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The present work consists of synthesizing a five-decorated aromatic amine derivatives. The decoration involves aromatic derivatives nano-platelets through an electric process using aromatic amine derivatives such as Sulfamethoxazole, 2-Amino-6-chloro benzothiole, Trimethoprim, 2-Amino benzoic acid, and 4-Amino phenol. This process occurs in an electric cell containing platinum electrodes with a voltage of 1.6 volts, resulting in the production of compound . These compounds were characterized and diagnosed using physical and spectroscopic methods, including infrared spectroscopy (FT-IR), -ray diffraction (XRD), electron microscopy (FESEM), atomic force microscopy (AFM), and -NMR.
Carbon is the chemical element with atomic number \(6\) and has six electrons which occupy \(1s^{2}\), \(2s^{2}\), and \(2p^{2}\) atomic orbitals. It can hybridize in sp, \(sp^{2}\), or \(sp^{3}\) forms. Discoveries of very constant nanometer-size sp2 carbon-bonded materials such as graphene [1]. In recent decades, research in the field of biotechnology has focused on nanotechnology and nanomaterials [2, 3]. Nanomaterials are especially well-suited for medical applications because of their unique properties, including facile synthesis, controllable size, tunable surface chemistry, large surface-to-volume ratios, and significant biocompatibility, all considered promising for almost all aspects of biotechnology to overcome the many limitations in existing conventional materials [4]. Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group \([R-N^{+}\equiv N]X^{-}\) where \(R\) can be any organic group such as an alkyl or an aryl, and \(X\) is an inorganic or organic anion, such as a halide [5]. In X-ray crystallography, the \(C-N^{+}\equiv N\) linkage is linear in typical diazonium salts. The \(N^{+}\equiv N\) bond distance in benzenediazonium tetrafluoroborate is \(1.083(3) \ \mathrm{A^{\circ}}\) [6], which is almost identical to that for dinitrogen molecule (\(N\equiv N\)). The decorations were prepared electrically by providing carbonium ions on the full aromatic rings through the preparation of diazonium salt, then electrical exposure by adjusting the voltage for surface decoration on graphene [7]. Diazonium salts react with several different functional groups, including 4-nitrobenzene diazonium trifluoroborate [8, 9, 10,11, 12, 13] and 4-bromobenzene tetrafluoroborate [14, 15].
The unlocalized electron from carbon to an aryl diazonium cation, after which an aryl radical releases \(N_{2}\) molecules, then forms an aryl radical and is covalently linked with a carbon atom to change the hybridization to \(Sp^{3}\), and the diazonium mechanism works on a wide range of carbons to transfer electrons in complex chemical structures. Among the important applications of diazonium salts are industrial and biological applications, including the industrial production of quickly dyed fabrics in water by immersing the fabric in an aqueous solution of diazonium compound, followed by immersion in a solution of the coupler (the electron-rich ring that undergoes electrophilic substitution). The main applications of diazonium compounds remain in the dye industry [16].
Vital dyes include Alkanediazonium ions, which are present in organic chemistry and are among the causative agents in carcinogens, and it is believed that Nitrosamine undergoes metabolic activation to produce canediazone [17, 18, 19, 20].
Sulfamethoxazole, 2-Amino-6-chloro benzo thiole, Trimethoprim, 2-Amino benzoic acid, 4-Amino phenol, and sodium nitrite were obtained from Alfa-Aser, Himedia, Scharlau, and Poison Roma as analytical grade.
Synthesis Decorations using the Same Electric Method [21]
Added (0.001 mol, 0.253 g) of amine derivatives (Sulfamethoxazole, 2-Amino-6-chloro benzo thiole, Trimethoprim, 2-Amino benzoic acid, 4-Amino phenol) in a flask containing an acidic solution (1:1 water:concentrated hydrochloric acid 37%) with the temperature constant during addition within the range \(0-5^{\circ}C\). In another beaker, (0.001 mol, 0.069 g) of sodium nitrite was dissolved in an appropriate amount of distilled water (DW) and added to the first solution gradually over 30 minutes while keeping the temperature within the range \(0-5^{\circ}C\) with stirring for 20-30 minutes in a dark atmosphere. After 24 hours, the product was washed with DIW water three times and dried at a temperature of \(50^{\circ}C\). This addition was done using the electric cell that contains platinum electrodes with a voltage of 1.6 volts.
