BAZI FENOLİK KİRLİLİKLERİN İMİDAZOL TÜREVLİ KALİKS[4]AREN İÇEREN MANYETİK NANOPARTİKÜLLER KULLANARAK SULU ÇÖZELTİLERDEN UZAKLAŞTIRILMASI

Bu çalışmada imidazol türevli kaliks[4]arenlerin sentezi, bu bileşiklerin [3-(2,3-epoksipropoksi)- propil]-trimetoksisilan (EPPTMS) modifiyeli Fe3O4 nanopartikülüne immobilize edilmesi ve elde edilen nanaparitküllerin bazı fenolik kirleticiler için adsorpsiyon özelliklerinin incelenmesi amaçlanmıştır. Bu amaçla ilk olarak hedef bileşikleri sentezlemek üzere bir dizi kaliks[4]aren türevi (1, 2, 3, 4, 5, 6, 8) literatür prosedürüne göre sentezlenmiş ve yapıları doğrulanmıştır. Bu bileşiklerden 6 nolu bileşik Mannich reaksiyonu ile imidazol ile etkileştirilerek hedef bileşik 7 elde edilmiştir. Diğer taraftan 8 nolu karşılıklı iki adet bromo grubu taşıyan kaliks[4]aren türevi yine imidazol ile etkileştirilerek diğer hedef bileşik olan 9 bileşiği sentezlenmiştir. Bu bileşikler daha sonra EPPTMS modifiyeli Fe3O4 nanopartikülüne immobilize edilerek imidazol grubu taşıyan kaliks[4]aren bağlı yeni manyetik nanopartiküller (K-7-BMN ve K-9-BMN) elde edilmiştir. Bu yeni nanopartiküller fenol (FEN), p- klorofenol (pKF) ve p-nitrofenol (pNF)’ün sulu çözeltiden adsorpsiyonunda adsorban olarak kullanılmıştır. Sonuçlar K-9-BMN’nin pH 6 da pKF için en yüksek adsorpsiyonu gerçekleştirdiğini, K-7- BMN’nin ise hiçbir fenolik tür için kayda değer bir adsorpsiyon göstermediğini ortaya çıkarmıştır. Adsorpsiyon sürecinde elektrostatik etkileşimler ve hidrojen bağı etkileşimlerinin özellikle önemli olduğu ve bunların ortam şartlarına bağlı olarak adsorban türlerinin yapısıyla yakından ilgili olduğu anlaşılmıştır.

Anahtar Kelimeler:

Kaliksaren, Fenolik kirlilik, Manyetik nanopartikül, Adsorpsiyon

Removal of Some Phenolic Pollutions from Aqueous Solutions by Magnetic Nanoparticles Containing Imidazole-Derivatized Calix[4]arene

In this paper, it was aimed to synthesize imidazole-derived calix[4]arenes, immobilize these compounds to [3-(2,3-epoxypropoxy)-propyl]-trimetoxysilane (EPPTMS) modified Fe3O4 nanoparticles and to investigate adsorption properties of the obtained nanoparticles for some phenolic pollutants. For this purpose, firstly, a series of calix[4]arene derivatives (1, 2, 3, 4, 5, 6, 8) were synthesized according to the literature procedures and their structures were verified to synthesize the target compounds. Compound 6 among of these compounds was reacted with imidazole by the Mannich reaction to achieve target 7. On the other hand, calix[4]arene derivative bearing two distal bromo groups 8 was also reacted with imidazole to achive other target compound 9. The structure of both compounds was confirmed by 1H NMR spectroscopy. Thus, two different calix[4]arene derivatives were prepared from both the lower region and the upper region of the calix[4]arene with functional imidazole groups. These compounds were then immobilized to the EPPTMS modified Fe3O4 nanoparticle to obtain calix[4] arene-bonded new magnetic nanoparticles (C-7-BMN and C-9-BMN) bearing the imidazole group. These new nanoparticles were used as adsorbents in the adsorption of phenol (PHE), p-chlorophenol (pCF) and p-nitrophenol (pNP) from the aqueous solution. Concentrations of solution were determined by HPLC and adsorption results were calculated. The results revealed that C-9-BMN performed the highest adsorption for pCF at pH 6, while C-7-BMN showed no remarkable adsorption for any phenolic species. It has been understood that electrostatic interactions and hydrogen bond interactions are particularly important in the adsorption process and they are closely related to the structure of the adsorbent species depending on the ambient conditions. As a result, using the C-9-BMN adsorbent prepared in this study, the adsorption method, pCF, which is a toxic phenolic species, was removed from the aqueous solutions in a remarkable efficiency.

Keywords:

