Volume 68, Issue 4

Analytical aspects of the determination of inorganic mercury (Hg) species by thermal desorption followed by atomic absorption spectrometry (AAS) detection were investigated in this work. Characteristic Hg release curves of the following species were observed: Hg0, HgCl2, HgO, HgSO4, HgS, and the Hg bound to humic acids. Particular attention was dedicated to the thermal stability and change of bond of Hg0 in the following matrices: sand, kaolinite, granite, peat, power plant ash, and soil. The bond of elemental Hg in environmental materials was described on basis of this experiment. Contaminated soil samples from two locations in the Czech Republic were investigated by thermal desorption analysis. Afterwards, the contents of volatile and plant-available Hg in the studied samples were determined. The determination of Hg0 using the thermal method was related to the results of liquid sequential extraction. The development of Hg speciation and the stability of Hg were assessed on basis of the data obtained. Thus, the analytical procedure used is a suitable tool for the study of inorganic Hg species in contaminated soils.

A novel non-enzymatic electrochemical sensor based on a nanoporous gold electrode modified with platinum nanoparticles was constructed for the determination of hydrogen peroxide (H2O2). Platinum nanoparticles exhibit good electrocatalytic activity towards hydrogen peroxide. The nanoporous gold (NPG) increases the effective surface area and has the capacity to promote electron-transfer reactions. With electrodeposition of Pt nanoparticles (NPs) on the surface of the nanoporous gold, the modified Au electrode afforded a fast, sensitive and selective electrochemical method for the determination of H2O2. The linear range for the detection of H2O2 was from 1.0 × 10−7 M to 2.0 × 10−5 M while the calculated limit of detection was 7.2 × 10−8 M on the basis of the 3σ/slope (σ represents the standard deviation of the blank samples). These findings could lead to the widespread use of electrochemical sensors to detect H2O2.

Amylases from Rhizopus oryzae and Rhizopus microsporus var. oligosporus were obtained using agro-industrial wastes as substrates in submerged batch cultures. The enzymatic complex was partially characterised for use in the production of glucose syrup. Type II wheat flour proved better than cassava bagasse as sole carbon source for amylase production. The optimum fermentation condition for both microorganisms was 96 hours at 30°C and the amylase thus produced was used for starch hydrolysis. The product of the enzymatic hydrolysis indicated that the enzyme obtained was glucoamylase, only glucose as final product was attained for both microorganisms. R. oligosporus was of greater interest than R. oryzae for amylase production, taking into account enzyme activity, cultivation time, thermal stability and pH range. Glucose syrup was produced using concentrated enzyme and 100 g L−1 starch in a 4 hours reaction at 50°C. The bioprocess studied can contribute to fungus glucoamylase production and application.

Amongst various carbon sources, xylan was found to be the sole inducer of endoxylanase production by Penicillium janthinellum MTCC 10889 in submerged cultivation. Endoxylanase synthesis by a xylan induced culture was initially repressed after a simultaneous addition of xylose, probably by the inducer exclusion mechanism, but it was resumed and achieved its highest level at a much later stage of growth (at 120 h). Xylose added after 30 h of growth cannot exert its full repressive effect. Although glucose was proved to be a more potent repressor than xylose, supplementation of salicin, an alcoholic β-glycoside containing d-glucose, with pure xylan resulted in an about 3.22 fold increase in the enzyme synthesis at 72 h followed by constant high production of the enzyme at least until the 144th h of growth. Inducing capacity of salicin in a xylan induced culture was significantly reduced when it was added after 30 h of growth. Addition of salicin and xylan help to partially overcome the repressive effect of xylose and glucose. Failure of salicin in recovering the endoxylanase synthesis in actinomycin D and cyclohexamide inhibited the xylan induced culture indicating that salicin cannot initiate the de novo synthesis of the enzyme.

