Yeni piridinil sübstitüe benzotiyoat ile metal iyonlarının yarışmalı sıvı-sıvı ekstraksiyonu: Deneysel çalışmalar, gerçek matriks uygulamaları ve DFT bulguları

Abstract

Bu çalışmada, S,S'-di(2-piridinil)-2,2'-ditiyodibenzotiyoat bileşiğinin metal iyonlarının karışımını içeren ortamlardan yarışmalı sıvı-sıvı iyon çiftleri ekstraksiyonu ile seçiciliği ve gerçek su matrikslerindeki metal giderim özellikleri araştırılmıştır. Zn²⁺, Mn²⁺, Cr³⁺, Fe³⁺, Co²⁺ ve Cu²⁺ iyonlarının karışımını içeren çözeltilerle gerçekleştirilen ekstraksiyon deneylerinde, ligandın özellikle Fe³⁺ iyonuna karşı yüksek seçicilik gösterdiği tespit edilmiştir. Ekstraksiyon verilerinin değişimi ICP-OES ile belirlenmiş ve en iyi ekstraksiyon verimi Fe³⁺ iyonu için (%44.12) elde edilmiştir. Nispi seçimlilik faktörleri, ligandın Fe³⁺ iyonunu diğer metal iyonlarına göre daha yüksek olarak ekstrakte ettiğini göstermiştir. Ayrıca, bileşiğin gerçek su matrislerindeki performansının belirlenmesi amacıyla göl, akarsu ve musluk suyu örneklerine metal giderim çalışmaları uygulanmıştır ve iyonların değişimi ICP-MS tespit edilmiştir. Ayrıca ligandın elektronik yapısı ve ekstraksiyon davranışı arasındaki ilişki yoğunluk fonksiyoneli teorisi (DFT) hesaplamaları ile incelenmiştir. Hesaplanan HOMO–LUMO enerji aralığı, kimyasal sertlik ve diğer küresel reaktivite parametreleri, ligandın özellikle yüksek yük yoğunluğuna sahip Fe³⁺ iyonlarıyla güçlü etkileşimler oluşturduğunu desteklemiştir. Elde edilen sonuçlar, S,S'-di(2-piridinil)-2,2'-ditiyodibenzotiyoat bileşiğinin çevresel su örneklerinden metal iyonlarının seçici uzaklaştırılmasında potansiyel bir ekstraksiyon ajanı olarak kullanılabileceğini göstermektedir.

Keywords

• Sudan metal uzaklaştırma
• yarışmalı metal ekstraksiyonu
• metal kompleksleşmesi
• içme suyu kalitesi
• DFT.

Competitive liquid–liquid extraction of metal ions with novel pyridinyl-substituted benzothioate: Experimental studies, real matrix applications and DFT insights

Abstract

In this study, the selectivity of the compound S,S'-di(2-pyridinyl)-2,2'-dithiodibenzothioate from media containing a mixture of metal ions was investigated using competitive liquid-liquid ion pair extraction, and its metal removal properties were studied in real water matrices. Extraction experiments conducted with solutions containing mixtures of Zn²⁺, Mn²⁺, Cr³⁺, Fe³⁺, Co²⁺, and Cu²⁺ ions revealed that the ligand exhibited particularly high selectivity towards the Fe³⁺ ion. The variation in extraction data was determined by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES), and the best extraction efficiency was obtained for the Fe³⁺ ion (44.12%). Relative selectivity factors showed that the ligand extracted the Fe³⁺ ion more efficiently than other metal ions. Furthermore, metal removal studies were conducted on lake, stream, and tap water samples to determine the performance of the compound in real water matrices, and ion exchange was detected by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The relationship between the electronic structure of the ligand and its extraction behavior was also investigated using density functional theory (DFT) calculations. The calculated HOMO–LUMO energy gap, chemical hardness, and other spherical reactivity parameters supported the strong interactions of the ligand, particularly with Fe³⁺ ions, which have a high charge density. The results indicate that S,S'-di(2-pyridinyl)-2,2'-dithiodibenzothioate can be used as a potential extraction agent for the selective removal of metal ions from environmental water samples.

