Piridin Sübstitüe Ftalosiyaninlerin Sentezi Ve Dna Bağlanma Özelliklerinin İncelenmesi
Piridin Sübstitüe Ftalosiyaninlerin Sentezi Ve Dna Bağlanma Özelliklerinin İncelenmesi
Dosyalar
Tarih
2017-02-2
Yazarlar
Moeını Alıshah, Maryam
Süreli Yayın başlığı
Süreli Yayın ISSN
Cilt Başlığı
Yayınevi
Fen Bilimleri Enstitüsü
Institute of Science and Technology
Institute of Science and Technology
Özet
Tetrapirol türevi olan ftalosiyaninler hem temel hem de uygulamalı çalışmalarda önemli bir bileşik sınıfını oluşturmaktadır. Ftalosiyanin halkasına istenilen özellikteki fonksiyonel grupların eklenebilmesi optik, elektronik ve katalitik özelliklerini değiştirmekte ve değişik uygulama alanlarında kullanılmasını sağlamaktadır. Bu özelliklerinden dolayı ftalosiyaninler boyar madde, fotokromik, elektrokromik malzemeler, sıvı kristaller, katalizör, kimyasal sensör, Langmuir-Blodgett filmlerinde gaz sensörü, fotokopi makinelerinde ve lazer yazıcılarda fotoaktif iletken, ve nonlineer optik maddeler gibi farklı alanlarda kullanılmaktadır. Ftalosiyaninlere fonksiyonel grup olarak suda çözünebilen grupların eklenmesiyle kanser tedavisinde de kullanılabilmesinin önü açılmıştır. Günümüzde ftalosiyaninler ikinci nesil fotoalgılayıcılar olarak kullanılmaktadırlar. Hematoporfirin türevi gibi birinci nesil fotohassaslaştırıcılarla karşılaştırıldığı zaman, metalli ftalosiyaninlerin 680 nm civarındaki Q bandının molar soğurma katsayısı çok daha büyüktür, bunun anlamı doğrudan dokudan geçebilmeleridir, sübstitüe ftalosiyanin türevlerine hidrofil gruplar eklenmesi sulu ortamda çözünürlüğü sağlamak için üzerinde çalışılan bir konudur. Suda çözünen gruplar içeren ftalosiyaninler biyo-bulunurluk ve in vivo dağılım üzerine kuvvetli bir etkide bulunurlar. İyonik gruplar ise ftalosiyaninlerin DNA’ya ve proteinlere (örneğin BSA) bağlanma olanağı kazandırır. Tez kapsamında ftalosiyanin halkasına çözünürlük sağlayacak uygun sübstitüe gruplar bağlanarak bunların çeşitli metal tuzlarıyla metaloftalosiyaninleri hazırlanmıştır. Bu amaçla ilk olarak iodophthalonitrile hazırlanarak Zn(CH3COO)2 la uygun çözücü ortamında tetraiyodoçinko ftalosiyanin sentezlenmiştir. Tipik Sonogashira tepkime koşulları altında, aşırı 2-etinilpiridin ve tetraiyodo ftalosiyanin arasındaki kenetlenme tepkimesi trietilamin içinde bakır(I) iyodür (CuI) ve bis(trifenilfosfin)paladyum(II) klorür ([Pd(PPh3)2Cl2]) katalizörlüğünde oda sıcaklığında ve azot atmosferinde 2,9(10),16(17),23(24)-tetrakis(3-piridiletinil)ftalosiyaninatoçinko(II) elde edilmiştir. Suda çözünen ftalosiyanin türevlerinin sentezi için, kuaterner türevlerin sentezlenebilmesi amacıyla reaksiyon ortamına piridin grupları ilave edilmiştir. Ftalosiyaninler aşırı miktarda dimetil sülfat ile reaksiyona sokulmuştur. Aynı yöntem uygulanarak Co(II) ftalosiyanin ve kuaterner türevi elde edeilmiştir. Sentezlenen yeni bileşiklerin yapıları 1H-NMR, FTIR ve UV-Vis teknikleri kullanılarak aydınlatılmıştır. Ftalosiyaninlerin agregasyon ve DNA, BSA-bağlanma özellikleri incelenmiştir.
