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OPEN Effect of graphene oxide on

modifying polyethersulfone
membrane performance and
its application in wastewater
treatment
Azam Marjani1, Ali Taghvaie Nakhjiri2, Maryam Adimi3, Hassan Fathinejad Jirandehi4 &
Saeed Shirazian5,6*
In the present paper, Graphene Oxide (GO) particles were prepared via Hummer method, and used
in synthesis of composite membranes. Polyethersulfone (PES) nanocomposite membranes were
synthesized via wet phase inversion technique, and using water as non-solvent. The membrane
morphology was investigated using scanning electron microscopy (SEM). Change in the membrane
surface hydrophilicity after modification was studied using contact angle measurements. The
performance of fabricated PES nanocomposite membranes was measured by evaluating pure water
flux, salt rejection, dye retention and heavy metals removal. The results indicated that by increasing
the filler percentage up to 5 wt.%, the contact angle between the water droplet and the membrane
surface was decreased and the droplet was more dispersed on the membrane surface which implies
higher hydrophilicity of the prepared nanocomposite membranes. Moreover, the experimental results
corroborated that addition of GO to the membrane significantly improved the pure water flux, salt
rejection and heavy metals removal, and can be used as a novel methodology for preparation of high
performance membranes in water treatment.

Over the last decades, substantial development in chemical industries has eventuated in an increment in the pro-
cessing speed and a reduction in energy consumption1. It has been recognized that separation and purification
of different materials is one of the most significant techniques in chemical and biochemical engineering which
has major contribution to total processing costs2–6. In order to implement the industrial processes, raw material
components must be separated and the obtained products should be purified as well. On the other hand, in the
majority of chemical industries, the requirement of separation procedures seems to be unavoidable to efficiently
manage the deleterious impressions of greenhouse gases on environment7–9. In this regard, membranes have been
developed for the efficient separation and purification of various types of materials in solid, liquid and gas states.
Although the membrane separation procedure is more recent than distillation, adsorption, crystallization and
liquid-liquid extraction, significant advancements have been observed in its application over the past two decades
due to the efficiency and ease of operation4,5,10–17.
Both polymeric and inorganic membranes have been developed for the purpose of separation and reaction.
Polysulfone-based membranes such as Polyethersulfone (PES) are utilized for the fabrication of nanofiltration
membranes because of their outstanding mechanical/thermal resistance, chemical compatibility and stability
over an extensive range of pH18. The main disadvantage of the PES membranes is its intrinsic hydrophobic nature.
Due to the absorption of organic impurities, these membranes are susceptible to fouling and blockage which leads

1
Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran. 2Department of Chemical Engineering,
Science and Research Branch, Islamic Azad University, Tehran, Iran. 3Department of Chemical Engineering, Farahan
Branch, Islamic Azad University, Farahan, Iran. 4Department of Chemistry, Farahan Branch, Islamic Azad University,
Farahan, Iran. 5Department for Management of Science and Technology Development, Ton Duc Thang University, Ho
Chi Minh City, Viet Nam. 6Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Viet Nam. *email:
[email protected]