Compounds (R1-R5)
Scheme (1): Synthesis steps of prepared compounds (R1-R5)
The apparatus used (uncorrected) for FT-IR spectra recording was FT-IR BURKER located at the University of Tikrit, Department of Chemistry, College of Education for Pure Science, Tikrit, Iraq. The spectra were recorded in the range of 400-4000 cm\({}^{-1}\). Morphology was determined using Scanning Electron Microscopy (FESEM-Belsorp TE SCAN Mini II, Czech Republic, Kashan University of Iran), X-Ray Powder Diffraction (XRD - Shimadzu 6000, Kashan University of Iran), Atomic Force Microscopy (AFM Icon, Bruke Q600 US, Kashan University of Iran), and \(H^{1}\)-NMR (Bruker, Kashan University of Iran).
Figure 1 shows the compound (R1). The infrared (FT-IR) spectrum of Sulfamethoxazole showed the emergence of a new absorption band due to the stretching of the carbonyl group (C = O) within the range (1616-1596) cm\({}^{-1}\), while the stretching group of (N=N) appeared at the range (1444 cm\({}^{-1}\)). A new absorption band belonging to \(\nu\)(C-H aromatic) appeared at (3039 cm\({}^{-1}\)), and another belonging to \(\nu\)N-H at (3263-4331 cm\({}^{-1}\)). The \(NH_{2}\) group disappeared.
Figure 2 illustrates the XRD of Compound (R1). The X-ray spectrum indicated an angle value of \((2\theta)= 30.3\) with a distance between layers (d) of 4.85 \(A^{\circ}\), a grain size (D) of 10.3, and the number of layers (n) as 3.53 [22].
Figure 3 represents the \(H^{1}\)-NMR of Compound (R1). It is observed that a signal of the instance group appears at the range (2.28), the amine group at the range (6.14), and an indication of the benzene ring at the range (7.5).
Figure 3: \(H^{1}\)-NMR for (R1)
Figure 4 illustrates the infrared spectrum (FT-IR) of Compound R2, 2-Amino -6-chloro benzo thiole. The spectrum reveals the presence of a new absorption band corresponding to the (N=N) stretch group in the range of 1479-1431 cm\({}^{-1}\). Additionally, a new absorption band emerges, attributed to (\(\nu\)C-H aromatic), observed at 3039 cm\({}^{-1}\). Furthermore, another absorption band, associated with (\(\nu\)N-H), is observed within the range of 3465-3402 cm\({}^{-1}\). The NH2 group is notably absent.
In Figure 5, the \(H^{1}\)-NMR spectrum of Compound R2 provides insight into the chemical structure. An indication of the (CH2-SH) group is observed at 2.48 ppm.
Figure 6 presents morphological images obtained through Field Emission Scanning Electron Microscopy (FESEM) of Compound R2. The images depict a process of semi-homogeneous diffusion of assemblages, suggesting the survival of formed outgrowths (2-Amino benzoic acid) denoted as (a). These outgrowths exhibit sharp peaks (b) with accompanying panels (c) and gaps (d) [23].
Figure 6: FESEM for (R2)
Figure 7 presents the infrared spectrum (FT-IR) of Compound R3, Trimethoprim. The spectrum reveals a new absorption band attributed to the carbonyl group (C=O) within the range of 1645-1676 cm\({}^{-1}\). Additionally, the (N=N) stretch group is observed in the range of 1419-1465 cm\({}^{-1}\), and a new absorption band related to (\(\nu\)C-H aromatic) emerges at 3164 cm\({}^{-1}\).
