Kumarin türevi bazı ftalosiyaninlerin sentezi ve karakterizasyonu

ÖZETKUMARİN TÜREVİ BAZI FTALOSİYANİNLERİN SENTEZİ VE KARAKTERİZASYONU Ftalosiyaninler (Pc), yüksek kimyasal ve fiziksel kararlılığa sahip mavi-yeşil renkli sentetik maddelerdir. İlk kez 1907’de o-siyanobenzamid’in sentezi sırasında yan ürün olarak keşfedildiğinden beri ftalosiyanin ve metal türevleri ile çok yaygın olarak çalışılmaktadır. Diğer taraftan sentezlenen ftalosiyanin bileşikleri kumarin (2H-1-benzopiran-2-on) türevleri içermektedir. Kumarinler benzopiranlar olarak bilinen bileşiklerin bir grubuna aittir. Antioksidanlar ve antikoagülantlar olarak analizlerde, lazerlerde ve klinik uygulamalarda floresans işaretleyici olarak, parfümeri ve besinlerde katkı maddesi olarak önemli role sahip bir bileşik grubudur. Sentezlenen ftalosiyanin bileşiklerinin bazıları taç eter birimleri de içermektedir. Taç eterler ilk kez 1967 yılında C.J.Pedersen tarafından sentezlenmiştir. İlk bulunuşlarından itibaren taç eterler pek çok alanda, özellikle, organik ve anorganik katyon, anyon, nötr moleküllerin taşıyıcı olarak kullanılmaktadır. Alkali metallerin (Na+, K+) iç oyuğa girmesi ile biyolojik sistemlerde membranlar boyunca iyon taşınımı mümkün olabilmiştir. Florojenik kumarin grupları taşıyan taç eterler floresans spektroskopisinde kullanılırlar. Ayrıca ftalosiyanin ve taç eter gibi önemli iki yapının kombinasyonundan oluşan ftalosiyanin bileşiklerinin ilginç farmakolojik özellikler gösterebilecekleri düşünülmektedir. Metalli ve metalsiz ftalosiyaninlerin en önemli dezavantajı organik çözücüler ve sudaki çözünürlüklerinin düşük olmasıdır. Periferal pozisyonlarında taç eter makrohalkaları veya alkil/alkoksi gibi uzun zincirli gruplar içeren ftalosiyaninlerin organik solventlerdeki çözünürlüğünde artış görülmüştür. Doktora tez çalışma konusu kapsamında periferal ve periferal olmayan pozisyonlarda taç eter, alkil, alkiloksi grupları içeren orijinal çeşitli metalsiz ve metalli ftalosiyanin bileşikleri sentezlenmiştir. 1H-NMR, FT-IR, UV-VIS, MS MALDI-TOF analiz metodları kullanılarak yapıları karakterize edilmiş ve aynı zamanda floresans spektroskopisi teknikleri ile de floresans özellikleri incelenmiştir. ABSTRACT THE SYNTHESIS AND CHARACTERIZATION OF SOME PHTHALOCYANINES WITH COUMARIN DERIVATIVE Phthalocyanines (Pcs) are blue-green coloured synthetic compounds with high chemical and physical stability. The compounds and its metallo derivatives have been studied very extensively since its first discovery in 1907 as a by-product in the synthesis of o-cyanobenzamide. On the other hand, we synthesized phthalocyanines bearing coumarin (2H-1-benzopyran-2-one) moieties. The coumarins belong to a group of compounds known as the benzopyrones. Coumarins are a group of compounds that have important roles as antioxidants and anticoagulants for use in analysis; as fluorescent markers, in lasers and clinical use; as additives in food and cosmetics. Also, we synthesized phthalocyanines containing crown ether moieties. Crown ethers was first synthesized in 1967 by C.J.Pedersen. The ability of crown ethers to form stable complexes with cations, mainly with alkali and alkaline earth cations, has spurred interest in these compounds. Crown ethers bearing fluorogenic coumarin groups are used in fluorescence spectroscopy. A combination of two potentially promising units (i.e. phthalocyanines and crown ethers) has yielded products showing interesting properties. A major disadvantage of phthalocyanines and metallophthalocyanines are their low solubility in organic solvents or water. Crown ether or long chain groups, such as alkyl/alkoxy substitution enhances the solubility of phthalocyanines in common organic solvents. In PhD thesis study, we synthesized original some novel metal free and metallo phthalocyanines bearing crown ether, alkyl, alkyloxy groups on peripheral and unperipheral positions. The structure of compounds were characterized with using 1H-NMR, FT-IR, UV-VIS, MS MALDI-TOF analysis methods and their fluorescence properties were investigated by fluorescence spectroscopy techniques