A flat sheet-supported liquid membrane (FSSLM) system, consisting of an ionic liquid, tricapryl-methylammonium chloride (Aliquat 336®) in octan-2-ol, is proposed as a means of recovering acetaminophen (Ac) from aqueous solutions; Ac is an active ingredient widely used in many pharmaceutical preparations. Several parameters which could affect the transport efficiency were examined, i.e., the strippant nature and concentration in the receiving solution, the diluent nature, carrier concentration, initial acetaminophen concentration in the feed solution, and the polymeric support type. A facilitated transport was obtained by impregnating the polymeric support with 10 vol. % of Aliquat 336® in octan-2-ol, 1 M NaOH as a receiving solution, and a feed solution of Ac dissolved in ultrapure water. The study was completed by using the FSSLM thus developed for extracting Ac from some drugs in frequent use in Tunisia (Analgan®, Doliprane®, and Fervex®).

In the past decade, ionic liquids have received great attention owing to their potential as green solvent alternatives to conventional organic solvents. In this work, hydrophobic achiral ionic liquids (1-butyl-3-methylimidazolium-hexafluorophosphate([bmim][PF6]), 1-octyl-3-methylimidazolium tetrafluoroborate([omim][BF4])) were used as solvents in chiral liquid-liquid extraction separation of mandelic acid (MA) enantiomers with β-cyclodextrin (β-CD) derivatives as hydrophilic chiral selectors preferentially forming complexes with (R)-enantiomers. Factors affecting the separation efficiency were optimised, namely the type of the extraction solvents and β-CD derivatives, concentrations of the β-CD derivatives and MA enantiomers, pH, and temperature. Excellent enantioseparation of MA enantiomers was achieved in the ionic liquid aqueous two-phase extraction systems under the optimal conditions of pH 2.5 and temperature of 5°C with the maximum enantioselectivity (α) of 1.74. The experimental results demonstrated that the ionic liquid aqueous two-phase extraction systems with a β-CD derivative as the chiral selector have a strong chiral recognition ability, which might extend the application of ionic liquids in chiral separation.

Conversion of high free fatty acids (FFA) containing acid oil (AO) to fatty acid methyl esters (FAME) using silica sulfuric acid (SSA) as a solid acid catalyst was investigated. Process parameters such as reaction temperature, reaction time, catalyst loading, and methanol to oil molar ratio were optimized using the Taguchi orthogonal array method. Maximum FFA conversion (97.16 %) was achieved under the optimal set of parameter values viz. 70°C, 4 mass % catalyst loading, and 1: 15 oil to methanol molar ratio after 90 min. SSA was reused three times successfully without a significant loss in activity. Biodiesel produced from AO met the international biodiesel standards. Determination of kinetic parameters proved that the experimental results fit the pseudo first order kinetic law.

Concentrations and interrelationships of twenty elements were studied in parasol mushroom and in the top layer of soil (0–10 cm) from the area of Kiwity (Poland). K, P, Mg, Ca, and Zn were found to be the most abundant elements in the mushroom. Higher concentrations of Fe, Mn, Na, Ni occurred in stipes then in caps, while Cd, Cr, Cu, Hg, Rb dominated in caps. Ag, Al, and Ba concentrations in caps and stipes were similar. Parasol mushroom is efficient in up-take and separation of Ag, Cd, Cu, Hg, K (in caps, the bioconcentration factor is BCF ≥ 100), Na, P, Rb (50 < BCF < 100), and Mg, Zn (BCF > 10) in its fruiting bodies, while Al, Ba, Ca, Co, Cr, Fe, Mn, Sr, and Pb are eliminated (BCF < 1). Parasol mushroom from rural forest area in the north-eastern region of Poland is of hygienic concern for human health because of toxic mercury and cadmium content in the edible caps, which are also rich in essential Cu, Fe, and their K, Mn, and Zn content is also high.

