Yasemin Baygu

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.

Comparative Investigation of Peripheral and Nonperipheral Zinc Phthalocyanine-Based Polycarbazoles in Terms of Optical, Electrical, and Sensing Properties

In this study, nonperipherally alkyl-linked carbazole conjugated novel zinc(II) phthalocyanine was synthesized by cyclotetramerization reaction of 6-(9 H-carbazol-9-yl)hexane-1-thiol and 3,6-bis(tosyloxy) phthalonitrile in a one-step reaction. Optical, electrical, and sensing properties of this super structured polycarbazole obtained by electropolymerization are compared with peripherally alkyl-linked polycarbazole-based zinc(II) phthalocyanine. It has been found that the attachment of alkyl-linked carbazoles to the phthalocyanine molecule in either peripheral or nonperipheral positions has a great effect on the optical and electrical properties and sensing ability of the resulting polycarbazole derivatives. P(n-ZnPc) has the highest electrochromic contrast (70.5%) among the derivatives of zinc(II) phthalocyanines in the literature. In addition to these, the sensor platform has been successfully established, and analytical optimizations have been carried out. When the sensors prepared with zinc(II) phthalocyanine are examined, it was specified that the n-ZnPc- co-TP/GOx was ranked first in the literature with high sensor response and stability. As a result, by changing of the peripheral and nonperipheral position of phthalocyanines, their physical properties can be tuned to meet the requirements of desired technological application.

Synthesis, characterization and photochemical properties of metallo porphyrazines substituted with alkyl linked carbazole, benzoazepine and phenothiazine moieties

Novel octa-phenotiazine, octa-benzoazepine and octa-carbazole substituted magnesium(II) (MgPz-I-III) and zinc(II) (ZnPz-I-III) porphyrazines were synthesized from 2,3-bis[6-(4a,10a-dihydro-phenothiazin-10-yl)-hexylsulfanyl]-but-2-enedinitrile (5), 2,3-bis [6-(4a,11a-dihydro-dibenzo[b,f]azepin-5-yl)-hexysulfan-yl]-but-2-enedinitrile (8) and 2,3-bis(6-carbazol-9-yl-hexylsulfanyl)-but-2-enedinitrile (10), respectively. These dinitrile derivatives 5, 8 and 10 were also prepared by the reaction of 1,2-dicyano-1,2-ethylenedithiolate di-sodium salt (4) with 10-(6-bromohexyl)-10H-phenothiazine (3), 5-(6-bromohexyl)-5H-diben-zo[b,f]azepine (7) and 9-(6-bromo-hexyl)-9H-carbazole (9), respectively. Porphyrazino-zinc(II) complexes were synthesized by one-step reaction using Zn(BuO)2 as a template agent. All the novel compounds were characterized by elemental analysis and different spectroscopic methods such as 1H NMR, 13C NMR, FT-IR, UV-Vis and mass. The photochemical properties including photodegradation and singlet...

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.

Synthesis, characterization and computational investigation of novel metalloporphyrazines containing 15-membered O2S2-donor macrocyclic moieties

New metalloporphyrazines (MgPz, ZnPz) containing peripheral tetrasubstitutions derived from 7,8-dihydro-6H,14H,19H-dibenzo[bj][1,12,5,8]-dioxadithiacyclopentadecine-16,17-dicarbonitrile (6) have been synthesized by a multistep reaction sequence and characterized. Compound 6 has been prepared by the reaction of 1,3-di(2-bromomethyl phenoxy) propane (3) or 1,3-di(2-iodomethylphenoxy) propane (4) which were prepared via bromination or iodination of {2-[3-(2-hydroxymethylphenoxy)propoxy]-phenyl}methanol (2) and cis-1,2-dicyano-1,2-ethylenedithiolate (5). The novel magnesium porphyrazine was prepared by the cyclotetramerization reaction of 6 with magnesium butoxide. The one-step synthesis of porphyrazinato zinc complex has been achieved without a reaction sequence by using dicyano compound (6) and zinc butoxide. The prediction of the geometry optimization, normal mode frequencies, 1H, 13C NMR, UV absorption spectra, chemical shifts, electronic properties and NBO analysis of the compound were examined by using ...