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to decreasing their life span19. In order to optimize the performance of nanofiltration membranes, they should
be modified prior to usage in separation. Increasing the membrane’s hydrophilicity is regarded as a good option
to improve membrane performance. Indeed, the modification techniques lead to a compromise between the
hydrophilicity and hydrophobicity nature of polymeric membranes, and improves the separation properties of
membranes in removal of ions and organic molecules from aqueous solutions20.
In recent years, one of the substances applied to remove contaminants and impurities from the water is
Graphene Oxide (GO) and its modified derivatives, which absorb suspended and water-soluble materials due to
its high surface area and functional groups. The first and most important investigation on membrane fabrication
incorporated with GO particles was reported by Nair et al.21. Further investigations were implemented by Cohen
et al., in which the ability of nanoporous Graphene for salt rejection in a reverse osmosis membrane has been sim-
ulated22. Zhang et al. studied the GO effect on the phase inversion process of the coagulation bath on morphology,
surface properties, mechanical strength, and separation properties of prepared membranes. The results proved
that increment in the amount of GO in the membrane structure significantly enhanced the amount of flux passing
through the membrane, the mechanical strength and the separation properties1. Zeinadini et al. evaluated the
performance of nanofiltration membranes using GO nanoparticles. In their study, the effect of GO nanoparticles
on the morphology and anti-fouling properties of membranes was investigated. The results illustrated that by
adding the GO to the membrane matrix structure, the amount of flux was increased. Moreover, the excellent dye
removal from industrial effluents has been obtained applying this type of membrane23.
Ganesh et al. prepared polysulfone mixed matrix membranes using graphene dispersion via fuzzy separation
technique. The difference in hydrophilicity was studied by measuring the surface wettability and water swelling.
The contact angle data demonstrated that the addition of GO to the membrane surface would increase the surface
hydrophilicity of prepared membranes24. Ionita et al. prepared polysulfone-GO nanocomposite and studied its
structure, surface properties and mechanical/thermal performances. The analyses showed great compatibility
and excellent dispersion of the polysulfone polymer matrix that was observed even for a very low amount of
GO25. Zhang et al. studied preparation of GO composite membranes for separation of pollutants from water. They
fabricated membranes with specific adsorption characteristics by blending approach. The prepared membranes
were used as adsorbent for removal of cationic and anionic dyes. They reported that the GO composite polymeric
membranes are great candidate for wastewater filtration26.
The main objectives of this paper are to experimentally synthesize the GO with modified Hummers method,
prepare the polymer membranes incorporated with GO particles using phase inversion method and investigate
the prepared Polyethersulfone nanocomposite membrane performance including pure water flux, salt rejection,
dye rejection, removal of heavy metals and fouling. Additionally, the membrane morphology/hydrophilicity are
studied using scanning electron microscopy (SEM) and contact angle experiments, respectively.

Experimental and Methodology

Synthesis of graphene oxide (GO). Hummer method was used for synthesis of GO particles27. 5 gr of
graphite powder (Fluka) was slowly added to a mixture of 100 ml sulfuric acid (Merck) and 12 ml phosphoric acid
(Merck), which was placed in ice bath under a magnetic stirrer. Then 2.5 gr of ammonium nitrate was added to
this mixture during 30 min. After that, 20 gr of potassium permanganate powder (Merck) was gradually added
to the mixture over 60 min, so that the temperature of the mixture should not be higher than 5 °C. After addition
of the abovementioned materials, the mixture was stirred at a temperature below 5 °C for another 120 min. At
this stage, the color of the mixture turns to black. Then, using an electric heater, the temperature of the mixture
was increased to 40 °C and consequently the mixture was homogeneous using an electrical stirrer for 1 hr. At this
point the color of the slurry becomes green. The temperature of this set was then increased to 98 °C and stirred
for 60 min. At the end of this period, the obtained solution was added dropwise to 400 ml frozen distilled water
and after 5 min, 15 ml of oxygenated water (Merck) was added. Finally, the solution was centrifuged and washed
4 times with deionized water and then washed once with hydrochloric acid 5% (Merck) and again, this procedure
was repeated twice with deionized water. The sample was vacuum-dried in an oven at 60 °C for 24 hrs.

Preparation of the PES/GO nanocomposite membranes. Polyethersulfone (PES, BASF Co.) was used
for preparation of membranes via phase inversion method. Different percentages of the filler (1, 3, 5 wt.%) relative
to the polymer matrix weight were selected and the nanocomposite membranes were fabricated for each of the
filler percentage. As an example, a nanocomposite membrane with 1 wt.% of filler is prepared using the following
procedure:
0.2 gr (1 wt.% relative to the PES polymer weight) of GO (as filler) was dispersed in 0.5 gr of N-Methyl-
2-pyrrolidone (NMP, Merck) solvent and was added to a homogeneous mixture of 2 gr of polymer (PES) and 1
gr of polyethylene glycol (PEG) homogenized in 6.48 gr of NMP solvent (total weight of the mixture is 10 gr).
The solution is then placed on a magnetic stirrer at 60 °C for 24 hr. After this period, the solution is cast using a
suitable blade onto a perfectly flat glass and immersed in the coagulation bath (room temperature, anti-solvent
water) for 30 s until the solvent displacement process and nanocomposite film formation occur (phase inversion
process). For other fillers, the same procedure as described was used and the nanocomposite membrane is pro-
vided considering this difference that the weight of the selected solvent for the polymer mixture (PES + PEG)
will vary for different percentages. Table 1 describes the applied compositions for preparing the nanocomposite
membranes. In all cases, PEG is considered as the controlling agent of membrane pore size.

