Band 67, Heft 4

A method for carbohydrate isomers (saccharide units) identification in flavonoid glycosides after hydrolysis by an HPLC system with two detectors (diode array UV-VIS detector and evaporative light scattering detector) was set up in this work. Experimental procedure was optimized with two types of model glycosides, namely rutin and hesperidin. The model glycosides were hydrolyzed to saccharide units and aglycone parts; the aglycone was characterized by its UV-VIS spectrum and the saccharide unit was identified by its retention time and elution profile (anomeric signals). Acidic and enzymatic hydrolyses were compared in the first step of the method; in acidic hydrolysis, trifluoracetic acid was used, while glucosidase, galactosidase, and hesperidinase were used in enzymatic hydrolysis. A complete enzymatic hydrolysis was achieved with hesperidin and neohesperidin, but not with 3-O-glycosides. The method was applied for the identification of a glycone from a glycoside isolated from Polygonum lapathifolium (Polygonaceae sp.).

A new metallomicellar system containing cerium(III), a macrocylic polyamine ligand, and the nonionic surfactant Brij35(polyoxyethylene(23) lauryl ether) was prepared and used as a catalyst in the hydrolysis of bis(4-nitrophenyl) phosphate (BNPP). Catalytic rate of the BNPP hydrolysis was measured kinetically using the UV-VIS spectrophotometric method. The results indicate that the metallomicellar system has relatively high stability and excellent catalytic function in the BNPP hydrolysis; also, the reaction rate of the BNPP catalytic hydrolysis increased by a factor of ca. 1 × 1010 compared to the BNPP spontaneous hydrolysis due to the catalytic effect of the active species and the local concentration effect of the micelles in the metallomicellar system. Experimental results also showed that the mono-hydroxy complex containing the macrocyclic polyamine ligand and cerium(III) is the real active species in the BNPP catalytic hydrolysis, and that the micelles provide a useful catalytic environment for the reaction. On basis of the research results, the reaction mechanism of BNPP catalytic hydrolysis has been proposed.

A series of tetracarboxylphthalocyanines (MPc(COOH)4, M = H, Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)) were anchored onto MCM-41 by the following procedures: functionalization of MCM-41 with (EtO)3SiCH2CH2CH2NH2 reacting with surface Si-OH, and anchoring MPc(COOH)4 onto MCM-41 with a substitution reaction between chloroformyl and amino groups. The samples were characterized by infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, N2 adsorption-desorption, and X-ray photoelectron spectroscopy. Catalytic activity of oxidation was tested using solutions of ethanethiol in petroleum ether and thiophene in octane; CoPc-CONH-MCM-41 displayed the highest conversion ratio of 90.15 % and 93.79 %, respectively.

A comparison of polymeric and ceramic membranes in the ultrafiltration process was studied and presented. This study was conducted on the separation of cadmium(II) ions, with particular reference to parameters such as hydrodynamic permeability coefficient, membrane fouling, amount of surfactant in the permeate, efficiency, and effectiveness of the process. The effect of ionic (SDS) and non-ionic (Rofam 10) surfactants or their mixture was investigated. The hydrodynamic permeability coefficient of the ceramic membrane was found to be much lower in comparison to those of the polymeric ones (1.69 × 10−7 m3 h−1 m−2 Pa−1, 5.66 × 10−7 m3 h−1 m−2 Pa−1, and 9.26 × 10−7 m3 h−1 m−2 Pa−1 for ceramic, CA, and PVDF, respectively). However, filtration of the surfactants solutions did not cause permanent blocking of pores and the surface of the ceramic membrane in contrast to the polymeric ones. No significant differences in surfactants permeation through the membranes tested were observed. Concentration of the surfactant in the permeate was lower than 1 CMC for the Rofam 10 solution and exceeded the CMC by about 40 % for the SDS solution. Better separation properties of polymer membranes for the separation of cadmium(II) ions from micellar systems were identified.

An experimental study on the removal of Cd2+ and Zn2+ through a supported liquid membrane using a mixture of mono-(2-etylhexyl) ester of phosphoric acid (M2EHPA) and bis-(2-etylhexyl) ester of phosphoric acid (D2EHPA) as carriers is presented. Parameters affecting the Cd2+ and Zn2+ pertraction such as feed concentration, carrier concentration, pH of the stripping phase, and TBP (tributyl phosphate) concentration were analyzed using the Taguchi method. Optimal experimental conditions for Cd2+ and Zn2+ pertraction were obtained using the analysis of variance (ANOVA) after a 6 h separation with the initial feed concentration of 8.9 × 10−4 mol L−1, carrier concentration of 20 vol. %, TBP concentration of 4 vol. %, and pH of 0.5. Then, under optimum conditions, a comparison of M2EHPA, D2EHPA, and bis-(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302) was performed. Effective pertraction of Cd2+ and Zn2+ using these carriers was observed in the following order: mixture of M2EHPA and D2EHPA, D2EHPA, Cyanex 302. It was also found that the presence of one metal ion in the feed solution reduces the pertraction rate of the other one.

