hasalettin deligöz

Identification of radiation-induced radical structure in azocalix[4]arene: an EPR study

Magnetic Resonance in Chemistry, Aug 16, 2013

A macrocyclic azocalix[4]arene (1) based ester derivative was synthesized. The single crystals of... more A macrocyclic azocalix[4]arene (1) based ester derivative was synthesized. The single crystals of azocalix[4]arene were produced by slow evaporation of concentrated ethyl acetate solutions. These single crystals were exposed to 60Co gamma rays with a dose rate of 0.980 kGy h‐1 for 48 and 72 h to produce a stable free radical. Electron paramagnetic resonance (EPR) measurements were performed in three mutually perpendicular planes of the single crystal in the magnetic field, in addition, temperature dependence of the EPR signal was studied between 120 K and 450 K. The spectra were found to be temperature and angular dependent. Analysis based on the spectra recorded showed that a free radical was formed by fission of a C–H bond. This radical is described as •CaHCbH3 The averages of the principal values of the hyperfine parameters and g‐factor are: g = 2.0034, AHa = 1.28 mT, AH1=H2 = 1.00 mT, and AH3 = 0.49 mT. Copyright © 2013 John Wiley &amp; Sons, Ltd.

Thermal Behaviors of Bisazocalix[4]arene Derivatives

Polycyclic Aromatic Compounds, 2016

ABSTRACT In this article, calix[4]arene (4) was prepared by debutylation and hydrolyses reacting ... more ABSTRACT In this article, calix[4]arene (4) was prepared by debutylation and hydrolyses reacting from 25,27-dibenzoyl-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene (2). Azocalix[4]arenes (6a-c) were coupled by linking 4-methoxy, 4-ethyl, and 4-nitroaniline to calix[4]arene (4) through a diazo-coupling reaction. Thermal behavior characteristics and decomposition routes of 25,26,27,28-tetrahydroxy-11,23-di(tert-butyl)-5,17-(p-substitue phenyl)azocalix[4]arene (6a-c) were investigated in air atmosphere by means of thermogravimetry (TG), differential thermogravimetry (DTG), and differential thermal analysis (DTA) analyses. It was found that the decomposition of all compounds complete with two exothermic stages which corresponded to removal of substitute groups (methoxy-, ethyl-, nitro-) and second stage rest of structure decomposition.

Synthesis and evaluation of fluorescence properties of Cu2+selective azocalix[4]arenes and their application in living cell imaging

Sensors and Actuators B: Chemical, 2016

The present article deals with the detailed complexation study along with exploration of possible... more The present article deals with the detailed complexation study along with exploration of possible utilization of 25,26,27,28-tetra-hydroxy-11,23-di-(tert-butyl)-5,17-di-(2-antracenyl)azocalix[4]arene(7) and 25,26,27,28-tetra-hydroxy-11,23-di-(tert-butyl)-5,17-di-(1-pyreneyl)azocalix[4]arene (8) as bio-imaging fluorescent probe to detect Cu2+ in human colon cell line, SW-620, observed by fluorescence microscopy. Complexation properties of ligands 7 and 8 toward selected transition metal ions have been investigated by UV–vis and fluorescence spectroscopies. It has been noticed that ligands 7 and 8 are not only proved to be an efficient Cu2+selective chromoionophore but also possess effective fluorescence properties by complexing with Cu2+ ions. The FTIR spectroscopic method has also been applied for further confirmation of the complexation phenomenon of ligands 7 and 8 with metal ion and were found to be adequate. Moreover, fluorescence microscopy studies showed that ligand 7 may be used as fluorescent probe to detect Cu2+ in living cells.

The synthesis and characterization of azocalix[4]arene based chemosensors and investigation of their properties

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2015

In the present study, azocalix[4]arenes were prepared by linking 4-methoxy, 4-methyl, 4-ethyl, 4-... more In the present study, azocalix[4]arenes were prepared by linking 4-methoxy, 4-methyl, 4-ethyl, 4-chloro, 4-bromo and 4-nitroaniline to calix[4]arene through a diazo-coupling reaction. A new family of azocalix[4]arene tetraester derivatives, (4a-f), have been prepared with the incorporation of ethyl ester units to azocalix[4]arene. Characterization of the synthesized azocalix[4]arenes was carried using elemental analyses, UV-vis, FT-IR and (1)H NMR spectroscopic techniques. The effect of varying pH levels and solvent types on the absorption ability of azocalix[n]arenes substituted with electron-donating and electron-withdrawing groups was examined. Thermal decomposition of azocalix[4]arene derivatives (4a-f) was investigated by means of thermogravimetry (TG), differential thermogravimetry (DTG) and differential thermal analysis (DTA) analyses. In conclusion of the examination of the extraction we found a selectivity characteristic of these compounds toward Ag(+), Hg(+) and Hg(2+) cations.

