SON KULLANMA TARİHİ GEÇMİŞ BİR İLACIN İNHİBİSYON ETKİNLİĞİ ÜZERİNE PROTONASYONUNUN DEĞERLENDİRİLMESİNE YÖNELİK TEORİK BİR YAKLAŞIM

Öz

Son kullanma tarihi geçmiş bir ilacın korozyon önleme etkinliğini aydınlatmak için kuantum teorik hesaplamalar yapılmıştır. Bu amaçla, kimyasal etkileşimlerin analizinde kullanılan ve moleküllerin elektronik yapısı hakkında ayrıntılı veriler veren moleküler orbital analizi, seçilen ilaç molekülünün nötr ve sulu formdaki elektronik özellikleri hakkında fikir edinmek için kullanılmıştır. Hesaplamalar, ilgili ilaç molekülünün moleküler yapısı ve inhibisyon etkinliği arasındaki ilişkiyi incelemek için yoğunluk fonksiyonel teorisi (DFT) kullanılarak (B3LYP) 6-311G**(d,p) baz seti seviyesinde gerçekleştirilmiştir. En yüksek dolu moleküler orbital enerji (HOMO), en düşük boş moleküler orbital enerji (LUMO), enerji boşluğu (ΔE), dipol moment (μ), iyonlaşma potansiyeli (I) elektron afinitesi (A), elektronegatiflik (χ), sertlik (η), yumuşaklık (σ), geri bağış (ΔEback-donation) ve transfer edilen elektronların fraksiyonu (ΔN) gibi çeşitli kuantum kimyasal tanımlayıcılar hesaplanmış ve inhibisyon etkinliği ile ilişkilendirilmiştir. Çalışılan ilaç molekülünün en olası nükleofilik ve elektrofilik reaktif bölgeleri hesaplanan Fukui indeksleri aracılığıyla analiz edilmiştir. Genel olarak, elde edilen teorik veriler kuantum kimyasal parametrelerinin inhibisyon performansı ile iyi korelasyon gösterdiğini ortaya koymaktadır.

Anahtar Kelimeler

• Yoğunluk Fonksiyonel Teorisi (DFT)
• İnhibisyon etkinliği
• Kuantum kimyasal tanımlayıcılar
• Fukui fonksiyonu

A THEORETICAL APPROACH TO THE ASSESSMENT OF PROTONATION ON INHIBITION EFFICIENCY OF AN EXPIRED DRUG

Öz

The quantum theoretical calculations were performed to elucidate the corrosion inhibition efficiency of an expired drug. For this purpose, molecular orbital analysis, which is used in the analysis of chemical interactions and gives detailed data about the electronic structure of molecules, was used to gain insight into the electronic properties of the selected drug molecule in neutral and aqueous form. The calculations were carried out at the (B3LYP) 6-311G**(d,p) basis set level utilizing density functional theory (DFT) to examine the relationship between the molecular structure and inhibition efficiency of the corresponding drug molecule. Various quantum chemical descriptors such as highest occupied molecular orbital energy (HOMO), lowest unoccupied molecular orbital energy (LUMO), energy gap (ΔE), dipole moment (μ), ionization potential (I), electron affinity (A), electronegativity (χ), hardness (η), softness (σ), back donation (ΔEback- donation) and fraction of electrons transferred (ΔN) were calculated and correlated to the inhibition efficiency. The most probable nucleophilic and electrophilic reactive sites of studied drug molecule were analyzed through computed Fukui indices. Overall, obtained theoretical data indicate that the quantum chemical parameters correlate well with the inhibition performance.