Kumarin türevi bazı ftalosiyaninlerin sentezi ve karakterizasyonu

KUMARİN TÜREVİ BAZI FTALOSİYANİNLERİN SENTEZİ VE KARAKTERİZASYONU Ftalosiyaninler (Pc), yüksek kimyasal ve fiziksel kararlılığa sahip mavi-yeşil renkli sentetik maddelerdir. İlk kez 1907’de o-siyanobenzamid’in sentezi sırasında yan ürün olarak keşfedildiğinden beri ftalosiyanin ve metal türevleri ile çok yaygın olarak çalışılmaktadır. Diğer taraftan sentezlenen ftalosiyanin bileşikleri kumarin (2H-1-benzopiran-2-on) türevleri içermektedir. Kumarinler benzopiranlar olarak bilinen bileşiklerin bir grubuna aittir. Antioksidanlar ve antikoagülantlar olarak analizlerde, lazerlerde ve klinik uygulamalarda floresans işaretleyici olarak, parfümeri ve besinlerde katkı maddesi olarak önemli role sahip bir bileşik grubudur. Sentezlenen ftalosiyanin bileşiklerinin bazıları taç eter birimleri de içermektedir. Taç eterler ilk kez 1967 yılında C.J.Pedersen tarafından sentezlenmiştir. İlk bulunuşlarından itibaren taç eterler pek çok alanda, özellikle, organik ve anorganik katyon, anyon, nötr moleküllerin taşıyıcı olarak kullanılmaktadır. Alkali metallerin (Na+, K+) iç oyuğa girmesi ile biyolojik sistemlerde membranlar boyunca iyon taşınımı mümkün olabilmiştir. Florojenik kumarin grupları taşıyan taç eterler floresans spektroskopisinde kullanılırlar. Ayrıca ftalosiyanin ve taç eter gibi önemli iki yapının kombinasyonundan oluşan ftalosiyanin bileşiklerinin ilginç farmakolojik özellikler gösterebilecekleri düşünülmektedir. Metalli ve metalsiz ftalosiyaninlerin en önemli dezavantajı organik çözücüler ve sudaki çözünürlüklerinin düşük olmasıdır. Periferal pozisyonlarında taç eter makrohalkaları veya alkil/alkoksi gibi uzun zincirli gruplar içeren ftalosiyaninlerin organik solventlerdeki çözünürlüğünde artış görülmüştür. Doktora tez çalışma konusu kapsamında periferal ve periferal olmayan pozisyonlarda taç eter, alkil, alkiloksi grupları içeren orijinal çeşitli metalsiz ve metalli ftalosiyanin bileşikleri sentezlenmiştir. 1H-NMR, FT-IR, UV-VIS, MS MALDI-TOF analiz metodları kullanılarak yapıları karakterize edilmiş ve aynı zamanda floresans spektroskopisi teknikleri ile de floresans özellikleri incelenmiştir. ABSTRACT THE SYNTHESIS AND CHARACTERIZATION OF SOME PHTHALOCYANINES WITH COUMARIN DERIVATIVE Phthalocyanines (Pcs) are blue-green coloured synthetic compounds with high chemical and physical stability. The compounds and its metallo derivatives have been studied very extensively since its first discovery in 1907 as a by-product in the synthesis of o-cyanobenzamide. On the other hand, we synthesized phthalocyanines bearing coumarin (2H-1-benzopyran-2-one) moieties. The coumarins belong to a group of compounds known as the benzopyrones. Coumarins are a group of compounds that have important roles as antioxidants and anticoagulants for use in analysis; as fluorescent markers, in lasers and clinical use; as additives in food and cosmetics. Also, we synthesized phthalocyanines containing crown ether moieties. Crown ethers was first synthesized in 1967 by C.J.Pedersen. The ability of crown ethers to form stable complexes with cations, mainly with alkali and alkaline earth cations, has spurred interest in these compounds. Crown ethers bearing fluorogenic coumarin groups are used in fluorescence spectroscopy. A combination of two potentially promising units (i.e. phthalocyanines and crown ethers) has yielded products showing interesting properties. A major disadvantage of phthalocyanines and metallophthalocyanines are their low solubility in organic solvents or water. Crown ether or long chain groups, such as alkyl/alkoxy substitution enhances the solubility of phthalocyanines in common organic solvents. In PhD thesis study, we synthesized original some novel metal free and metallo phthalocyanines bearing crown ether, alkyl, alkyloxy groups on peripheral and unperipheral positions. The structure of compounds were characterized with using 1H-NMR, FT-IR, UV-VIS, MS MALDI-TOF analysis methods and their fluorescence properties were investigated by fluorescence spectroscopy techniques

