Yaşar Gök

Synthesis and Characterization of New Metal-free and Metallophthalocyanines Containing Macrobicyclic Moieties

The metal-free 5,10 and metallophthalocyanines 11–13 (M = Ni, Zn, Cu) fused in peripheral positions with diazadithiatetraoxa or diazahexaoxamacrobicycles have been prepared by bicyclotetramerization of the newly synthesized isoindolinediimine derivatives of cryptands 4,9 or dicyano substituted macrobicycles 3,8 in the presence of the corresponding metal salts or a strong organic base. The new compounds have been characterized by elemental analysis, 1H and 13C-NMR, IR, UV-visible and mass spectral data.

Zinc(II) phthalocyanine fused in peripheral positions octa-substituted with alkyl linked carbazole: Synthesis, electropolymerization and its electro-optic and biosensor applications

Zinc(II) phthalocyanine fused in peripheral positions octa-substituted with alkyl linked carbazole has been prepared by cyclomerization reaction of 4,5-bis(6-carbazole-9-yl-hexylsulfanil)phthalonitrile in the presence of anhydro Zn(II) acetate and a strong organic base (DBU). Synthesis steps were optimized and higher efficiency synthesis was achieved. The purpose of combining of carbazole moieties with phthalocyanine on the peripheral position is to enhance some properties such as photo and electrochemical properties because of strong electron-donating properties of carbazole group. This molecule has been electrochemically polymerized and the electrical and optical properties of the resulting conductive polymer have been investigated. Amperometric detection was carried out following oxygen consumption at -0.7V vs. the Ag reference electrode in phosphate buffer (50mM, pH 6.0). The novel biosensor showed a linear amperometric response for glucose within a concentration range of 0.05mM to 1.5mM (LOD: 0.024mM). This result shows that modification of the proposed biosensor by copolymerization have provided to give perfect response to different glucose concentrations. Because of its superior spectral and electrochemical properties and contained zinc metal which can act as a mediator during biochemical reactions, this material has been used as a glucose biosensor platform to detection for real samples.

Fourier transform infrared spectral evaluation for the differentiation of clinically relevant Trichophyton species.

Routine mold identification methods have been established to provide actual data to facilitate reliable diagnoses in clinical laboratories, as well as the management of infection and health practice planning, particularly for dermatophytes. Some species of the Trichophyton genera, particularly T. rubrum and T. mentagrophytes complexes, exhibit more complexity in species recognition. In this study, the intriguing technique of Fourier-transform infrared (FT-IR) spectroscopy is evaluated for species recognition of Trichophyton spp. A total of 32 reference isolates, belonging to T. mentagrophytes (n=7), T. rubrum (n=21) complexes and Arthroderma spp. (n=4), were included in the study. Numerous spectral window FTIR spectroscopy data were analyzed by principal component analysis and hierarchical clustering was performed. There were not any spectral ranges presenting clusters at the main Trichophyton species (e.g. T. rubrum, T. mentagrophytes and Arthroderma spp.). Notably, only T. violaceum (including T. yaoundei and T. soudanense) was clustered in several ranges. In intra-species evaluation, T. erinacei, belonging to the T. mentagrophytes complex, was distinguishable by FT-IR spectroscopy with different spectral range calculations. We suggested that further research with several reference and clinical isolates of Trichophyton species will be crucial to accurately identify intra-species of T. rubrum and T. mentagrophytes complexes.

Evaluation of Mononuclear Ni(II) Complex of a Tetra-cryptanded Vic-dioxime and its Model Compound 14-Membered N2O2S2-Macrobicyclic Ligand as Pb2+, Cd2+, and Hg2+ Extractants

Abstract A macrobicyclic ligand and its mononuclear Ni(II) complex were studied as extractants for Pb2+, Cd2+, and Hg2+. The metal picrates were used for extraction experiments. The solutions of the ligands in chloroform and dichloromethane were used as organic phases. The most effective transport was observed for Cd2+ picrate among the tested metal picrates with dichloromethane. The effect of pH on the extraction efficiency was evaluated for both organic solvents. The cations were stripped from the organic phase with 0.75 M nitric acid and the ligands were determined spectrophotometrically in the proper wavelength. The recovery% values of the ligands were calculated at pH 3.5.

