Synthesis and characterization of a new dyestuff polymer soluble in alkaline aqueous media

Novel dyestuff polymers were successfully obtained through oxidative polymerization technique. The synthesized Schiff base and its polymer were soluble in alkaline＇aqueous medium and they have various colors in different solutions. Also, it can be said that the synthesized compounds are suitable as coloring agent （dyestuff） for textile applications. Fluorescence properties of the compounds were determined in DMF with different concentrations （mg/L）. Poly-tris（4- aminophenyl）methanol （P-TAPM） has quite high emission and excitation intensity values. Optical and electrochemical band gaps of the polymers were lower than those of the monomers indicating the more conjugated structure of the polymers. The oxidized states of the novel dyestuff compounds were examined by cyclic voltammetry （CV） technique. The solid state conductivity measurements showed that the synthesized polymers were semiconductors when exposed to the iodine vapour their conductivities could be increased. P-TAPM had the highest undoped conductivity. Thermal characterizations of the synthesized compounds were carried out by TG-DTA and DSC methods.     

Reinvestigation of the regioselectivity of deprotonation of ketone dimethylhydrazones

The lack of regioselectivity in the deprotonation of ketone dimethylhydrazones by lithium diethylamide has been determined by ¹³C NMR spectroscopy of deuterium labelled samples.     

Peroxidase/H2O2 catalyzed oxidative oligomerization of 1-aminopyrene

A new florescent oligo(aminopyrene) (OAP) was successfully synthesized by enzymatic approach. For this, H₂O₂ and Horse Radish peroxidase (HRP) were used as catalyst and oxidant, respectively. The structures of monomer and oxidation product were confirmed by NMR, FT-IR and UV-Vis measurements. The oxidation product was characterized by gel permeation chromatography (GPC), thermogravimetry (TG), differential scanning calorimetry (DSC), cyclic voltammetry (CV), photoluminescence (PL) and scanning electron microscopy (SEM) analyses. OAP was soluble in a wide range of organic solvents. UV-Vis spectrum of the OAP showed a dramatic red shift compared to that of the monomer. The optical and electrochemical band gaps of OAP were found to be 1.65 and 1.56 eV, respectively. OAP emitted turquoise color in THF and green color in toluene. SEM observations indicated the presence of a heterogeneous cauliflower like morphology.     

Combined HPLC-CUPRAC (cupric ion reducing antioxidant capacity) assay of parsley, celery leaves, and nettle

This study aims to identify the essential antioxidant compounds present in parsley (Petroselinum sativum) and celery (Apium graveolens) leaves belonging to the Umbelliferae (Apiaceae) family, and in stinging nettle (Urtica dioica) belonging to Urticaceae family, to measure the total antioxidant capacity (TAC) of these compounds with CUPRAC (cupric ion reducing antioxidant capacity) and ABTS spectrophotometric methods, and to correlate the TAC with high performance liquid chromatography (HPLC) findings. The CUPRAC spectrophotometric method of TAC assay using copper(II)-neocuproine (2,9-dimethyl-1,10-phenanthroline) as the chromogenic oxidant was developed in our laboratories. The individual antioxidant constituents of plant extracts were identified and quantified by HPLC on a C18 column using a modified mobile phase of gradient elution comprised of MeOH-0.2% o-phosphoric acid and UV detection for polyphenols at 280 nm. The TAC values of HPLC-quantified antioxidant constituents were found, and compared for the first time with those found by CUPRAC. The TAC of HPLC-quantified compounds accounted for a relatively high percentage of the observed CUPRAC capacities of plant extracts, namely 81% of nettle, 60-77% of parsley (in different hydrolyzates of extract and solid sample), and 41-57% of celery leaves (in different hydrolyzates). The CUPRAC total capacities of the 70% MeOH extracts of studied plants (in the units of mmol trolox g⁻¹ plant) were in the order: celery leaves > nettle > parsley. The TAC calculated with the aid of HPLC-spectrophotometry did not compensate for 100% of the CUPRAC total capacities, because all flavonoid glycosides subjected to hydrolysis were either not detectable with HPLC, or not converted to the corresponding aglycons (i.e., easily detectable and quantifiable with HPLC) during the hydrolysis step.     