Nono Hidroksi-2H-1-Benzopiran-2-on türevi Ftalosiyanin bileşiklerinin sentezi ve özelliklerinin incelenmesi

MONO HİDROKSİ-2H-1-BENZOPİRAN-2-ON TÜREVİ FTALOSİYANİN BİLEŞİKLERİNİN SENTEZİ VE YAPILARININ AYDINLATILMASI Kumarin (2H-1-benzopiran-2-on) ve bazı türevleri yararlı farmakolojik aktiviteye sahip doğal bileşiklerin önemli bir sınıfını oluştururlar. Antibakteriyel, antikoagülan, antikanserojenik, hipotermal gibi fizyolojik özellikleri ve etkin fluoresans vermelerinden dolayı bu tür bileşiklerin ve türevlerinin sentezi ile ilgili pek çok çalışma literatüre geçmiştir. Antikanserojen amaçlı kanser tedavisinde fotodinamik belirteç olarak kullanılan diğer önemli bir bileşik sınıfı da ftalosiyaninlerdir. Bu sınıf bileşikler kimyasal olarak kararlıdırlar ve fotodinamik aktiviteleri yüksektir. Yapılan bu çalışma, kumarin ve ftalosiyaninlerin önemli biyolojik ve kimyasal özellikleri dikkate alınarak gerçekleştirilmiş ve kumarin türevi ftalosiyaninler sentezlenerek literatüre ilk defa bu tür bileşiklerin girmesi hedeflenmiştir. Deneysel çalışma sırasında önce, başlangıç bileşiklerinden 7-hidroksi-4-metilkumarin Pechmann reaksiyonu ile sentezlenmiş, bir diğer başlangıç maddesi olan 7-merkapto-4-metilkumarin ise satın alınmıştır. Bu bileşikler ayrı ayrı 4-nitroftalonitril ile reaksiyona sokularak, 7-(3,4-disiyanofenoksi)-4-metilkumarin ve 7-(3,4-disiyanofeniltiyo)-4-metilkumarin sentezlenmiştir. Bu bileşiklerden 7-(3,4-disiyanofeoksi)-4-metilkumarin kolon kromatografisi ile THF kullanılarak saflaştırıldı. Daha sonra bu bileşikler üzerinden metalsiz ve çinko (II) metalli ftalosiyaninler sentezlendi. Sentezlenen kumarin türevi ftalosiyaninler çözünürlük farkından yararlanılarak, değişik çözücülerle ekstraksiyon işlemleri sonucu saflaştırıldılar. Sentezlenen 7-(3,4-disiyanofenoksi)-4-metilkumarin, 7-(3,4-disiyanofeniltiyo)-4-metilkumarin ve kumarin türevi ftalosiyaninlerin yapıları UV-Visible, FT-IR, H-NMR ve C-NMR spektrumları ile aydınlatıldı. Anahtar Kelimeler: Kumarin (2H-1-benzopiran-2-on), Ftalosiyanin Kimya Anabilim Dalı, Organik Kimya Programı Mayıs 2005 A. Aslı ESENPINAR SUMMARY THE SYNTHESIS OF SOME MONO HYDROXY- 2H-1- BENZOPYRAN-2-ONE DERIVATIVES OF PHTHALOCYANIN COMPOUNDS AND CHARACTERIZATION OF THEIR STRUCTURES Coumarin (2H-1-benzopyran-2-one) and their derivatives are an important class of natural compounds. They have useful pharmaceutical activities. These compounds have many biological activities such as antibacterial, anticoagulant, anticarcinogenecity, hypothermal. Another important class of compounds are phthalocyanines. They have anticarcinogenecity properties and are chemically stable which are being used as PDT (in Photodynamic Theraphy). In