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Surface Morphological and Quantum Chemical Studies of Some

Expired Drug Molecules as Potential Corrosion Inhibitors for Mild
Steel in Chloride Medium

R. Ganapathi Sundaram , G. Vengatesh , M. Sundaravadivelu

PII: S2468-0230(20)30833-6
DOI: https://doi.org/10.1016/j.surfin.2020.100841
Reference: SURFIN 100841

To appear in: Surfaces and Interfaces

Received date: 3 August 2020

Revised date: 13 November 2020
Accepted date: 22 November 2020

Please cite this article as: R. Ganapathi Sundaram , G. Vengatesh , M. Sundaravadivelu , Sur-
face Morphological and Quantum Chemical Studies of Some Expired Drug Molecules as Poten-
tial Corrosion Inhibitors for Mild Steel in Chloride Medium, Surfaces and Interfaces (2020), doi:
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 Surface Morphological and Quantum Chemical Studies of Some Expired Drug
Molecules as Potential Corrosion Inhibitors for Mild Steel in Chloride Medium

R. Ganapathi Sundaram1, 2, 4*, G. Vengatesh3 and M. Sundaravadivelu3

1
Department of Science and Humanities, Faculty of Chemistry, K. Ramakrishnan College of Engineering
(Autonomous), Samayapuram, Trichy, Tamil Nadu 621 112, India
2
Department of Chemistry, Maruthupandiyar College, Vallam, Thanjavur, Tamil Nadu 613 403, India
3
Department of Chemistry, The Gandhigram Rural Institute (Deemed to be University), Gandhigram, Dindigul,
Tamil Nadu 624 302, India
4
Principal Advisor, Srimathy Padmavathi Vidhyalaya, Velippalayam, Nagapattinam, Tamil Nadu 611 001, India
*
Telephone: + 91 9750177802, *E-mail: chemistryganpath17@gmail.com, *Orcid id: 0000-0002-1814-9415

Abstract
Three anti-diabetic drug based biomolecules (Acarbose, Voglibose and Miglitol) were
investigated for their corrosion inhibitive effect on mild steel in 700 ppm NaCl solution.
Corrosion tests were conducted using weight loss measurements, electrochemical
measurements, surface morphologies, quantum chemical studies and molecular dynamics
simulation techniques. The results showed increasing corrosion inhibition efficiency with
increasing concentrations of all studied biomolecules. The addition of Zn ion (synergistic
effect) increased the inhibition of acarbose, voglibose and miglitol on mild steel to a
considerable extent. The anodic mode of inhibition mechanism was proposed for the effect of
examined inhibitors, as revealed by Tafel polarization technique. Adsorption process of all
the investigated inhibitors on the mild steel surface obeys the Langmuir adsorption isotherm.
The surface morphologies of the mild steel were studied using SEM and EDXA. The
experimental results are well correlate with the quantum chemical and molecular dynamics
simulation results. The trend of corrosion protection efficiency of the drug based biomolecule
is Ac > Vo > Mi as observed from experimental, theoretical and simulation studies.

Keywords: Mild steel; Biomolecules; Adsorption; Electrochemical techniques; SEM/EDXA;

Molecular dynamics;

1. INTRODUCTION
Corrosion of materials is a major industrial problem in all over the world that has attracted a
lot of investigations in recent years in various metals [1-5]. Some of the metals are naturally
stable, but in some specific cases material appearances is unstable and have the natural
tendency to react with their environments to form a stable state. Mild steel is a widely used
metal because of it's excellent mechanical and thermal properties in various fields such as the
production of the rod, sheets, tubes and in the formation of alloys, but mild steel undergoes
corrosion in the presence of acid and chloride environments. The use of inhibitors is an
essential and effective method for the protection of metallic materials against corrosion.
Many researchers have studied the effects of various types of organic and inorganic
compounds used as inhibitors on the corrosion resistance of mild steel in a different
environment [6-13]. The organic compounds mainly used to inhibit the corrosion of mild
steel and other metallic materials. The effectiveness of organic inhibitors depends on nature,
the order of the metallic surface, chemical composition of the metal surface and the structure
of the inhibitor. The inhibitors, which have O, N and S simultaneously, provide a better
inhibition performance [14]. The usage of some inhibitors have been controlled the toxicity

1
and lower inhibitory efficiency at small concentration. Therefore, the studies have started to
focus on finding novel, cheap, non-toxic and effective corrosion inhibitors [15-17]. In this
view, drugs constitute a potential class of corrosion inhibitors due to their non-toxicity and
their green nature. But a major issue in the use of fresh drugs is the high cost compared to
that of other organic corrosion inhibitors. Date expired drugs are being tested for corrosion
inhibition nowadays [18-20]. Use of date expired drugs as a corrosion inhibitor can solve
environmental and economical problems: limitation of environmental pollution with
pharmaceutically active compounds and reduction of the disposal costs of date expired drugs
[15]. Synergistic effect existing between organic compound and zinc ions on the inhibition of
metal corrosion have been studied by several researchers [21-24]. There are great efforts to
use drugs as corrosion inhibitors for steel in acid medium [25-27] but the use of date expired
drugs as corrosion inhibitors for steel in chloride medium (neutral aqueous environment) is
limited.

