a three-dimensional porous solid composed of infinite FeO4(OH)2 cluster connected by 1,4-benzenedicarboxylate (H2BDC)
ligand using solvothermal method of synthesis and the encapsulation process was also carried out to produce a composite
composed of silver nanoparticle (AgNP). The synthesized materials were characterized using Powder X-ray Diffractometer
(PXRD), Scanning Electron Microscope coupled with Electron Diffraction X-ray Spectrometer (SEM–EDS) and Fourier
Transform Infrared (FT-IR) Spectroscopy. The Ag@MIL-53(Fe) composite exhibits a remarkable antifungal activity against
Aspergillus flavus using a poison plate method. This can be attributed to the therapeutic nature of nanoparticle with a range
of 55–64% growth inhibition rate as the concentration of the Ag@MIL-53(Fe) was increased. Minimum lethal concentrations (MLC) were observed to be 40 μg/mL and 15 μg/mL for the prepared MIL-53(Fe) and the Ag@MIL-53(Fe) composite,
respectively.
Keywords Metal–organic frameworks · Nano-composite · Aspergillus flavus · Antifungal test
1 Introduction
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s42250-019-00102-w) contains
supplementary material, which is available to authorized users.
* Vincent O. Adimula
vincentadimula@gmail.com
1
Department of Chemistry, Faculty of Physical Sciences,
University of Ilorin, P.M.B. 1515, Ilorin, Nigeria
2
Department of Industrial Chemistry, Faculty of Physical
Sciences, University of Ilorin, P.M.B. 1515, Ilorin, Nigeria
3
Analytical-Environmental and Membrane Nanotechnology
Research Group, Department of Chemical Science,
University of Johannesburg, Doornfentein, PO Box 17011,
2028 Johannesburg, South Africa
4
Department of Chemistry, University of Lagos, Akoka,
Lagos, Nigeria
5
Department of Chemical Sciences, Redeemers University,
Ede, Nigeria
Metal–organic frameworks (MOFs) are coordination polymers that extend into two, three-dimensional networks [1].
These materials need to be strong bonding metal centers
linked by organic ligands to form a geometrically welldefined structure [1]. Metal organic frameworks (MOFs)
have received great attention in recent years, due to their
fascinating architectures and topologies (low density, high
specific surface and pore volume) as well as their increasing properties and potential applications such as functional
materials, catalysis, separation (adsorption), gas storage and
drug delivery [2–5]. Metal–organic frameworks also known
as porous coordination networks and porous coordinated
polymers refer to similar but not the same general type of
materials [6, 7]. MOFs’ well-defined and large pore structure makes it possible for them to be used to stabilize and
control the formation of metal nano-particles within their
structure [8]. The MIL (Material Institute Lavoiser) series
of MOFs have been especially reported as versatile materials
which have been tested in various applications ranging from
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gas adsorption/separation, gas storage, catalysis, and drug
loading. Moreover, there is continued search for materials
which can achieve controlled ion release thereby exhibiting antimicrobial properties. MOFs have been proposed as
materials which show promising possibility for antimicrobial
application. Recently, silver-based MOFs have been reported
to show excellent antimicrobial activity, just as two cobaltimidazolate MOFs were reported to show interesting antibacterial activity against the growth of Pseudomonas putida
and Escherichia coli. The HKUST-1 (i.e. Hong Kong University of Science and Technology metal organic framework
(MOF) consisting of copper ion linked by 1,3,5-benzenetricarboxylic acid) has been reported to have a pore system
which provides access to the binuclear metal centres. The Cu
ion metal centres are capable of been disconnected resulting
in the MOF acting as a means of ions which are biologically
active [9–11].
Silver nanoparticles (AgNPs) have been presented as
broad-spectrum antimicrobial agents that have been widely
utilized in products such as personal care and pharmaceutical products. The silver ions present in the core of the nanoparticles are reported to be responsible for the biological
activity of the NPs. However, experimental findings reveal
that the silver ions alone are not always responsible for the
biological action of the NPs [12].