Permeation tests. In order to determine the hydrophilicity of the nanomembranes surface, the permeability
test was applied. All permeability experiments were performed in a cell with dead-end mode to using circularly
cut membranes with an effective surface area of 3.73 cm2. The applied external pressure is supplied by a nitrogen
gas cylinder which is capable of generating pressure up to 12 bar. The membrane is first cut and inserted according

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NMP solvent PES PEG Weight percent

Sample (%) (%) (%) of filler (%)
M0 70 20 10 0
M1 69 20 10 1
M2 67 20 10 3
M3 65 20 10 5

Table 1. Compositions used for preparing the nanocomposite membranes.

Figure 1. The nanofiltration cell used in the experiments.

to the size of the nanofiltration cell loading portion. As a feed solution, distilled water is used and the permea-
bility test is performed by adjusting the external pressure between 1 to 7 bar for 1 min for each applied pressure.
Then, from the volume of effluent, the effective membrane area, the operation time, net water flow is reported.
The operation is performed for all prepared nanomembranes. Figure 1 illustrates the nanofiltration cell used in
this work. For conducting the salt rejection experiments using the membrane samples, 0.01 M of NaCl, MgSO4
and Na2SO4 salt solutions were used. The applied operational pressure was 5 bar. The conductivity method was
used to determine the concentration of samples passed through the loaded membranes inside the nanofiltration
cell. All measurements have been conducted twice and the average values are reported throughout the paper. The
variability was calculated to be less than 10% for all measurements.
The permeation flux is calculated as follows:
V
Flux =
At (1)
where V is the volume of permeated solution (L), A is the membrane surface area (m ), and t is the experiment
2

time (h).

Dye and heavy metals removal tests. 10 ppm of methylene blue (MB) and methyl orange (MO) solu-
tions were applied to conduct the dye removal experiments using the prepared membrane samples. The applied
operational pressure was 5 bar. The test time for each membrane sample was 60 seconds. UV spectroscopic
method was used to determine the concentration of samples permeated through the membranes. In order to carry
out the heavy metals removal experiments using membrane samples, 10 ppm ZnSO4.7H2O, 10 ppm CuSO4.5H2O
and 2500 ppm Cd (NO3)2.4H2O salt solutions were used. The applied operational pressure was 5 bar. The test time
for each membrane sample was 60 seconds. The conductivity method was utilized to determine the concentration
of membrane-loaded samples in nanofiltration cells.

Fouling tests. Bovine serum albumin (BSA) solution in 100 ppm phosphate buffer (PBS: 50 mM, pH:7.4)
was used to perform the membrane fouling test. The test was performed in two modes, i.e. dynamic and static.
In the dynamic mode, the nanofiltration cell was used for the test in which the membrane sample was cut to the
appropriate size for the test. First, at a pressure of 5 bar for 60 s, the pure water flux was measured (Jw1). Then, the
nanofiltration cell was filled with BSA solution in 100 ppm PBS, and the protein flux was measured at the same
pressure and duration. Then, after washing the membrane, the pure water flux rate was again measured (Jw2) and
flux recovery ratio (FRR) was reported for the membranes using the following equation:
Jw 2
FRR =
Jw1 (2)
This procedure was performed for all membrane samples and the results were reported. In the static type,
the membrane samples were first cut in equal sizes with an effective surface area of 0.5 cm2 and the samples were
immersed in phosphate buffer solution (PBS) for 2 hr. After this period, the samples were extracted from phos-
phate buffer solution and each sample was individually placed in test tubes filled with 5 ml of protein solution in a

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Figure 2. IR spectra of graphite and graphene oxide.

Figure 3. The TEM image of synthesized graphene oxide.