Synthesis and characterization of new metal-free and nickel(II) phthalocyanines containing hexaazadioxa macrobicyclic moieties

Novel symmetrically tetrasubstituted metal-free and metallophthalocyanines (5) and (6) which contain four hexaazadioxamacrobicycles on peripheral positions, have been synthesized. Macrobicyclic compound 3 and has been prepared by reaction of (1,3,6,9,11,14- hexaazatricyclo[12.2.1.16,9])octadecane (1) with 1,2-bis(2-iodoethoxy)-4,5-dibromobenzene (2). Compound 4 has been synthesized by reaction of compound 3 with CuCN in dry DMF. The target symmetrical phthalocyanines were separated by column chromatography and characterized by elemental analyses, 1H, 13C–NMR, IR, UV–Visible and FAB mass spectroscopies.

Synthesis and characterisation of new porphyrazinato magnesium containing macrobicyclic moieties

Novel porphyrazinato magnesium (MgPz) containing symmetrically four diaza-tetrathia-macrobicycles on peripheral positions was synthesized by the cyclotetramerisation reaction of 5,8,16,23-tetrathia-1,12-diazabicyclo[9.7.7]pentacosane-6-en-6,7-dicarbodinitril (9), which was prepared by sequence reaction of N-tosyl-bis[3-bis(tosyloxypropyl)] amine (1) and disodium cis-1,2-dicyano-1,2-ethylenedithiolate (8). Elemental analysis, IR, NMR, MS and UV–vis data confirmed the ability of bulky cryptand moieties to induce steric isolation of Pz core in the solid state.

Synthesis and characterization of new copperphthalocyanine carrying mixed donor macrocyclic moieties

The new phthalocyanine peripherally substituted with a twelve-membered dioxadiaza macrocycle was synthesized by cyclotetramerization of 1,2-bis(2-{4′-[(4′-methylphenyl)-sulphonyl]-1′,7′-dioxa-4′,10′-diazacyclododecane})-4,5-dicyanobenzene (4) which was obtained from 1,2-bis(2-{4′-[(4′-methylphenyl)sulphonyl]-1′,7′-dioxa-4′,10′-diazacyclododecane})-4,5-dibromobenzene (3). Metallophthalocyanine was also prepared by the reaction of the dicyano-substituted macrocycle in the presence of anhydrous CuCN. The new compounds were characterized by a combination of elemental analysis, 1H and 13Cu2009NMR, IR, electronic and mass spectroscopies.

ATR-FTIR Spectroscopy Highlights the Problem of Distinguishing Between Exophiala dermatitidis and E. phaeomuriformis Using MALDI-TOF MS

The present study compared two chemical-based methods, namely, matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-TOF MS) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, to understand the misidentification of Exophiala dermatitidis and Exophiala phaeomuriformis. The study utilized 44 E. dermatitidis and 26 E. phaeomuriformis strains, which were partially treated with strong acids and bases for further evaluation. MALDI-TOF MS and ATR-FTIR spectroscopy data of the two Exophiala species were compared. Data groupings were observed for the chromic acid- and nitric acid-treated species when the black yeast sources were categorized as creosoted-oak sleepers, concrete sleepers, or dishwasher isolates. The MALDI-TOF MS data for the metalloenzyme-containing regions were consistent with the ATR-FTIR spectroscopy data. These results indicated that environmental isolates might contain metals not found in human isolates and might interfere with chemical-based identification methods. Therefore, MALDI-TOF MS reference libraries should be created for clinical strains and should exclude petroleum-associated environmental isolates.

The first synthesis and characterization of new metal-free and metallophthalocyanine containing 33-membered crown ether moieties

The synthesis and characterization of novel metal-free and metallophthalocyanines, fused symmetrically in non-peripheral positions with four octaoxamacrocycle has been synthesized by cyclotetramerization of the 2,5,8,11,14,20,23,26,29,32-decaoxatricyclo [31.2.2.115,19]octatriconta-1(36),15,17,19(38),33(37),34-hexaene-34,35-dicarbonitrile (5) which was prepared by the reaction of 3,6-bis[2-(2-{2-[2-(toluene-4-sulphonyl)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-phthalonitrile (3) and 1,3-dihydroxybenzene (4). The novel compounds were characterized by using elemental analysis, 1H, 13C NMR, IR, UV-vis and MS spectral data.

The synthesis and characterization of new phthalocyanines containing hexaazadithia macrobicyclic moieties

The new metal-free and metallo phthalocyanines (4) and (5) bearing four tetrasubstituted hexaazadithia macrobicycles on peripheral positions, have been synthesized. Phthalonitrile (3) has been synthesized from the reaction of (1,3,6,9,11,14 hexaazatricyclo [12.2.1.16,9]) (1) and 1,2-bis(2-iodomercaptoethyl)-4,5-dicyanobenzene (2). The new compounds were characterized by elemental analysis, and IR, 1H, 13C-NMR, UV-Visible and mass spectral data.