Synthesis of Novel Nano-Sulfonamide Metal-Based Corrosion Inhibitor Surfactants

The synthesis of novel corrosion inhibitors and biocide metal complex nanoparticle surfactants was achieved through the reaction of sulfonamide with selenious acid to produce a quaternary ammonium salt. Platinum and cobalt surfactants were then formed by complexing the first products with platinum (II) or cobalt (II) ions. The surface properties of these surfactants were then investigated, and the free energy of form micelles (ΔGomic) and adsorption (ΔGoads) was determined. The obtained cationic compounds were evaluated as corrosion inhibitors for carbon steel dissolution in 1N HCl medium. The results of gravimetric and electrochemical measurements showed that the obtained inhibitors were excellent corrosion inhibitors. The anti-sulfate-reducing bacteria activity known to cause corrosion of oil pipes was obtained by the inhibition zone diameter method for the prepared compounds, which were measured against sulfate-reducing bacteria. FTIR spectra, elemental analysis, H1 NMR spectrum, and 13C labeling were performed to ensure the purity of the prepared compounds.


Introduction
Worldwide, corrosion is one of the greatest problems that educational and industrial divisions must solve because it has a negative effect on the economy of developing and developed countries [1,2]. Corrosion, which results from the presence of a carbon steel in acidic medium, can be reduced by adding corrosion inhibitors in modest amounts [3][4][5][6][7][8][9]. The majority of commercially available acid inhibitors are organic molecules containing heteroatoms, such as sulfur [10], oxygen [11], nitrogen [12,13], and phosphorous. Many heterocyclic compounds containing nitrogen atoms have been found to be excellent inhibitors of steel corrosion in acidic environments [14][15][16][17][18]. Quaternary ammonium salt (QAS) is a famous product utilized in numerous applications of corrosion inhibition of oil pipes. Most of the world's QAS production involves cationic surfactants, which are widely used on different types of industrial oil protection equipment as well as on closed cooling systems. Synthesis and mass production of these inhibitors have been the primary focus of recent research in science and chemical engineering [19][20][21][22][23]. Biocides are chemical compounds that are capable of preventing or suppressing the growth of bacteria and fungi in different environments. The defeating strategy against lethal microorganisms, especially in the industrial field, involves the use of environmental biocides to protect the environment and

Synthesis of Sulfonamide Hydrogen Selenites IIa
To carry out the synthesis process, stoichiometric amounts of selenious acid were mixed with sulfonamide in diethyl ether at 25 • C with vigorous shaking until precipitation was complete. Then, products were filtered and washed with acetone and were recrystallized by petroleum ether [35]. The products were designated as IIa and have the general formula: RNH 3  Platinum or cobaltsulfonammonium hydrogen selenite complexes were prepared by refluxing two moles of sulfonammonium hydrogen selenites (IIa) with one mole of platinum or cobalt hydrogen selenite in ethyl alcohol for two hours. The products were designated as (IIb,c), as shown in Figure 1. Platinum or cobaltsulfonammonium hydrogen selenite complexes were prepared by refluxing two moles of sulfonammonium hydrogen selenites (IIa) with one mole of platinum or cobalt hydrogen selenite in ethyl alcohol for two hours. The products were designated as (IIb,c), as shown in figure 1.     4 ) may be formulated as expected with the chemical structure shown in (Figure 2

Green Synthesis with Solid State Reaction in Ball Mill for Complex Nanoparticles
The method of synthesizing organic compounds using a ball mill as a reactor is an environmentally safe method for using green chemistry. By comparing this technique with normal solution methods, it presents many advantages, such as reducing the number of solvents used, thereby reducing the number of volatile compounds. Heavy mixing in the solid state helps disintegration and mobility for rapid friction among molecules in a short amount of time. For non-polar and polar solvents, mixing problems are reduced. The energy used to complete the reaction is reduced due to the optimum use of energy in the reaction mixture. The nano-sized particles of Co and Pt complexes were achieved by mixing them very well with cyclodextrin oligosaccharides using ceramic mortar . Finally, both were ground using a ball mill model PM 200(TMAXC-Fujian,China) at 300 rpm for 3 h.