Di-substituted azocalix[4]arenes containing chromogenic groups: synthesis, characterization, extraction, and thermal behavior

Tetrahedron, 2013

In this study, the synthesis of chromogenic di-substituted azocalix[4]arene derivatives is descri... more In this study, the synthesis of chromogenic di-substituted azocalix[4]arene derivatives is described. Six novel azocalix[4]arenes (4a–f)were prepared by linking 4-methoxy, 4-methyl, 4-ethyl, 4-chloro, 4-bromo, and 4-nitroaniline to 25,26,27,28-tetrahydroxy-11,23-di-(tert-butyl)calix[4]arene through a diazo-coupling reaction, and were characterized by elemental analysis, FTIR, 1H NMR spectra and thermogravimetric analysis (TGA). The complexing properties of these compounds were studied by the liquid–liquid extraction of selected metal cations (Sr2+, Ag+, Hg+, Hg2+, Co2+, Ni2+, Cu2+, Pb2+, Cr3+, Al3+). It has been observed that di-substituted azocalix[4]arenes showed a high affinity for Ag+, Hg+, and Hg2+ ions, but almost no affinity to other metals. The colors of these azocalix[4]arenes were compared with respect to effect of varying pH on the absorption ability. Thermal behaviors of these compounds were also reported by means of thermogravimetry (TG) and thermal analysis (DTA).

Studies on Compounds of Uranium(M) with Two vic Dioxime Derivatives of Gilixi[4]Arene

Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 1998

... 3-3 CD Gutsche and K C Nam, J Am Chem SOC , I-14.6153 (1988) 23 H Deligoz, M Tavasli and M Yi... more

Synthesis and Ion Binding Properties of a p-Keto-oxime and a vic -Dioxime Derivative of Calix[6]arene

Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 1996

... 22. M. Yilmaz, and H. Deligoz, Synth. React. Inorg. Met. -0rg. Chem., 3 67 (1993). 23. $. Can... more

Synthesis and Metal Complexation of Avic-Dioxime Derivative of Calix [6] Arene

Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 1993

... T. Nagasaki, S. Shinkai, and T. Matsuda, J. Chern. SOC., Perkin Trans. I., 2617 (1990). 12. M... more

Ab initio studies of NMR chemical shifts for calix[4]arene and its derivatives

Structural Chemistry, 2009

... Izzet Kara Æ Hasan Hüseyin Kart Æ Nuri Kolsuz Æ O¨ zlem O¨ zen Karakus Æ ... I. Kara (&am... more ... Izzet Kara Æ Hasan Hüseyin Kart Æ Nuri Kolsuz Æ O¨ zlem O¨ zen Karakus Æ ... I. Kara (&amp;amp;amp;amp;amp;amp;) Faculty of Education, Department of CIET, Pamukkale University, Denizli 20070, Turkey e-mail ... Dr. Celal SIMSEK (Dean) for the financial support of the research laboratory in which the ...

Synthesis and structure elucidation of 25,26,27,28-tetramethylcalix[4]arene tetraketone using 1D and 2D NMR spectroscopies

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2010

The (1)H and (13)C NMR spectra of the new calix[4]arene-based tetraketone were completely assigne... more The (1)H and (13)C NMR spectra of the new calix[4]arene-based tetraketone were completely assigned by one- and two-dimensional homo- and heteronuclear experiments ((1)H-(1)H COSY, (1)H-(13)C HMQC, and HMBC) at 400 and 100MHz, respectively, at 25 degrees C standard pulse sequence. (1)H and (13)C spectra were measured at room temperature for 25,26,27,28-tetramethylcalix[4]arene tetraketone (1). (13)C[(1)H], DEPT and NMR techniques were used to distinguish the methyl, methylene and methine carbon resonance signals of calix[4]arene 1. Correlation of 1D ((1)H, (13)C[(1)H], DEPT) and 2D (HMQC and HMBC) NMR data was used to completely assign various overlapping and broad signals of calix[4]arene 1. Heteronuclear multibond correlation (HMBC) studies were used to completely assign various carbon resonances. Our results show that the conformation of calix[4]arene 1 in the solution is very similar to the cone conformation reported in the literature.

