Band 63, Heft 3

Determination of neomycin trisulphate (NMS) in a dosage form (Neox and Neosol) was carried out by capillary isotachophoresis (cITP) with conductometric detection. The following electrolytes: leading: 10 mmol dm−3 sodium acetate + 0.08 % hydroxyethylcelulose (HEC) and acetic acid to pH = 5.5, and terminating: 10 mmol dm−3 β-alanine were tested for isotachophoretic separation of NMS. The calibration curve was linear over the range of 10.00 mg dm−3 to 100.00 mg dm−3 with LOD = 5.69 mg dm−3 and LOQ = 18.96 mg dm−3. The results were compared to the conductometric determination of NMS with: ammonium molybdate (VI), silver nitrate (V) and Reinecke salt. Good accuracy was obtained from conductometric titration of NMS with Reinecke salt, the recoveries being as follows: 100 % (RSD = 1.99 %); 96.17 % (RSD = 2.10 %) and 95.22 % (RSD = 1.55 %) for NMS in pure form, Neosol and Neox, respectively.

A new rhodamine-based Hg2+-selective fluorescent probe (I) was designed and synthesized. Compound I displays excellent selective and sensitive response to Hg2+ over other transition metal ions in neutral aqueous solutions. I itself is a colorless, nonfluorescent compound. Upon addition of Hg2+ to its solution, the thiosemicarbazide moiety of I undergoes an irreversible desulfurization reaction to form the corresponding 1,3,4-oxadiazole (II), a colorful and fluorescent product, causing instantaneous development of visible color and strong fluorescence emission. Based on this mechanism, a fluorogenic probe for Hg2+ was developed. The fluorescence increases linearly with the Hg2+ concentration up to 0.8 μmol L−1 with the detection limit of 9.4 nmol L− (3σ).

A simple and rapid flow-injection spectrophotometric method for the determination of iron(III) and total iron is proposed. The method is based on the reaction between iron(III) and O-acetylsalicylhydroxamic acid (AcSHA) in a 2 % methanol solution resulting in an intense violet complex with strong absorption at 475 nm. Optimum conditions for the determination of iron(III) and the interfering ions were tested. The relative standard deviation for the determination of 5 μg L−1 iron(III) was 0.85 % (n = 10), and the limit of detection (blank signal plus three times the standard deviation of the blank) was 0.5 μg L−1, both based on the injection volumes of 20 μL. The method was successfully applied in the determination of iron(III) and total iron in water and ore samples. The method was verified by analysing a certified reference material Zn/Al/Cu 43XZ3F and also by the AAS method.

The estimation of parameters in semi-empirical models is essential in numerous areas of engineering and applied science. In many cases, these models are described by a set of ordinary-differential equations or by a set of differential-algebraic equations. Due to the presence of non-convexities of functions participating in these equations, current gradient-based optimization methods can guarantee only locally optimal solutions. This deficiency can have a marked impact on the operation of chemical processes from the economical, environmental and safety points of view and it thus motivates the development of global optimization algorithms. This paper presents a global optimization method which guarantees ɛ-convergence to the global solution. The approach consists in the transformation of the dynamic optimization problem into a nonlinear programming problem (NLP) using the method of orthogonal collocation on finite elements. Rigorous convex underestimators of the nonconvex NLP problem are employed within the spatial branch-and-bound method and solved to global optimality. The proposed method was applied to two example problems dealing with parameter estimation from time series data.

The aim of this study was to investigate the changes in carbohydrate components and the crystalline structure in hemp bast fibers by adding ethyl acetate to acetic acid/water pulping processes. It was found that ethyl acetate added to acetic acid/water process had a positive effect on yield, viscosity and carbohydrate components in pulp. It was assumed that the delignification ratio increased by adding ethyl acetate to aqueous acetic acid pulping. Xylose content in hemp bast fibers was affected more negatively in the ethyl acetate/acetic acid/water process than in the acetic acid/water one. Crystallinity and crystallite size were higher in pulp sample obtained by the acetic acid/water process without ethyl acetate.

Acylation of anisole and 3-methylanisole was performed with several acylating reagents (acetylation by AcCl and Ac2O and bromoacetylation by BrAcCl and (BrAc)2O) over different solid acid catalysts. The reaction conditions were optimized with respect to the acylation reagent, overall yield, solid acid catalyst, and the products selectivities. While acylation of anisole with acetyl chloride or acetic anhydride resulted in its full conversion to para-substituted acetophenone, the use of bromoacetyl bromide or bromoacetic anhydride yielded also the ortho-substituted product. Acylation of 3-methylanisole also yielded both para- and ortho-substitutions, and the products distribution was affected by the reaction conditions and catalyst type. It was found that while more acidic catalysts (caesium salt of heteropolyacid and zeolites) were the most active towards anisole acylation, the most active catalysts for the acylation of 3-methylanisole were ion-exchange catalysts. Employing HY-740 zeolite resulted in the highest ortho-selectivity in the acylation of anisole with bromoacetyl bromide and bromoacetic anhydride and in the acylation of 3-methylanisole with acetic anhydride.

