Taç eterlerin metal iyonları ile kompleksleşmesinin kondüktometriye Job’s Plot yönteminin uygulanması ile belirlenmesi

Baki Çiçek, Ümit Çalışır

Öz


Bu çalışma kapsamında benzo-tiyo ve benzo-okso taç eterler ile metal iyonları arasındaki iyon-dipol etkileşmeleri Job’s Plot yönteminin kondüktometriye uyarlanmasıyla belirlendi (Çözücü sistemi: %50 Asetonitril/su). Daha önce verilen mikrodalga sentez yöntemi kullanılarak yeniden sentezlenen U1 (bis(1,2-dibenzo) oktatiyo tetrakarbonil-29-crown-6), U2 (bis(1,2-dibenzo) tetratiyo tetrakarbonil-29-crown-6) taç eterlerinin NaCl, KCl, MgCl2, CaCl2, ZnCl2, FeSO4, AgNO3, CoCl2 metal tuzlarıyla komplesleşmeleri incelendi. Taç eter-katyon kompleksinin kompleksleşme oranı, kompleksleşme sabiti (Ke) ve Serbest Gibbs Enerjisi (ΔGθ ) hesaplandı. Kondüktometri ile gerçekleştirilen çalışmalara göre U1 bileşiği için kompleksleşme sabiti Na+ > Zn2+ > Ca2+ > Ag+ > K+ > Mg2+ > Co2+ > Fe2+ yönünde azalırken, U2 bileşiği için Zn2+ > Fe2+ > Na+ > K+ > Co2+ > Ag+ > Ca2+ > Mg2+ yönünde değiştiği gözlemlenmiştir. Bu çalışma sonuçlarına göre taç eterler metal sensörü, biyoorganizmalardaki enzimler için inhibitör veya aktivatör ve sanayi-çevre uygulamalarında metal iyonlarının giderimi için kullanılabilirler.


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Referanslar


Zhou, Q.Z., He, C.L., Gu, H.N., Miao, Q.M., Zhai, C.X., Convenient synthesis of aryl-incorporated ditosylates and their application in preparation of crown ethers with higher yield, Chinese Chemical Letters, 19, 911–914, (2008).

Pedersen, C.J., Cyclic Polyethers and Their Complexes with Metal Salts, Journal of the American Chemical Society, 89, 10, 2495-2496, (1967).

Pedersen, C.J., Macrocyclic Polyethers: Dibenzo-18-Crown-6 Polyether and Dicyclohexyl-18-Crown-6 Polyether, Organic Syntheses, 52, 66, (1972).

Pedersen, I.S., Prize, N., Crown, C.E., Chapter 2 Crown Ethers, 10, 34–54, (1987).

Parker, D., Macrocycle Compounds-Synthesis, II. Series, Oxford University Press, New York, 1996.

Water, L.G.A.V., Driessen, W.L., Glenny, M.W., Reedijk, J., Schröder, M., Selective and reversible extraction of heavy metal-ions by mixed-donor crown ether-modified oxirane and thiirane resins, Reactive and Functional Polymers, 51, 33–47, (2002).

Yordanov, A.T., Roundhill, D.M., Solution extraction of transition and post-transition heavy and precious metals by chelate and macrocyclic ligands, Coordination Chemistry Reviews, 170, 93–124, (1998).

Lu, T., Wang, X., Tan, M., Liu, Y., Inoue, Y., Hakushi, T., Studies on rare-earth complexes with crown ethers. Part XXV. Synthesis, characterization, and structure of the complexes of lanthanite nitrates with 13-crown-4, Helvetica Chimica Acta, 76, 241–247, (1993).

Bruening, R.L., Tarbet, B.J., Krakowiak, K.E., Bruening, M.L., Izatt, R.M., Bradshaw, J.S., 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, 1014–1017, (1991).

Çiçek, B., Çakir, Ü., Azizoglu, A., The associations of macrocyclic ethers with cations in 1,4-dioxane/ water mixtures; Potentiometric Na+ and K+ binding measurements and computational study, Journal of Inclusion Phenomena and Macrocyclic Chemistry, 72,121–125, (2012).

Çakir, Ü., Çiçek, B., Yildiz, Y.K., Alkan, M., Solvent effect upon ıon-pair extraction of different sodium dyes using some crown ethers, Journal of Inclusion Phenomena and Macrocyclic Chemistry, 34, 153–165, (1999).

Çiçek, B., Onbaşıoğlu, Z., Synthesis and characterization of 1,3,4-thiadiazole-2,5-dithio crown ethers, Heterocyclic Communication, 22, 329–332, (2016).

Çakir, Ü., Çiçek, B., Extraction-ability and -selectivity of tetra-aza-crown ethers for transition metal cations, Transition Metal Chemistry, 29, 263–268, (2004).

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, 572–577, (2016).

Çalışır, Ü., Benzo-tiyo crown eterlerin sentezi ve ekstraktif özelliklerinin incelenmesi, Yüksek Lisans Tezi, Balıkesir Üniversitesi, Fen Bilimleri Enstitüsü, Balıkesir, 2014.

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, 505–511, (2017).

Çiçek, B., Yıldız, A., Synthesis, Metal ion complexation and computational studies of thio oxocrown ethers, Molecules, 16, 8670–8683, (2011).

Litvinova, V.V., Anisimov, A.V., Thiacrown compounds: synthesis and properties, Chemistry of Heterocyclic Compounds, 35, 12–22, (1999).

ÇİÇEK, B., ÇALIŞIR, Ü., Bazı karbazol schiff bazlarının katyon bağlama özelliklerinin kondüktometrik incelenmesi, Balıkesir Üniversitesi Fen Bilim. Enstitüsü Dergisi, 19, 246–256 (2017).

Çiçek, B., Synthesis of tetra-aza coronands and determination of complexity capabilities by potentiometric, conductometric and liquid-liquid extraction methods, PhD Thesis, Balikesir University, Institute of Science and Technology, Balikesir, 2002.

Çiçek, B., Çakır, Ü., Erk, Ç., The determination of crown–cation complexation behavior in dioxane/water mixtures by conductometric studies, Polymers for Advanced Technologies, 836, 831–836, (1998).

Erk, Ç., 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).

Çakir, Ü., Çiçek, B., Erk, Ç., The associaton constants of macrocyclic ether-cation interections in dioxane / water mixtures, part II, Journal of Inclusion Phenomena and Macrocyclic Chemistry, 275–278, (1998).

Job, P., Formation and stability of ınorganic complexes in solution., Annali di Chimica, 9, 113–203, (1928).

Yang, L., Zhu, W., Fang, M., Zhang, Q., Li, C., A new carbazole-based Schiff-base as fluorescent chemosensor for selective detection of Fe3+ and Cu+, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 109, 186–92, (2013).

Nabeshima, T., Tsukada, N., Nishijima, K., Ohshiro, H., Yano, Y., Remarkably selective Ag(+) extraction and transport by thiolariat ethers., The Journal of Organic Chemistry, 61, 4342–4350, (1996).

Huang, C.Y., Determination of binding stoichiometry by the continuous variation method: The Job Plot, Methods in Enzymology, 87, 509–525, (1982).

Ijeri, V.S., Srivastava, A.K., Complexation of macrocyclic compounds with mono-, di- and tri-valent transition and heavy metal ions in 90% (v/v) DMSO + water medium, Polyhedron, 22, 569–574, (2003).


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