this study, synthesis of coumarins and phthalocyanines were realized due to their spacious biological and chemical properties. Consequently, phthalocyanines with coumarin derivative were performed. The goal of this work is the preparation of some novel phthalocyanines containing coumarin moieties. In experimental study, at first 7-hydroxy-4-methylcoumarin was synthesized by Pechmann condensasyon reaction. Another compound, 7-mercapto-4-methylcoumarin was purchased. Then these compounds were treated with 4-nitrophthalonitrile respectively. 7-(3,4-Dicyanophenoxy)-4-methylcoumarin and 7-(3,4-dicyanophenylthio)-4-methylcoumarin were obtained. 7-(3,4-Dicyanophenoxy)-4-methylcoumarin was purified with THF by using silica gel column chromatography. Metal free and metallo phthalocyanines with zinc (II) metal were synthesized from their precursor. The purification of these phthalocyanines with coumarin moieties were made by extraction with various solvent. The structure of new 7-(3,4-dicyanophenoxy)-4-methylcoumarin, 7-(3,4-dicyanophenylthio)-4-methylcoumarin and phthalocyanines with coumarin moieties were determined based on the results of spectroscopic methods such as UV-Visible, FT-IR, H-NMR and C-NMR. Keywords: Coumarin (2H-1-benzopyran-2-one), Phthalocyanin May 2005 A. Asl

HEAVY METAL ANALYSIS OF THE GEDIZ RIVER, TURKEY

This paper drives the mathematical discussion of heavy metals level of As, Pb, Cd, Ni, Cu, Co and Cr in the samples collected from the Gediz Delta. In 2006, several scientists from Ege University Faculty of Fisheries declared the data of eight different stations belonging to the basin to observe the natural and anthropogenic effect in the sediment of the delta. Based on these data, we try to look at the results with a more comprehensive mathematical perspective and attract the attention to the Gediz Basin with holistic discussions. Land use in the watershed and a data set comprised of observations of 7 heavy metals from 8 locations are described. In order to interpret the anthropogenic effect of contamination of the river, statistical analyses are performed. In the study, by investigation a covariance matrix indicates the strength of bivariate relationships, a dendrogram shows hierarchical clustering into different groups, and factor analysis indicates three distinct eigenvectors. In addition, one can find three indices Contamination Factor (CF), Enrichment Factor (EF), and Pollution Load Index (PLI) developed by Canadian sedimentologists. The fact that the findings in the discussion belong to 2006 permits the authors to understand the recent condition more clearly. The level of pollution from the past is comparable.WOS:00050193660006

