Development of a novel,fast, simple,nonderivative HPLC method with direct UV measurement for quantification of memantine hydrochloride in tablets

Fast, simple, accurate, and reproducible reverse phase‐high‐performance liquid chromatography method with direct ultraviolet measurement of memantine hydrochloride in tablets was developed, without any chemical derivatization pretreatment. Three main problems appear during chromatographic analysis of memantine: detection, achieving appropriate column retention, and limited choice of mobile phase components, as a result of memantine molecular structure. Among more than 35 tested columns, the best retention and peak symmetry yielded two C8 and three C18 columns with different characteristics, at a temperature of 30°C, mobile phase composed of 1%, v/v, acetonitrile and 99%, v/v, of 0.05–0.1% phosphoric acid or 2.5–5 mmol phosphate buffer, at flow rate of 1 mL/min and injection volume of 5 µL. The retention time of memantine was between 2.6 and 4 min. Both mobile phase concepts showed perfect linearity, precision, and accuracy. This is the first successful and reproducible direct reverse phase‐high‐performance liquid chromatography–ultraviolet quantification method for memantine.     

Crystal structure,thermal behavior,and microbiological activity of a thiosemicarbazide-type ligand and its cobalt complexes

The synthesis of a potentially bioactive mixed-valence Co^III/Co^II complex with 2-acetylpyridine S-methylisothiosemicarbazone (HL) ligand is described. The crystal and molecular structure of the formed [Co^IIIL₂][Co^IICl₃ py]·Me₂CO (I) compound (py stands for pyridine) is determined by single-crystal X-ray crystallography. It’s thermal decomposition along with the decomposition of the ligand and six structurally related complexes with formulas [CoL₂]NO₃·MeOH (1), [CoL₂]Br·MeOH (2), [CoL₂]HSO₄·MeOH (3), [CoL₂]₂[Co^II(NCS)₄] (4), [Co(HL)(L)]I₂·2MeOH (5), and [Co(HL)(L)][Co^IICl₄]·MeOH (6) was determined by simultaneous TG/DSC measurements. The decomposition pattern is evaluated using TG/DTA-MS data. The results were related to the solvent/moisture content and the decomposition mechanism of the compounds. The antimicrobial activity of the ligand and of all the complexes was tested in vitro for selected gram-negative and gram-positive bacteria and fungi. The activity of the ligand against all tested bacteria is comparable with those obtained for standard antibiotics, while it is less active against fungi. Surprisingly, the activity of the complexes is very low. The low antimicrobial activity of the complexes may be in connection with their high thermodynamic and kinetic inertness in solution. The results are also supported by the relatively high thermal stability of the complexes.     

Synthesis and biological evaluation of two novel 2′-substituted tiazofurin analogues

Two novel tiazofurin analogues, 2-(2-benzamido-2-deoxy-β-d-ribofuranosyl)thiazole-4-carboxamide 4 and 2-(2-azido-2-deoxy-β-d-ribofuranosyl)thiazole-4-carboxamide 5, have been synthesized starting from d-glucose and evaluated for their in vitro cytotoxicity against several human leukaemia and solid tumour cell lines.     

1:1 and 1:2 Complexes of Mercury(II) Halides with 1,3-Thiazolidine-2-thione. Spectral, Thermal, and Crystal Structure Studies

The series of compounds of the general formulae HgX₂(tzdtH) and HgX₂(tzdtH)₂ (X = Cl, Br, I; tzdtH = 1,3-thiazolidine-2-thione) have been prepared, as well as Hg(tzdt)₂. IR, ¹H, and ¹³C NMR spectral data of the complexes indicate thione donation, which is confirmed by the crystal structure analyses of [HgBr₂(tzdtH)]₂, [HgI₂(tzdtH)]₂, and HgI₂(tzdtH)₂. The structures of [HgBr₂(tzdtH)]₂ and [HgI₂(tzdtH)]₂ consist of centrosymmetric doubly bridged dimers, but they are not isostructural. The asymmetry in the HgX₂Hg bridge is more pronounced in the bromo than in the iodo derivative [S–Hg–X(terminal) is 138.19(9)° for X = Br and 123.49(10)° for X = I], which is accompanied by the stronger Hg–S covalent bond in the bromo than in the iodo complex [2.435(4) vs. 2.510(3) Å]. The Hg–X(bridging) (X = Br, I) bond distances are shorter than the sum of van der Waals radii for mercury and X. Dimeric centrosymmetric complex units are held together only by van der Waals forces in [HgI₂(tzdtH)]₂, while in [HgBr₂(tzdtH)]₂ there is an intramolecular hydrogen bond of N–H Br type (3.34(1) Å). HgI₂(tzdtH)₂ exists as a mononuclear tetrahedral complex with two long Hg–S [2.672(1) Å] and two short Hg–I bond distances [2.688(1) Å] related by a twofold axis. The molecules of HgI₂(tzdtH)₂ are linked into infinite chains along the c axis by intermolecular N–H S [3.38(1) Å] hydrogen bonds.     

