Bazı monomerik ve polimerik kaliksarenlerin sentezi ve enzim-mimik özelliklerinin incelenmesi
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Dosyalar
Tarih
2010-06-25
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Yayıncı
Selçuk Üniversitesi Fen Bilimleri Enstitüsü
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Bu çalışma, monomerik ve polimerik yapıdaki kaliks[4]aren türevlerinin sentezlenmesini ve sentezlenen bu türevlerin transaçilaz enzim-mimik olarak kullanılma özelliklerinin incelenmesini kapsamaktadır. Senztez bölümü iki kısımdan oluşmaktadır. Birinci bölümde monomerik, ikinci bölümde ise polimerik kaliks[4]arenlerin sentezi gerçekleştirldi. Monomerik kaliks[4]arenin sentez çalışmaları da ikili ve dörtlü gruplar taşıyan kaliks[4]arenler olmak üzere iki seri halinde yapıldı. Birinci seri için ilk olarak p-ter-bütilkaliks[4]aren (1) başlangıç maddesi olarak sentezlendi ve dibenzoil türevine (2) dönüştürüldükten sonra p-ter-bütil gruplarından 1,3-distal pozisyondaki iki tanesi seçimli olarak giderildi. Elde edilen bileşik (3), hidroliz edilerek benzoil grupları da giderildi ve 4 elde edildi. Daha sonra 4, p-pozisyonu üzerinden dimetilamino türevine (5) dönüştürüldükten sonra metil iyodürle etkileştirilerek 6 elde edildi. Son olarak 6, önce uygun rektifler kullanılarak ikili imidazol, triazol ve triazol ester bağlı türevleri (7-9) ve daha sonrada triazol ester-bağlı kaliks[4]arenin hidroliziyle de 10 da sentezlenerek bu seri tamamlandı. Diğer yandan monomerik kaliks[4]arenlerin ikinci sentez serisi için başlangıç bileşiğinin (1) tüm ter-bütil grupları giderilerek 11, bu serinin başlangıç maddesi olarak sentezlendi. Daha sonra 11, önce tetraaminometilli türevine (12) sonrada metil iyodür ile etkileştirilerek 13'e dönüştürüldü. Son olarak 13, uygun rektifler kullanılarak dörtlü imidazol ve triazol türevleri (14 ve 15) de sentezlenerek bu seri de tamamlandı. Sentez bölümünün ikinci kısmında ise sentezlenen monomerik kaliks[4]aren türevleri kullanılarak polisiloksan yapısına sahip (20-23), Merrifield (24-27) ve TentaGel (28) destekli polimerik yapıdaki kaliks[4]arenler hazırlandı. Bu amaçla ilk olarak monomerik kaliks[4]arenler 7, 8, 14 ve 15, önce 3-glisidoksipropiltrietoksisilan ile etkileştirilerek trietoksisilan türevlerine (16-19) daha sonra da tetraetoksilan ile polimerleştirilerek kaliks[4]aren bazlı polisiloksan reçineleri (20-23) hazırlandı. Ayrıca 7, 8, 14 ve 15, uygun şartlarda Merrifield reçinesine bağlanarak Merrifield-destekli polimerler (24-27) hazırlandı. Son olarak triazol ester-bağlı kaliks[4]aren 10, uygun şartlarda amino bağlı TentaGel reçinesine bağlanarak Tentagel-destekli polimer (28) hazırlandı. Hazırlanan tüm bileşiklerin yapıları, FTIR, 1H NMR, 13C NMR, element analiz, ve TGA gibi yapı analiz teknikleri kullanılarak aydınlatıldı. Enzim-mimik çalışmaları, monomerik ve polimerik kaliks[4]arenler ile olmak üzere iki kısımda gerçekleştirildi. İlk olarak monomerik kaliks[4]arenlerin katalitik etkinliklerini belirlemek amacıyla bu bileşikler, p-nitrofenil asetatın hidrolizinde katalizörler (7, 8, 10, 14 ve 15) olarak kullanıldı. Ayrıca reaksiyon katalizörsüz olarak da gerçekleştirilerek karşılaştırma yapıldı. Daha sonra çalışmalar daha detaylı olarak gerçekleştirildi. Öncelikle optimum pH'ı belirlemek amacıyla hidroliz reaksiyonu farklı pH değerlerinde gerçekleştirildi. Daha sonra reaksiyon kinetiği ile ilgili olarak Michaelis-Menten verilerini belirlemek amacıyla hidroliz reaksiyonu, farklı substrat konsantrasyonları kullanılarak gerçekleştirildi ve ilgili veriler hesaplandı. Ayrıca katalizörlerin farklı substratlara karşı davranışını belirlemek için hidroliz reaksiyonu farklı substratlar kullanılarak gerçekleştirildi Enzim-mimik çalışmalarının ikinci bölümünde ise hazırlanan polimerik kaliks[4]arenler, katalizör olarak kullanıldı. Katalizörlerin Michaelis-Menten verileri belirlenerek katalitik etkinlikleri belirlendi. Diğer taraftan hidroliz reaksiyonu farklı miktardaki polimerler kullanılarak da gerçekleştirildi. Son olarak enzim-mimik çalışmalarında polimerik katalizörlerle geri kazanım ve yeniden kullanım çalışmaları gerçekleştirildi ve bu şekilde sentezlenen polimerik kaliksarenlerin kullanılabilirlik dereceleri belirlendi.
