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.

Clinical course of autoimmune thyroid diseases in women with prolactinomas: Results from a prospective study in a single tertiary centre.

INTRODUCTION: Several retrospective and cross-sectional studies have revealed a higher prevalence of autoimmune thyroid diseases (AITD) with a predominance of autoimmune hypothyroidism in prolactinoma patients compared to the general population. To date, we have no data on the clinical course of AITD in these patients. The aim of this prospective study was to assess the clinical course of AITD in female patients with prolactinomas compared to an age- and thyroid-risk factors-matched control group. MATERIALS AND METHODS: The study population consisted of 144 females (71 patients/73 controls) who underwent approximately a 6-year follow-up. Physical examination, thyroid ultrasound and laboratory testing (measurement of antibodies to thyroglobulin, thyroid peroxidase, TSH-receptor; serum TSH and FT4 levels) were performed twice - at the baseline and at the follow-up visits. RESULTS: AITD were diagnosed in 26.8% (n=19) of the patients and 9.6% (n=7) of the controls (p=0.007) at baseline visit. At the end of the follow-up (FU), these percentages increased to 33.8% (n=24) among the patients versus 12.3% (n=9) in the control group (p=0.002). Hypothyroidism was significantly more frequent in prolactinoma patients than in controls at the end of the study (19.7% vs. 4.1%; p=0.003). Two prolactinoma patients had hyperthyroidism at the baseline visit and restored euthyroid state with negative TSH-receptor antibodies during the follow-up. We did not observe hyperthyroidism in the control group. Among the hypothyroid subsets, the average daily levothyroxine dose at FU visit varied from 25 to 200mcg in the prolactinoma group compared to 25 to 50mcg in the control group. CONCLUSIONS: Female patients with prolactinomas seem to be prone to autoimmune hypothyroidism. As a pathogenetic mechanism, we could suggest the selective immunomodulatory action of PRL predominantly on cell autoimmunity, complement activation and antibody-dependent cytotoxicity, resulting in earlier and more rapid progression of Hashimoto's thyroiditis towards hypothyroid state in genetically predisposed individuals.

Use of a Hydrophobic Azo Dye for the Centrifuge-Less Cloud Point Extraction-Spectrophotometric Determination of Cobalt.

The hydrophobic azo dye 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR, H2L) was studied as part of a system for the centrifuge-less cloud point extraction (CL-CPE) and spectrophotometric determination of traces of cobalt. The extracted 1:2 (Co:HTAR) complex, [CoIII(HL-)(L2-)]0, shows an absorption maximum at 553 nm and contains HTAR in two different acid-base forms. Optimum conditions for its formation and CL-CPE were found as follows: 1 × 10-5 mol L-1 of HTAR, 1.64% of Triton X-114, pH of 7.8, incubation time of 20 min at ca. 50 °C, and cooling time of 30 min at ca. -20 °C. The linear range, limit of detection, and apparent molar absorptivity coefficient were 5.4-189 ng mL-1, 1.64 ng mL-1, and 2.63 × 105 L mol-1 cm-1, respectively. The developed procedure does not use any organic solvents and can be described as simple, cheap, sensitive, convenient, and environmentally friendly. It was successfully applied to the analysis of artificial mixtures and real samples, such as steel, dental alloy, rainwater, ampoules of vitamin B12, and saline solution for intravenous infusion.

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.

Extraction-Chromogenic System for Cobalt Based on 5-Methyl-4-(2-thiazolylazo) Resorcinol and Benzalkonium Chloride.

The interaction between CoII and 5-methyl-4-(2-thiazolylazo)-resorcinol (MTAR) was studied in a water-chloroform system, in the presence or absence of benzalkonium chloride (BZC) as a cationic ion-association reagent. The optimum pH, concentration of the reagents and extraction time for the extraction of Co were found. In the presence of BZC, the extracted ion-associate could be represented by the formula (BZ+)[CoIII(MTAR2-)2], where MTAR is in its deprotonated form. The following extraction-spectrophotometric characteristics were determined: absorption maximum, molar absorptivity, Sandell's sensitivity, limit of detection, limit of quantification, constant of extraction, distribution ratio and fraction extracted. In the absence of BZC, the extraction is incomplete and occurs in a narrow pH range. The extracted chelate contains one deprotonated and one monoprotonated ligand: [CoIII(MTAR2-)(HMTAR-)].

Study on the Complex Formation and the Ion-Association of Anionic Chelate of Molybdenum(VI) with Bidentate Ligand and the Cation of 2,3,5-Triphenyl-2?-tetrazolium Chloride.

The complex formation between the anionic chelate of molybdenum(VI) with the bidentate ligand of 3,5-dinitrocatechol (3,5-DNC) and its ion-association with the cation of 2,3,5-triphenyl-2?-tetrazolium chloride (TTC) in the liquid-liquid extraction system Mo(VI)?3,5-DNC?TTC?H2O?CHCl3 were studied by spectrophotometry. The validity of Beer's law was checked and some analytical characteristics of the system were calculated under the optimum conditions for the chelate formation and extraction. The effect of various co-existing ions and reagents on the process of chelate formation and ion-association was investigated. The molar ratio of the components in the ion-associated complex Mo(VI)-3,5-DNC-TTC was determined by independent methods. The association process in aqueous phase and the extraction equilibria were investigated and quantitatively characterized by the following equilibrium constants: association constant, distribution constant, extraction constant and recovery factor. Based on this, a reaction scheme, a general formula and a structural formula of the complex were suggested.