Evaluation of Anti-sulfate-Reducing Bacteria Activity
The inhibition zone diameter (Iz D) Method: a filter paper sterilized disc saturated with a measured quantity of the sample was placed on a plate containing a solid bacterial medium (nutrient agar broth) that had been heavily seeded with the spore suspension of the tested bacteria. After incubation, the diameter of the clear zone of inhibition surrounding the sample was taken as a measure of the inhibitory power of the sample against the particular test organism. All sulfate-reducing bacteria were provided by a culture collection of the Regional Center for Mycology and Biotechnology (RCMB), Al-Azhar University, Cairo, Egypt.

Weight Loss Measurements
The carbon steel specimens have a composition of (wt %): 0.21 C, 0.035 Si, 0.25 Mn, 0.082 P, and the remainder is Fe. The carbon steel sheets of 2.5 cm × 2.0 cm × 0.6 cm were abraded with emery papers (grades 320, 500, 800 and 1200) and then washed with distilled water and acetone. After weighing accurately, the specimens were immersed in a 250 mL beaker containing 200 mL of 0.5 M hydrochloric acid alone or with 50, 100, 200, or 400 ppm by weight of the inhibitors used at 25 °C. After different immersion time inter-

Green Synthesis with Solid State Reaction in Ball Mill for Complex Nanoparticles
The method of synthesizing organic compounds using a ball mill as a reactor is an environmentally safe method for using green chemistry. By comparing this technique with normal solution methods, it presents many advantages, such as reducing the number of solvents used, thereby reducing the number of volatile compounds. Heavy mixing in the solid state helps disintegration and mobility for rapid friction among molecules in a short amount of time. For non-polar and polar solvents, mixing problems are reduced. The energy used to complete the reaction is reduced due to the optimum use of energy in the reaction mixture. The nano-sized particles of Co and Pt complexes were achieved by mixing them very well with cyclodextrin oligosaccharides using ceramic mortar. Finally, both were ground using a ball mill model PM 200 (TMAXC-Fujian, China) at 300 rpm for 3 h.

Evaluation of Anti-Sulfate-Reducing Bacteria Activity
The inhibition zone diameter (Iz D) Method: a filter paper sterilized disc saturated with a measured quantity of the sample was placed on a plate containing a solid bacterial medium (nutrient agar broth) that had been heavily seeded with the spore suspension of the tested bacteria. After incubation, the diameter of the clear zone of inhibition surrounding the sample was taken as a measure of the inhibitory power of the sample against the particular test organism. All sulfate-reducing bacteria were provided by a culture collection of the Regional Center for Mycology and Biotechnology (RCMB), Al-Azhar University, Cairo, Egypt.

Weight Loss Measurements
The carbon steel specimens have a composition of (wt %): 0.21 C, 0.035 Si, 0.25 Mn, 0.082 P, and the remainder is Fe. The carbon steel sheets of 2.5 cm × 2.0 cm × 0.6 cm were abraded with emery papers (grades 320, 500, 800 and 1200) and then washed with distilled water and acetone. After weighing accurately, the specimens were immersed in a 250 mL beaker containing 200 mL of 0.5 M hydrochloric acid alone or with 50, 100, 200, or 400 ppm by weight of the inhibitors used at 25 • C. After different immersion time intervals of 1, 3, 6, and 24 h, the specimens were taken out, washed, dried, and weighed accurately. The corrosion rate (K) and the inhibition efficiency (η %) were calculated using the following equations [36]. where W is the average weight loss of three parallel carbon steel sheets (one specimen in each beaker), S is the total area of the steel specimen, and t is immersion time. W corr and W corr(inh) are the corrosion rates obtained in the absence and the presence of inhibitors, respectively.

Polarization Measurements
Electrochemical measurements are made in the traditional cylindrical cells made of Pyrex glass with a triple electrode, the working electrode (WE) in the form of steel rods embedded with polytetrafluoroethylene (PTFE; the Free Zone of the electrode that was exposed to the analysis of the electrical 0.7 cm 2 ) and saturated calomel electrode (SCE), a platinum electrode used as auxiliary, and a standard electrode, respectively. Polarization measurements were carried out using a potentiostat (Wenking, Wuhan, China). The working electrode was immersed in the test solution for 45 min to reach the open circuit potential. (The carbon steel used in the polarization measurements was identical to that used in the weight loss measurements.) Next, the working electrode was polarized in both cathodic and anodic directions. In terms of accuracy of the calculated slopes, the values were compared with the obtained data from the software calculations accompanied with a potentiostat (Wenking, Wuhan, China), and the accuracy was 4%. The values of corrosion current density (I Corr ) were calculated via extrapolation of the straight part of the Tafel lines. A standard ASTM glass electrochemical cell was used, and the platinum electrode was used as an auxiliary electrode. The potential increased with a speed of 2 mV min −1 , starting from −200 mV to +200 mV with respect to the open circuit potential (OCP) versus corrosion potential (E Corr ) [36].

