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    Multistep Synthesis of Phosphazene Derivative of Chenodeoxycholicacid (CDCA)
    (Taylor & Francis Ltd, 2014) Turkyilmaz, Murat; Genc, Fatma
    A new and more effective compound was synthesized by combining bile acid (chenodeoxycholic acid) and phosphazene. The synthesis started with chenodeoxycholic acid (CDCA). In the first step CDCA was converted to the CDCA methyl ester (methyl-4-(hexadecahydro-3,7-dihydroxy-10,13-dimethyl-1H-cyclopenta[a]phenanthren-17-yl) pentanoate). The mesylate was prepared from the methyl ester of CDCA and converted to the azide ester of CDCA by an S(N)2 reaction. The azide group at C-3 of chenodeoxycholic acid methyl ester was converted to an amino group (3-methyl-4-(3-amino-hexadecahydro-7-hydroxy-10,13-dimethyl-1H-cyclopenta[a]phenanthren-17-yl)pentanoate). Then, this compound was allowed to react with hexachlorocyclotriphosphazene in toluene under an argon atmosphere. The structures of the synthesized chenodeoxycholic acid derivatives and of the new phosphazene compound were confirmed by FTIR, H-1, C-13, P-31, C-13-DEPT NMR, MALDI-TOF mass spectra and elemental analysis.
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    Some Ternary Phenylmethoxybis(tetrazolium) Complexes of Vanadium(IV,V) and Their Constants of Association
    (Croatian Chemical Soc, 2012) Gavazov, Kiril Blazhev; Racheva, Petya Vasileva; Lekova, Vanya Dimitrova; Dimitrov, Atanas Nikolov; Turkyilmaz, Murat; Genc, Fatma
    Several liquid-liquid extraction systems containing vanadium {vanadium(IV) or vanadium(V)}, azoderivative of resorcinol {ADR: 4-(2-pyridylazo)-resorcinol (PAR) or 4-(2-thiazolylazo)-resorcinol (TAR)} and (phenylmethoxibis)tetrazolium salts {MBT: 3,3'-(3,3'-dimetoxy-4,4'-biphenylene)-bis(2,5-diphenyl-2H-tetrazolium) chloride (Blue Tetrazolium, BT) or 3,3'-(3,3'-dimetoxy-4,4'-biphenylene)-bis[2,5-di(4-nitrophenyl)-2H-tetrazolium] chloride (Tetranitroblue Tetrazolium, TNBT)} were studied. The optimum operating conditions and compositions of the extracted species were found. The constants of association (beta) between MBT2+ and the anionic V-ADR chelates (Chel(n-)) were calculated. Previously reported negative linear relationship between log beta and the number of nitro groups included in tetrazolium cation (N-nitro) was discussed taking into account the obtained results and literature data for V ADR MBT complexes of the same class, in which MBT is BT or 3,3'-(3,3'-dimetoxy-4,4'-biphenylene)bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium] chloride (Nitroblue Tetrazolium, NBT). (doi: 10.5562/cca1885)
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    Ternary complexes of vanadium(IV) with 4-(2-pyridylazo)-resorcinol (PAR) and ditetrazolium chlorides (DTC)
    (Versita, 2010) Genc, Fatma; Gavazov, Kiril B.; Turkyilmaz, Murat
    Complex formation and liquid-liquid extraction have been studied for ternary complexes of vanadium(IV) with 4-(2-pyridylazo)-resorcinol (PAR) and ditetrazolium chlorides (DTC) in a water-chloroform medium. The specific ditetrazolium compounds investigated were i) 3,3'-(4,4'-biphenylene)-bis(2,5-diphenyl-2H-tetrazolium) chloride (Neotetrazolium chloride, NTC); ii) 3,3'-(3,3'-dimetoxy-4,4'-biphenylene)-bis(2,5-diphenyl-2H-tetrazolium) chloride (Blue Tetrazolium chloride, BTC); and iii) 3,3'-(3,3'-dimetoxy-4,4'-biphenylene)bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium] chloride (Nitro Blue Tetrazolium chloride, NBT). Molar absorptivity coefficients and the composition of the complexes have been calculated. Association constants (beta) have also been obtained for the interactions between the vanadium(IV) - PAR anionic chelates [VO(PAR)(2)](2-) (I) and [VO(OH)(2)(PAR)(2)](4-) (II), and ditetrazolium cations (DT2+). Some special features of NBT as an extraction-spectrophotometric reagent for vanadium(IV) have been discussed. Unlike NTC and BTC which form complexes with both I and II, NBT associates only with II. The pH interval for complete extraction of (NBT(2+))(2)[VO(OH)(2)(PAR)(2)] is broader and allows work at lower pH values the other ion-associates of V(IV, V)-PAR that were studied. NBT is -therefore the appropriate reagent both for direct V(IV) determination and for V(IV)/V(V) separation. Some additional characteristics for the V(IV)-PAR-NBT-water-chloroform system have been determined: extraction constant, distribution constant, recovery factor, limit of detection and limit of quantification. Beer's law is valid up to 1.4 mu g mL(-1) vanadium(IV) with molar absorptivity coefficient of 3.55 x 10(4) L mol(-1) cm(-1) at lambda(max)=559 nm.
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    A theoretical study on 1H-indole-2,3-dione complexes with lithium, sodium, and potassium cations
    (Springer, 2024) Genc, Fatma; Kandemirli, Fatma; Dalgic, Serap Senturk
    ContextA comparative study of the change in different properties of electronic and structural of the free 1H-indole-2,3-dione molecule and its complexes has been obtained. HOMA analysis was performed to investigate the effects of lithium sodium and potassium cations on the aromaticity of lithium sodium and potassium complexes of 1H-indole-2,3-dione.MethodsSeveral 1H-indole-2,3-dione complexes with lithium, sodium, and potassium cations were optimized at the B3LYP/6-311G(d,p) level. The cation and pi interaction has been investigated from different aspects, including interaction energy calculations, charge transfer values, and changes in the aromaticity of the ring upon complexation. The charge transfer and natural population analysis for the complexes were performed with the natural bond orbital (NBO) analysis. The properties of bond critical points in complexes were studied by applying the quantum theory of atoms in molecules (QTAIM). Finally, the aromaticity change of phenyl induced upon complex formation was evaluated by applying the harmonic oscillator model of aromaticity (HOMA). [Li-INa]+ and [[Li-INb]+ were optimized with the wB97XD function using a version of Grimme's D2 dispersion model, and the absorption energy was compared with the calculation made with the B3LYP functional.