Charge Transfer Complexes Formed by Heterocyclic Thioamides and Tetracyanoethylene: Experimental and Theoretical Study.

Tetracyanoethylene (TCNE) as one of the most versatile organic compounds is involved in various chemical reactions with electron transfer. Charge transfer complexes (CTCs) of a few antioxidants, nitrogen containing thioamides [pyrrolidine-2-thione (I), 1,3-H-imidazolidine-2-thione (II), 1,3-H-Imidazoline-2-thione (III), pyridine-2-thione (IV), 5-trifluoromethylpyridine-2-thione (V), 4-trifluoromethylpyrimidine-2-thione (VI), quinoline-2-thione (VII), 3,4,5,6-tetrahydropyrimidine-2-thione (VIII)] as π-donors and TCNE as π-acceptor were studied. The DFT PCM/UB3LYP/6-31++G(d,p) and SA-CASSCF quantum chemical calculations were used to study the structures and relative stabilities of these complexes in the ground and lowest excited electronic states. The formation of a weak molecular associates in the chloroform and acetonitrile solutions was confirmed by UV/vis and IR absorption spectroscopy. The stability constants and molar extinction coefficients were estimated by UV/vis spectroscopy. The highest stability in acetonitrile is found for associates formed by quinoline-2-thione and pyridine-2-thione with TCNE, the lowest one is found for CTC formed by imidazolidine-2-thione. Molecular associate formed by pyridine-2-thione and TCNE has the greatest stability in the chloroform solution. 5-Trifluoromethylpyridine-2-thione and 4-trifluoromethylpyrimidine-2-thione do not form CTC in CH3CN due to the presence of an electron acceptor group in the molecules. The molar extinction values of CTC vary within the range of 0.4 × 103 to 1.0 × 104 M-1 cm-1. An analytical strategy of thioamides identification based on wavelength and intensity of CTCs absorption band has been suggested.

Preparation of Reactive Indicator Papers Based on Silver-Containing Nanocomposites for the Analysis of Chloride Ions.

In recent decades, metal-containing nanocomposites have attracted considerable attention from researchers. In this work, for the first time, a detailed analysis of the preparation of reactive indicator papers (RIPs) based on silver-containing nanocomposites derived from silver fumarate was carried out. Thermolysis products are silver-containing nanocomposites containing silver nanoparticles uniformly distributed in a stabilizing carbon matrix. The study of the optical properties of silver-containing nanocomposites made it possible to outline the prospects for their application in chemical analysis. RIPs were made by impregnating a cellulose carrier with synthesized silver fumarate-derived nanocomposites, which change their color when interacting with chlorine vapor. This made it possible to propose a method for the determination of chloride ions with preliminary oxidation to molecular chlorine, which is then separated from the solution by gas extraction. The subsequent detection of the active zone of RIPs using colorimetry makes it possible to identify mathematical dependences of color coordinates on the concentration of chloride ions. The red (R) color coordinate in the RGB (red-green-blue) system was chosen as the most sensitive and promising analytical signal. Calibration plots of exponential and linear form and their equations are presented. The limit of detection is 0.036 mg/L, the limits of quantification are 0.15-2.4 mg/L, and the time of a single determination is 25 min. The prospects of the developed technique have been successfully shown in the example of the analysis of the natural waters of the Don River, pharmaceuticals, and food products.

Silver Itaconate as Single-Source Precursor of Nanocomposites for the Analysis of Chloride Ions.

At present, conjugated thermolysis of metal-containing monomers is widely used as single-source precursors to obtain new metal- and metal oxide-containing nanocomposites. In this study, a detailed analysis of the main stages of conjugated thermolysis of silver itaconate was carried out. The obtained nanocomposites containing silver nanoparticles are evenly distributed in a stabilizing carbon matrix. The structural characteristics and properties of the resulting nanomaterials were studied using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). We have developed a method of test analysis of chlorides using paper modified with the obtained silver-containing nanocomposites. The analysis technique is based on the in situ conversion of chlorides to molecular chlorine, its dynamic release, and colorimetric detection using NP-modified paper test strips. A simple installation device is described that allows this combination to be realized. The proposed approach seems promising for nanoparticle-based determinations of other analytes that can be converted into volatile derivatives.