Scanning Electron Microscopy (SEM)
After dipping carbon steel samples in acidic solution, corrosion of the samples was tested with different concentrations of the corrosion inhibitor products to investigate the optimal concentration of each inhibitor at which the corrosion decreased. Exposing the samples for SEM also directly aided in studying the surface's morphology.

Surface Properties of the Prepared Cationic Surfactants
As shown in Table 1 and Figure 3, after complexing ammonium hydrogen selenite with Co or Pt ions, a high depression in CMC, Y cmc , A min value was observed for compounds designated as IIa, IIb and IIc compared to those of the complex designated as IIa. This may be because metal complexes have specific properties in water. The complexes in the solutions aggregate as units, which can increase the volume due to repulsion between the hydrophobic chain of the complexes and water molecules that can occur. An increase in Pc20, Π CMC , and Γ max value was observed for compounds designated as IIb and IIc in comparison to the complex designated as IIa. This may be attributed to the double chain of hydrocarbon groups in metal complexes, which by its role, increases the hydrophobicity, thereby causing an increase in the concentration at the interface (maximum surface excess Γ max ). Froing of the great number of molecules at the interface leads to an increase in the effectiveness of Π CMC and a greater reduction in surface tension at critical micelle concentration [37]. All the result values of ∆G ads and ∆G mic were negative, which is considered evidence for carrying them out directly without increasing the temperature of the reaction system. An increase in Pc20, ΠCMC, and Γmax value was observed for compounds designated as IIb and IIc in comparison to the complex designated as IIa. This may be attributed to the double chain of hydrocarbon groups in metal complexes, which by its role, increases the hydrophobicity, thereby causing an increase in the concentration at the interface (maximum surface excess Γmax). Froing of the great number of molecules at the interface leads to an increase in the effectiveness of ΠCMC and a greater reduction in surface tension at critical micelle concentration [37]. All the result values of ΔGads and ΔGmic were negative, which is considered evidence for carrying them out directly without increasing the temperature of the reaction system.

Corrosion Inhibitor Activity for Oil Pipes
Sulfate-reducing bacteria (SRB) are considered reducers of sulfate, and their growth and reproduction cause oil pipe and equipment corrosion. This can lead to the loss of economy, and cause environmental, health, and safety hazards. Stabilized mixed culture accumulates with sulfate reducing bacteria. In many industrial sectors such as the oil and gas industry, it is important to minimize the evolution of hydrogen sulfide gas which can result from SRB activity. The results of the synthesized cationic surfactants against sulfur-reducing bacteria are recorded in Table 2. Table 2. Inhibition zone diameter (mm/mg sample) for the synthesized cationic surfactants against sulfate-reducing bacteria. IIa  22  IIb  20  IIc  18 As shown from Table 2, the novel products have high antibiological activity against SRB, while this activity also increased as we notice from the table. When products form complexes that have two hydrocarbon groups, hydrophobicity adsorption at the bacterial membrane increases. The protein and lipid molecules of the complex mobilize with the hydrocarbons of the inhibitor and the membrane breaks down, inhibiting the growth of DNA and thus no reproduction. Platinum complexes produced the best results, possibly because platinum is an oxidizing chemical agent that acts as a reduction inhibitor, reducing sulfide generation and slowing anaerobic growth (SRB). The specific activity of the tested bacteria was closely related to the rate of H2S generation and the generation time was in-