Keywords

• Metal removal from water
• competitive metal extraction
• metal complexation
• drinking water quality
• DFT

References

1. Günay, A., Su Kimyası ve Kimyasal Temel İşlemler. Ders Notları. Balıkesir, (2016).
2. Edzwald, J.K., Water quality and treatment: A handbook on drinking water. 6th edition. USA: American Water Works Association & American Society of Civil Engineers & McGraw-Hill, (2011).
3. Syeed, M.M.M., Hossain, M.S., Karim, M.R., et al. Surface water quality profiling using the water quality index, pollution index and statistical methods: A critical review. Environmental and Sustainability Indicators, 18, 100247, (2023). https://doi.org/10.1016/J.INDIC.2023.100247.
4. Li, Y., Chen, B., Yang, S., et al. Advances in environmental pollutant detection techniques: Enhancing public health monitoring and risk assessment. Environment International, 197, 109365, (2025). https://doi.org/10.1016/J.ENVINT.2025.109365.
5. Briffa, J., Sinagra, E., Blundell, R. Heavy metal pollution in the environment and their toxicological effects on humans. Heliyon, 6, e04691, (2020). https://doi.org/10.1016/J.HELIYON.2020.E04691.
6. Jomova, K., Alomar, S.Y., Nepovimova, E., et al. Heavy metals: toxicity and human health effects. Archives of Toxicology, 99, 153–209, (2024). https://doi.org/10.1007/S00204-024-03903-2.
7. Jaishankar, M., Tseten, T., Anbalagan, N., et al. Toxicity, mechanism and health effects of some heavy metals. Interdisciplinary Toxicology, 7, 60, (2014). https://doi.org/10.2478/INTOX-2014-0009.
8. Pedersen, C.J., Cyclic polyethers and their complexes with metal salts. Journal of the American Chemical Society, 89, 7017–36, (1967). https://doi.org/https://doi.org/10.1021/ja01002a035.