This study comprises the synthesis of monomeric and polymeric calix[4]arene derivatives and the investigation of their use as transacylase enzyme-mimics. Synthesis section consisting of two parts. It was performed the synthesis of monomeric calix[4]arenes in first part while the preparation of polymeric calix[4]arenes in second part. The study of synthesis for di- and tetra-substituted monomeric calix[4]arenes was carried out in two serials. For the first series, p-tert-butylcalix[4]arene (1) was synthesized as a starting material and it was firstly converted to its dibenzoyl derivative, and then two tert-butyl groups in 1,3-distal position were selectively removed. After its hydrolysis the obtained compound was firstly converted to its dimethylamino derivative and then compound 6 was synthesized by treatment of 5 with methyl iodide. Finally, with the synthesis of firstly di-imidazole-, -triazole- and -triazole ester-bonded derivatives by using suitable reagents, and then with the hydrolysis of 9 to obtain 10 it was completed one series. On the other hand for the second series of the synthesis of monomeric calix[4]arenes, 11 was synthesized by removing the all tert-butyl groups of the 1 as starting material. 11 was firstly converted to its methylamine derivative (12) and then 13 was synthesized by reacting of 12 with methyl iodide. Finally, with the synthesis of di-imidazole- and ?triazole it was completed second series of the monomeric calix[4]arenes. Polymeric calix[4]arenes having three polymeric backbone (siloxane, Merrifield- and TentaGel-supported) were prepared by using monomeric calix[4]arenes in the second of synthesis section. For this purpose it was firstly prepared triethoxysilane derivatives (16-19) by the treatment of 7, 8, 14 and 15 3-glycidoxypropyl triethoxysilane and then their polymerization of them gave calix[4]arene-based polysiloxane resins (20-23). Also it was Merrifield-supported calix[4]arene polymers (24-27) were prepared by binding of the 7, 8, 14 and 15 to Merrifield resin under suitable conditions. Finally by the binding of the triazol ester-bonded calix[4]arene (10) to TentaGel resin under suitable conditions, TentaGel-supported polymer (28) it was prepared. Structures of the all monomers and polymers were chracterized by the techniques of structure analysis such as FT-IR, 1H NMR, 13C NMR, elemental analysis and TGA. Enzyme-mimic studies were separately carried out with monomeric and polymeric calix[4]arenes. Firstly to understand the catalytic powers of monomeric calix[4]arenes (7, 8, 10, 14 and 15) were used in the hydrolysis of the p-nitrophenyl acetate as catalysts. Also hydrolysis reaction was performed without catalyst for comparison. After that the studies were detailed. For this aim, firstly to determine the opitmum pH, hydrolysis were performed under different pH conditions. Also hydrolysis were done by using various substrate concentrations to calculate the Michaelis-Menten kinetic data. Finally the hydrolysis were performed with various substrates to see the behavior of catalysts toward substrates such as p-nitrophenyl acetate, p-nitrophenyl palmitate and bis-p-nitrophenyl carbonate. On the other hand, hydrolysis reaction were carried out with polymeric calix[4]arenes and then it was determined their Michaelis-Menten kinetic data. Also it was done in different amounts of polymers to learn the effect of the polymer amount to hydrolysis. Finally in this part, it was carried out recovery and reuse studies of the polymeric catalysts.