Antibacterial Activity of the Prepared Surfactants against Sulfate-Reducing Bacteria Corrosion Inhibitor Activity for Oil Pipes
Sulfate-reducing bacteria (SRB) are considered reducers of sulfate, and their growth and reproduction cause oil pipe and equipment corrosion. This can lead to the loss of economy, and cause environmental, health, and safety hazards. Stabilized mixed culture accumulates with sulfate reducing bacteria. In many industrial sectors such as the oil and gas industry, it is important to minimize the evolution of hydrogen sulfide gas which can result from SRB activity. The results of the synthesized cationic surfactants against sulfur-reducing bacteria are recorded in Table 2. Table 2. Inhibition zone diameter (mm/mg sample) for the synthesized cationic surfactants against sulfate-reducing bacteria. IIa  22  IIb  20  IIc  18 As shown from Table 2, the novel products have high antibiological activity against SRB, while this activity also increased as we notice from the table. When products form complexes that have two hydrocarbon groups, hydrophobicity adsorption at the bacterial membrane increases. The protein and lipid molecules of the complex mobilize with the hydrocarbons of the inhibitor and the membrane breaks down, inhibiting the growth of DNA and thus no reproduction. Platinum complexes produced the best results, possibly because platinum is an oxidizing chemical agent that acts as a reduction inhibitor, reducing sulfide generation and slowing anaerobic growth (SRB). The specific activity of the tested bacteria was closely related to the rate of H 2 S generation and the generation time was inversely proportional to these activities. The rate of bacterial resistance to metal ions was directly proportional to the rate of microbiologically induced corrosion (MIC) of carbon steel.  different concentrations, respectively. It is obvious that a gradual increase in inhibitor concentrations from 1 × 10 −4 to 1 × 10 −2 M by weight reduces the K values considerably. At 1 × 10 −4 M by weight of the II b and IIc inhibitors, the K values of carbon steel were high. In contrast, increasing the inhibitor concentration to 1 × 10 −2 M by weight decreases K to the lowest value. This is due to an increase in the number of adsorbed inhibitor molecules on the metal surface caused by an increase in the inhibitor concentration in the medium. In turn, this improves surface protection and slows the metal dissolution reaction. The number of inhibitor molecules adsorbed on the metal surface increases as the inhibitor concentration increases. As a result, this increases the surface area covered by inhibitor molecules and consequently decreases the dissolution of metal due to the reaction of metal by corrosive ions in the medium [37].

Electrochemical Evaluation Potentiodynamic Polarization Spectroscopy
Cathodic and anodic current for carbon steel corrosion in 1 M HCl in the presence of 1 × 10 −2 to 1 × 10 −4 M by weight of the synthesized inhibitors II b , IIc at 25 • C.  Table 5. The corrosion currents decreased in the presence of the inhibitors as indicated by low values, such as 0.06, 0.04, 0.02, and 0.24 mA cm −2 for 1 × 10−4 to 1 × 10 −2 M by weight of II b respectively. Surface coverage (θ) of the carbon steel by the inhibitor molecules was determined by using the values of the corrosion currents in the following equation [38]: θ = (i corr(uninh) − I corr(inh) )/(I corr(uninh) ) where I corr (uninh) is the corrosion current density with the presence of different inhibitors and I corr(inh) is the corrosion current density in the absence of the different inhibitors.
tion [43]. When the inhibitor concentration increases, corrosion decreases. With increasing inhibitor concentrations, the protective coating adsorbed onto the metal surface tends to be more complete. This is supported by the increase in corrosion current densities and the increase in η%. When the corrosion potential shifts to values greater than 85 mV (compared to the corrosion potential without inhibitors), the inhibitors are categorized as cathodic or anodic [44]. However, for all the inhibitors tested, the Ecorr displacement is less than 85 mV. As a result, these inhibitors are known as mixed-type inhibitors [45,46].   Corrosion inhibition efficiencies can be calculated from the previous values with different concentrations of the inhibitors using the following equation [39]: η% =(I corr(uninh) − I corr(inh) )/(I corr(uninh) ) × 100 As shown in Table 5, at 1 × 10 −2 M by weight, the value of i corr in the case of IIc (0.020 mA cm −2 ) is smaller than that of II b , while accordingly, the values of inhibition efficiencies in the presence of IIc (94.68) is greater than that of IIb (83.01%). From the polarization curves displayed in Figure 4, the decrease in the two reactions at the cathode and anode occurs in the absence of the synthesized corrosion inhibitors but not in the presence of them. Additionally, increasing the concentration from 1 × 10 −4 M to 1 × 10 −2 M by weight increases inhibition. It may be that the presence of inhibitors in higher concentrations reduced the anodic dissolution and suppressed the reduction of hydrogen ions [40,41]. As shown in Figure 4, by increasing the concentration of the synthesized product, the cathodic current densities sharply decreased, which may be due to the formation of a covered separation film which developed from a single layer of the synthesized product onto the cathodic sites of the carbon steel [42]. The corrosion current densities increased slowly at the start of anodic polarization, and the anodic polarization was mostly facilitated by the positive shift in polarization potential. This indicates that the adsorption rate of the inhibitor molecules on the carbon steel surface is greater than their desorption rate and that the adsorption process controls the anodic reaction (as in Figure 5). The polarization behavior was comparable, implying that the inhibitor molecules are fully adsorbed from the solution to the carbon steel surface and that increasing the concentration increases their inhibition action [43]. When the inhibitor concentration increases, corrosion decreases. With increasing inhibitor concentrations, the protective coating adsorbed onto the metal surface tends to be more complete. This is supported by the increase in corrosion current densities and the increase in η%. When the corrosion potential shifts to values greater than 85 mV (compared to the corrosion potential without inhibitors), the inhibitors are categorized as cathodic or anodic [44]. However, for all the inhibitors tested, the E corr displacement is less than 85 mV. As a result, these inhibitors are known as mixed-type inhibitors [45,46].