30 °C water bath for 24 hr to reach equilibrium. The amount of adsorbed protein on the surface of each membrane
was determined by comparing the absorption intensity of the protein solutions before and after the experiment.
UV-vis spectroscopy (model 8453, Agilent, U.S.A) at 280 nm was used to measure the absorption intensity.

Results and Discussion

Investigation of synthesized graphite and graphene oxide IR spectra. As can be seen in Fig. 2, the
IR spectrum of GO indicates the presence of many factors on the graphite sheet after oxidation. A broad peak
is seen above 3000 cm−1, which is justified due to the O-H stretching of the surface functional groups as well as
absorption of water molecules on the GO layers. OH may exist in form of alcoholic, phenolic, and carboxylic
acid. The strong peak at 3426 cm−1 corresponds to the O-H stretching of the GO surface groups and is confirmed
by the strong band at 1032 cm−1 (related to the C-O stretch). The 1720 cm−1 band is associated with the C=O
carboxyl group (COOH). The peak around 1589 cm−1 is related to the epoxide bond and the bending vibration of
water molecules in the GO matrix, whereas the IR spectra of graphite indicate no specific properties, confirming
that the graphite is successfully oxidized to GO by the applied synthesis method.

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Figure 4. The SEM image of synthesized graphene oxide.

Figure 5. XRD spectra of graphite and graphene oxide.

TEM and SEM images of graphene oxide. Transmission electron microscopy (TEM) is considered as it
is an effective method for describing the morphology of GO. As illustrated in Fig. 3, the graphene oxide plates are
seen as a flat surface. The TEM image confirms the correct and successful synthesis of GO nanostructure. Figure 4
illustrates the SEM images of graphene oxide. According to the image, it is observed that the plates are spaced
apart and segregated in some places19.

Investigation of graphite and graphene oxide XRD. Figure 5 obviously depicts the XRD pattern of
graphite and graphene oxide. Based on the figure, for the graphene oxide, an intense peak is seen around 10.9°
which is the characteristic peak of pure GO. In addition, comparison of the GO and graphite X-ray diffraction
patterns corroborates that an area of the spectrum is out of alignment. Sharp branches appear at relatively high
intensities which indicate the presence of more oxygenated functional groups caused by graphene oxide GO
(increasing the number of oxygenated sites).

Nanocomposite membranes surface morphology. The FESEM images of the fabricated membranes surface
are shown in Fig. 6. It is clearly observed that the surface of PES unmodified membranes (A) are smoother than those
membranes that are modified by different weight percentages of GO (B, C, D). Also, FESEM images of cross-section
membranes are shown in Fig. 7. It can be seen that the presence of GO in the polymer matrix of the PES membranes
has eventuated in the formation of more finger-like porous structure. The latter can be attributed to the enhancement
of solvent replacement with nonsolvent (water) during phase inversion process, with increasing GO content which is of
hydrophilic nature. It is also seen that the membranes surface was greatly smooth by the addition of GO particles, con-
firming well dispersion of GO in the polymer matrix. The FESEM images obtained from the membraness demonstrate
that by increasing the GO content from 1 wt.% to 5 wt.%, the membrane porosity is increased.

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Figure 6. FESEM images from the surface of nanocomposite membranes. A:M0, B:M1, C:M2, D:M3.

Figure 7. Cross-section FESEM images of prepared membranes.

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Figure 8. Water flux for GO-PES nanocomposite membranes with different filler percentages as function of
pressure.

Figure 9. Salt rejection percentage for GO-PES nanocomposite membrane with different filler percentages.

Nanocomposite membrane performance for modifying the pure water flux. Figure 8 represents
the obtained experimental data for the fabricated membranes with 0, 1, 3 and 5 wt.% GO filler content at different
applied operational pressures. As seen, increase in the operational pressure caused a significant improvement in
the water flux which is due to porous structure of the prepared membranes. Moreover, by increasing the filler
content, the pure water flux is increased which is justified due to increasing the membrane hydrophilicity and
porosity caused by increasing the amount of GO filler. As shown, increment in the applied operational pressure,
the water flux for all membrane samples is increased. The figure illustrates that the highest amount of pure water
flux is obtained for the nanocomposite membrane with 5 wt.% filler.