9. Satoru, T., Kazunori H.H., Studies on diphenyl ether derivatives. V. Synthesis of dibenzo[b,g][1,5]thiazocines. Pharmaceutical Society of Japan, 93, 991–6, (1973).
10. Saturu, T., Hideaki W., Studies on diphenyl ether derivatives. VI. Synthesis of dibenzo[b,g][1,5]thiazonecine oxide derivateives. Pharmaceutical Society of Japan 98, 997–1002, (1972).
11. Vriesema, B.K., Buter, J., Kellogg, R.M., Synthesis of aza macrocycles by nucleophilic ring closure with cesium tosylamides. Journal of Organic Chemistry, 49, 110–3, (1984). https://doi.org/10.1021/jo00175a022.
12. Yu, H.R., Hu, J.Q., Lu, X.H., et al. Insights into the effects of 2:1 “sandwich-type” crown-ether/metal-ıon complexes in responsive host–guest systems. Journal of Physical Chemistry B 119, 1696–705, (2015). https://doi.org/10.1021/JP5079423.
13. Erk, C., Cakir, U., Cicek, B., Estimation of Li+, K+ and Ca2+ complexation with 12 crown-4, 15 crown-5 and 18 crown-6 using a Na+ISE in dioxane-water, part IV - Cation equilibrium constants of macrocyclic ethers with ion selective electrodes. Mikrochimica Acta, 132, 79–82, (1999).
14. Bradshaw, J.S., Izatt, R.M., Crown ethers: the search for selective ıon ligating agents. Accounts of Chemical Research, 30, 338–45, (1997). https://doi.org/10.1021/ar950211m.
15. Çiçek, B., Ergün, A., Çalışır, Ü., et al. Experimental and theoretical studies on the synthesis, electronic structure and biphasic extraction properties of functionalized thia-crown ethers. Russian Journal of Physical Chemistry B, 20, 396–406, (2026). https://doi.org/10.1134/S1990793125701763.
16. Bruening, R.L., Tarbet, B.J., Krakowiak, K.E., et al. Quantitation of cation binding by silica gel bound thiamacrocycles and the design of highly selective concentration and purification columns for palladium(II), gold(III), silver(I), and mercury(II). Analytical Chemistry, 63, 1014–7, (1991). https://doi.org/10.1021/ac00010a016.
17. Çiçek, B., Ergun, A., Gençer, N., Synthesis and evaluation in vitro effects of some macrocyclic thiacrown ethers on erythrocyte carbonic anhydrase I and II. Asian Journal of Chemistry 24, 1–3, (2012).
18. Çakir, Ü., Çiçek, B., Extraction-ability and -selectivity of tetra-aza-crown ethers for transition metal cations. Transition Metal Chemistry, 29, 263–8, (2024).
19. Calisir, U., Çiçek, B., Comparison of classic and microwave-assisted synthesis of benzo-thio crown ethers, and investigation of their ion pair extractions. Journal of Molecular Structure, 1148, 505–11 (2017). https://doi.org/10.1016/j.molstruc.2017.07.081.
20. Lindoy, L.F., Transition metal complexes of synthetic macrocyclic ligands, Chemical Society Reviews, 16, 421–41, (1974).
21. Canbolat, M., Çalışır, Ü., Çiçek, B., Microwave-assisted synthesis of aromatic thiadiazol crown ethers and determination of complexation properties with metal ıons by application of job′s plot method to conductometry. ChemistrySelect 7, e202200944, (2022). https://doi.org/10.1002/slct.202200944.
22. Çiçek, B., Çalışır, Ü., Bazı karbazol schiff bazlarının katyon bağlama özelliklerinin kondüktometrik incelenmesi. Journal of Balıkesir University Institute of Science and Technology, 246–56 (2017). https://doi.org/10.25092/baunfbed.342381.
23. Çalişir. Ü., Çi̇çek, B., Taç eterlerin metal iyonları ile kompleksleşmesinin kondüktometriye Job’s Plot yönteminin uygulanması ile belirlenmesi. Journal of Balıkesir University Institute of Science and Technology, 21, 840–54, (2019). https://doi.org/10.25092/BAUNFBED.654501.
24. Çiçek, B., Aza-18-crown-6 modifiye karbon nanotüplerin sentezi, karakterizasyonu ve adsorpsiyon kapasitesinin belirlenmesi. Journal of Balıkesir University Institute of Science and Technology, 23, 873–87, (2021). https://doi.org/10.25092/BAUNFBED.937736.
25. Çakir, Ü., Çiçek, B., Yildiz, Y.K., et al. Solvent effect upon ıon-pair extraction of different sodium dyes using some crown ethers. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 34, 153–65, (1999).
26. Çalışır, Ü., Synthesis and characterization of some benzothioate derivatives and investigation of extractions with Cr3+, Co2+, Cu2+, Mn2+, Fe3+, Zn2+ ions. Journal of Balıkesir University Institute of Science and Technology, 24, 212–21, (2022). https://doi.org/10.25092/baunfbed. 937720.
27. Çiçek, B., Çalışır, Ü., The investigation of complexation properties and hard-soft acid-base relationship between thiacrown ethers and metal ions. Letters in Organic Chemistry, 13, 572–7, (2016). https://doi.org/10.2174/15701786136661609061053.
28. Çalışır, Ü., S,S’-Dipyridin-2-yl 2,2’-disulfanedidibenzenecarbotioate: Microwave assisted synthesis, characterization, and investigation of metal extraction properties. In: Koç Akran S, Akkemik E, Taş F, et al., editors. International Siirt Scientific Research Congress, Siirt: ISPEC Publishing House; p. 539–46, (2021).