So this work is set to study, compare the inhibition performance of three anti-diabetic drug
based biomolecules like acarbose (Ac), voglibose (Vo) and miglitol (Mi) (Fig. 1) and
investigate the synergistic effect of these inhibitors on mild steel in a neutral aqueous
environment. The choice of these drugs as corrosion inhibitor for mild steel in chloride
medium is based on the presence of heteroatoms, low cost and easily available in the market
under the trade name of Abacus-50, Volix and Elitox. And also these compounds are an
alpha-glucosidase inhibitors (AGIs) type of drugs, used for lowering post-prandial blood
glucose levels in people with diabetes mellitus. This type of drugs delays the absorption of
glucose thereby reducing the risk of macrovascular complications. AGIs are very safe and
effective oral anti-diabetic agent in patients with diabetes and prediabetes. Particularly
acarbose, the only oral anti-diabetic drug approved for the treatment of prediabetes, can help
to improve clinical management across the dysglycamic disease continuum [28]. P.Singh et
al [29] have studied similar anti-diabetic (Gliclazide) drug as corrosion inhibitor on mild steel
in acid medium. A.Singh et al also used anti-diabetic drug (Metformin) as corrosion inhibitor
[30]. However, there is a scarcity of available literature on the use of expired anti-diabetic
drugs as corrosion inhibitors on mild steel in chloride medium. The corrosion inhibition
studies were investigated using weight loss measurements, Tafel polarization curves and
electrochemical impedance spectroscopy (EIS). Surface analytical techniques such as SEM
and EDXA were used to find the nature of protective film formed on the metal surface. The
binding sites and binding interactions were theoretically evaluated using quantum chemical
study and molecular dynamic stimulation studies. For all these studies, the aqueous solution
of 700 ppm chloride has been chosen as corrosion medium because the groundwater contains
600-700 ppm chloride content [31,32].

Figure 1
2. EXPERIMENTAL
2.1. Materials
A stock solution of acarbose, voglibose and miglitol were prepared by recrystallization with
ethanol and it is used for all the experimental purposes. The mild steel specimens contain (wt
%) 0.104 C, 0.58 Mn, 0.035 P, 0.026 S, 0.03 Si and rest of iron. The specimens were abraded
with 1/0, 2/0, 3/0, 4/0, 5/0, 6/0 and 7/0 emery papers, cleaned with acetone and dried. The
dimensions of the specimen with 3.5×1.5×0.2 cm were used for weight loss study and
1.0×1.0×0.1cm were used for SEM and EDXA studies.

2
2.2. Weight loss studies
In all weight loss experiments, the abraded and duplicate specimens were weighed and
immersed in a beaker containing 100 ml of test solution with and without inhibitor using
glass hooks. Weight loss studies were initially made with 50 ppm and 100 ppm of the
inhibitor concentration and then after the addition of 25 ppm of Zn ions to the test solution.
The specimens were immersed for a period of 7 days in all the test solutions. After seven
days, the specimens were reweighed after washing and drying. The corrosion rate (W) and
inhibition efficiency (η %) were calculated using the following formulas [33].

( )
( )

( )
[ ] ( )

where m1 and m2 are the weight of the specimens before and after immersion respectively, S
is the total surface area of the specimen and t is the time of immersion. Wi and Wo are the
corrosion rate in the presence and absence of inhibitors respectively.

2.3. Electrochemical studies

Electrochemical studies like Tafel polarization and Impedance Spectroscopy (IS)
measurements were carried out using electrochemical analyzer model CHI 760D. These
electrochemical experiments were carried out in the conventional three-electrode cell with a
1cm2 of mild steel as a working electrode, platinum as the counter electrode and saturated
calomel electrode as the reference electrode. The working electrode was abraded with
different grades of emery papers (1/0-1/7), cleaned with acetone and then used. Before each
electrochemical measurement, the electrode was immersed in a test solution to run open
circuit potential (EOCP) to attain a steady state. Electrochemical impedance spectra in the form
of Nyquist plots and Bode plots were recorded using EOCP value in the frequency range from
10 kHz to 0.1 Hz. The impedance parameters such as fmax and charge transfer resistance (Rct)
were obtained from the Nyquist plots. The double layer capacitance (Cdl) and inhibition
efficiencies (η %) were obtained from the following equations [33].

( ) ( )

( )
[ ] ( )

i 
where Rct and Rct are the charge transfer resistance values measured with and without Ac, Vo
and Mi inhibitors respectively.

The Tafel polarization study was made in the potential range of ±300 mV with respect to
EOCP value. The corrosion potential (Ecorr), corrosion current (Icorr), anodic Tafel slope (βa)
and cathodic Tafel slope (βc) were obtained by extrapolation of anodic and cathodic regions
of the Tafel plots. The values of inhibition efficiency (η %) were calculated from Icorr values
using the equation:

3
 ( )
[ ] ( )

where Iicorr and Iocorr are the corrosion current density with and without Ac, Vo and Mi
inhibitors respectively.

2.4. Surface studies

The abraded and cleaned mild steel specimens were immersed in 700 ppm chloride solution
in the presence and absence of the inhibitors. After seven days, the specimens were taken out,
washed with distilled water and dried. The SEM and EDXA spectra of the samples were
obtained using VEGA3-TESCAN and BRUKER model respectively.

FT-IR spectra were also recorded with a frequency ranging from 4000 – 400 cm-1 with a
resolution of 4 cm-1 for the pure molecules as well as the molecules adsorbed on mild steel in
700 ppm NaCl solution without and with the addition Zn in KBr matrix using JASCO 460
PLUS spectrophotometer.

2.5. Quantum chemical studies

All the quantum chemical parameters were performed using Gaussian 09W software [34].
Full geometry optimizations of Ac, Vo and Mi structures were run by using B3LYP
functional with 6-311 G (d, p) basis set in the gas phase. Some of the chemical parameters
were calculated in this study include chemical hardness (η), chemical softness (s), electron
affinity (A) and dipole moment (µ) by using the equations [35].

( )
( ) ( )

( )
( ) ( )

Electron affinity (A), Ionization potential (I) are related to the EHOMO and ELUMO respectively,
as in the equations:

( )

( )

Chemical hardness (η), Chemical softness (s) describes the capacity of an atom or group of
atoms to donate and receive electrons and is estimated by using the equations:

( )
( )

( )

4
2.6. Molecular dynamics simulation study
Molecular dynamics (MD) simulations were performed using forcite module of BIOVIA
Material studio software [36]. Herein, we had chosen the Fe (110) surface for simulation. The
interactions between Fe (110) surface and inhibitor molecules are carried out in a simulation
box (37.23 x 37.23 x 48.24 Å3) with periodic boundary conditions. A vacuum slab of 30 Å
heights is built above the Fe (110) surface. Ten layers of iron atoms were used to ensure that
the depth of the surface was more significant than the non-bond cut-off radius used in the
calculation. The stimulation was done by the COMPASS force field. The interaction Energy
(Einteract) between Fe (110) and inhibitive molecule were calculated as follows:

( ) ( )

( )

where Etotal is the total energy of Fe (110) surface and adsorbed inhibitor molecules, Esurface is the
energy of the metal surface and Einhibitor is the energy of the inhibitors. The binding energy of
the inhibitor molecule is the negative value of the interaction energy [37].