GO-PES nanocomposite membrane performance in salt removal. Using the conductivity appara-
tus, the conductivity data of each sample of salt solution passed through the loaded membranes in nanofiltration
cells were obtained during the rejection process. To obtain the concentration of salt samples passing through
these membranes, standard solutions were prepared at lower concentrations than the feed solution and by draw-
ing the calibration diagrams, the concentration of these samples were determined. The rejection percentage of
different salts can be calculated using the following equation:
 C 
R(%) = 1 − P  × 100
 Ca  (3)
Figure 9 demonstrates the salt rejection percentage for GO-PES nanocomposite membranes with filling per-
centages of 0, 1, 3 and 5 wt.%. As can be seen, increment of the filler percentage from 0 to 3 wt.% causes an
increase in the amount of salt rejection, however the rejection decreases for the samples prepared with 5 wt.% of
filler. This could be attributed to the appropriate distribution of GO particles which results in a better interaction
with the ionic salt species. In other words, at optimum amount of filler (3 wt.%) GO particles are well dispersed in
the polymeric matrix, and the number of active sites involved in the membrane surface increases, which eventu-
ates in the highest rate of rejection. In the values above 3 wt.%, a slight decrease in the rate of rejection is observed

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Figure 10. Dye rejection percentage of various GO-PES nanocomposite membranes with different filler
percentages.

which can be due to the accumulation of fillers on the membrane structure. Indeed, 3 wt.% filler can be consid-
ered as the optimum GO particles loading for preparation of nano-composite membranes. Moreover, the salt
rejection results demonstrate that the highest percentage of rejection is obtained for NaCl salt and the lowest one
is for MgSO4 salt, which could be attributed to the hydration size of ions for mass transfer through the membrane
pores, ions diffusivity, and electrostatic interaction with the membrane.

Evaluation of the GO-PES nanocomposite membrane performance for dye removal. Using the
spectrophotometer apparatus, the absorption data related to each of the dye solution samples passed through the
membranes in the nanofiltration cells were obtained to measure the membrane rejection efficiency for dye. To
achieve the concentration of dye samples passing through these membranes, standard solutions were prepared
at concentrations lower than those of the feed solution and the concentration of these samples was determined
by plotting calibration diagrams. The rejection percentages of MB and MO dyes for GO-PES nanocomposite
membranes with filler percentages of 0, 1, 3 and 5 wt.% are illustrated in Fig. 10. To prevent the blockage of the
nanocomposite membrane pores and increase the dye removal efficiency, the active surface and the initial layer
of the nanocomposite membrane should be made of polymeric materials. These polymeric materials should have
high ion charge density on the surface. Moreover, the ion charge type must be similar with the ion charge of the
dyes present in the effluent so that the electrostatic repulsion between the dye molecules and the nanocompos-
ite membrane reaches its maximum. It can be seen that the rejection of methyl orange (MO) dye in all range of
filler percentages is higher than that of methylene blue (MB) dye. Since the prepared nanocomposite membrane
surface has negative charge and considering the cationic feature of MO and MB and also the effect of Donan
phenomenon (electrostatic repulsion), it can be said that the rejection of MO is more than MB28. The interaction
between the dyes and the membrane surface can be electrostatic, π-π and covalent. Moreover, it is also seen that
the best separation performance has been obtained for the samples with 3 wt.% of filler which is due to well dis-
tribution of particles.

Heavy metals removal. The metal ions removal from aqueous solutions is attributed to two types of elec-
trostatic and Van der Waals interactions. The electrostatic interaction is related to the surface charges created
on the absorbent surface and Van der Waals interaction is associated to the functional groups coordination
with the metal ions. In GO, the graphite carbon network with sp2 hybridization is strongly disrupted, and the
carboxyl groups are placed on the edges. The presence of OH and COOH groups in GO enables the metal ions
to be coordinated. Metal ions compete with each other for creating these interactions and behave differently
in dealing with nanocomposites. Ultimately, metal ions are removed with a three-step mechanism involving
the external diffussion of metall ions, diffussion into the nanocomposite and absorption in the nanocomposite.
The removal percentage of different metals applying GO-PES nanocomposite membrane with filler percent-
ages of 1, 3, and 5 wt.% is demonstrated in Fig. 11. As can be seen, by increasing the filler content to 3 wt.%,
the removal percentages of zinc, cadmium and copper ions increase substantially and then decrease. Also, at
the 3 wt.% of filler, the highest and the lowest removal percentage is related to zinc and cadmium metal ions,
respectively.

