Extractive Spectrophotometric Determination and Theoretical Investigations of Two New Vanadium(V) Complexes.

Two new vanadium (V) complexes involving 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) and tetrazolium cation were studied. The following commercially available tetrazolium salts were used as the cation source: tetrazolium red (2,3,5-triphenyltetrazol-2-ium;chloride, TTC) and neotetrazolium chloride (2-[4-[4-(3,5-diphenyltetrazol-2-ium-2-yl)phenyl]phenyl]-3,5-diphenyltetrazol-2-ium;dichloride, NTC). The cations (abbreviated as TT+ and NTC+) impart high hydrophobicity to the ternary complexes, allowing vanadium to be easily extracted and preconcentrated in one step. The complexes have different stoichiometry. The V(V)-HTAR-TTC complex dimerizes in the organic phase (chloroform) and can be represented by the formula [(TT+)[VO2(HTAR)]]2. The other complex is monomeric (NTC+)[VO2(HTAR)]. The cation has a +1 charge because one of the two chloride ions remains undissociated: NTC+ = (NT2+Cl-)+. The ground-state equilibrium geometries of the constituent cations and final complexes were optimized at the B3LYP and HF levels of theory. The dimer [(TT+)[VO2(HTAR)]]2 is more suitable for practical applications due to its better extraction characteristics and wider pH interval of formation and extraction. It was used for cheap and reliable extraction-spectrophotometric determination of V(V) traces in real samples. The absorption maximum, molar absorptivity coefficient, limit of detection, and linear working range were 549 nm, 5.2 × 104 L mol-1 cm-1, 4.6 ng mL-1, and 0.015-2.0 µg mL-1, respectively.

A centrifuge-less cloud point extraction-spectrophotometric determination of copper(II) using 6-hexyl-4-(2-thiazolylazo)resorcinol.

A simple, cheap, and environmentally friendly centrifuge-less cloud point extraction procedure was developed for the preconcentration of traces of Cu(II) before its spectrophotometric determination. It is based on a complexation reaction with the hydrophobic azo reagent 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR), in which a complex with a stoichiometric ratio of 1:1 and an absorption maximum at 535 nm is formed. The experimental conditions for Cu(II) determination were found: HTAR concentration (8 × 10-6 mol mL-1), mass fraction of the surfactant Triton X-114 (2.2%), pH (5.9, ammonium acetate buffer), and incubation time (10 min at 60 °C). The linear range, limit of detection, molar absorption coefficient and preconcentration factor were calculated to be 4.5-254 ng mL-1, 1.34 ng mL-1, 2.54 × 105 L mol-1 cm-1, and 10, respectively. The effect of foreign ions was studied, and the proposed procedure was applied to the analysis of water samples and a saline solution for intravenous infusion.

Complex Formation in a Liquid-Liquid Extraction System Containing Vanadium(IV/V), 2,3-Dihydroxynaphtahlene and Thiazolyl Blue.

Liquid-liquid extraction systems for VIV/V containing 2,3-dihydroxynaphtahlene (DN) and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (thiazolyl blue, MTT) were studied. The optimum conditions for VIV and VV extraction were found. VIV is extracted in chloroform as a 1:2:2 complex (V:DN:MTT) with lmax = 570 nm and e570 = 2.9´104 dm3 mol-1 cm-1. However, this wavelength was found unsuitable for precise spectrophotometric measurements due to time dependent absorbance changes. VV forms predominantly a 1:1:1 complex with lmax = 335 nm. The calibration graph for this oxidation state is linear in the range of 0.06-1.5 mg cm-3. The molar absorptivity, Sandell's sensitivity and limit of detection were calculated to be 1.6 ´ 104 dm3 mol-1 cm-1, 3.2 ng cm-2 and 0.02 mg cm-3, respectively. The ground-state equilibrium geometries of the anionic parts of the extracted ion-associates, [VIVO(DN2-)2]2-and [VVO2(DN2-)]-, were optimized at the BLYP/6-31++G* level of theory.

Ion-association complexes of gallium(III)-4-(2-pyridylazo)-resorcinol anionic chelates and dicationic tetrazolium reagents.

The formation and liquid-liquid extraction of ion-association complexes between gallium(III)-4-(2-pyridylazo)resorcinol (PAR) anionic chelates and cations of four ditetrazolium chlorides (DT2+) were studied: Neotetrazolium chloride (NTC), Blue Tetrazolium chloride (BTC), Nitro Blue Tetrazolium chloride (NBT) and Tetranitro Blue Tetrazolium chloride (TNBT). The optimum extraction-spectrophotometric conditions, composition of the extracted species {1:2:1 and/or 1:2:2 (Ga:PAR:DT)}, some equilibrium constants {constants of association (beta), constants of distribution (KD and constants of extraction (Kex)} and analytical characteristics {molar absorptivity (epsilon), Sandell's sensitivity, intervals of adherence to Beer's law, etc.} were found. Relationships involving the number of nitro groups in DT2+ (Nnitro; DT2+ = BT2+, NBT2+ and TNBT2+) or molecular mass of DT2+ (MM; DT2+ = NT2+ and BT2+) were discussed: Log beta =f(Nnitro), Log KD =f(Nnitro), Log Kepsilon=f(Nnitro), Log epsilon =f(Nnitro) and Log beta = f(Log MM).

Nitroderivatives of catechol: from synthesis to application.

Nitroderivatives of catechol (NDCs) are reviewed with special emphasis on their complexes and applications. Binary, ternary and quaternary NDC complexes with more than 40 elements (aluminum, arsenic, boron, beryllium, calcium, cobalt, copper, iron, gallium, germanium, magnesium, manganese, molybdenum, niobium, rare earth elements, silicon, tin, strontium, technetium, thallium, titanium, uranium, vanadium, tungsten, zinc and zirconium) are discussed and the key characteristics of the developed analytical procedures - tabulated. The bibliography includes 206 references.