Study on the Chelate Formation and the Ion-association of Anionic Chelate of Molybdenum(VI) with 3,5-Dinitrocatechol and Monotetrazolium Cation.

The equilibria of the chelate formation and ion-association in the liquid-liquid extraction system Mo(VI)‒3,5-DNC‒INT‒H2O‒CHCl3 were studied by spectrophotometry. The optimum conditions for the chelate formation and extraction of the ion-associated complex formed between the anionic chelate of Mo(VI)‒3,5-dinitrocatechol (3,5-DNC) and the cation of 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT) were established. The validity of Beer's law was checked and some analytical characteristics were calculated. The effect of various co-existing ions and reagents on the process of complex formation was investigated. The molar ratio of the components in the ternary ion-associated complex Mo(VI)-3,5-DNC-INT was determined by independent methods. The association process in aqueous phase and the extraction equilibria were investigated and quantitatively characterized. The following key constants of the processes were calculated: association constant, distribution constant, extraction constant and recovery factor. Based on this, a reaction scheme, a general formula and a structure of the complex were suggested.

Study on the Equilibria of the Complex Formation of the Ion-pair of Germanium(IV) with 4-Nitrocatechol and 1,4-Diphenyl-3-(phenylamino)-1H-1,2,4-triazole.

The complex formation of the ion-pair formed between the anionic chelate of Ge(IV)-4-nitrocatechol (4-NC) and the cation of 1,4-diphenyl-3-(phenylamino)-1H-1,2,4-triazole (Nitron, Nt) in the liquid-liquid extraction system Ge(IV)-4-NC-Nt-H2O-CHCl3 was studied by spectrophotometry. The optimum extraction-spectrophotometric conditions for the complex formation were established. The validity of Beer's law was checked and some analytical characteristics of the system were calculated. The effect of co-existing ions and reagents on the process of complex formation was investigated. The association process in aqueous phase and the extraction equilibria were studied and quantitatively characterized. The following key constants of the processes were calculated: association constant, distribution constant, extraction constant and recovery factor. The molar ratio of the reagents was determined by independent methods. A reaction scheme and a general formula of the complex were suggested.

Study on the Complex Equilibria of Molybdenum(VI) with 3,5-Dinitrocatechol and Ditetrazolium Salt.

The complex formed between an anionic chelate of Mo(VI)-3,5-dinitrocatechol (3,5-DNC) with the cation of 3,3'-(3,3'-dimethoxy-4,4'-biphenylene)bis(2,5-diphenyl-2H-tetrazolium chloride) (Blue Tetrazolium Chloride, BTC) in the liquid-liquid extraction system Mo(VI)-3,5-DNC-BTC-H2O-CHCl3 was studied. The optimum conditions for the complex formation and extraction of the ion-associated complex were established by spectrophotometry. The molar ratio of the reagents was determined by independent methods. The validity of Beer's law was checked and some analytical characteristics were calculated. The association process in aqueous phase and the extraction equilibria were investigated and quantitatively characterized. The following key constants of the processes were calculated: association constant, distribution constant, extraction constant and recovery factor. Based on this, a reaction scheme, a general formula and a structure of the complex were suggested.

Complex Formation in a Liquid-Liquid Extraction System Containing Co(II), 4-(2-Thiazolylazo)resorcinol and Monotetrazolium Salt.

The ion-associated complex formed between anionic chelate of Co(II)-4-(2-Thiazolylazo)resorcinol (TAR) with the monotetrazolium cation of 2-(4-Iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT) in the liquid-liquid extraction system Co(II)-TAR-INT-H(2)O-CHCl(3) was studied by the spectrophotometric method. The optimum extraction conditions of Co(II) were found. The extraction equilibria were studied. The equilibrium constants, the recovery factor and some analytical characteristics were calculated. The validity of Beer's law was checked. The molar ratio of the components in the ternary ion-associated complex Co(II)-TAR-INT was determined. The general formula of the complex was suggested. The effect of various foreign ions and reagents on the process of complex formation in the liquid-liquid extraction system was studied.

Ternary ion-association complexes of cobalt with 4-(2-pyridylazo)resorcinol and tetrazolium salts.

The formation of ternary ion-association complexes of Co(II) with 4-(2-pyridylazo)resorcinol (PAR) and tetrazolium salts (TS) - (3-(4,5-dimethylThiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) and 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (TV) - were investigated with the aid of the extraction-spectrophotometric method. The optimum conditions for the extraction of Co(II) were found. On the basis of the experimental data and their mathematical treatment the association process in aqueous phase and extraction process was investigated quantitatively. The molar ratios of the components in the associates were determined. The results show that the extracted species could be represented with the general formula (TS)[CoH(PAR)(2)]. The following key constants were calculated: association constant, distribution constant, extraction constant and recovery factor. The validity of Beer's law was checked and some analytical characteristics were calculated.