Thioamides as radical scavenging compounds: Methods for screening antioxidant activity and detection.

Heteroaromatic thiols and thiones attracted the attention of chemists, pharmacologists and biochemists because of participation in the interception of free radicals. For the first time offered independent and reliable methods for evaluating of the antioxidant activity of thioamides-derivatives of pyridine, quinoline, imidazole, triazole, tetrazole, pyrimidine, pyrrolidine and 7-mercapto-4-methylcoumarin -based on kinetic parameters of the thioamide reaction with chromogenic radical (rate constant, M(-1)min(-1) and time to decrease concentration of test free radical by 50%, TEC50, min) or thermodynamics of the thioamides reaction with molecular iodine (extent of thioamide conversion, %). To compare the antioxidant activity of thioamides and widely used standard-antioxidant Trolox (6-Hydroxy-2,5,7,8-tetramethylchromane-2-carboxylic acid) we have proposed to use a value of relative antioxidant activity constant. As it was established, the kinetics of interaction between the chromogenic radical and thioamides in the presence of an excess of 2,2'-diphenyl-1-picrylhydrazyl (DPPH) is described by the kinetics of the pseudo first order with respect to the reacting components. A kinetic-spectrophotometric method for the quantification of heteroaromatic thioamides is elaborated and was tested in the analysis of urine. Thioamides were detected at concentrations of 1.53µgml(-1), RSD=4.6% (2-mercaptoimidazole, V), 2.08µgml(-1), RSD=1.8% (1-methylimidazoline-2-thione, VI), 1.45µgml(-1), RSD=4.3% (2-mercaptopyridine, IX).The proposed procedures show good precision and accuracy of the results obtained.

Synthesis and structure of interaction products of quinoline-2(1H)-thione with molecular iodine.

The behavior of quinoline-2(1H)-thione, which is a potential antithyroid drug toward molecular iodine, was investigated. The ability of quinoline-2(1H)-thione to form the outer-sphere charge-transfer complex C9H7NS·I2 with iodine molecular in dilute chloroform solution has been studied by UV-vis spectroscopy (lgß=3.85). The crystal structure of the new salt 2-(quinoline-2-yldisulfanyl)quinolinium triiodide - product of irreversible oxidation of quinoline-2(1H)-thione was determined by X-ray diffraction. The 2-(quinoline-2-yldisulfanyl)quinolinium cations form dimers through π-π-stacking interaction between quinoline rings. Strong intramolecular interactions are observed between iodine - sulfur atoms and iodine - hydrogen atoms with shortened contacts (less of sum of van der Waals contacts). It is noteworthy that two perfectly centrosymmetrical anions I3(-) form a very short contact I(3)⋯I(3') 3.7550(5) so we can state the formation of the dianion I(6)(2-). Therefore the formation and topology of polyiodide species depend on the characteristics, such as shape, size and charge, etc., of the counter cation, 2-(quinoline-2-yldisulfanyl)quinolinium, which is considered as templating agent.

Spectroscopic and structural investigation of interaction product of 8-mercaptoquinoline with molecular iodine.

The behavior of 8-mercaptoquinoline, which is a potential antithyroid drug toward molecular iodine was investigated. The ability of 8-mercaptoquinoline to form the outer-sphere charge-transfer complex C9H7NS·I2 with iodine molecular in dilute chloroform solution has been studied by UV/vis spectroscopy (lgß=3.14). The crystal structure of the new salt 8-(quinoline-8-yldisulfonyl)quinolinium triiodide - product of irreversible oxidation of 8-mercaptoquinoline was determined by X-ray diffraction. Intramolecular hydrogen bond of N-H⋯N type is presented in the organic cation. The triiodide ion is the nearly centrosymmetrical anion. The 8-(quinoline-8-yldisulfanyl)quinolinium cations form dimers through π-π-stacking interaction between quinolinium rings. The reduced intramolecular interactions are observed between iodine - sulfur atoms and iodine-hydrogen atoms with shortened contacts (less of sum of van-der-waals contacts).