A typical MOF which has found several applications in
a variety of processes is the iron−benzenedicarboxylate
(MIL-53(Fe)) MOF. This material is constructed from a
combination of 1,4-benzenedicarboxylate (BDC) linker and
FeO4(OH). Some potential applications of the MIL-53(Fe)
MOF include gas storage/separation, drug loading and delivery, and adsorption. The MIL-53(Fe) has been recently presented as having photocatalytic property in the degradation
of organic dyes, and introduction of functionalities into the
MIL-53(Fe) material is able to achieve great improvements
in their photocatalytic performance [13–15].
The incorporation of active metal nano-particles into
metal–organic frameworks is relevant for a number of
potential applications involving heterogeneous catalysis
and gas storage [16, 17]. Intercalation is usually achieved
via decomposition of volatile organic precursors although
it can be achieved using wetness impregnation, mechanical
and co-precipitation methods [16, 18–24]. Palladium and
ruthenium nanoparticles have been reportedly incorporated
into MOF-5 using the chemical vapour deposition technique
[17] while Cu-Pd nanoparticles were successfully intercalated into MIL-101 [24], and both materials were reported
to exhibit enhanced catalytic activity in the oxidation of
CO than the unincorporated MOFs or the separate nanoparticles, and the incorporation of these nano-particles
into the MOFs structure allowed for effective reactions at
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low temperature. The presence of Pd-Ru and Cu-Pd nanoparticles were confirmed by TEM and XRD analyses [25].
Obtaining catalysts having optimally tuned adsorbate binding property is of great research interest. The study of this
category of catalysts involves using density functional theory to determine the ensembles, the ligand, and effects of
strain in the close-packed material which has been alloyed
using transition metals particularly RhAu, PdAu, and PtAu
bimetallic materials. The preparation of Ag–Ir (silver–iridium) alloys as solid-solution nanoparticles and their use as
catalysts has been reported. The Ag–Ir NPs were found to
have higher selectivity toward the C═O hydrogenation in
α,β-unsaturated aldehydes and croton-aldehyde, resulting
in crotyl alcohol which has high industrial value. Also, the
incorporation of Ag–Ir NPs in the pores of Co3O4 leads to
about 56% enhancement in selectivity. The performance of
bimetallic and single metal surfaces for the reduction of
nitrite has been shown to be rapidly enhanced using binding energies of ammonia (NH3), nitrogen (N), and nitrogen
gas (N2) to describe the reactivity through catalyst modeling using the density functional theory (DFT) calculations
[26–28].
There have been reports of preparation of Ag nanoparticles of MOFs such as MIL-101, MIL-53(Al), and silver
phosphate composite of MIL-53(Fe), however, to the best
of our knowledge, there is no literature report of the antifungal activity of MIL-53(Fe) silver-nanocomposite against the
Aspergillus flavus, in particular.
The disease Aspergillosis is a common fungal infection which is ubiquitous in nature and occurs in birds and
occasionally in man by exposure to Aspergillus fungi. The
genus Aspergillus comprises of about 185 species of which
20 species of these have been reported to cause opportunistic infections in man. The species include Aspergillus fumigatus which is the most common specie isolated,
Aspergillus flavus and Aspergillus niger, Aspergillus
clavatus, Aspergillus glaucus group, Aspergillus terreus,
Aspergillus oryzae, Aspergillus nidulans. Less commonly
isolated species include the Aspergillus ustus and Aspergillus versicolor which have been reported to be less opportunistic pathogens. Disease states associated with aspergillosis include cutaneous aspergillosis, cerebral aspergillosis,
meningitis, endocarditis, myocarditis, pulmonary aspergillosis, osteomyelitis, otomycosis, onychomycosis, sinusitis,
endophthalmitis, hepatosplenic aspergillosis, and Aspergillus fungemia, disseminated aspergillosis may arise thereof
[29, 30].
In this study, we report the synthesis and characterization
of MIL-53(Fe), and the incorporation of silver-nanoparticles
into its framework. The antifungal activity of the synthesized MOF and its nano-composite were investigated against
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Aspergillus flavus using disc diffusion method (poison plate
method). The antifungal activity of the MOFs materials,
[MIL-53(Fe)] and Ag@MIL-53(Fe), were compared based
on the zone of inhibition.