Synthesis and characterization of some novel cadmium(II) complexes with 3-hydroxypicolinic acid (3-OHpicH): Crystal and molecular structures of [CdI(3-OHpic)(3-OHpicH)(H2O)]2, [Cd(3-OHpic)2(H2O)2] and [Cd(3-OHpic)2]n

Cadmium(II) complexes of 3-hydroxypicolinic acid, namely [CdI(3-OHpic)(3-OHpicH)(H₂O)]₂ (1), [Cd(3-OHpic)₂(H₂O)₂] (2) and [Cd(3-OHpic)₂]_n (3) were prepared and characterized by spectroscopic methods (IR, NMR) and their molecular and crystal structures were determined by X-ray crystal structure analysis. Complexes 1 and 2 were prepared in similar reaction conditions using different cadmium(II) salts: cadmium(II) iodide and cadmium(II) acetate dihydrate, respectively, while 3 was prepared by recrystallization of 2 from N,N-dimethylformamide solution. Various coordination modes of 3-OHpicH in 1–3 were established in the solid state: bidentate N,O-chelated mode in 1 and 2, monodentate mode through the carboxylate O atom from zwitterionic ligand in 1 and bidentate N,O-chelated and bridging mode in 3. In the DMF solution of all prepared complexes, only monodentate mode of 3-OHpicH binding to cadmium(II) through the carboxylate O atom was established by ¹H, ¹³C, ¹⁵N and ¹¹³Cd NMR spectroscopy.     

Diamond coating deposition by synergy of thermal and laser methods—A problem revisited

Diamond coatings were deposited by synergy of the hot filament CVD method and the pulse TEA CO₂ laser, in spectroactive and spectroinactive diamond precursor atmospheres. Resulting diamond coatings are interpreted relying on evidence of scanning electron microscopy as well as microRaman spectroscopy. Thermal synergy component (hot filament) possesses an activating agent for diamond deposition, and contributes significantly to quality and extent of diamond deposition. Laser synergy component comprises a solid surface modification as well as the spectroactive gaseous atmosphere modification. Surface modification consists in changes of the diamond coating being deposited and, at the same time, in changes of the substrate surface structure. Laser modification of the spectroactive diamond precursor atmosphere means specific consumption of the precursor, which enables to skip the deposition on a defined substrate location. The resulting process of diamond coating elimination from certain, desired locations using the CO₂ laser might contribute to tailoring diamond coatings for particular applications. Additionally, the substrate laser modification could be optimized by choice of a proper spectroactive precursor concentration, or by a laser radiation multiple pass through an absorbing medium.     

Solvent and Structural Effects on the UV–Vis Absorption Spectra of Some 4,6-Disubstituted-3-Cyano-2-Pyridones

A series of 4,6-disubstituted-3-cyano-2-pyridones was synthesized and their UV?CVis absorption spectra were recorded in the region 200?C600?nm in the set of selected solvents. The effects of solvent dipolarity/polarizability and solvent?Csolute hydrogen-bonding interactions on the spectral shifts were analyzed by means of the linear solvation energy relationship concept of Kamlet and Taft. The influence of solvents as well as substituents on the 2-pyridone/2-hydroxypyridine tautomeric equilibration was evaluated. The absorption band maximum of the 2-hydroxypyridine form is found to appear at a shorter wavelength than that of the 2-pyridone form in all investigated solvents. The replacement of the methyl and phenyl groups at position 6 of the pyridone ring, by a hydroxy group, significantly changes the solvatochromic behavior of the investigated pyridones.     

Development and Evaluation of a Kinetic‐Spectrophotometric Method for Determination of Arginine

A kinetic method for the determination of micro quantities of amino acid arginine (Arg) is described in this paper. The catalytic activity of cobalt in the reaction of oxidation of purpurin (1,2,4‐trihydroxy‐antraquinone, PP) by hydrogen peroxide in alkaline buffer solution decreases in the presence of micro quantities of arginine, because of the formation of the complex. Operating conditions for the successful determination of arginine were optimized. The optimized conditions yielded a theoretical detection limit of 1.45 μg mL^?1. Kinetic equations are proposed for the investigated process. The interference effects of certain foreign ions and amino acids upon the reaction rate were studied and removed in order to assess the selectivity of the method. The developed procedure was successfully applied to the determination of arginine in various pharmaceutical samples. The typical feature of this procedure is that determination can be carried out at room temperature and in a short analysis time. The newly developed method is simple, inexpensive and efficient for use in the analysis of a large number of samples.     

Supramolecular solid-state structure,potential energy surfaces and evaluation of antiproliferative effect of 2-benzothiazolylhydrazone derivatives in vitro

The in situ condensation reaction of 2-hydrazinobenzothiazole with salicylaldehyde, 3,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2-hydroxy-1-naphthaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde and 6-methoxy-2-naphthaldehyde produced 9 hydrazone Schiff bases (L1–L9, respectively) which were identified and characterized by elemental analysis, IR and NMR spectroscopy. The crystal and molecular structures of four Schiff bases (L1, L7–L9) have been determined by the single-crystal X-ray diffraction method confirming the imino form of L1 and the amino tautomeric form of L7–L9 compounds. Molecular structure analysis also confirmed that reported compounds are E-isomers relative to exo C = N imino bond. The N_hydrazino–H group of amino tautomers forms N_hydrazino–H···N_thiazolyl intermolecular hydrogen bonds shaping molecules into R ₂ ² (8) rings, while imino tautomer of L1 forms C(4) infinite helical chains via N_thiazolyl–H···N_hydrazino type of intermolecular hydrogen bond. The methoxy group (L7–L9) further shaped these primary supramolecular synthons into different supramolecular arrangements via C–H···O, C–H···N and C–H···S intermolecular hydrogen bonds. The role of aryl substituents in the shaping and stabilization of supramolecular architectures of L1, L7–L9 is supported by quantum chemical calculations. Strong antiproliferative effects on tumor cells and cytotoxic effects on fibroblasts are shown for all ligands L1–L9 with exception of L6 and L7 that had no effect on fibroblast cells.     

Synthesis,characterization and biological activity of copper(II) complexes with ligands derived from β-amino acids

Transition Metal Chemistry - Two copper(II) complexes with ligands derived from β-amino acids, 2-(1-aminocyclohexyl)acetic acid L1 and 2-(1-amino-4-(tert-butyl)cyclohexyl)acetic acid L2, were...