3. RESULTS AND DISCUSSION

3.1. Weight loss measurements
The corrosion behavior of mild steel in 700 ppm NaCl solution in the presence and absence
of different concentrations of inhibitors Ac, Vo and Mi were studied. The weight loss
technique carried out in room temperature and the data obtained after 7 days of immersion
are shown in Table 1. The inhibition efficiency increased with increasing inhibitors
concentrations as well as Zn ion. It indicates that more inhibitor molecules are adsorbed on
the mild steel surface [38,39]. It also indicates that Zn ion involves in the inhibition
efficiency, which enhanced retardation of metal dissolution in the NaCl media. The data in
Table 1 shows that the inhibition efficiency of the tested inhibitors (Ac, Vo and Mi) follow
the order of Ac > Vo > Mi. The better inhibition efficiency of Ac (Acarbose) could be
assigned to the presence of a large number of oxygen atoms in its high molecular weight (Fig.
1). Better inhibition efficiency obtained in 100 ppm of inhibitor with 25 ppm of Zn ion
addition, a further increase in the concentration of inhibitors and Zn ion does not cause any
significant change in the η %.

Table 1

3.2. Adsorption isotherm

The corrosion rate is sufficiently decreased when the addition of inhibitor, because the
inhibitor molecules were adsorbed on the surface of mild steel. The inhibitor adsorption
steady state tends to attain a state of quasi-equilibrium. The nature of quasi-equilibrium of
adsorption can be investigated using appropriate adsorption isotherm [40]. In this study, the
adsorption of the studied inhibitors (Ac, Vo and Mi) were clearly fits into the Langmuir
adsorption isotherm. The adsorption isotherm plot obtained using weight loss value and the
adsorption isotherm plots are (Cinh/θ vs. Cinh) shown in Fig. 2. The correlation coefficient (R2)
and slope value are near unity (Table 2) indicate that adsorption of all the three inhibitors
obeys the Langmuir adsorption isotherm, this isotherm represented in the following equation.

( )

5
where θ is the surface coverage, Cinh is the concentration of the inhibitors and Kads, is the
equilibrium constant for the adsorption/desorption process.

The value of Kads was obtained from the intercept of isotherm plot Fig. 2. The Kads value of
studied inhibitors are following order Ac > Vo > Mi. The higher value of Kads indicates that
more efficient adsorption of the inhibitor on the metal surface and hence better corrosion
inhibition efficiency [41,42]. The standard free energy of adsorption (ΔG0ads) related to the
Kads. ΔG0ads can be calculated by the following relation [33].

( ) ( )

where 55.5 is the molar concentration of water in solution (mol L-1), R is the universal gas
constant and T is the absolute temperature.

The value of ΔG0ads for the studied inhibitors Ac, Vo and Mi are shown in Table 2. The
values of ΔG0ads are negative in all inhibitors, it indicates that inhibitor and metal interaction
is a spontaneous phenomenon. From Table 2, the ΔG0ads value of the inhibitors are -20.75
(Ac), -20.31 (Vo) and -20.08 (Mi). These values are less or slightly higher than that of
generally denoted physical adsorption value (-20 kJ mol-1). It indicates that studied inhibitors
obey physical adsorption [43,44].

Table 2

Figure 2

3.3. Electrochemical impedance spectroscopy (EIS)

The Nyquist plots of mild steel in the absence and presence of Ac, Vo and Mi are shown in
Fig. 4 and the calculated EIS parameters are shown in Table 3. The existence of capacitive
loops is not perfect semicircle as expected from the theory of EIS. The deviation from ideal
semicircle shape is generally attributed to the frequency dispersion of interfacial impedance
which arises due to surface roughness, impurities, adsorption of inhibitors and as well as to
the inhomogeneities of the surface [45,46]. The impedance spectra were analyzed using the
simple equivalent circuit model shown in Fig. 3. The model consists of the solution resistance
(Rs), charge transfer resistance (Rct) and double layer capacitance (Cdl).

Figure 3

As seen in Fig. 4, the diameter of the semicircle increases after the addition of inhibitors (Ac,
Vo and Mi) to the test solution. This increase more and more pronounced with the addition of
Zn ion (additive). It is evident from these results, Zn ion also play a vital role in the inhibition
process. Based on Table 3, it is clear that the Rct values increased and the Cdl values decreased
with increasing inhibitor concentration. These results may be attributable to the adsorption of
the inhibitor on the mild steel surface increases and decrease its electrical capacity by
displacing water molecules and other ions which are adsorbed on its surface.

Figure 4

The inhibition efficiency (η %), in the absence of Zn ion at the optimum concentration (100
ppm) for the three inhibitors Ac, Vo and Mi are 75.80 %, 74.75 % and 70.25 % respectively.

6
The inhibition efficiency in the presence of 25 ppm Zn ion and the inhibitors Ac, Vo and Mi
are 82.92 %, 82.26 % and 76.80 % respectively. These results may be attributable to the
adsorption of the inhibitors and Zn ion onto the metal/solution interface.

Table 3
Bode plots with and without inhibitors are shown in Fig. 5. It is gathered from these figures
that the phase angle is higher in solution containing inhibitor and Zn ion than in the blank
solution. This reveals that increases in phase angle shift with inhibitors Ac, Vo and Mi shows
a gradual approach of phase angle toward the ideal capacitive behavior suggesting the
formation of a protective film of inhibitors on the electrode surface [47-49].