Intramolecular metal-ligand OH/π (MLOH/π) and metal-ligand NH/π (MLNH/π) interactions in transition metal complexes between aqua or ammine ligand and ligand containing a C6-aromatic ring were investigated in crystal structures deposited in the Cambridge Structural Database (CSD). These intramolecular interactions appear in 38 structures with aqua ligand as the hydrogen atom donor and in 10 structures with ammine ligand as the hydrogen atom donor. Among all these complexes only one is negatively charged, 14 are positively charged and 33 are neutral indicating that the overall charge of the molecule has an influence on the XH/π (X = O or N) interactions. Energy estimated by DFT calculations is approximately 19 kJ mol−1 for the MLOH/π interactions and approximately 15 kJ mol−1 for the MLNH/π interactions.

A study of a series of new types of copper(II) and rhenium(IV) macrocyclic complexes, important macrocyclic molecular magnets, is reported. A detailed description of crystal structure and magnetic behavior of mononuclear copper(II) macrocyclic compounds: CuL1(ClO4)2 (L1 = N-d-2,4,4,9,11,11-hexamethyl-1,5,8,12-tetraazacyclotetradeca-2,9-diene), CuL2(ClO4)2 (L2 = N-d-7,14-diisopropyl-5,12-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) and of heteropolynuclear complexes: [CuL1][ReCl4(ox)] · DMF and [(CuL2)(ox)ReCl4] is presented. The results indicate that all compounds behave as weak interacting magnets.

Contrary to other N-(pyridyl)nitramines, the title compound cannot be rearranged to 3-amino-2-nitropyridine or other isomers. Hypothetical products of its transformation under influence of concentrated sulphuric acid, viz. 3-hydroxypyridine, 3,3′-azoxypyridine and 3,3′-azopyridine, were obtained from 3-nitro- and 3-aminopyridine in oxidation and reduction reactions. N-(3-Pyridyl)nitramine was prepared and rearranged in concentrated sulphuric acid. 3-Hydroxypyridine and 3,3′-azoxypyridine were isolated from the reaction mixture, other products were identified by the HPLC and GCMS methods. The results indicate that N-(3-pyridyl)hydroxylamine is an intermediate formed from N-(3-pyridyl)nitramine under the influence of concentrated sulphuric acid. The reaction path, leading to the final products, is discussed in context of the mechanism of nitramine rearrangement.

Although thienopyridines attract attention because of their biological activities, they have not been used as ligands in coordination compounds. Thieno[2,3-b]pyridine was prepared by known procedures; by reduction of 2-nitrothiophene, and reaction of the resulting 2-thienyl ammonium salt with malondialdehyde tetramethylacetal in the presence of zinc chloride. The same procedure was used for the preparation of a new derivative, 2-methylthieno[2,3-b]pyridine, starting from 2-methyl-5-nitrothiophene. The thienopyridines were used in the synthesis of coordination compounds. Chlorides, isothiocyanates, acetates, and chloroacetates of copper(II), nickel(II), or cobalt(II) were used as starting salts. The prepared complexes were characterized by elemental analysis and FT IR. Structures of the four complexes were determined by single-crystal X-ray diffraction analysis.

Ethyl 6-O-tert-butyldimethylsilyl-3,4-di-O-acetyl-2-thio-α-D-fructofuranoside (Va), its β-analog (Vb); as well as benzyl 6-O-tert-butyldimethylsilyl-3,4-di-O-acetyl-2-thio-α-D-fructofuranoside (Xa) and its β-analog (Xb), having an unprotected OH group at C-1, were prepared by sequential synthesis starting from commercially available D-fructose. These compounds represent suitable nucleophiles for the preparation of model carbohydrate mimetics of a glycosyltransferase inhibitor type in transition state. The structures of all compounds were confirmed by NMR spectral data and elemental analyses.