The potential of legume flours (lentil and bean) in bakery applications was investigated. The study indicated that legume flours were characterised by high protein (27.30–27.35 mass %) and total dietary fibre (14.91–21.52 mass %), relatively high water holding capacity (4.71–5.42 g g−1), and good emulsifying properties (emulsifying capacity: 32.73–46.96 cm3 per 100 cm3 and emulsion stability: 60.52–90.90 cm3 per 100 cm3). Fine wheat flour was partially substituted with 10 mass %, 20 mass %, and 30 mass % levels of lentil and bean flours in order to study their farinographic characteristics and baking behaviour. The addition of legume flours increased water absorption capacity (from 58.50 mass % to 74.90 mass %) and dough development time (from 3.50 min to 5.50 min), whereas dough stability was reduced (from 6.67 min to 2.30 min). The presence of legume flours in dough negatively affected the physical parameters of baked rolls and resulted in the reduction in volume, specific volume, and cambering. Sensory evaluation showed that the most acceptable baked rolls were obtained when the wheat-legume blend flour containing 10 mass % of legume flour was applied. Higher levels of legume flours in the products adversely affected the shape, crust colour, crumb elasticity, and hardness of the final products.

The novel complex [Cu(men)2][Cu2Cd2Cl2(CN)6] (I) was isolated from the aqueous-ethanol system containing CuCl2, men (men = N-methylethane-1,2-diamine) and K2[Cd(CN)4] in the presence of dilute hydrochloric acid and chemically and spectroscopically characterised. The crystal structure of I consists of [Cu2I(CN)6] and [Cd2Cl2(CN)6] building units bridged by cyanide ligands and forms a three-dimensional skeleton with cavities. [Cu(men)2]2+ cations in which two men ligands are chelated (mean Cu-N is 2.033(6) Å) are located in the cavities. The coordination polyhedron around the Cu(II) atoms is formed as a tetragonal bipyramidal by two weaker axial Cu-Cl bonds (2.8642(12) Å) with chlorido ligands from the skeleton. The Cu(I) and Cd(II) atoms in the skeleton exhibit tetra-(CuC4 chromophore) and penta-coordination (CdN3Cl2), respectively. The temperature-dependent susceptibility measurements indicate a Curie-Weiss-like behaviour and the presence of weak anti-ferromagnetic interaction.

The structure of styryl dye, 2-[(E)-2-(4-dipropylaminophenyl)-1-ethenyl]-1,3,3-trimethyl-3H-indolium chloride (I), was investigated using methods such as UV-VIS, fluorescence spectroscopy, and NMR (1H, 13C, APT, HMQC, COSY) and also by examining its electrochemical properties. A study of the acid-base properties revealed the existence of three different forms of the dye. The mechanisms of protolysis and hydrolysis are discussed. The reagent exists in a reactive single-charged form I + over a wide range of acidity (pH 4–11). The optimum analytical wavelength of the singlecharged form is 550 nm, where the molar absorptivity is 5.51 × 104 L mol−1 cm−1. The values of the optimum analytical wavelength and molar absorptivity of the protolysed and hydrolysed forms are: λ max(I-H2+) = 380 nm, ɛ(I-H2+) = 2.01 × 104 L mol−1 cm−1; λ max(I-OH) = 320 nm, ɛ(I-OH) = 1.12 × 104 L mol−1 cm−1. A theoretical study of the spectral and chemical properties of I was carried out by performing quantum chemical calculations.

A series of water-soluble carboxymethyl chitosan (CMCS)/poly(propylene glycol) (PPG) blend films with various CMCS/PPG mole ratios were prepared by the solution casting method. Morphology of the CMCS/PPG blend films was investigated by scanning electron microscopy (SEM). Thermal, mechanical, and chemical properties of the CMCS/PPG blend films were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile tests, and contact angle tests. It was found that the introduction of PPG can markedly affect the morphology and the properties of CMCS films.