Figure 5

3.4. Potentiodynamic polarization measurements

Potentiodynamic polarization measurements were made for the mild steel in 700 ppm NaCl
solution in the presence and absence of Ac, Vo and Mi at room temperature. The
potentiodynamic polarization curves are shown in Fig. 6. It is clear from the blank Tafel
curve that there is no apparent change in the pure NaCl and pure Zn and hence it is clear that
Zn alone does not alter the corrosion rate of mild steel. But in the case of Fig. 6, more
deviation is present in the Tafel curve of inhibitors and Tafel curve of Zn ion added inhibitors
solution. It indicates that Zn ion plays a vital role in inhibition efficiency. As it can be seen
from Fig. 6, in all the inhibitors when concentration increases and adding Zn ion the Tafel
curves move towards more positive side. It indicates that inhibitors predominantly control the
anodic reaction. It is further evidenced by the Ecorr values. The Ecorr difference between the
blank and inhibitor is more than 85 mV [50]. The maximum shift in Ecorr was 211 mV
towards anodic direction indicating that these inhibitors predominately control the anodic
reaction (Fig. 6, Table 4). From the data in Table 4, the presence of inhibitors decreases the
Icorr value. The addition of Zn ion obtained the maximum lower value of Icorr. The decrease in
Icorr value increases in the inhibition efficiency due to the increased in the blocked fraction of
mild steel surface. The order of inhibition efficiency is Ac > Vo > Mi.

Figure 6

Table 4

3.5. SEM measurements

The SEM images of mild steel are shown in Fig 7. Fig 7a shows hard surface and containing
a large number of bits and cavities because this plate is immersed in NaCl in 7 days [51]. Fig
7b, exhibits smooth surface because the inhibitor is forming a thin film on the metal surface
during the immersion period. Fig 7c, exhibit a smoother surface compared to Fig 7b, showing
the involvement of Zn ion improving the inhibition efficiency. The above result indicates that
the studied inhibitor molecules hinder the dissolution of mild steel in 700 ppm NaCl medium.

Figure 7

3.6. EDXA investigation

The EDXA spectra of mild steel electrode are shown in Fig 8. In Fig 8a and Table 5 contain
the sodium ion, chloride ion and oxygen indicating that corrosion occurs on the metal surface.
In the Fig 8b-d and Table 5, the chloride, sodium content are reduced, oxygen content
increases and in addition nitrogen is also present. All these observations indicate the

7
formation of protective film on the metal surface. In addition, the presence of Zn in Fig 8e-g
and Table 5, confirms occurrence of synergistic effect on the metal surface.

Figure 8

Table 5
3.7. FT–IR analysis
FT-IR spectra were recorded for the characterization of the pure compound (Ac), scratched
protective film formed Ac without and with the addition of Zn over the iron metal surface are
given in Fig 9. The frequencies are shown in Table 6.

Figure 9

Table 6

FT-IR spectrum of the pure compound (Ac) shows the frequency bands of the –OH, C–O
stretching, N–H and –OH bending groups at 3416 cm–1, 1106 cm–1, 1611 cm–1and 1391 cm–1
respectively. From Fig 9b, it is found that the C–O stretching frequency has changed from
1106 cm–1 to 1054 cm–1 and the N–H bending frequency shifted from 1611 cm–1 to 1621 cm–1.
The –OH stretching frequency has decreased from 3416 cm–1 to 3408 cm–1 and –OH bending
frequency increased from 1391 cm–1 to 1402 cm–1. This is due to the shift of the electron
clouds of C–O, –OH and N–H band towards Fe2+ ion formed on the metal surface. This
results indicate that the formation of inh–Fe2+ complex on the mild steel surface. After film
formation with Zn (Fig 9c), the spectrum shows the frequency of the same bands (C–O
stretching, N–H bending, –OH stretching and –OH bending) at 1126 cm–1, 1629 cm–1, 3448
cm–1and 1438 cm–1 respectively. Thus, FT-IR spectral study leads to the conclusion that the
investigated inhibitor is coordinated to Fe2+ through the oxygen atom of –OH group and the
nitrogen atom of N–H group. The band at 1438 cm–1 is appeared in Fig 9c may be due to the
formation of Zn (OH)2.

3.8. Quantum chemical calculation

The structure and electronic properties of the molecule are investigated and analyzed using
frontier molecular orbital theory (FMOT). According to the FMOT, chemical reactivity of the
molecule is strongly related to the highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) of the interacting species [52]. Other reactivity
parameters calculated using HOMO and LUMO values are obtained from equation 6-13 [53]
and calculated values in gaseous and aqueous phases are presented in Table 7 (a) and (b). In
order to understand the interaction of drug molecules on mild steel surface, its interaction in
water (aqueous), the medium for the corrosion inhibition process, was first probed.
Comparison of EHOMO and ELUMO values (In Table 7 (a) and (b)) obtained for drug molecules
in gaseous phase and aqueous phase reveals a decrease in EHOMO and ELUMO going from
gaseous to aqueous medium, which favours the electron accepting ability of drug molecules
in the neutral form [54]. The optimized structure, HOMO and LUMO orbitals are shown in
Fig. 10. In general, the energy of HOMO is associated with the electron donating ability of a
molecule and the energy of LUMO is associated with the electron accepting ability of a
molecule [55]. The higher the value of HOMO of inhibitor, the easier is to donate an electron
to the unoccupied d-orbital of the metal and the lower value of LUMO of inhibitor, the easier
is to accept an electron to the metal [55,56].

Figure 10

8
From Table 7 (a) and (b), higher and lower value of HOMO and LUMO indicate that electron
donating and accepting tendency present in the inhibitor molecules. In the same way, the
energy difference between HOMO and LUMO (ΔE) is considered as the essential descriptor
of the reactivity of an inhibitor. A molecule with a large value of ΔE is stable and low
reactivity, while molecule with small values of ΔE is associated with highly reactive. It is
observed from Table 7, Ac has smaller ΔE as compared with Vo and Mi. The softness and
hardness of the molecule related to the ΔE. The soft molecule which has low ΔE, while hard
molecule which has high ΔE [57]. The soft molecule act as good corrosion inhibitor
compared with the hard molecule. The dipole moment (µ) is the measure of polarity in a bond
and is related to the distribution of electrons in a molecule [40]. It is often used for the
prediction of the relative ability of corrosion inhibitors. The inhibitor with large dipole
moment tends to form strong dipole-dipole interactions with the metal, resulting in strong
adsorption. The Ac inhibitor exhibit high dipole moment compared to the other two inhibitors
Vo and Mi. Based on frontier orbital energies, the inhibition efficiency obey the order: Ac >
Vo > Mi.