Calixarene, Phenolic pollution, Magnetic nanoparticle, Adsorption,

PDF

___

Akceylan, E., Uyanik, A., Eymur, S., Sahin, O., Yilmaz, M., 2015. Calixarene-proline functionalized iron oxide magnetite nanoparticles(Calix-Pro-MN): An efficient recyclable organocatalyst for asymmetricaldol reaction in water, Applied Catalysis A: General, 499, 205-212.
Akpinar, M., Temel, F., Tabakci, B., Ozcelik, E., Tabakci, M., 2019. A phenyl glycinol appended calix[4]arene film for chiral detection of ascorbic acid on gold surface. Anal. Biochem. 583, 113373.
Bieber, V.S., Ozcelik, E., Cox, H. J., Ottley, C.J., Ratan, J.K., Karaman, M., Tabakci, M., Beaumont, S.K., Badyal, J.P.S., 2020. Capture and release recyclable dimethylaminomethyl-calixarene functional cloths for point-of-use removal of highly toxic chromium water pollutants. ACS Appl. Mater. Interfaces 12(46), 52136–52145.
Dalbavie, J.-O., Regnouf-de-Vains, J.-B., Lamartine, R., Lecocq, S., Perrin, M., 2000. Complexation of Cobalt(II) at the Upper Rim of Two New Calix[4]arene/Bipyridine-Based Podands. European Jurnal of Inorganic Chemistry 683-691.
Deveci, E. Ü., 2014. Fenol Ve Fenol Türevi Bileşiklerin Biyolojik Parçalanabilirliği. ISEM2014, 664-672.
Dinçyürek, Ö., 2006. Termik Santral Uçucu Kül Tiplerinin Atıksulardaki Fenolün Adsorpsiyon Yöntemi ile Giderim Etkinliklerinin Karşılaştırılması. Yüksek Lisans Tezi, Çukurova Üniversitesi, 95.
Dogan, M., Temel, F., Tabakci, M., 2020. High-Performance Adsorption of 4-Nitrophenol onto Calix[6]arene-Tethered Silica from Aqueous Solutions. Journal of Inorganic and Organometallic Polymers and Materials, 30(10) 4191-4202.
Ekin Dolaksiz, Y., Temel, F., Tabakci, M., 2018. Adsorption of phenolic compounds onto calix[4]arene-bonded silica gels from aqueous solutions. Reactive and Functional Polymers, 126, 27-35.
Erdemir, S., Tabakci, B., Tabakci, M., 2016. A highly selective fluorescent sensor based on calix[4]arene appended benzothiazole units for Cu2+, S2−and HSO4− ions in aqueous solution. Sens. Actuators B Chem. 228, 109-116.
Erdemir, S., Ahmed Ahmed, H.M., Tabakci, B., 2019. Fast and reversible “turn on” fluorescent sensors based on bisphenol-a for Zn2+ in aqueous solution. J. Fluoresc. 29, 1079-1087.
Gutsche, C. D., Iqbal M., 1990. p-tert-butylcalix[4]arene, Organic Syntheses. 68, 234.
Li, Z.T., Ji, G.Z., Zhao, C.X.,Yuan, S.D., Ding,H., Huang, C.,Du, A.L.,Wei, M., 1999. Self-Assembling Calix[4]arene [2]Catenanes. Preorganization, Conformation, Selectivity, and Efficiency. J. Org. Chem., 64, 3572-3584.
Ozcelik, E., Temel, F., Erdemir, S., Tabakci, B., Tabakci, M., 2019. QCM sensors coated with calix[4]arenes bearing sensitive chiral moieties for chiral discrimination of 1-phenylethylamine enantiomers. J. Incl. Phenom. Macrocycl. Chem. 95, 35-48.
Tabakcı, B., 2010. Bazı Monomerik ve Polimerik Kaliksarenlerin Sentezi ve Enzim-Mimik Özelliklerinin İncelenmesi. Doktora Tezi, Selçuk Üniversitesi, Fen Bilimleri Enstütüsü, Konya.
Tabakci, B. Alici, O., Karatas, I., 2013. 4-tert-Butylcalix[4]arene having nitrile pendant groups as Hg2+ selective receptors. Talanta 106, 92-96.
Tabakci, M., 2008. Immobilization of calix[6]arene bearing carboxylic acid and amide groups on aminopropyl silica gel and its sorption properties for Cr(VI). Journal of Inclusion Phenomena and Macrocyclic Chemistry, 61, 53-60.
Tabakci, M. ve Yilmaz, M., 2008. Sorption characteristics of Cu(II) ions onto silica gel-immobilized calix[4]arene polymer in aqueous solutions: batch and column studies, Journal Hazardous Materials, 151 (2-3), 331-338.
Tabakci, M., Tabakci, B., Beduk, A. D., 2012. Synthesis and application of an efficient calix[4]arene-based anion receptor bearing imidazole groups for Cr(VI) anionic species Tetrahedron, 68, 4182-4186.
Temel, F., Ozcelik, E., Ture, A.G., Tabakci, M., 2017. Sensing abilities of functionalized calix[4]arene coated QCM sensors towards volatile organic compounds in aqueous media. Appl. Surf. Sci. 412, 238-251.
Temel, F., Erdemir, S., Tabakci, B., Akpinar, M., Tabakci, M., 2019. Selective chiral recognition of alanine enantiomers by chiral calix[4]arene coated quartz crystal microbalance sensors. Anal. Bioanal. Chem. 411, 2675-2685.
Temel, F., 2020. One novel calix[4]arene based QCM sensor for sensitive, selective and high performance-sensing of formaldehyde at room temperature. Talanta, 211, 120725.
Temel, F., Kutluay, S., 2020. Investigation of high-performance adsorption for benzene and toluene vapors by calix[4]arene based organosilica (CBOS). New Journal of Chemistry, 44(30) 12949-12961.
Temel, F., Turkyilmaz, M., Kucukcongar, S., 2020. Removal of methylene blue from aqueous solutions by silica gel supported calix[4]arene cage: Investigation of adsorption properties. European Polymer Journal, 125, 109540.
Wu, C.-S., Xiong, Z.-H., Li, C., Zhang, J.-M., 2015. Zeolitic imidazolate metal organic framework ZIF-8 with ultra-high adsorption capacity bound tetracycline in aqueous solution. RSC Advances, 5, 82127-82137.
Yong, Y., Bai, Y., Li, Y., Lin, L., Cui, Y., Xia, C., 2008. Preparation and application of polymergrafted magnetic nanoparticles for lipase immobilization. Journal of Magnetism and Magnetic Materials, 320, 2350–2355.