Docking Study
Docking investigations based on potent-protein interactions are used to explain the biological results. Figure 6 shows all of the docking computations. Protein data library was used to obtain the X-ray crystal structures of the following bacterial strains: A. fumigatus (ID [47]; 5HWC), G. Candidum (ID [48]; 4ZZt), S. Pneumoniae (ID [49]; 5LJI), and E. Coli (ID [50]; 3t88), respectively. The following are the essential backbone amino acid residues retrieved via X-rays analysis: Tyr27, Asp38, Arg55, Ile57, and Tyr83 for 5HWC; Arg339, Arg251, Glu212, and Asp259 for 4ZZW; Gly 60, Glu97, Cys99, Asp92, Thr15, Asn14, Ser90, and Thr58 for 5LJI; Tyr57, Asn42, Thr203, Arg188, and Glu213 for 3t88. These amino acid residues hindered microbial action through chelating with reference inhibitors. Ag/TNTs-P400 was the most effective at docking into kinase receptors. MOE-scoring for the most stable docking model was used to evaluate the binding affinity of complexes (inhibitor-kinase) ( Figure 6). With an MMFF94 force field, the complexes were energyminimized until the gradient for the restricted convex was minimized to 0.05 kcal/mol. IIb was the most effective at docking onto kinase receptors. MOE-scoring was used to identify the most stable docking model used to evaluate the binding affinity of complexes (inhibitor-kinase) ( Figure 6). For all kinases, the studied sample was successfully docked onto active sites. In Figure 6, the hydrogen bond interactions between the ligand and the receptor were discovered in the construction of active nanocomposites. The hydrophobic cation-π interactions at a distance >6 Å are not shown in Figure 7. In the absence of Hbond interactions, IIa docked onto the active sites 5HWC, 4ZZt, 5LJI, and 3t88, which gave insignificant binding energies (Figure 7). The sample has the greatest binding score (G =~−4 Kcal/mol) against the 4ZZt active site. and E. Coli (ID [50]; 3t88), respectively. The following are the essential backbone amino acid residues retrieved via X-rays analysis: Tyr27, Asp38, Arg55, Ile57, and Tyr83 for 5HWC; Arg339, Arg251, Glu212, and Asp259 for 4ZZW; Gly 60, Glu97, Cys99, Asp92, Thr15, Asn14, Ser90, and Thr58 for 5LJI; Tyr57, Asn42, Thr203, Arg188, and Glu213 for 3t88. These amino acid residues hindered microbial action through chelating with reference inhibitors. Ag/TNTs-P400 was the most effective at docking into kinase receptors. MOE-scoring for the most stable docking model was used to evaluate the binding affinity of complexes (inhibitor-kinase) ( Figure 6). With an MMFF94 force field, the complexes were energy-minimized until the gradient for the restricted convex was minimized to 0.05 kcal/mol. IIb was the most effective at docking onto kinase receptors. MOE-scoring was used to identify the most stable docking model used to evaluate the binding affinity of complexes (inhibitor-kinase) ( Figure 6). For all kinases, the studied sample was successfully docked onto active sites. In Figure 6, the hydrogen bond interactions between the ligand and the receptor were discovered in the construction of active nanocomposites. The hydrophobic cation-π interactions at a distance >6 Å are not shown in Figure 7. In the absence of H-bond interactions, IIa docked onto the active sites 5HWC, 4ZZt, 5LJI, and 3t88, which gave insignificant binding energies (Figure 7). The sample has the greatest binding score (G =~ −4 Kcal/mol) against the 4ZZt active site.
The kinase reset inhibition potency assumed the following pattern: 5LJI>3t88 >5HWC, with promising binding score values (Figure 7). Amino acid residues interact with samples by forming significant E.H.B of H-bonds with energies ranging from ~ −8 to −5 kcal/mol. Against the 4ZZt binding pocket, the studied materials had the highest stabilization energy (Eint = −8.267 kcal/mol). On the other hand, those found at the 3t88 active site had the lowest stabilization energy (Eint = −2.140 kcal/mol). In comparison to 5LJI binding pockets, 5HWC binding pockets yielded less stabilization energy (Figure 7). The kinase reset inhibition potency assumed the following pattern: 5LJI>3t88 >5HWC, with promising binding score values (Figure 7). Amino acid residues interact with samples by forming significant E.H.B of H-bonds with energies ranging from~−8 to −5 kcal/mol. Against the 4ZZt binding pocket, the studied materials had the highest stabilization energy (E int = −8.267 kcal/mol). On the other hand, those found at the 3t88 active site had the lowest stabilization energy (E int = −2.140 kcal/mol). In comparison to 5LJI binding pockets, 5HWC binding pockets yielded less stabilization energy (Figure 7). (c) (d) Figure 7. The Docked most active complexes into the electrostatic surface active sites of IDs: 3T88,5HWC and 5LJI using MOE tool [32].