Table 7

3.9. Mulliken charges and Fukui function analysis

The atomic charges of the studied inhibitor molecules provide information about the
selectivity of the atom’s interaction with the metal surface. The atoms with the highest
negative charge have more tendencies to donate electrons to the metal surface [58,59]. In the
same way atoms with positive charge have more tendencies to accept electrons from the
metal surface. Table 8, 9 and 10 show the calculated Mulliken charges for the non-hydrogen
atoms for the neutral, cationic and neutral forms of inhibitors (Ac, Vo and Mi). It was found
out from the Mulliken charges that the oxygen, nitrogen and some carbon atoms have the
highest negative charge. This confirms the interaction of the oxygen, nitrogen atoms with the
metal surface. Furthermore, some carbon atoms carry positive charges. These are the sites in
which the molecules could accept electrons from the metal surface.

The condensed Fukui function analysis provides information about the nucleophilic and
electrophilic behaviors as well as charge distribution of the molecules. The nucleophilic and
electrophilic Fukui functions can be calculated using the finite (FDA) difference
approximation as follows [60,61].

For electrophilic attack ( ) ( ) (16)

For nucleophilic attack ( ) ( ) (17)

For the free radical attack ( ) ( ) (18)

where, qk( ), qk( - 1) and qk( + 1) are charge values of atom k for neutral, anion and
cation state of the studied molecule, respectively. The preferred site for the nucleophilic
attack is the atom/region in the molecule where the highest value of f+ is found, while the site
for the electrophilic attack is the atom/region in the molecule where the highest value of f- is
found [62]. Morell et al. [63,64], have recently proposed a dual descriptor Δf(r) which is
defined as the difference between the nucleophilic and electrophilic Fukui functions and is
given by,

9
 ( ) ( )
If Δf(r) > 0, then the site is favored for a nucleophilic attack, whereas if Δf(r) < 0, then the
site may be favored for an electrophilic attack. The calculated Fukui function values are
reported in Table 8, 9 and 10. The isosurface of the electrophilic attack (f-) and nucleophilic
attack (f+) Fukui function is plotted in Fig. 11.

Table 8

Table 9

Table 10

In Table 8, 9 and 10, the preferred site for electrophilic attack (shown by the highest value of
f- and the more negative value of Δf) are C2, C6, C22-25, C43-45 and C74 in Acarbose, C1,
C2 and N26 in Voglibose and C3 and N7 in Miglitol. The nucleophilic attack (shown by the
highest value of f+ and Δf) would preferably occur at C18, N20, O26, O41, O51, C54, O61,
C76 and O81 in Acarbose, at C5, C3, C23 and C28 in Voglibose at C2, C4, C5 and C16 in
Miglitol. The above result confirms that the studied inhibitors contain both electrons donating
and accepting tendency.

Figure 11

3.10. Molecular dynamics simulation

Nowadays, molecular dynamic simulations have emerged as a modern and powerful
theoretical tool to describe the interactions between the inhibitor and metallic surface [65-68].
As a consequence, the side and top views of the best adsorption configuration of the inhibitor
over Fe (110) surface are depicted in Fig. 12. The calculated interaction and binding energies
are presented in Table 11. From Fig. 12, it is noticed that the studied inhibitor molecules are
adsorbed on the Fe (110) surface with almost parallel or flat orientation. It confirms the
inhibitor molecules blocking the large area for the adsorption and thus higher inhibition
efficiency is expected and is also observed accordingly. The binding energy indicates the
stability of the adsorptive system and the more positive value suggests the higher inhibition
efficiency [69]. From Table 11, the binding energy of the inhibitors Ac, Vo and Mi are
292.35, 121.37 and 103.45 kJ mol-1, respectively. The adsorption system of Ac is more stable
and yields better inhibition performance.

Figure 12

Table 11

3.11. Mechanism of Inhibition

A clarification of mechanism of inhibition requires a full knowledge of the interaction
between the drug molecules and the mild steel surface. The inhibitory mechanism includes
the drug molecules adsorption on the mild steel surface dipped in 700 ppm chloride solution.
The organic corrosion inhibitor could be adsorbed on the metal/alloy surface and form a
protective film to improve the corrosion impedance of metal/alloy by decreasing the
corrosion rate [70]. Most of the drug molecules have atleast one polar unit with heteroatoms
like oxygen, nitrogen and sulphur which are act as the reaction sites for the adsorption
process. The adsorption of drug molecules on the surface of mild steel is mainly endorsed due

10
to the presence of heteroatoms (O and N) in the investigated drug molecules. It is well
documented that ‘N’ and ‘S’ constitute a good adsorption centers, due to their high
polarizability and lower electronegativity, and compounds having these heteroatoms behaved
as good inhibitors. The highest negative charge was located only on ‘O’ and ‘N’ heteroatoms
excluding ‘S’ which suggests that these centers have highest electron density and would
preferentially interact with the mild steel (Fe) surface [71]. In addition, iron (mild steel) has a
greater affinity to co-ordinate with ligands bearing unshared electron pairs of heteroatoms
and hence formation of protective film [72-74]. The formations of protective layer on the
corroding sites of mild steel surface through the physical or chemical adsorption or through
both of them cause the reduction of control the corrosion rate [75]. In the present
investigation, the values of ΔG 0 ads are around - 20 kJ mol-1. Hence, showing that adsorption
of anti-diabetic drug molecules on the surface of mild steel predominantly take place by
physical adsorption.