Identification of radiation‐induced radical structure in azocalix[4]arene: an EPR study

Magnetic Resonance in Chemistry, 2013

A macrocyclic azocalix[4]arene (1) based ester derivative was synthesized. The single crystals of... more A macrocyclic azocalix[4]arene (1) based ester derivative was synthesized. The single crystals of azocalix[4]arene were produced by slow evaporation of concentrated ethyl acetate solutions. These single crystals were exposed to 60Co gamma rays with a dose rate of 0.980 kGy h‐1 for 48 and 72 h to produce a stable free radical. Electron paramagnetic resonance (EPR) measurements were performed in three mutually perpendicular planes of the single crystal in the magnetic field, in addition, temperature dependence of the EPR signal was studied between 120 K and 450 K. The spectra were found to be temperature and angular dependent. Analysis based on the spectra recorded showed that a free radical was formed by fission of a C–H bond. This radical is described as •CaHCbH3 The averages of the principal values of the hyperfine parameters and g‐factor are: g = 2.0034, AHa = 1.28 mT, AH1=H2 = 1.00 mT, and AH3 = 0.49 mT. Copyright © 2013 John Wiley & Sons, Ltd.

A study on thermal behaviors of mono ethyl ester azocalix[4]arene derivatives

Journal of Thermal Analysis and Calorimetry, 2014

In the present study, thermal stabilities of five new family of azocalix[4]arene mono ethyl ester... more In the present study, thermal stabilities of five new family of azocalix[4]arene mono ethyl ester derivatives, 4a–e, were investigated using thermogravimetry, differential thermogravimetry, and differential thermal analysis methods. It was found that all compounds showed thermal stability up to 236 °C averagely. After this temperature, decomposition of compounds starts gradually. The decomposition routes of 4a–c compounds are similar and occur with two stages. Ester alkyl groups decompose and remove from the structure in the first stage. Second stage corresponds to rest of structure decomposition. The decomposition routes of the 4d–e compounds are different from the decomposition routes of the 4a–c compounds. These compounds include halogen, and decomposition reactions realize with three and four stages respectively.

Synthesis and characterization of azocalix[4]arene ester and ketone derivatives incorporated in a polymeric backbone with bisphenol-A and their cation-binding properties

Journal of the Iranian Chemical Society, 2012

This study comprises synthesis and characterization of azocalix[4]arene compounds having copolyme... more This study comprises synthesis and characterization of azocalix[4]arene compounds having copolymeric structures. The novel bisazocalixphenol-A and copolymer containing pendant azocalix[4]arene units with ester (5) and ketone (6) functionalities at their lower rim have been synthesized via diazo-coupling reaction. The phase transfer study is performed by liquid–liquid extraction method. It has been deduced from the observations that their precursors 25,26,27-tribenzoyloxy-28-hydroxy-5-(4-aminophenylazo)calix[4] arene (3), 25,27-diacetoniloxy-26,28-dihydroxy-5,17-(4-aminophenylazo)calix[4]arene (4) and bisazocalixphenol-A (5) show a good phase transfer affinity towards selected transition metal cations, unlike copolymer (6). These compounds are studied by the selective extraction of Fe3+ cation from the aqueous phase into the organic phase and it is carried out using compounds 1–6. It is observed that the reduced azocalix[4]arene 4 is the most efficient (82.93 %) carrier of all compounds (3–6) in the extraction of Fe3+ at pH 5.4.

A Brief Review on the Thermal Behaviors of Calixarene-Azocalixarene Derivatives and Their Complexes

Journal of Macromolecular Science, Part A, 2012

Calixarenes have been widely regarded as an important class of macrocyclic host molecules, due to... more Calixarenes have been widely regarded as an important class of macrocyclic host molecules, due to their efficient and highly selective binding properties towards specific metal ions. Azocalixarenes, containing single conjugated chromophore azo (‒N˭N‒) group in p- positions are synthesized by “one-pot” procedures with satisfactory yields. Their structures (as solid and liquid) are elucidated by UV-Vis, FT-IR, H and C-NMR spectroscopic methods, as well as elemental analysis techniques. Thermal stability of calixarenes is very important because of their potential applications in high temperature processes such as the dyeing of textile fibers, ink-jet printing and photocopying and in high technology areas such as lasers and electro-optical devices. In this paper all the thermal studies of parent calix[n]arenes, azocalix[4]arene derivatives and their complexes containing lower and upper rim functionalized groups are reported. All the thermo analytical results such as the temperature ranges and peak temperatures of thermal decomposition steps and amount of volatile pyrolysis products were emphasized. The effect of substituted groups and their positions on the thermal stability of calixarenes were investigated.