Anahtar Kelimeler

• Density Functional Theory (DFT)
• Inhibition efficiency
• Quantum chemical descriptors
• Fukui function

Kaynakça

1. Li, X., Deng, S. and Xie X., “Experimental and Theoretical Study on Corrosion Inhibition of Oxime Compounds for Aluminium in HCl Solution”, Corrosion Science, 81, 162–175, 2014.
2. Kokalj, A., “Is the Analysis of Molecular Electronic Structure of Corrosion Inhibitors Sufficient to Predict the Trend of Their Inhibition Performance”, Electrochimica Acta, 56, 745–755, 2010.
3. Khaled, K. F., Abdelshafi, N. S., El-Maghraby, A. A., Aouniti, A., Al-Mobarak, N. and Hammouti, B., “Alanine as Corrosion Inhibitor for Iron in Acid Medium: A Molecular Level Study”, International Journal of Electrochemical Science, 7, 12706–12719, 2012.
4. El-Haddad, M. N. and Fouda, A. S., “Electroanalytical, Quantum and Surface Characterization Studies on Imidazole Derivatives as Corrosion Inhibitors for Aluminum in Acidic Media”, Journal of Molecular Liquids, 209, 480–486, 2015.
5. Safak, S., Duran, B., Yurt, A. and Türkoğlu, G., “Schiff Bases as Corrosion Inhibitor for Aluminium in HCl Solution”, Corrosion Science, 54, 251–259, 2012.
6. Raja, P. B., Ismail, M., Ghoreishiamiri, S., Mirza, J., Ismail, M. C., Kakooei, S. and Rahim, A. A., “Reviews on Corrosion Inhibitors: A Short View”, Chemical Engineering Communications, 203, 1145–1156, 2016.
7. Nazeer, A. A. and Madkour, M., “Potential Use of Smart Coatings for Corrosion Protection of Metals and Alloys: A Review”, Journal of Molecular Liquids, 253, 11–22, 2018.
8. Nabatipour, S., Mohammadi, S. and Mohammadi, A., “Synthesis and Comparison of Two Chromone Based Schiff Bases Containing Methoxy and Acetamido Substitutes as Highly Sustainable Corrosion Inhibitors for Steel in Hydrochloric Acid”, Journal of Molecular Structure, 1217, 128367, 2020.