A simple, sensitive and selective spectrophotometric method for simultaneous determination of tretinoin and minoxidil using partial least square (PLS) calibration and H-point standard addition method (HPSAM) is described. The results of the H-point standard addition method show that minoxidil and tretinoin can be determined simultaneously with the concentration ratio of tretinoin to minoxidil varying from 2: 1 to 1: 33 in mixed samples. A partial least squares multivariate calibration method for the analysis of binary mixtures of tretinoin and minoxidil was also developed. The total relative standard error for applying the PLS method to eleven synthetic samples in the concentration range of 0–10 μg mL−1 tretinoin and 0–32 μg mL−1 minoxidil was 2.59 %. Both proposed methods (PLS and HPSAM) were also successfully applied in the determination of tretinoin and minoxidil in several synthetic pharmaceutical solutions.

The paper describes results obtained within the study of factors affecting the process of an antifungal drug — terbinafine hydrochloride adsorption on two different adsorbents — charcoal and silicagel. The effects of the adsorbent area, pH value, temperature and additives (polymers — methyl cellulose and hydroxypropyl cellulose) were analyzed and their impact on the adsorption of terbinafine was derived. The increase of pH and temperature, and the presence of additives decreased the amount of terbinafine adsorbed on the adsorbents. Terbinafine is currently applied both perorally and topically. Hydrogels, i.e. compositions of a drug, additives and water, are, due to their advantageous properties, preferred topical dosage forms. Mass fraction of additives of 1 % to 4 % were studied from the view point of drug release. This study shows that both the sort and the concentration of polymers influence the drug release from hydrogels significantly.

Hollow fibre based liquid phase microextraction (HF-LPME) with high performance liquid chromatography (HPLC) was developed for the determination of alkaloids in Corydalis yanhusuo. Three alkaloids (protopine, tetrahydropalmatine, tetrahydroberberine) were extracted from a 10 mL alkaline sample (donor phase) to an organic phase impregnated in the pores of the hollow fibre, and then, they were extracted to an acidic solution (acceptor phase) in the lumen of the fibre. The extract was determined directly by HPLC. Parameters affecting the HF-LPME include the organic solvent, pH of the donor and the acceptor phase, the extraction time and the stirring speed were investigated systematically. To minimize the error of the injection, palmatine was added as an internal standard (I.S.). Under optimal conditions, calibration curves were obtained in the range of 0.1–1.0 mg L−1 with a reasonable linearity (r 2 > 0.993) and the limits of detection (LODs) ranged between 10.0 × 10−3 mg L−1 and 13.7 × 10−3 mg L−1. Additionally, enrichment factors with 100 to 184-fold were obtained. The method was then applied to the crude extract of Corydalis yanhusuo successfully.

In this article, novel chemiluminescence mechanisms between norfloxacin and cerium(IV) in an acidic medium were studied. Chemiluminescence spectra of the present system were recorded observing three maximum emissions at about 475 nm, 550 nm, and 620 nm, respectively. The results indicate that the chemiluminescence peaks located at 475 nm and 620 nm can be ascribed to the emission of a singlet oxygen, while the chemiluminescence emission at 550 nm occurred in course of the reaction between acidic cerium(IV) and the phenolic intermediate. Under optimum conditions, the chemiluminescence intensity was linear with the concentration of norfloxacin over the range of 2.0 × 10−8−1.0 × 10−5 g mL−1 and the detection limit of 1.0 × 10−8 g mL−1 (S/N = 3). The relative standard deviation was 1.94 % for a 4.0 × 10−7 g mL−1 norfloxacin solution considering eleven repeated measurements. The present chemiluminescence system was successfully applied in the determination of norfloxacin in pharmaceutical preparations and concentration-time profiles in urine.

A rapid and simple as well as sensitive inductively coupled plasma mass spectrometry (ICP-MS) method for the determination of cobalamin is described. Cobalamin in human urine and medicine tablet solutions was converted on-line into free cobalt ions in acid medium, the cobalt ions were then detected by ICP-MS. Cobalamin was determined by measuring the increase of integral counts per second intensity, which was linear over the cobalamin concentration range of 1.0 × 10−10 g mL−1 to 8.0 × 10−5 g mL−1, and the limit of detection was 0.05 ng mL−1 (3σ). At the pump rate of 30 rotations per minute, one analysis cycle of cobalamin, including sampling and washing, could be accomplished in 0.5 min with the relative standard deviations of less than 5 %. The proposed procedure was applied successfully in monitoring cobalamin in human urine without any pretreatment process and in rapid determination of cobalamin in multivitamin tablets.

The surface of Porapak Q was characterized by inverse gas chromatography (IGC) carried out by the determination of dispersive and specific adsorption components of Porapak Q surface, calculating γsd and -ΔH as parameters, respectively. An interpretation was given based on the chemical structure of Porapak Q. The obtained results were confirmed through the surface Lewis acidity and basicity constants, K a and K b, respectively, correlating well with the determined thermodynamic parameters.