In Figure 8, the \(H^{1}\)-NMR spectrum of Compound R3 provides further insights. A signal at 3.57 ppm is attributed to the CH2 group, while another signal at 3.61 ppm corresponds to the (OCH3) group. Additionally, a signal at 6.60 ppm indicates the presence of the amine group.
Figure 9 displays Atomic Force Microscopy (AFM) images of Compound R3 (Trimethoprim). The images reveal the presence of clustered surface protrusions with nanoscale dimensions (a), sharp and divergent volcanic peaks (b) with longitudinal plates (c), and clear gaps between the stratified assemblies (d) [24].
Figure 9: AFM for ( R3)
Figure 10 illustrates the infrared spectrum (FT-IR) of Compound R4, 2-amino benzoic acid. The spectrum exhibits a new absorption band attributed to the stretching carbonyl group (C=O) within the range of 1712-1633 cm\({}^{-1}\). The (N=N) stretch group is observed in the range of 1508-1392 cm\({}^{-1}\), and a new absorption band related to (\(\nu\)C-H aromatic) emerges at 3055 cm\({}^{-1}\). Additionally, an absorption band at 3500 cm\({}^{-1}\) is attributed to the (\(\nu\)O-H) group.
In Figure 11, morphological images obtained through Field Emission Scanning Electron Microscopy (FESEM) for Compound R4 are presented. A noticeable change in the shapes of the plaques is observed, indicating the efficiency of 2-amino benzoic acid. The non-homogeneous nature of the sample surfaces is evident, with clear cavities between the plates, forming a distinctive pattern in the cracks (p) and clusters spread in a semi-regular manner (c). The surface also displays a structural pattern with different shapes of crystals (d) [24].
Figure 11: (FESEM) for ( R4)
Figure 12 presents the infrared spectrum (FT-IR) of Compound R5, 4-amino phenol. The spectrum reveals a new absorption band attributed to the carbonyl group (C=O) within the range of 1755-1693 cm\({}^{-1}\). The (N=N) stretching group is observed in the range of 1517-1357 cm\({}^{-1}\), and a new absorption band related to (\(\nu\)C-H aromatic) emerges at 3656 cm\({}^{-1}\). Furthermore, an absorption band at 3072-3168 cm\({}^{-1}\) is assigned to the \(\nu\)(O-H) group.
In Figure 13, Atomic Force Microscopy (AFM) images for Compound R5 are presented. The images exhibit clustered surface protrusions with nano-scale dimensions (a), sharp and divergent volcanic peaks (b) with longitudinal plates (c), and clear gaps between the stratified assemblies (d).
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The physical measurements conducted in this study confirm the structural integrity of the synthesized nanocomposites. The synthesis method, deemed of medium difficulty, yielded nanoproducts with excellent efficiency. These nanocomposites exhibit potential applicability in various fields.
The author expresses gratitude to the College of Education for Pure Science, Department of Chemistry, Tikrit University, Tikrit, Iraq, for providing laboratory facilities, including Infrared Spectrometry (FT-IR). Additionally, appreciation is extended to Kashan University, Iran, for assisting in compound measurements, including X-Ray Powder Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Atomic Force Microscopy (AFM), and \(H^{1}\)-NMR analysis (Bruker, Kashan University of Iran).
No external funding, grants, support, or company contributions were received for this research. This work represents independent research conducted by Reem Suhail Najm.
Reem Suhail Najm contributed to the synthesis of aromatic derivatives of nanoplatelets using the electrophoretic method. Additionally, she played a role in photography, data collection, and material collection.
The results have undergone comprehensive analysis, including visualization, investigation, conceptualization, and formal analysis. The validity of the prepared compounds is confirmed through various physical properties such as color, infrared spectrometry, X-ray diffraction measurements, and morphological imaging through FESEM and AFM. \(H^{1}\)-NMR was also employed for characterization.
The authors declare no known competing financial interests or personal relationships that could have influenced the work reported in this paper.
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