The antioxidant activity (AA), total phenolic content (TPC) and total flavonoids content (TFC) in Dong quai (DQ, Angelica sinensis) raw materials and dietary supplements (DS) containing this plant were determined using the CUPRAC, FRAP and fluorescence methods. The antioxidant activity for DQ aqueous extracts revealed by CUPRAC was (1330.45 ± 1.30) μmol Trolox equivalent (TE) per 100 g of dry mass (DM), whereas the antioxidant activity as determined by FRAP was (1813.9 ± 2.0) μmol of TE per 100 g of DM. Lower values were noted for the fluorescence method than for CUPRAC and FRAP (ranging from (35.96 ± 0.3) to (304.6 ± 1.4) μmol of TE per 100 g of DM). The highest TPC values were determined for an aqueous extract of DQ ((3330.3 ± 2.3) μmol of TE per 100 g of DM), while TFC for ethanolic extracts of DQ was ((146.50 ± 0.5) mg of quercetin equivalent (QE) per 100 g of DM). Cinnamic acid, isomers of benzoic acid and derivatives of quercetin were analysed by HPLC-PDA. The ferulic acid concentration in an ethanolic extract of DQ was (21.83 ± 0.07) mg per 100 g of DM. Of the flavonols detected, rutin exhibited the highest concentration in ethanolic extract of DQ ((3.32 ± 0.13) mg of QE per 100 g of DM). Other phytochemicals (alkaloids, saponins, flavonoids, anthraquinones, tannins, steroids, etc.) were identified by phytoscreening colour reaction. The results were analysed by principal component analysis (PCA), cluster analysis and one-way ANOVA tests.

Three types of conducting polymers, polyaniline (PANI), poly(N-methylaniline) (PNMA), poly(N-ethylaniline) (PNEA) were electrochemically deposited on pencil graphite electrode (PGE) surfaces characterized as electrode active materials for supercapacitor applications. The obtained films were electrochemically characterized using different electrochemical methods. Redox parameters, electro-active characteristics, and electrostability of the polymer films were investigated via cyclic voltammetry (CV). Doping types of the polymer films were determined by the Mott-Schottky method. Electrochemical capacitance properties of the polymer film coating PGE (PGE/PANI, PGE/PNMA, and PGE/PNEA) were investigated by the CV and potentiostatic electrochemical impedance spectroscopy (EIS) methods in a 0.1 M H2SO4 aqueous solution. Thus, capacitance values of the electrodes were calculated. Results show that PGE/PANI, PGE/PNMA, and PGE/PNEA exhibit maximum specific capacitances of 131.78 F g−1 (≈ 436.50 mF cm−2), 38.00 F g−1 (≈ 130.70 mF cm−2), and 16.50 F g−1 (≈ 57.83 mF cm−2), respectively. Moreover, charge-discharge capacities of the electrodes are reported and the specific power (SP) and specific energy (SE) values of the electrodes as supercapacitor materials were calculated using repeating chronopotentiometry.

ZnO nanostructures were synthesised in a hydrothermal reaction of zinc acetate in the presence of molybdophosphoric acid (H3[PMo12O40]) as well as its vanadium-substituted acid (H4[PMo11VO40]) at various times, temperatures, and concentrations. The ZnO nanostructures were characterised by X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. The results demonstrated that the synthesised products are crystalline with a zincite hexagonal phase. Various ZnO nanostructures, such as nanoparticles, microrods, and nanosheets, were produced by changing the experimental conditions. The photocatalytic degradation of methyl orange was also investigated using the ZnO nanoparticles thus prepared. These particles exhibited high performance in the photocatalytic degradation of MO and almost 100 % decolourisation occurred within only 20 min.

I2 is an effective promoter for the synthesis of 2,3-unsaturated glycosides via Ferrier glycosylation. This reaction was used in the present work for the synthesis of O-glycosylated Fmoc amino acid building blocks. This metal-free reaction afforded the desired products with good to excellent yields with good α-selectivity.