Photophysical, photochemical and BSA binding/BQ quenching properties of quaternizable coumarin containing water soluble zinc phthalocyanine complexes

The non-peripherally (np-QZnPc) and peripherally (p-QZnPc) tetrakis-[7-oxo-(3-[(2-diethylaminomethyliodide)ethyl)]-4-methylcoumarin]-Phthalocyaninatozinc complexes have been prepared by quaternization of non-peripherally and peripherally tetrakis[7-oxo-(3-[(2-diethylamino)ethyl)]-methylcoumarin] phthalocyaninato zinc complexes with methyliodide in dimethylsulfoxide (DMSO). The new quaternized zinc phthalocyanine complex (np-QZnPc) has been characterized by elementel analysis, MALDI-TOF, IR and UV-vis spectral data. The photophysical and photochemical properties of the peripherally and non-peripherally quaternized tetrakis-3-[(2-diethylamino)ethyl]-7-oxo-4-methylcoumarin substituted zinc phthalocyanines are reported. The effects of the position of the substituents and the aggregation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes for complexes np-ZnPc/p-ZnPc in DMSO and for complexes np-QZnPc/p-QZnPc in DMSO, phosphate buffered solution (PBS) and PBS+Triton-X 100 solutions. The fluorescence of the tetra-substituted quaternized zinc phthalocyanine complexes (np-QZnPc/p-QZnPc) are effectively quenched addition of 1,4-benzoquinone (BQ) and this study also presented the ionic zinc phthalocyanine complexes strongly bind to bovine serum albumin (BSA). (C) 2011 Elsevier B.V. All rights reserved.WOS:0002918325000352-s2.0-79956273333PubMed: 2153649

MATHEMATICAL MODELING OF COVID-19 PHENOMENON; THE CASES: GERMANY, ISRAEL AND CANADA

Epidemic diseases are described as a pandemic that affects the enormous majority of the world, spreads rapidly among people, and causes deaths. Negative effects, the number of casualties, rates of spread, and the duration of the commencement and the end of such outbreaks differ from each other and depend on the regions of effect, the processes of the vaccination studies, and cure. Recently a virus has been discovered which has caused a pandemic that has threatened all the world: COVID-19. It is a kind of coronavirus that emerged originally among chickens in 1960s. This essay introduces COVID-19 cases using a mathematical method. It carefully examines data from worldometers, makes models, and estimations. The data discussed under titles such as Total Case, Outside China, Active Case, Total Cured, Critical Case, Germany, Israel, and Canada are analyzed without isolating their context. While the maximum-minimum ranges and standard deviations of the variables are displayed by a descriptive analysis, binary relations are observed by the correlation matrix. While the homogeneous distribution of the data is determined by factor analysis, hierarchical groups are expressed by cluster analysis. Future estimations are presented by data models presented to the reader with nine different variables.WOS:00058849360003

Synthesis and properties of crown ether functionalized coumarin substituted zinc phthalocyanine

The novel 6,7-[15-crown-5]-3-[p-(2,3-dicyanophenoxy)phenyl]coumarin (1) and its non-peripherally substituted zinc phthalocyanine complex (2) have been prepared and characterized by elemental analysis, H-1 NMR (for compound 1), MALDI-TOF, FT-IR and UV-Vis spectral data. Fluorescence intensity changes of compound 1 have been determined by addition of Na+ or K+ ions at 25 degrees C in THF. The effects of the chromenone crown ether substituent of the phthalocyanine molecule on the photophysical (fluorescence quantum yield and lifetime) and photochemical (singlet oxygen generation and photodegradation) properties were also investigated. The fluorescence of the zinc phthalocyanine complex is effectively quenched by addition of 1,4-benzoquinone (BQ). (C) 2011 Elsevier Ltd. All rights reserved.Research Foundation of Marmara University, Commission of Scientific Research Project (BAPKO)Marmara University [FEN-A-090909-0302]We are thankful to the Research Foundation of Marmara University, Commission of Scientific Research Project (BAPKO) [FEN-A-090909-0302] for supporting this study.WOS:0002943167000202-s2.0-8005231152