4. CONCLUSIONS
Based on the above discussions the following conclusions are drawn.
 The anti-diabetic drug based biomolecules acarbose (Ac), voglibose (Vo) and miglitol
(Mi)) show good inhibition efficiency for the protection of mild steel in 700 ppm
NaCl medium. The effectiveness of these inhibitors increases when adding a lower
concentration of Zn ion (synergistic effect).
 The inhibitor molecules are adsorbed on the mild steel surface, it blocking the active
corrosion sites and obeying Langmuir adsorption isotherm. The corrosion active
surface area decreases with the addition of inhibitor-Zn ion mixture.
 Tafel polarization study shows that the studied inhibitors predominately control the
anodic reaction. The physical adsorption phenomenon and adsorption of the inhibitor
on the metal surface is spontaneously proposed from the obtained values of ΔGoads.
 The SEM analysis reveals all the investigated inhibitors create a smooth uniform
surface on mild steel and surface containing atoms of the adsorbed inhibitors, which is
confirmed by EDXA.
 Theoretical DFT calculation and FT-IR study confirm the lone pair of oxygen and
nitrogen helps to form a protective film on the mild steel surface.
 Results from the experiments (Weight loss, EIS and Tafel polarization), DFT and
molecular dynamic simulation data are in reasonable agreement confirming that Ac is
a better corrosion inhibitor than Vo and Mi.
 The ranking of inhibition ability of these anti-diabetic molecules follows the order
Ac > Vo > Mi.
Author Statement

R. Ganapathi Sundaram: Methodology, Writing - Original draft preparation, Writing – Reviewing,

Editing and Validation, G. Vengatesh: Data Curation, Resources, Conceptualization, Software,
Visualization and Investigation, M. Sundaravadivelu: Supervision.

Disclosure statement
The authors declare that there is no conflict of interests regarding the publication of this
paper.

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Graphical Abstract

Figure Captions:

Figure 1. Molecular structure of the studied drug-based biomolecules

Figure 2. Langmuir plots for three drug based biomolecules (Acarbose, Voglibose and
Miglitol)

Figure 3. Equivalent circuit model for fitting of all EIS curves

Figure 4. Nyquist plots for mild steel in 700 ppm NaCl solution containing various
concentrations of Acarbose, Voglibose Miglitol and companies with Zn ion

Figure 5. Bode plots for mild steel in 700 ppm NaCl solution containing various
concentrations of Acarbose, Voglibose, Miglitol and synergistic with Zn ion

18
Figure 6. Tafel polarization curves for mild steel in 700 ppm NaCl solution in the presence
and absence of inhibitors (Acarbose, Voglibose and Miglitol) and companies with Zn ion

Figure 7. SEM micrograph for (a) mild steel in 700 ppm NaCl in the absence of inhibitor, (b)
mild steel in the presence of Ac inhibitor and (c) mild steel in the presence of Ac inhibitor
with 25 ppm of Zn ion

Figure 8. EDXA image for (a) mild steel in 700 ppm NaCl in the absence of inhibitors, (b-d)
mild steel in the presence of inhibitors and (e-g) mild steel in the presence of inhibitors with
25 ppm of Zn ion

Figure 9. FT-IR spectra for (a) pure compound (Ac), (b) inhibitor film formation (Ac) on
mild steel in 700 ppm NaCl and (c) inhibitor with 25 ppm of Zn ion film formation on mild
steel in corrosive medium

Figure 10. Optimized structure (left), HOMO (center) and LUMO (right) distribution for
inhibitor molecules

+ -
Figure 11. Illustration of the Fukui f and f function isodensity of the studied inhibitor
molecules (isodensity = 0.0040)

Figure 12. Molecular simulations for the most favorable modes of adsorption obtained for
the investigated inhibitors on Fe (110) surface side view (left) and top view (right)

19
Fig.1

Fig.2

20
Fig.3

21
Fig.4

22
Fig.5

23
 Fig.6

a) b) c)

Fig.7

24
Fig.8

25
a) b)

c)

Fig.9

26
Fig.10

27
Fig.11

28
 Fig.12

Table Captions:

Table 1: Weight loss data for mild steel in 700 ppm NaCl in the absence and presence of
different concentrations of inhibitors-Zn ion additives at room temperature

Medium Concentration Weight loss Corrosion rate η (%)

(ppm) (mg) (mmy-1)
Blank 0 59.87 39.91 -
50 15.06 10.03 74.84
Ac 100 10.56 7.03 82.36
100+25 8.07 5.37 86.52
50 17.04 11.35 71.53
Vo 100 12.13 8.08 79.73

29
 100+25 9.23 6.15 84.58
50 18.68 12.45 68.79
Mi 100 13.02 8.67 78.25
100+25 10.46 6.97 82.52

Table 2: Adsorption isotherm values for mild steel in 700 ppm NaCl containing Ac, Vo and
Mi inhibitors

Molecule Correlation Slope Kads -ΔG0ads

coefficient (R2) values (M-1) (kJ mol-1)
Ac 0.9966 1.0428 68.29 20.75
Vo 0.9947 1.0477 57.28 20.31
Mi 0.9974 1.0580 52.24 20.08

Table 3: EIS data for mild steel in 700 ppm NaCl Containing inhibitors-additives Zn ion at
different concentration

Medium Concentration Rct Ymax Cdl η

(ppm) (Ώcm2) (Ώcm2) (μFcm-2) (%)
Blank 0 668.673 330.411 0.72 -
25 (Zn) 773.975 381.052 0.54 -
50 2488.939 1212.699 0.052 73.13
Ac 100 2763.884 1390.442 0.041 75.80
100 + 25 3916.308 1924.808 0.021 82.92
50 2040.125 1003.802 0.077 67.22
Vo 100 2648.708 1322.329 0.045 74.75
100 + 25 3769.578 1863.869 0.022 82.26
50 2055.744 1013.401 0.076 67.47
Mi 100 2247.503 1110.603 0.063 70.25
100 + 25 2883.183 1428.841 0.038 76.80

30
 Table 4: Tafel polarization data for mild steel in 700 ppm NaCl Containing inhibitors-
additives Zn ion at different concentrations