Hydroxyapatite (HA) has many applications in medicine as a biocompatible and bioactive biomaterial. Numerous studies have shown that modification of the HA surface can improve its biological and chemical properties. However, little is known about the surface properties of modified materials. In this paper the influence of organic polymers: polyethylene glycol (PEG) and polyhydroxyethyl methacrylate (pHEMA) on the surface properties and surface chemistry of hydroxyapatite (HA) is presented. The surface properties of modified HA were characterised by the FT-IR, XPS, BET, and zeta potential measurements. Specific surface area was determined by BET. Infrared and XPS spectra confirmed the presence of PEG and pHEMA on the surface of HA. The BET N2 adsorption revealed slight changes in the HA surface chemistry after grafting modification. The surface chemical properties of the HA were considered to be based on the zeta potential. The decrease in zeta potential results in the increasing stability of the modified material and also in the reduction of bacterial adhesion. The reaction for surface modification of HA is proposed and described.

An efficient method has been developed for the synthesis of a novel β-keto ester-containing pyranoquinoline compound, i.e., ethyl 4-oxo-3,4-dihydro-1H-pyrano[3,4-b]quinoline-3-carboxylate. The method entails a two-step synthesis. The first step involves the Williamson-type reaction of ethyl 2-bromomethyl-3-quinoline-3-carboxylate with ethyl hydroxyacetate in anhydrous benzene to afford the intermediate ethyl 2-[(2-ethoxy-2-oxoethoxy)methyl]quinoline-3-carboxylate. The second step includes the Dieckmann condensation reaction of the resulting intermediate in the presence of sodium ethoxide in anhydrous toluene to afford the desired pyranoquinoline containing β-keto ester moiety. Keto-enol tautomerism of the compound thus obtained was investigated by spectroscopic methods.

Twenty acid chlorides, 4-(mono/di-benzyloxy)-4-ketobutanoyl chlorides (Ia–XXa) were synthesised by the reaction of monoesters of succinic acid with thionyl chloride. The product thus obtained (4-benzyloxy-4-ketobutanoyl chlorides) was treated with diethylcadmium to convert it into the corresponding keto-esters (Ib–XXb), the mono/di-benzyl-γ-ketohexanoates, with a good yield. All the compounds thus prepared were characterised by physical, spectroscopic (UV-VIS, IR, 1H NMR, 13C NMR), and mass measurements techniques.

Complexation reactions between water-soluble and -insoluble reactants were shown to occur in aqueous media in the presence of normal or reverse surfactant micelles, in significantly higher yields at lower temperatures compared to those achieved in neat organic solvents. The highest yield enhancement in the complexation of novel water-insoluble bis(2-amino-1,3,4-thiadiazolyl)methane and 1,4-bis(2-amino-1,3,4-thiadiazolyl)benzene ligands with Cu(II) ions was achieved in the sodium bis(2-ethylhexyl)sulfosuccinate (AOT)-heptane-water reverse micellar system at the hydration ratio of 15. The results revealed that AOT normal micelles cause a change in the reaction mechanism together with the enhancement of the complex formation. The observed micellar effects were rationalized on basis of the properties of bulk solvents, surfactants and ligands, considering the solvation and hydration ratios of reverse micelles. The results have proved the dependence of complex yield on the amount and accordingly also on the properties of water in the micellar core, indicating that the yield can be maximized by the optimization of the hydration ratio.

Three ligands of 2-pyridinylmethylene-8-quinolinyl (L1), methyl-2-pyridinylmethylene-8-quinolinyl (L2), and phenyl-2-pyridinylmethylene-8-quinolinyl (L3), Schiff bases were synthesised by direct condensation of 8-aminoquinoline with 2-pyridinecarboxaldehyde, 2-acetylpyridine, or 2-benzoylpyridine. They coordinated to Fe(II) ion in a 1: 2 mole ratio followed by treatment with iodide ions affording complexes with a general formula [Fe(L)2]I2·2H2O, (L = L1, L2, or L3). Spectrophotometric evaluation of the kinetics of base catalysed hydrolysis of these complex cations was carried out with an aqueous solution of NaOH in different ratios of water/methanol binary mixtures. Kinetics of the hydrolysis followed the rate law (k 2[OH−] + k 3[OH−]2)[complex]. Reactivity trends and their rate constants were compared and discussed in terms of ligand structure and solvation parameters. The methanol ratio affects the hydrolysis as a co-solvent which was analysed into initial and transition state components. The increase in the rate constant of the base hydrolysis of Fe(II) complexes, as the ratio of methanol increases, is predominantly caused by the strong effect of the organic co-solvent on the transition states.