2 Experimental
transform infrared (FTIR) spectrum was measured using a
Shimadzu 8400 s spectrophotometer with KBr. The samples
were mixed with KBr in the ratio 1:10 and pelletized, and
the spectra were recorded over a range of 400–4000 cm−1.
Scanning electron microscopy (SEM) images and energydispersive X-ray (EDX) analysis of the synthesized MOFs
were obtained using a TESCAN Vega 3 XMU scanning electron microscope.
2.1 Materials
Terephthalic acid (99%), Silver(I)nitrate (AgNO3, 99%), and
iron(III)nitrate nonahydrate (Fe(NO3)3∙9H2O, 99%) were
obtained from Sigma Aldrich Ltd., Germany. N,N-dimethylformamide (DMF, 99%) and triethylamine (TEA, 99%)
were obtained from was obtained from British Drug House
Ltd., England. All chemicals obtained were used as received.
2.2 Synthesis of MIL‑53(Fe)
MIL-53(Fe) was prepared by a modification to the procedure described by Zhang et al. [31] Iron(III)nitrate nonahydrate (2 mmol) and terephthalic acid (2 mmol) were dissolved separately in 10 mL dimethyl formamide (DMF),
mixed together, and three drops of TEA was added to the
mixture, and transferred into a 25 mL Teflon lined hydrothermal reactor, placed in an oven, and heated at 150 °C
for 24 h. Thereafter, the reactor was allowed to cool slowly
to room temperature. The product formed was recovered
by centrifugation (using 80-2 Electronic desktop centrifuge, 1000 rpm, room temp.) for 3 min, and washed with
200 mL distilled water and dried and stored in a desiccator
(Scheme 1).
2.3 Characterization of the Synthesized MIL‑53(Fe)
The powder X-ray diffraction (PXRD) analysis was carried out on an Empyrean XRD X-ray diffractometer using
a CuKα-radiation operating at 30 kV and 40 mA. Fourier
2.4 Preparation of MIL‑53(Fe) Silver‑nanoparticles
(Ag@MIL‑53(Fe))
The Ag@MIL-53(Fe) was prepared by a modification to the
procedure reported by Liang et al. [32]. Anhydrous ethylene glycol (15 mL) was heated in the oven at 160 °C for 1 h.
Degassed MIL-100(Fe) (100 mg) was dispersed in 6 mL of
ethylene glycol solution containing 28 mg AgNO3 by ultrasonication for 10 min and a separate ethylene glycol solution
(6 mL) containing 30 mg of polyvinylpyrrolidone (PVP) surfactant was also prepared. Polyvinylpyrrolidone (PVP) was
utilized to guard against framework degradation. These two
suspensions were simultaneously added slowly to the heated
ethylene glycol and the mixture further heated at 160 °C for
20 min. The silver-nanoparticle loaded MIL-53(Fe) was thereafter allowed to cool to room temperature and centrifuged at
14,000 rpm for 5 min, washed with 50 mL acetone five times
to remove unincorporated nano-particles (Scheme 2).
2.5 Antifungal Activity
The inhibitory or stimulatory activity of the synthesized
MIL-53(Fe) and its composites, Ag@MIL-53(Fe), on
micro-organisms was determined by following the procedure described by Obaleye et al. [33]. The antifungal activity
was studied using a potato dextrose agar on which 1.0 cm
diameter walls was punched and three different concentrations (5%, 10%, 15% m/v in distilled water) of the MOFs and
its composite were utilized.
Scheme 1 Equation showing
the solvothermal synthesis of
MIL-53(Fe)
Scheme 2 Equation showing
the preparation of the Ag@
MIL-53(Fe)
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2.6 Determination of Minimum Lethal
Concentration (MLC)
period of 24 h and evidence of growth observed. The MLC
was thus noted.