Medium Concentration ba bc - Ecorr Icorr R η

2
(ppm) (mV/dec) (mV/dec) (mV/SCE) (mA/cm ) (Ohm) (%)
Blank 0 4.648 6.334 682.0 0.05321 744.0 -
25 (Zn) 4.512 6.382 686.0 0.05696 700.0 -
50 5.100 4.728 558.0 0.01185 3734.8 77.72
Ac 100 5.136 5.029 486.0 0.007332 5833.6 86.22
100 + 25 5.418 4.925 473.0 0.004431 9488.0 91.67
50 5.137 4.680 520.0 0.01376 3218.5 74.14
Vo 100 4.891 4.583 534.0 0.008527 5382.2 83.97
100 + 25 5.355 5.147 471.0 0.005055 8189.8 90.49
50 5.471 5.165 594.0 0.01438 2843.7 72.97
Mi 100 5.254 4.814 503.0 0.009809 4402.7 81.56
100 + 25 5.129 4.941 489.0 0.006097 7081.3 88.54

Table 5: Atomic percentage of elements found in EDXA analysis for blank and inhibitors in
mild steel

Atom %
Element Blank
Acarbose Voglibose Miglitol Acarbose-Zn Voglibose-Zn Miglitol-Zn
Fe 91.49 49.59 66.14 65.94 44.35 57.56 64.44
O 2.05 49.36 33.17 27.69 52.51 33.47 26.40
N - 0.52 0.33 5.17 0.39 1.29 4.02
Zn - - - - 1.02 1.44 1.50
Na 0.44 0.17 - 0.33 0.89 5.81 1.62
Cl 0.22 0.19 0.13 0.21 0.10 0.06 1.32
P 0.14 0.08 0.23 0.08 0.41 0.38 0.33
S 0.09 0.09 - 0.22 0.32 - 0.18

31
 Table 6: FT-IR absorption spectral values before film formation of Ac, after film formation
of Ac without and with Zn

Responsible Group Before film After film After film

formation formation formation
of Ac (cm-1) of Ac (cm- of Ac with
1
) Zn (cm-1)
–OH stretching 3416 3408 3448
N–H bending 1611 1621 1629
C–O stretching 1106 1054 1126
–OH bending 1391 1402 1438

Table 7: Quantum chemical reactivity descriptors calculated for investigated inhibitors (a) in
gaseous phase and (b) an aqueous phase

(a) In gaseous phase

Molecule EHOMO ELUMO ΔE Total µ I A η S (eV)

(eV)
(eV) (eV) (eV) Energy (E) (D) (eV) (eV)

Ac -6.23 -1.73 4.50 -2387.8 4.94 6.23 1.73 2.25 0.22

Vo -6.38 -0.39 5.99 -975.0 4.82 6.38 0.39 2.99 0.16
Mi -5.81 -0.32 5.49 -745.9 2.54 5.81 0.32 2.74 0.18
(b) An aqueous phase

Molecule EHOMO ELUMO ΔE Total µ I A η S

(eV) (eV) Energy (E)
(eV) (D) (eV) (eV) (eV) (eV)

Ac -5.28 -1.45 3.83 -2386 5.25 5.28 1.45 1.91 0.26

Vo -5.92 1.59 7.52 -974 6.06 5.92 -1.59 3.75 0.13

Mi -5.49 1.64 7.13 -745 3.55 5.59 -1.64 3.61 0.14

32
Table 8: Mulliken atomic charges, condensed Fukui functions and dual descriptor of the
inhibitor Acarbose

Mulliken Atomic Charges (a.u) Fukui’s Function (a.u)

Atom Neural Anion Cation fk+ fk- fko Δf (r)
(N) (N+1) (N-1)
C1 -0.0145 0.0788 0.0297 0.0933 -0.0442 0.0246 0.1375
C2 -0.1425 -0.8846 -0.0628 -0.7421 -0.0798 -0.4109 -0.6624
C3 0.0660 0.0741 0.0696 0.0081 -0.0037 0.0022 0.0118
C4 0.0482 -0.1197 0.0506 -0.1679 -0.0024 -0.0851 -0.1655
C5 0.1328 0.0181 0.1367 -0.1147 -0.0039 -0.0593 -0.1108
C6 -0.0407 -0.4024 -0.0239 -0.3617 -0.0169 -0.1893 -0.3448
O9 -0.5993 -0.5089 -0.6177 0.0904 0.0184 0.0544 0.0719
O11 -0.6185 -0.6694 -0.6318 -0.0509 0.0132 -0.0188 -0.0641
O13 -0.6332 -0.5866 -0.6558 0.0466 0.0226 0.0346 0.0241
C18 -0.0988 0.2648 -0.2886 0.3635 0.1898 0.2767 0.1737
N20 -0.5921 -0.1787 -0.5812 0.4134 -0.0109 0.2013 0.4243
C22 0.0937 -0.3283 0.0886 -0.4220 0.0051 -0.2084 -0.4271
C23 0.0099 -0.7910 0.0172 -0.8009 -0.0073 -0.4041 -0.7937
C24 0.1225 -0.2672 0.1260 -0.3896 -0.0035 -0.1966 -0.3861
C25 0.2978 0.0018 0.2973 -0.2960 0.0005 -0.1477 -0.2964
O26 -0.5213 -0.1293 -0.5261 0.3920 0.0048 0.1984 0.3871
C29 0.0844 -0.0350 0.0925 -0.1193 -0.0081 -0.0637 -0.1112
C31 -0.3771 -0.4277 -0.3742 -0.0506 -0.0029 -0.0268 -0.0477
O37 -0.6195 -0.5448 -0.6004 0.0747 -0.0190 0.0278 0.0937
O39 -0.6697 -0.5245 -0.6811 0.1452 0.0113 0.0783 0.1339
O41 -0.5157 -0.0387 -0.5304 0.4770 0.0146 0.2458 0.4624
C42 0.1058 -0.1744 0.1075 -0.2802 -0.0017 -0.1409 -0.2785
C43 0.1403 -0.7107 0.1394 -0.8510 0.0009 -0.4251 -0.8519
C44 0.3160 -0.5803 0.3143 -0.8963 0.0017 -0.4473 -0.8980
C45 0.0779 -0.1480 0.0774 -0.2259 0.0005 -0.1127 -0.2264
C46 -0.0588 -0.1283 -0.0562 -0.0695 -0.0025 -0.0360 -0.0670
O49 -0.6036 -0.6168 -0.5920 -0.0133 -0.0116 -0.0124 -0.0016
O51 -0.5261 -0.2358 -0.5290 0.2902 0.0030 0.1466 0.2872