Characterization of polypyrrole/azocalix[4]arene salts: Electrical properties and thermal stability

Journal of Applied Polymer Science, 2010

Aysegul Uygun,1 Ayse Gul Yavuz,1 Songul Sen,2 Fatma Deligoz,1 Ozlem Ozen Karakus,3 Hasalettin Del... more

Investigation of the Formation of Humic Acids from Lignite by Using Model Compounds

Energy Sources, 1991

... llgin lignite (original) 5.10 1.12 Ilgin lignite (HA) 8.20 4.80 Tunsbilek lignite (original) ... more

A versatile approach toward chemosensor for Hg2+ based on para-substituted phenylazocalix[4]arene containing mono ethyl ester unit

Dyes and Pigments, 2014

ABSTRACT In the present study, six new azocalix[4]arenes have been synthesized by reacting calix[... more ABSTRACT In the present study, six new azocalix[4]arenes have been synthesized by reacting calix[4]arene with p-substituted aniline and ethyl bromoacetate. Characterization of these compounds has been used by elemental analyses, UV Vis, FT-IR and H-1 NMR spectroscopic studies. Their phase transfer studies have been performed by using liquid liquid extraction procedure. With respect to the chromogenic behavior of hosts upon metal ion complexation, mono ethyl ester azocalix[4]arene derivatives have shown a significant selectivity toward Hg2+ and Hg+ over many other cations. It has been deduced that these new compounds are selective ionophores toward metal cations (Na+, K+, Sr2+, Ag+, Hg+, Hg2+, Co2+, Ni2+, Cu2+, Zn2+, Cr3+, Al3+ and La3+).

Efficient and Selective Extraction of Fe 3+ by Mono- and Di-Azocalix[4]arene Derivatives

Analytical Letters, 2010

... 1995). Reports on the binding of iron(III) metal ions are still limited with respect to those... more

Synthesis and characterization of tetrakis- derivatives of bisphenol-A with 4-phenylazoaniline and 5-(4-aminophenylazo)-25,26,27-tribenzoyloxy- 28-hydroxycalix[4]arene

Journal of Applied Polymer Science, Apr 19, 2011

The synthesis of tetrakis‐ derivatives of bisphenol‐A containing azo groups at their 2,2′,6,6′‐po... more The synthesis of tetrakis‐ derivatives of bisphenol‐A containing azo groups at their 2,2′,6,6′‐positions is reported. Novel examples of bisphenol‐A, coupled with diazonium salts and derived from 4‐phenylazoaniline and 5‐(4‐aminophenylazo)‐25,26,27‐tribenzoyloxy‐28‐hydroxycalix [4]arene, have been synthesized. It has been observed that the coupling reaction of diazonium salt obtained from 4‐phenylazoaniline with bisphenol‐A gives tetrakis‐ while those derived from 5‐(4‐aminophenylazo)‐25,26,27‐tribenzoyloxy‐28‐hydroxycalix [4]arene give partially substituted bisphenol‐A analogues. The newly prepared tetrakis‐azo substituted bisphenol‐A compounds (1 and 2) are characterized by using UV‐vis, FT‐IR, 1H‐NMR spectroscopic methods as well as elemental analysis techniques. These azo compounds give rise to bathochromic shifts in the absorption spectra, which can even be detected by “naked eye.” © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Synthesis and characterization of three novel azocalix[4]arene Schiff base derivatives and their selective copper extraction

Journal of The Iranian Chemical Society, Jan 3, 2012

ABSTRACT The synthesis and characterization of three novel Schiff bases of azocalix[4]arene and t... more ABSTRACT The synthesis and characterization of three novel Schiff bases of azocalix[4]arene and their selective copper extraction are described. The preparation of azocalix[4]arenes (1c, 2c and 3c) has been achieved by the condensation of 2-hydroxy-3-methoxybenzaldehyde with the amine group of upper rim mono-, di- and tetra-(aminophenylazo) calix[4]arene in ethanol. The synthesized products (1c, 2c and 3c) are characterized by both 1H and 13C NMR techniques, IR spectroscopy and elemental analysis. Extraction capabilities of interested derivatives of azocalix[4]arene from aqueous phase into organic phase are also examined. While extraction of Ag+, Hg+ and Hg2+ cations gave strong complexes with azo groups, extraction of Cu2+ cation is found to be highly effective with –CH=N– and neighboring –OH groups.

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