The procedure described by Obaleye et al. [33] was adopted
in order to determine the MLC. Sterile stoppered test tubes
were utilized and the growth medium for the Aspergillus
flavus added. This was followed by subsequent addition of
0.05 mL aliquots of MIL-53(Fe) and its composites, Ag@
MIL-53(Fe), from a volume of 0.1 mL to 5.0 mL. This
represented 10 to 500 μg/mL, in a final mixture of 10 mL.
Standard volume to represent the inoculum (0.2 mL each of
the test), in which the MIL-53(Fe) and its composites, Ag@
MIL-53(Fe), are omitted, and another in which the Aspergillus flavus test organism is omitted was also prepared. The
tubes were all incubated at a temperature of 35 °C for a
3 Results and Discussion
3.1 Fourier Transform Infrared (FT‑IR) Spectra
The FTIR spectra of the synthesized MIL-53(Fe), in its
hydrated form and after immersing in ethylene glycol
solution accompanied by heat treatment (MIL-53(Fe)@
et), and the Ag@MIL-53(Fe) composite are presented in
Fig. 1. The ν(C=O) vibrations in the carboxyl group was
observed at 1660 cm −1 in the three products which is
consistent with reported values for coordinated C=O in
Ag@MIL-53(Fe)
-1
-1
748 cm
ν(C-H)
1660 cm
ν(C=O)
Tranmittance (%)
MIL-53(Fe)@et
-1
1660 m-1
748 cm
ν(C-H)
MIL-53(Fe)
-1
1660 m
-1
748 cm
ν(C-H)
ν(C=O)
Wavenumbers (cm-1)
Fig. 1 FTIR spectra for MIL-53(Fe) and its nano-composite
Fig. 2 Comparison PXRD
pattern of the MOFs and its
nano-composite
54.08 0
64.33 0
Relative Intensity
Ag@MIL-53(Fe)
MIL-53(Fe)@et
10 °
16 °
25 °
MIL-53(Fe) hydrated
2θ (0)
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literature [34]. A value of 160 cm−1 was obtained for the
Δ(ʋasymm(COO–) − ʋsym(COO–)), which indicates a bidentate coordination mode of the carboxyl group to the metal
ion [35, 36] while the ν(C–H) bending vibrations of the benzene rings was observed at 748 cm−1 [37].
The FTIR spectra of the synthesized MIL-53(Fe) and that
of the Ag@MIL-53(Fe) showed similar peaks indicating that
the incorporated silver nano-particles did not alter the structure of the MIL-53(Fe) [38].
3.2 Powder X‑ray Diffraction (PXRD) Analysis
PXRD patterns of the synthesized MIL-53(Fe) and
the Ag@MIL-53(Fe) composite (Fig. 2) showed good
Fig. 3 SEM image of a MIL53(Fe); b MIL-53(Fe)@et; c
Ag@MIL-53(Fe) Composite
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agreement with that reported in literature [32, 33] which
confirms the successful synthesis of the material. Furthermore, the incorporation of silver nano-particles was
observed to not alter the framework of the MOF compared
to the report of framework decomposition during solution based infiltration of metal ions into MOFs [19, 38].
Characteristic 2θ peaks at 54.08 ° and 64.33° observed in
the PXRD pattern of the prepared Ag@MIL-53(Fe) was
absent in the MIL-53(Fe). This indicates the successful
incorporation of silver nano-particles in the MIL-53(Fe)
framework at the same time retaining the integrity of
the MOF structure. Furthermore, there was no observed
changes in the PXRD patterns of the synthesized MIL53(Fe) and the ethylene glycol treated MIL-53(Fe) (i.e.
MIL-53(Fe)@et), indicating that treatment of MIL-53(Fe)
in hot ethylene glycol does not alter the structural framework of the prepared MOF.
possible phase changes. It was observed from the SEM
images at a magnification of 5000 × that the surfaces
remained rough-like in the MIL-53(Fe) and MIL-53(Fe)@
et. The MIL-53(Fe) showed non-homogeneous, stick-like
particle shapes (Fig. 3) which was retained in the MIL53(Fe)@et (Fig. 3). The particles of the Ag@MIL-53(Fe)
composite was observed to be bulky having rough surfaces
(Fig. 3) compared to the MIL-53(Fe) particles. This can
be attributed to the presence of silver-nanoparticles in the
framework [39].