Synthesis and Characterization of New Phthalocyaninato Cobalt Complexes Containing Crown Ether Linked 1,8-Disubstituted Anthraquinones

The synthesis of novel cobalt(II) phthalocyanine complexes, peripheral symmetrically derived from 5,28-dioxo-5,11,12,14,15,22,23,25,26,27-decahydro-10H-4,6-methanotribenzo [e,n,q][1,4,7,10,13,19] tetraoxadiazacyclohenicosine-18,19-dicarbodinitrile or 5,28-dioxo-11,12,14,15,22,23,25,26-octahydro-5H-4,6-methanotribenzo [h,q,f] [1,4,7,10,13,16]hexa-oxacyclohenicosine-18,19-dicarbodinitrile were performed. These compounds were prepared starting 4,5-dihydroxy-1,2-phthalonitrile and 1,8-bis{[2-[2-{[(4-methylphenyl) sulfonyl]oxy}ethoxy]ethyl]amino}-9,10-anthracenedione or 1,8-bis[2-(2-iodoethoxy)ethoxy]-9,10-anthracenedione. Cobalt phthalocyanine complexes were prepared from dinitrile compounds and anyhydro cobalt(II)chloride. The novel compounds were characterized by a elemental analysis, FT-IR, UV-vis, 1H NMR, 13C NMR, and MS.

The Extraction Ability and Sensitivity of Porphyrazine Derivatives Towards Some Transition Metal Cations

The synthesis of novel metal-free and magnesium porphyrazines, peripherally substituted with dithia-dioxa (S2O2) and tetrathia (S4) 14-membered macrocycles were performed by cyclotetramerization of (6Z)-1,3,4,9,10,12-hexahydro-2,5,8,11-benzo-dioxadithiacyclotetradecine-6,7-dicarbodinitrile (3) or (6Z)-1,3,4,9,10,12-hexahydro 2,5,8,11-benzotetrathiacyclotetradecine-6,7-dicarbodinitrile (5). The metal-free porphyrazines have been obtained by known route. The structure of compounds were characterized by elemental analysis and 1H, 13C NMR, IR, UV-vis, and MS spectral data. The solvent extraction properties of the synthesized compounds towards some metal cations, such as Ag(I), Hg(II), Cu(II), Mn(II), Cr(III), Ni(II), Pb(II), and Zn(II) have been investigated. The effect of Cu2+, Mn2+, Ni2+, Pb2+, Sr2+, Al3+, Zn2+, Ba2+, Cd2+, Co2+, Hg2+, and Ag+ ions on the absorption spectra of the compounds were investigated by means of spectrophotometric method. Magnesium porphyrazine with S2O2 (6) interacted within Hg2+ ion specifically of all the tested metal ions.

Synthesis, characterization and complexation properties of a novel Mg-porphyrazine with metal ions in acetonitrile-chloroform

The synthesis and characterization of a novel metal derivative of a peripherally symmetrically tetrasubstituted porphyrazine derived from 25,26-dioxa-6,7,9,10,15,16,18,19-octahydro-25H-1,24-methanodibenzo[q,t][1,4, 13,16,17,10]tetraoxadithiacyclohenicosine-12,13-dicarbonitrile was carried out. The influence of metal cations such as Zn2+, Fe2+, Mn2+, Ni2+, Co2+, Hg2+ and Cu2+ on the spectroscopic properties of the ligands, the starting material dinitrile and MgPz were investigated in acetonitrile-chloroform solution (1/1) by means of absorption spectrometry. Absorption spectra showed isosbestic points in the spectrophotometric titration of Cu2+ and Hg2+ with MgPz ligand. The results of spectrophotometric titration experiments disclosed the complex stability constant of the novel ligand, MgPz with Cu2+ and Hg2+ cations.