Synthesis, characterization, and photophysical and photochemical properties of 3-(4-phenyloxy)coumarin containing metallo- and metal-free phthalocyanines

The synthesis of novel zinc, cobalt, indium, and metal-free phthalocyanines carrying four 3-(4-phenyloxy)couma- rins in the periphery/nonperiphery were prepared by cyclotetramerization of 3-[4-(3,4-dicyanophenyloxy)phenyl]coumarin (2)/3-[4-(2,3- dicyanophenyloxy)phenyl]coumarin (3). The novel chromogenic compounds were characterized by elemen- tal analysis, 1H NMR, mass spectra, F-IR, and UV-vis spectral data. The effects of the coumarin units on the zinc, indium, and metal-free phthalocyanine complexes (2a/3a, 2c/3c, 2d/3d) were also investigated.WOS:0003455598000152-s2.0-8491579148

Chromenone 12-crown-4 substituted zinc phthalocyanine complexes: Investigation of spectral, photophysical and photochemical properties

The synthesis of novel 6,7-[(12-crown-4)-3-[p-(3,4-dicyanophenoxy)phenyl]coumarin (1), 6,7-[(12-crown-4)-3-[p-(2,3-dicyanophenoxy)phenyl]coumarin (2), and their corresponding tetra-(chromenone 12-crown-4)-substituted zinc (II) phthalocyanine complexes (3 and 4) have been prepared. These new compounds have been characterized by elementel analysis, H-1 NMR (1 and 2), MALDI-TOF, IR and UV-Vis spectral data. The fluorescence intensity changes for 1 and 2 by addition of Na+ or K+ ions have been determined at 25 degrees C in THF. Intensity of the binding Na+- and K+-complexes (1 and 2) have decreased. The effects of the chromenone crown ether on the phthalocyanine molecule concerning photophysical and photochemical properties are also investigated. Photodegredation, singlet oxygen, fluorescence quantum yields, and fluorescence lifetimes of zinc phthalocyanine complexes (3 and 4) are also examined in DMSO. (C) 2011 Elsevier B.V. All rights reserved.Scientific the Research Found (BAPKO) of Marmara UniversityMarmara University [FEN-A-090909-0302]We are thankful to the Scientific the Research Found (BAPKO) (FEN-A-090909-0302) of Marmara University.WOS:0002966750000942-s2.0-80052933135PubMed: 2179511

Synthesis and electrochemical properties of crown ether functionalized coumarin substituted cobalt and copper phthalocyanines

The synthesis of novel 6,7-[15-crown-5]-3-[p-(3,4-dicyanophenoxy)phenyl]coumarin (1)/6,7-[15-crown-5]-3-[p-(2,3-dicyanophenoxy)phenyl]coumarin (2) and their peripherally/non-peripherally cobalt and copper phthalocyanine complexes (3-6) have been prepared and characterized by elementel analysis, H-1-NMR, MALDI-TOF, FT-IR and UV-Vis spectral data. Fluorescence intensity changes of compound 1 and 2 have been determined by addition of Na+ or K+ ions at 25 degrees C in THF. The effect of substitution type on the redox and aggregation behaviour of the compounds was investigated by voltammetry and in situ spectroelectrochemistry. (C) 2011 Elsevier B.V. All rights reserved.Research Foundation of Marmara UniversityMarmara University [FEN-A-090909-0302]We are thankful to the Research Foundation of Marmara University, Commission of Scientific Research Project (BAPKO) FEN-A-090909-0302.WOS:00029655760000