Phthalocyanines, being tetrapyrrole derivatives, constitute an important class of compounds both in basic researches and in applied sciences. Adding desired functional groups to the periphery of phthalocyanine rings changes its optical, electronic and catalytic properties and enables them to be used in different areas. Owing to these properties, phthalocyanines have been used in dyestuffs, photochromic and electrochromic materials, liquid crystals, catalysts, chemical sensors, gas sensors in the form of Langmuir-Blodgett films, and non-linear optical materials. Adding water-soluble groups to phthalocyanines as functional groups has also enabled them to be researched in the therapy of cancer. Today, phthalocyanines are being used as second-generation photosensitizers. Compared with the first-generation photosensitizers such as hematoporphyrin derivative, metallophthalocyanines have a much higher extinction coefficient of the Q‑band near 680 nm, which means that they are efficiently excited directly through tissue, whereas the introduction of hydrophilic groups into substituted phthalocyanine derivatives has been performed in order to achieve solubility in aqueous media. Phthalocyanines having water soluble groups have a strong influence on the bioavailability and in vivo distribution. While the ionic groups provide binding of phthalocyanines to DNA and proteins (e.g. BSA). Within the scope of this thesis, suitable substituents were attached to the phthalocyanine rings and metallophthalocyanines were synthesized by incorporating different metal ions. For this purpose, iodophthalonitrile was synthesized as a first step and tetraiodozinc phthalocyanine was synthesized with zinc acetate as the metal ion in a suitable solvent. Under typical Sonogashira reaction conditions, the cross-coupling reaction between an excess of 2-ethynyl pyridine and tetraiodo-metallophthalocyanines in triethylamine with copper(I)iodide (CuI) and bis(triphenylphosphine)palladium(II)chloride [Pd(PPh3)2Cl2] as catalysts at room temperature under nitrogen atmosphere produced 2,9(10),16(17),23(24)-tetra-(3-pyridylethynyl) phthalocyaninato zinc(II). For the synthesis of water-soluble phthalocyanine derivatives, pyridine groups were introduced into the reaction to synthesize quaternized derivatives. The phthalocyanines were reacted with excess amount of dimethyl sulfate. The same method was applied to obtain Co(II) phthalocyanine and its quaternary derivative. The new compounds were characterized 1H-NMR, FTIR and UV-Vis techniques. The aggregation and binding to DNA and BSA properties were investigated.
Phthalocyanines, being tetrapyrrole derivatives, constitute an important class of compounds both in basic researches and in applied sciences. Adding desired functional groups to the periphery of phthalocyanine rings changes its optical, electronic and catalytic properties and enables them to be used in different areas. Owing to these properties, phthalocyanines have been used in dyestuffs, photochromic and electrochromic materials, liquid crystals, catalysts, chemical sensors, gas sensors in the form of Langmuir-Blodgett films, and non-linear optical materials. Adding water-soluble groups to phthalocyanines as functional groups has also enabled them to be researched in the therapy of cancer. Today, phthalocyanines are being used as second-generation photosensitizers. Compared with the first-generation photosensitizers such as hematoporphyrin derivative, metallophthalocyanines have a much higher extinction coefficient of the Q‑band near 680 nm, which means that they are efficiently excited directly through tissue, whereas the introduction of hydrophilic groups into substituted phthalocyanine derivatives has been performed in order to achieve solubility in aqueous media. Phthalocyanines having water soluble groups have a strong influence on the bioavailability and in vivo distribution. While the ionic groups provide binding of phthalocyanines to DNA and proteins (e.g. BSA). Within the scope of this thesis, suitable substituents were attached to the phthalocyanine rings and metallophthalocyanines were synthesized by incorporating different metal ions. For this purpose, iodophthalonitrile was synthesized as a first step and tetraiodozinc phthalocyanine was synthesized with zinc acetate as the metal ion in a suitable solvent. Under typical Sonogashira reaction conditions, the cross-coupling reaction between an excess of 2-ethynyl pyridine and tetraiodo-metallophthalocyanines in triethylamine with copper(I)iodide (CuI) and bis(triphenylphosphine)palladium(II)chloride [Pd(PPh3)2Cl2] as catalysts at room temperature under nitrogen atmosphere produced 2,9(10),16(17),23(24)-tetra-(3-pyridylethynyl) phthalocyaninato zinc(II). For the synthesis of water-soluble phthalocyanine derivatives, pyridine groups were introduced into the reaction to synthesize quaternized derivatives. The phthalocyanines were reacted with excess amount of dimethyl sulfate. The same method was applied to obtain Co(II) phthalocyanine and its quaternary derivative. The new compounds were characterized 1H-NMR, FTIR and UV-Vis techniques. The aggregation and binding to DNA and BSA properties were investigated.
Açıklama
Tez (Yüksek Lisans) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 2017
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2017
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2017
Anahtar kelimeler
Piridin Sübstitüe Ftalosiyaninler,
Suda Çözünür Ftalosiyaninler,
Çinko Ftalosiyaninler,
Kobalt Ftalosiyaninler,
Ftalosiyaninlerin Dna'ya Bağlanma Özellikleri,
Pyridine Substituted Phthalocyanines,
Water-soluble Phthalocyanines,
Zinc Phthalocyanines,
Cobalt Phthalocyanines,
Dna Binding Properties Of Phthalocyanines