Conclusions
This work aimed to synthesize novel antibiotic quaternary ammonium nano-surfactants based on sulfonamide with selenious acid and complexed with plati and cobalt surfactant. We used FTIR spectra, elemental analysis, H1 NMR spectrum 13C labeling to investigate the surface behaviors of these surfactants as free energy to micelles (ΔGomic) and adsorption (ΔGoads). In 1N HCl media, we assessed the gene cationic compounds as corrosion inhibitors for carbon steel. Gravimetric and electroc ical studies revealed that the studied inhibitors are excellent corrosion inhibitors. Th ti-sulfate-reducing bacteria activity, which causes the corrosion of oil pipes, was obta by the inhibition zone diameter method for the prepared compounds, which meas against sulfate-reducing bacteria. Particle size scaled into the nano-range, which requ investigation via transmitted electron microscope (TEM). Finally, the DFT using B3 and the 6-311G* correlation function was applied for the investigated probes. DFT MEPs were also used to identify the interaction compound's behavior over heavy met water formation.

Conclusions
This work aimed to synthesize novel antibiotic quaternary ammonium salt nanosurfactants based on sulfonamide with selenious acid and complexed with platinum and cobalt surfactant. We used FTIR spectra, elemental analysis, H1 NMR spectrum, and 13C labeling to investigate the surface behaviors of these surfactants as free energy to form micelles (∆G omic ) and adsorption (∆G oads ). In 1N HCl media, we assessed the generated cationic compounds as corrosion inhibitors for carbon steel. Gravimetric and electrochemical studies revealed that the studied inhibitors are excellent corrosion inhibitors. The anti-sulfate-reducing bacteria activity, which causes the corrosion of oil pipes, was obtained by the inhibition zone diameter method for the prepared compounds, which measured against sulfate-reducing bacteria. Particle size scaled into the nano-range, which required investigation via transmitted electron microscope (TEM). Finally, the DFT using B3LYP and the 6-311G* correlation function was applied for the investigated probes. DFT and MEPs were also used to identify the interaction compound's behavior over heavy metal for water formation.

Data Availability Statement:
The data presented in this study are contained within the article.