1,1-Diacetates derivatives were prepared using the direct condensation of aldehydes with acetic anhydride in the presence of silica-supported boron sulfonic acid (SiO2/B(SO4H)3) as a tri-functional inorganic Brønsted acid catalyst under solvent-free conditions at ambient temperature. The salient features of this methodology are: (i) cheaper process ready availability of the catalyst; (ii) versatility; (iii) high regio-selectivity of the procedure and recyclable property of the catalyst.

Due to an increasing demand for effective anti-cancer drugs, an oxopyrrolidine-based ligand, sodium 1-(3-(2-aminoethylamino)propyl)-5-oxopyrrolidine-2-carboxylate, was synthesised by the sodium hydride-assisted coupling of pyroglutamic acid with 1,3-diiodopropane under a nitrogen atmosphere. The intermediate thus formed was allowed to react with ethylenediamine in acetonitrile. The ligand formed individual complexes with Cu(II) and Ni(II) metal ions, respectively. The complexes were relatively resistant to degradation in PBS at physiological pH. The DNA-binding constants (K b) for the ligand, copper and nickel complexes were 2.09 × 104 M-1, 2.37 × 104 M-1 and 2.11 × 104 M-1, respectively, revealing the strong binding of these complexes with DNA. Haemolysis assays indicated that the ligand and its complexes were less toxic to rabbit RBCs than doxorubicin. Lipinski’s parameters calculated for the reported compounds indicated their good oral bioavailability. All the compounds exhibited good activities towards MCF-7 (wild type) cancer cell lines. The results of in silico studies, DNA-binding and anti-cancer activities indicated that the reported compounds might be interacting with DNA as one of their possible mechanisms of action.

The characterisation of smectite clay, charcoal and prepared clay-charcoal composites was carried out through the X-ray diffractometry, energy dispersive X-ray spectroscopy (EDS), simultaneous thermal analysis (TGA/DTA), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The analysis revealed the composites to have different characteristics from the precursor clay and charcoal, and a peak displacement (d 001) was observed through the X-ray diffraction; this suggests the incorporation of charcoal into the clay lamellas and the formation of a new phase. Tests of adsorption with methylene blue dye were also carried out to evaluate the percentage of dye removal by the adsorbent, in which the composites presented better results than charcoal, indicating great potential for industrial use. A 23 factorial design was employed to evaluate the influence of temperature, ionic strength and pH on the adsorption of methylene blue using the AV50 composite that presented the best adsorption efficiency.

The aim of this study was to assess the role and proportional representation of depolymerisation and thermoxidation reaction paths in the systems paper/gum arabic (GA)/historical ink during various accelerated ageing methods. The historical inks under study are iron-gall, bistre, and sepia. The results indicate that thermoxidation represents only a minor reaction path in the ageing of paper/GA/ink systems except for the iron-gall ink and the light-thermal method of accelerated ageing. The iron-gall ink accelerates both reaction paths of ageing, i.e. thermoxidation and depolymerisation; in this case, thermoxidation might become the prevailing degradation reaction path. For the sepia ink, an anti-depolymerisation stabilising effect in thermal methods of ageing has been detected. Considering the thermoxidation reaction path, the results even suggest that a compound preventing thermoxidation is formed during the thermally accelerated ageing in air and in 100 mg L−1 of NO2. In the light-thermal ageing, the most stable sample is the Whatman paper (W)/GA/bistre ink.

Naturally occurring organic acids are reported to be highly efficient promoters of the Beckmann rearrangement. Citric, oxalic, tartaric, malic, succinic, malonic, and fumaric acids efficiently promote the Beckmann rearrangement under solvent-free conditions and thermal and microwave irradiation. Tartaric acid was found to be the best promoter of the Beckmann rearrangement under conventional conditions as well as under microwave irradiation. Compared with conventional heating, microwave irradiation provides higher reaction rate and slightly higher yields.