9. Li, X. H., Deng, S. D. and Fu, H., “Inhibition by Tetradecylpyridinium Bromide of The Corrosion of Aluminium in Hydrochloric Acid Solution”, Corrosion Science, 53, 1529–1536, 2011.
10. Pi, J., Chen, M., Chen, T., Wang, Q., Cheng, S. and Fu C., “Corrosion Inhibition Effect of 1-Phenyl-5-Mercaptotetrazole on Nickel-Aluminum Bronze in Seawater: A Combined Experimental and Theoretical Study”, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 666, 131354, 2023.
11. Salem, A. M., Wahba, A. M., El Hossiany, A. and Fouda A. S., “Experimental and Computational Chemical Studies on The Corrosion Inhibitive Properties of Metamizole Sodium Pharmaceutical Drug Compound for CS in Hydrochloric Acid Solutions”, Journal of the Indian Chemical Society, 99, 100778, 2022.
12. Bashir, S., Thakur, A., Lgaz, H., Min Chung, I. and Kumar, A., “Corrosion Inhibition Performance of Acarbose on Mild Steel Corrosion in Acidic Medium: An Experimental and Computational Study”, Arabian Journal for Science and Engineering., 45 (6), 4773–4783, 2020.
13. Bahir, A. A., “Evaluation of Expired Linezolid and Norfloxacin Drugs as Proficient Environmentally Safe Inhibitors for Mitigation of Aluminum Corrosion in Sodium Chloride Medium”, Chemical Data Collections, 42, 100960, 2022.
14. Mohamedien, H. A., Kamal, S. M., Taha, M., El-Deeb, M. M. and El-Deen, A. G., “Experimental and Computational Evaluations of Cefotaxime Sodium Drug as An Efficient and Green Corrosion Inhibitor for Aluminum in NaOH Solution”, Materials Chemistry and Physics, 290, 126546, 2022.
15. Vaszilcsin, N., Kellenberger, A., Dan, M.L., Duca, D.A., Ordodi, V.L., “Efficiency of Expired Drugs Used as Corrosion Inhibitors: A Review”, Materials, 16, 5555, 2023.
16. Dohare, P., Chauhan, D.S., Hammouti, B., Quraishi, M.A., “Experimental and DFT Investigation on The Corrosion Inhibition Behavior of Expired Drug Lumerax on Mild Steel in Hydrochloric Acid”, Analytical and Bioanalytical Electrochemistry, 9, 762–783, 2017.
17. Abdallah, M., Soliman, K.A., Al-Gorair, A.S., Al Bahir, A., Al-Fahemi, J.H., Motawea, M.S., Al-Juaid, S.S., “Enhancing the Inhibition and Adsorption Performance of SABIC Iron Corrosion in Sulfuric Acid by Expired Vitamins. Experimental and Computational Approach”, RSC Advances, 11, 17092–17107, 2021.
18. Tajabadipour, H., Mohammadi-Manesh, H., Shahidi-Zandi, M., “Experimental and Theoretical Studies of Carbon Steel Corrosion Protection in Phosphoric Acid Solution by Expired Lansoprazole and Rabeprazole Drugs”, Journal of the Indian Chemical Society 99, 100285, 2022.
19. Gikonyo, D., Gikonyo, A., Luvayo, D. and Ponoth, P., “Drug Expiry Debate: The Myth and The Reality”, African Health Sciences, 19(3), 2737–2739, 2019.
20. Allal, H., Belhocine, Y. and Zouaoui, E., “Computational Study of Some Thiophene Derivatives as Aluminium Corrosion Inhibitors”, Journal of Molecular Liquids, 265, 668–678, 2018.
21. Nwankwo, H. U., Olasunkanmi, L. O. and Ebenso, E. E., “Experimental, Quantum Chemical and Molecular Dynamic Simulations Studies on The Corrosion Inhibition of Mild Steel by Some Carbazole Derivatives”, Scientific Reports., 7, 2436, 2017.
22. Ammouchi, N., Allal, H., Belhocine, Y., Bettaz, S. and Zouaoui, E., “DFT Computations and Molecular Dynamics Investigations on Conformers of Some Pyrazinamide Derivatives as Corrosion Inhibitors for Aluminum”, Journal of Molecular Liquids, 300, 112309, 2020.
23. Saha, S. K., Ghosh, P., Hens, A., Murmu, N. C. and Banerjee, P., “Density Functional Theory and Molecular Dynamics Simulation Study on Corrosion Inhibition Performance of Mild Steel by Mercapto-Quinoline Schiff Base Corrosion Inhibitor”, Physica E, 66, 332–341, 2015.
24. Kaya, S., Banerjee, P., Saha, S. K., Tuzun, B. and Kaya, C., “Theoretical Evaluation of Some Benzotriazole and Phospono Derivatives as Aluminum Corrosion Inhibitors: DFT and Molecular Dynamics Simulation Approaches”, RSC Advances, 6, 74550, 2016.