Elemental composition of MIL-53(Fe) and the Ag@MIL53(Fe) composite are presented in Fig. 4a, b, respectively.
The EDX spectrum of the selected region in the SEM images
of the Ag@MIL-53(Fe) composite (Fig. 4b) shows the Agrich region of spheres and the carbon-rich smooth surface of
the micro-rods revealing the presence of Ag nanoparticles on
the surface of the MIL-53(Fe) and the uniform distribution
of carbon and oxygen atoms in the nano-composite.
3.3 SEM–EDX Analysis
3.4 Antifungal Activity
SEM images of the prepared compounds were obtained
at a magnification of 5000 ×. This was selected in order
to clearly observe the phases of the compounds and the
The antifungal activity study of the synthesized MOFs
revealed that the Ag@MIL-53(Fe) composite has better antifungal activity at concentrations of 50, 100, and 150 ppm
Fig. 4 EDS spectrum of a MIL53(Fe); and b Ag@MIL-53(Fe)
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Table 1 Antifungal activity of MOFs and its nano-composite against
Aspergillus flavus
S/N
Concentrations
(ppm)
1.
50
2.
100
3.
150
Sample code
% inhibition
MA
MB
MC
MA
MB
MC
MA
MB
MC
23.60
39.75
55.27
43.47
54.65
59.62
59.62
60.86
63.97
Significant increase in zone of inhibition as the concentrations of the
MOFs increases is observed in Table 1
MA hydrated MIL-53(Fe), MB dehydrated MIL-53(Fe), MC Ag@
MIL-53(Fe)
(Table 1), compared to the MIL-53(Fe). This can be attributed to the presence of Ag nanoparticles in the nano-composite which improves its antifungal activity [40] and the
small particle size of the nano-composite which enables ease
of penetration into the cell wall of the Aspergillus flavus
thereby affecting the cell membrane and growth of the cell.
The capping agent polyvinylpyrrolidone (PVP) surfactant
was observed to enhance the dispersion of the nanoparticles
thereby improving the performance of the material. It was
observed that the PVP capping agent properly encapsulated
the Ag@MIL-53(Fe) nanoparticles thereby enhancing its
stability. The MLC of the prepared MIL-53(Fe) and the
Ag@MIL-53(Fe) composite was observed to be 40 μg/mL
for the MIL-53(Fe) and 15 μg/mL for the Ag@MIL-53(Fe),
giving % inhibition values of 17.92% and 16.37% respectively. The Ag@MIL-53(Fe) exhibited better activity against
the fungi tested, and this can be attributed to the presence of
the silver ions in the composite [9, 12].
4 Conclusion
MIL-53(Fe) was synthesized and its Ag@MIL-53(Fe)
composite successfully prepared using polyvinylpyrrolidone (PVP) surfactant. The antifungal activity of the
MOFs and its composite was tested against Aspergillus
flavus and the activities of the MOFs were compared
based on the zone of inhibition. The Ag@MIL-53(Fe)
was observed to have better antifungal activity against the
Aspergillus flavus fungi at the various concentrations used
which may be due to the therapeutic nature of the silver
nanoparticles present in the framework. This work thus
presents the Ag@MIL-53(Fe) as an effective antifungal
agent against Aspergillus flavus. This indicates the capability of the Ag@MIL-53(Fe) to be used as an antifungal
agent in the treatment of fungal infections arising from the
Aspergillus flavus.
Acknowledgements Prof. A. C. Tella is grateful to the Royal Society
of Chemistry for the award of 2015 research fund. Authors Dr. H. K.
Okoro and Prof J. C. Ngila are grateful to the U.J. Global Excellence
and Stature Scholarship for running cost paid by Water Research Commission WRC Project No; K5/2365. Dr. Caliphs Zvinowanda thanks
NRF-SA/Egypt collaboration grants No; 108685.
Compliance with Ethical Standards
Conflict of interest On behalf of all authors, the corresponding author
states that there is no conflict of interest.
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