Spectrophotometric determination of ascorbic acid using copper(II)-neocuproine reagent in beverages and pharmaceuticals

The proposed method for ascorbic acid (Vitamin C) (AA) determination is based on the oxidation of AA to dehydroascorbic acid with a Cu(II)-2,9-dimethyl-1,10-phenanthroline (neocuproine (Nc)) reagent in ammonium acetate-containing medium at pH 7, where the absorbance of the formed bis(Nc)-copper(I) chelate is measured at 450 nm. This chelate was formed immediately and the apparent molar absorptivity for AA was found to be 1.60 × 10⁴ dm³ mol⁻¹ cm⁻¹. Beer's law was obeyed between 8.0 × 10⁻⁶ and 8.0 × 10⁻⁵ M concentration range. The relative standard deviation for 90 μg AA was 3%. The Cu(II)-Nc reagent is a milder and therefore more selective oxidant than the conventional Fe(III)-1,10-phenanthroline (phen) reagent used for the same assay. This feature makes the proposed method superior for real samples such as fruit juices containing weak reductants such as citrate, oxalate and tartarate that otherwise produce positive errors in the Fe(III)-phen method when equilibrium is achieved. The developed method was applied to a number of commercial fruit juices, pharmaceutical preparations containing Vitamin C, and red wine. The meta-bisulfite content of wine was removed with an anion exchanger at pH 3 prior to analysis, and a difference extractive–spectrophotometric method of AA assay in wine was developed so as to suppress the interferences caused by wine anthocyanins and polyphenols. The findings of the developed method for fruit juices and pharmaceuticals were also statistically compared with those of HPLC so as to establish it as a reliable novel method.     

Chemical Oxidative Synthesis and Characterization of Poly(8-hydroxyquinoline) Particles

The chemical oxidative polymerization (OP) of 8-hydroxyquinoline (HQ) in an organic medium leaded to the formation of the C-2 and C-4 linking poly (8-hydroxyquinoline) (PHQ). The structure of PHQ was confirmed by UV-Vis, FT-IR, and ¹H-NMR. The characterization of polymer was performed by TG-DTA, differential scanning calorimetry, dynamic mechanical analysis, dynamic light scattering, size exclusion chromatography, X-ray diffraction, cyclic voltammetry, atomic force microscope, photoluminescence and solubility tests. The fluorescence spectrum of PHQ exhibited an emission peak at approximately 525 nm in DMSO. Accordingly, it was found PHQ emitted green light whereas HQ emitted yellow light in DMSO solvent. Optical band gaps (E_g) of PHQ was calculated to be 3.31 eV. The electrical conductivities of iodine doped-PHQ and undoped-PHQ were measured with four-point probe technique. Magnetic particles was prepared by chemical precipitation of mixed Fe(II) and Fe(III) salts and modified with HQ by using an in situ chemical oxidation polymerization method in organic medium.     

Evolution of magnetic and structural properties of TiO2 with Co-doping

This paper presents the phase formations and magnetic properties of Co-doped TiO₂ synthesized by the colloidal and ammonium nitrate melt techniques (ANMT). The phase formations and ferromagnetic properties were studied with XRD and SQUID magnetometry. Crystallization of the TiO₂ rutile lattice was completed at 1000 °C and that was preserved during annealing up to 1300 °C. For the samples annealed at 1200 °C, elemental analysis has shown that the colloidal technique leads to a single-phase rutile with cobalt concentration of almost nothing even in the initially 0.5 mol Co-added samples. Further increase of annealing temperature results in the appearance of other Ti-phases in addition to the rutile. On the other hand, it is quite interesting that these samples show ferromagnetic behavior. The samples synthesized by the ANMT method contain larger amounts of Co compared to the colloidal technique.