Analysis of the contact angle data for GO-PES nanocomposite membranes. Figure 12 obviously
demonstrates the contact angles between the water droplet and the surface of GO-PES nanocomposite mem-
branes with the filler percentages of 0, 1, 3 and 5 wt.%. It is illustrated from the figure that as the filler percentage
increases, the droplet is more dispersed on the membrane surface. In other words, by increasing the filler percent-
age, the hydrophilic nature of the membrane surface increases substantially.

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Figure 11. Percentage removal of zinc, cadmium and copper ions using various GO-PES nanocomposite
membranes with different filler percentages.

Figure 12. The schematic illustration of the contact angles between water droplets and GO-PES nanocomposite
membrane surface for different filler percentages.

Figure 13. The results of dynamic fouling tests of GO-PES nanocomposite membranes. M1: neat membrane,
M2: 1 wt.%, M3: 3 wt.%, M4: 5 wt.%. t = 60 s, pressure = 5 bar.

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Effective surface Adsorbed protein on

Membrane area (cm2) membrane (ppm/cm2)
Neat 0.5 87.48
1% 0.5 72.30
3% 0.5 55.20
5% 0.5 38.08

Table 2. Amount of adsorbed protein on the surface of membranes.

Analysis of membrane fouling. Dynamic tests. The dynamic test results of fouling for the prepared
membranes are shown in Fig. 13. It is clearly seen that by increasing the percentage of GO in the membrane struc-
ture, FRR percentage is increased until 3 wt.% of GO, and then decreased for 5 wt.% filler. The reason could be due
to aggregation of GO particles in the membrane pores at high loading which results in more fouling compared to
other membrane samples.

Static tests. The results of static membrane fouling are reported in Table 2 in terms of adsorbed protein on the
surface of membranes prepared with different filler percentages. It is seen that the highest amount of protein
adsorption is for the neat polymeric membrane (with no filler), and the lowest is for the sample with 5 wt.%
GO particles. The protein adsorption decreases with increasing the amount of filler which is attributed to the
enhancement of membrane hydrophilicity with increasing filler percentage.

Conclusions
In the present study, GO particles were applied to modify the PES membranes. GO was synthesized using the
Hummer method, and charachterized by IR, TEM, and XRD analyses. The results proved that by modifying the
membranes, their properties such as water flux, water absorption, hydrophilicity, and anti-fouling was improved
considerably. By increasing the weight percent of GO filler from 0 to 3 wt.%, the rejection amount of different salts
increases which is justified due to improving the membrane surface charge and its proper distribution. Increase
in the amount of GO loading up to 3 wt.% improves the removal efficiency of heavy metals but increasing the
GO to 5 wt.% slightly decreases the removal performance compared to the 3 wt.% sample. The reason for this
phenomenon may be due to the accumulation of additives on the membrane surface, which makes pinhole on the
membrane surface. It is well percieved that among the fabricated membranes, the membrane with 3 wt.% of GO
as an additive performed better than the other membranes in separation.

Received: 25 September 2019; Accepted: 11 December 2019;

Published: xx xx xxxx

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Author contributions
Azam Marjani, Ali Taghvaie Nakhjiri, Maryam Adimi, Hassan Fathinejad Jirandehi, saeed shirazian Azam
Marjani: Designed and performed experiments, Supervised the research Ali Taghvaie Nakhjiri: Analysed data,
Designed and performed experiments Maryam Adimi: co-wrote the paper Hassan Fathinejad Jirandehi: co-wrote
the paper saeed shirazian: Co-wrote and revised the paper.

Competing interests
The authors declare no competing interests.

Additional information
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