25. Neese, F., “The ORCA Program System”, Wiley Interdisciplinary Reviews: Computational Molecular Science, 2, 73-78, 2012.
26. Neese, F., “Software Update: The ORCA Program System, Version 4.0”, Wiley Interdisciplinary Reviews: Computational Molecular Science, 8, 1327-1332, 2017.
27. Hanwell, M. D., Curtis, D. E., Lonie, D. C., Vandermeersch, T., Zurek, V. and Hutchison, G. R., “Avogadro: An Advanced Semantic Chemical Editor, Visualization, and Analysis Platform”, Journal of Cheminformatics, 4, 17, 2012.
28. Knizia, G., “Intrinsic Atomic Orbitals: An Unbiased Bridge Between Quantum Theory and Chemical Concepts”, Journal of Chemical Theory and Computation, 9, 4834, 2013.
29. Lu, T. and Chen, F., “Multiwfn: A Multifunctional Wavefunction Analyzer”, Journal of Computational Chemistry, 33, 580-592, 2012.
30. Lu, T. and Chen, F., “Quantitative Analysis of Molecular Surface Based on Improved Marching Tetrahedra Algorithm”, Journal of Molecular Graphics and Modelling, 38, 314-323, 2012.
31. Humphrey, W., Dalke, A. and Schulten, K., “VMD - Visual Molecular Dynamics”, Journal of Molecular Graphics and Modelling, 14, 33-38, 1996.
32. Madkour, L. H., Kaya, S. and Obot, I. M., “Computational, Monte Carlo Simulation, and Experimental Studies of Some Arylazotriazoles (AATR) and Their Copper Complexes in Corrosion Inhibition Process”, Journal of Molecular Liquids, 260, 351–374, 2018.
33. Verma, C., Quraishi, M. A. and Singh, A., “2-Amino-5-nitro-4,6-diarylcyclohex-1- ene-1,3,3-tricarbonitriles as New and Effective Corrosion Inhibitors for Mild Steel In 1 M HCl: Experimental and Theoretical Studies”, Journal of Molecular Liquids, 212, 804–812, 2015.
34. Adamo, C. and Jacquemin, D., “The Calculations of Excited-State Properties with Time-Dependent Density Functional Theory”, Chemical Society Reviews, 42, 845-856, 2013.
35. Al Zoubi, W. and Ko, Y. G., “Self-assembly of Hierarchical N-Heterocycles-Inorganic Materials into Three-Dimensional Structure for Superior Corrosion Protection”, Chemical Engineering Journal, 356, 850–856, 2019.
36. Koopmans, T., “Ordering of Wave Functions and Eigenenergies to The Individual Electrons of An Atom”, Physica, 1, 104–113, 1933.
37. Li, D. Z., Zhang, S. G., He, B. and Zhang, L. C., “Quantum Chemistry Study of The Inhibitive Properties of Benzimdiazoles”, Computers and Applied Chemistry, 26, 324–328, 2009.
38. Khaled, K. F. and Al-Qahtani, M. M., “The Inhibitive Effect of Some Tetrazole Derivatives Towards Al Corrosion in Acid Solutions: Chemical Electrochemical and Theoretical Studies”, Materials Chemistry and Physics, 113, 150–158, 2009.
39. He, T., Emori, W., Zang, R. H., Okafor, P. C., Yang, M. and Cheng, C. R., “Detailed Characterization of Phellodendron Chinense Schneid and Its Application in The Corrosion Inhibition of Carbon Steel in Acidic Media”, Bioelectrochemistry, 130, 107332, 2009.
40. Khaled, K. F. and Al-Qahtani M. M., “The Inhibitive Effect of Some Tetrazole Derivatives Towards Al Corrosion in Acid Solutions: Chemical Electrochemical and Theoretical Studies”, Materials Chemistry and Physics, 113, 150-158, 2009.
41. Obot, I. B., Onyeachu, I. B. and Umoren, S. A., “Pyrazines as Potential Corrosion Inhibitors for Industrial Metals and Alloys: A Review”, Journal of Bio- and Tribo-Corrosion, 4, 1-13, 2018.
42. Li, X. H., Deng, S. D., Fu, H. and Li, T. H., “Adsorption and Inhibition Effect of 6- Benzylaminopurine on Cold Rolled Steel in 1.0 M HCl”, Electrochimica Acta, 54, 4089–4098, 2009.
43. Kokalj, A. and Kovacevic, N., “On the Consistent Use of Electrophilicity Index And HSAB-Based Electron Transfer and Its Associated Change of Energy Parameters”, Chemical Physics Letters, 507, 181–184, 2011.
44. Ayers, P. W., Morrison, R. C. and Roy, R. K., “Variational Principles for Describing Chemical Reactions: Condensed Reactivity Indices”, Journal of Chemical Physics, 116, 8731–8744, 2002.