This study comprises the synthesis of monomeric and polymeric calix[4]arene derivatives and the investigation of their use as transacylase enzyme-mimics. Synthesis section consisting of two parts. It was performed the synthesis of monomeric calix[4]arenes in first part while the preparation of polymeric calix[4]arenes in second part. The study of synthesis for di- and tetra-substituted monomeric calix[4]arenes was carried out in two serials. For the first series, p-tert-butylcalix[4]arene (1) was synthesized as a starting material and it was firstly converted to its dibenzoyl derivative, and then two tert-butyl groups in 1,3-distal position were selectively removed. After its hydrolysis the obtained compound was firstly converted to its dimethylamino derivative and then compound 6 was synthesized by treatment of 5 with methyl iodide. Finally, with the synthesis of firstly di-imidazole-, -triazole- and -triazole ester-bonded derivatives by using suitable reagents, and then with the hydrolysis of 9 to obtain 10 it was completed one series. On the other hand for the second series of the synthesis of monomeric calix[4]arenes, 11 was synthesized by removing the all tert-butyl groups of the 1 as starting material. 11 was firstly converted to its methylamine derivative (12) and then 13 was synthesized by reacting of 12 with methyl iodide. Finally, with the synthesis of di-imidazole- and ?triazole it was completed second series of the monomeric calix[4]arenes. Polymeric calix[4]arenes having three polymeric backbone (siloxane, Merrifield- and TentaGel-supported) were prepared by using monomeric calix[4]arenes in the second of synthesis section. For this purpose it was firstly prepared triethoxysilane derivatives (16-19) by the treatment of 7, 8, 14 and 15 3-glycidoxypropyl triethoxysilane and then their polymerization of them gave calix[4]arene-based polysiloxane resins (20-23). Also it was Merrifield-supported calix[4]arene polymers (24-27) were prepared by binding of the 7, 8, 14 and 15 to Merrifield resin under suitable conditions. Finally by the binding of the triazol ester-bonded calix[4]arene (10) to TentaGel resin under suitable conditions, TentaGel-supported polymer (28) it was prepared. Structures of the all monomers and polymers were chracterized by the techniques of structure analysis such as FT-IR, 1H NMR, 13C NMR, elemental analysis and TGA. Enzyme-mimic studies were separately carried out with monomeric and polymeric calix[4]arenes. Firstly to understand the catalytic powers of monomeric calix[4]arenes (7, 8, 10, 14 and 15) were used in the hydrolysis of the p-nitrophenyl acetate as catalysts. Also hydrolysis reaction was performed without catalyst for comparison. After that the studies were detailed. For this aim, firstly to determine the opitmum pH, hydrolysis were performed under different pH conditions. Also hydrolysis were done by using various substrate concentrations to calculate the Michaelis-Menten kinetic data. Finally the hydrolysis were performed with various substrates to see the behavior of catalysts toward substrates such as p-nitrophenyl acetate, p-nitrophenyl palmitate and bis-p-nitrophenyl carbonate. On the other hand, hydrolysis reaction were carried out with polymeric calix[4]arenes and then it was determined their Michaelis-Menten kinetic data. Also it was done in different amounts of polymers to learn the effect of the polymer amount to hydrolysis. Finally in this part, it was carried out recovery and reuse studies of the polymeric catalysts.
Açıklama
Anahtar Kelimeler
Kaliksarenler, Katalizör, Polimer, İmidazol, Triazol, Calixarene, Catalyst, Polymer, Imidazole, Triazole
Kaynak
WoS Q Değeri
Scopus Q Değeri
Cilt
Sayı
Künye
Tabakcı, B. (2010). Bazı monomerik ve polimerik kaliksarenlerin sentezi ve enzim-mimik özelliklerinin incelenmesi. Selçuk Üniversitesi, Yayımlanmış doktora tezi, Konya.