33
 C54 0.0497 0.4406 0.0593 0.3908 -0.0096 0.1906 0.4004
C55 0.2850 0.0907 0.2861 -0.1943 -0.0011 -0.0977 -0.1932
C56 0.1246 -0.5934 0.1254 -0.7181 -0.0007 -0.3594 -0.7173
C57 0.1107 0.0921 0.1134 -0.0186 -0.0027 -0.0106 -0.0159
C59 0.0484 0.0853 0.0476 0.0369 0.0008 0.0189 0.0361
O61 -0.6185 -0.6045 -0.6177 0.0140 -0.0008 0.0066 0.0148
O63 -0.5938 -0.5405 -0.5949 0.0534 0.0011 0.0272 0.0523
O65 -0.5984 -0.6531 -0.5914 -0.0547 -0.0069 -0.0308 -0.0478
O67 -0.5367 -0.0951 -0.5402 0.4416 0.0035 0.2226 0.4380
O72 -0.6194 -0.5573 -0.6153 0.0621 -0.0041 0.0290 0.0661
C74 0.0821 -0.4015 0.0804 -0.4836 0.0017 -0.2409 -0.4853
C76 -0.0259 0.2132 -0.0274 0.2391 0.0015 0.1203 0.2375
O79 -0.6116 -0.6133 -0.6151 -0.0017 0.0035 0.0009 -0.0052
O81 -0.4963 -0.1533 -0.4987 0.3429 0.0024 0.1727 0.3405
O84 -0.6377 -0.4983 -0.6570 0.1393 0.0193 0.0793 0.1200
O87 -0.6209 -0.5319 -0.6238 0.0891 0.0029 0.0460 0.0862

Table 9: Mulliken atomic charges, condensed Fukui functions and dual descriptor of the
inhibitor Voglibose

Mulliken Atomic Charges (a.u) Fukui’s Function (a.u)

Atom Neural Anion Cation fk+ fk- fko Δf (r)
(N) (N+1) (N-1)
C1 0.4677 -0.0351 0.0415 -0.5028 0.4262 -0.0383 -0.9290
C2 0.4879 0.1551 0.1851 -0.3328 0.3028 -0.0150 -0.6356
C3 -0.0531 0.0881 0.0841 0.1412 -0.1372 0.0020 0.2783
C4 0.0487 0.0918 0.0940 0.0431 -0.0454 -0.0011 0.0885
C5 -0.1895 0.1049 0.1460 0.2944 -0.3355 -0.0206 0.6299
C6 -0.0599 -0.0328 -0.0097 0.0270 -0.0502 -0.0116 0.0772
O9 -0.5010 -0.5256 -0.6189 -0.0246 0.1179 0.0466 -0.1426
O13 -0.5816 -0.6053 -0.6493 -0.0237 0.0677 0.0220 -0.0914
O15 -0.6043 -0.6199 -0.6562 -0.0156 0.0519 0.0181 -0.0675
O21 -0.5801 -0.6032 -0.6312 -0.0230 0.0510 0.0140 -0.0740

34
 C23 -0.8195 -0.2687 -0.2483 0.5508 -0.5712 -0.0102 1.1220
N26 -0.3651 -0.4597 -0.5886 -0.0946 0.2235 0.0644 -0.3180
C28 -0.2981 -0.0222 0.0421 0.2759 -0.3402 -0.0322 0.6160
C30 0.0133 -0.0451 -0.0349 -0.0585 0.0482 -0.0051 -0.1067
C33 -0.0346 -0.0351 -0.0392 -0.0005 0.0047 0.0021 -0.0052
O36 -0.5528 -0.5930 -0.5759 -0.0402 0.0231 -0.0085 -0.0633
O38 -0.6656 -0.6388 -0.5671 0.0268 -0.0984 -0.0358 0.1252

Table 10: Mulliken atomic charges, condensed Fukui functions and dual descriptor of the
inhibitor Miglitol

Mulliken Atomic Charges (a.u) Fukui’s Function (a.u)

Atom Neural Anion Cation fk+ fk- fko Δf (r)
(N) (N+1) (N-1)
C1 -0.1272 -0.1560 -0.0901 -0.0288 -0.0371 -0.0330 0.0083
C2 -0.2475 -0.0025 0.1069 0.2450 -0.3544 -0.0547 0.5995
C3 0.2447 0.0875 0.0987 -0.1571 0.1459 -0.0056 -0.3031
C4 -0.0982 0.1020 0.1236 0.2003 -0.2219 -0.0108 0.4221
C5 -0.1780 0.0488 0.0771 0.2269 -0.2551 -0.0141 0.4820
N7 -0.0766 -0.3507 -0.4995 -0.2741 0.4229 0.0744 -0.6970
C8 -0.0791 -0.1479 -0.0715 -0.0688 -0.0076 -0.0382 -0.0611
C11 -0.0053 -0.0374 0.0175 -0.0322 -0.0228 -0.0275 -0.0094
O14 -0.5565 -0.5948 -0.5962 -0.0383 0.0397 0.0007 -0.0780
C16 -0.2128 -0.0879 -0.0557 0.1248 -0.1571 -0.0161 0.2819
O19 -0.5199 -0.5892 -0.5807 -0.0693 0.0608 -0.0043 -0.1301
O21 -0.5446 -0.6015 -0.6417 -0.0569 0.0971 0.0201 -0.1540
O23 -0.5683 -0.5933 -0.6400 -0.0250 0.0718 0.0234 -0.0967
O25 -0.5683 -0.5891 -0.5833 -0.0208 0.0149 -0.0029 -0.0358

35
 Table 11: Outputs and descriptors calculated by the Molecular dynamics simulation for
adsorption of the inhibitors on Fe (110) surface

Molecule Total energy Interaction Binding Deformation dEad/dNi

(a.u) energy energy energy
(kJ/Mol) (kJ/Mol) (kJ/Mol)
Ac -126.11 -292.35 292.35 12.07 -280.28
Vo -70.93 -121.37 121.37 5.17 -116.20
Mi -64.23 -103.45 103.45 4.80 -98.65

36