29. Çalışır, Ü., Benzo-tiyo crown eterlerin sentezi ve ekstraktif özelliklerinin incelenmesi. Balıkesir University, MSC thesis, (2014).
30. Çiçek, B., Ergün, A., Çalışır, Ü., et al. Experimental and theoretical studies on the synthesis, electronic structure and biphasic extraction properties of functionalized thia-crown ethers. Russian Journal of Physical Chemistry B, 20, 396–406, (2026). https://doi.org/10.1134/S1990793125701763.
31. Badreddin Musatat, A., Kılıçcıoğlu, İ., Kurman, Y., et al. Antimicrobial, antiproliferative effects and docking studies of methoxy group enriched coumarin‐chalcone hybrids. Chemistry & Biodiversity, 20, e202200973, (2023). https://doi.org/10.1002/cbdv.202200973.
32. Vektariene, A., Vektaris, G., Svoboda, J., A theoretical approach to the nucleophilic behavior of benzofused thieno[3,2-b]furans using DFT and HF based reactivity descriptors. Arkivoc 2009, 311–29, (2009). https://doi.org/10.3998/ark.5550190.0010.730.
33. Plotnikova, M.D., Shein, A.B., Scherban, M.G., et al. Experimental and theoretical investigation of (E)-5-{[4-(dimethylamino)benzylidene]amino}-1,3,4-thiadiazole-2(3H)-thione (DATT) as an acid corrosion inhibitor of mild steel. International Journal of Corrosion and Scale Inhibition 12, 1365–91, (2023). https://doi.org/10.17675/2305-6894-2023-12-4-1.
34. Çalışır, Ü., Çiçek, B., S,S’-bis(2-piridinil)-2,2’-ditiyosalisiltiyoat bileşiğinin demir (III) iyonu ile kompleksleşme özelliklerinin in silico incelenmesi. Afyon Kocatepe University Journal of Sciences and Engineering, 24, 1087–93, (2024). https://doi.org/10.35414/akufemubid.1472359.
35. Çalışır, Ü., Camadan, Y., Çiçek, B., et al. Synthesis, characterizations of aryl-substituted dithiodibenzothioate derivatives, and investigating their anti-Alzheimer’s properties. Journal of Biomolecular Structure and Dynamics, 41(5), 1828-1845, (2023). https://doi.org/10.1080/07391102.2021.2024884.
36. Chidiebere, C.W., Duru, C.E., Mbagwu, J.P.C., Application of computational chemistry in chemical reactivity: a review. Journal of the Nigerian Society of Physical Sciences, 3, 292–7, (2021). https://doi.org/10.46481/jnsps.2021.347.
37. Talmaciu, M.M., Bodoki, E., Oprean, R., Global chemical reactivity parameters for several chiral beta-blockers from Density Functional Theory Viewpoint. Medicine and Pharmacy Reports, 89, 513–8, (2016). https://doi.org/10.15386/cjmed-610.
38. Miranda-Quintana, R.A., Heidar-Zadeh, F., Fias, S., et al. Molecular interactions from the density functional theory for chemical reactivity: Interaction chemical potential, hardness, and reactivity principles. Frontiers in Chemistry, 10, (2022). https://doi.org/10.3389/fchem.2022.929464.
39. Kaya, M.O., Demirci, T., Ozdemir, O., et al. Synthesis, inhibition effects, molecular docking and theoretical studies as Paraoxonase 1 (PON1) inhibitors of novel 1,4-dihydropyridine substituted sulfonamide derivatives. Medicinal Chemistry Research, 32, 841–55 (2023). https://doi.org/10.1007/S00044-023-03029-7.
40. Parr, R.G., Pearson R.G., Absolute hardness: companion parameter to absolute electronegativity. Journal of American Chemistry Society, 105, 7512–6, (1983). https://doi.org/10.1021/ja00364a005.
41. Koopmans, T., Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den Einzelnen Elektronen Eines Atoms. Physica, 1, 104–13, (1934). https://doi.org/10.1016/S0031-8914(34)90011-2.
42. Parr, R.G., Pearson, R.G., Absolute hardness : companion parameter to absolute electronegativity. Journal of American Chemistry Society, 105, 7512–6, (1983).
43. Pearson, R.G., Absolute electronegativity and hardness: application to ınorganic chemistry. Inorganic Chemistry, 27, 734–40, (1988).
44. Pearson, R.G., Hard and soft acids and bases. Journal of American Chemistry Society, 85, 3533–9, (1963). https://doi.org/10.1021/ja00905a001.
45. Kaya, M.O., Dandan, E., Demirci, T., et al. Density functional theory, molecular-docking studies and ınhibition effects of pharmaceutical active ıngredients on xanthine oxidase. Pharmaceutical Chemistry Journal, 58, 1650–8, (2025). https://doi.org/10.1007/S11094-025-03320-4.
46. Parr, R.G., Szentpály, L.V., Liu, S., Electrophilicity index. Journal of American Chemistry Society, 121, 1922–4, (1999). https://doi.org/10.1021/ja983494x.
47. Chattaraj, P.K., Sarkar, U., Roy, D.R., Electrophilicity index. Chemical Reviews, 106, 2065–91, (2026). https://doi.org/10.1021/cr040109f.
48. Demirci, T., Badreddin Musatat, A., Kaya, M.O., et al. In silico investigation of tetrazole and oxadiazole compounds as inhibitors of the dengue virus NS5 protein: Synthesis, DFT, ADME and molecular docking analysis. Chemico-Biological Interactions, 418, 111608, (2025). https://doi.org/10.1016/J.CBI.2025.111608.
49. Kumar, A., Hartland, S., Computational strategies for sizing liquid−liquid extractors. Journal of Industrial and Engineering Chemistry, 38, 1040–56, (1999). https://doi.org/10.1021/IE980455L.