Volume 62, Issue 5

Ninety-three water samples were categorized into five classes as the tap, mineral, mineral carbonated, spring, and spring carbonated water, or, alternatively, into four or three categories — with all spring water samples together or as tap, mineral, and spring water, respectively. The samples originated from four European countries and thirty-one chemical descriptors (concentrations of contained elements) were used for their characterization. Analytical measurements were performed by mass spectrometry with inductively coupled plasma, allowing the determination of individual nuclides. Different water categories were characterized by chemometrical techniques, mainly by principal component analysis, cluster analysis, linear and quadratic discriminant analyses, correlation analysis, and ANOVA. Their role was to discover the nuclides important for distinct characterization of individual water categories as well as to assess the possibility of water samples from different countries being recognized from the increased/decreased content of some elements. The enhanced content of Cd, Cu, Zn, Bi, and Fe was characteristic for tap water samples, whilst mineral water samples were characterized by the elevated concentration of Sr, Li, B, Ni, Co, As, and Sb. The classification results were successful and close to 100 %, which was proved by the leave-one-out cross-validation procedure.

Possibilities of membrane technology and the use of membrane processes in wastewater treatment were investigated. The main focus was the monitoring of the starting phase of a domestic wastewater treatment plant. Experimental part of the study was realized at the municipal wastewater treatment plant (WWTP) Devínska Nová Ves — Bratislava during the period from February 2005 to September 2006. The system was stable without any external chemical treatment of the membrane modules and the permeate quality was very high. Observed decrease of COD and BOD5 values ranged between 91 % and 98 %. The process of nitrification was very successful considering its high efficiency (> 95 %).

Design of affinity membrane adsorbers for the purification of biomolecules requires a consideration of loading, washing, and elution. Modelling and simulation of membrane adsorbers in literature is, however, strongly focused on the loading step. Therefore, in this work, a complete process model which takes all the different steps into account was developed. Breakthrough experiments in which human IgG was captured onto and eluted from Sartobind Protein A downscale modules were used for model validation and for estimation of the required model parameters. The experimentally observed breakthrough curves were independent of the applied flow rate and from these results linear correlations between lumped kinetic parameters and linear velocity were determined. During elution, desorption was best described by an irreversible reaction of first order in H+ concentration. Applicability of the developed model to computer-aided design was illustrated through a process analysis study in which the influence of the amount of loaded protein per cycle on the process yield and productivity was investigated.

Synthesis and characterization of six copper(II) and cobalt(II) octahedral complexes [M(6-OHpic)2(H2O)2] (6-OHpic is 6-hydroxypicolinato), [M(2-OHnic)2(H2O)2] (2-OHnic is 2-hydroxynicotinato), [Cu(6-OHnic)2(H2O)2] (6-OHnic is 6-hydroxynicotinato) as well as [Co(H2O)6](6-OHnic)2 are reported. Their characterization was carried out using elemental analysis, infrared, and magnetic measurements. Based on IR spectra, N,O-coordination of 6-OHpic (via the oxygen atom of the carboxyl group and the nitrogen atom of the pyridine ring), O,O-asymmetrically chelating coordination of the carboxyl groups as well as ionic coordination of 6-OHnic and chelating O,O-coordination (through the oxygen atom of the carboxyl group and the oxygen atom of the amide group) of keto(amide) tautomer of 2-OHnic were supposed. Moreover, crystal structures of 2-OHnicH and the complex [Co(2-OHnic)2(H2O)2]) were determined by X-ray single crystal structure analysis. The system of hydrogen bonds predominantly stabilizes the keto(amide) tautomer of both 2-hydroxynicotinic acid and 2-OHnic anion in the cobalt(II) complex. Intermolecular hydrogen bonds (between the oxygen atom of the amide group and the hydrogen atom of the NH group) interconnect two neighbouring molecules of 2-OHnicH forming dimers. Cobalt(II) in complex [Co(2-OHnic)2(H2O)2] has nearly a regular compressed tetragonal bipyramidal arrangement.

Six new title compounds in the form of Cd(cyclobutylamine)2M′(CN)4 · 2G (M′ = Cd or Hg; G = benzene, 1,2-dichlorobenzene, or 1,3-dichlorobenzene) have been prepared in powder form. Their spectral data were found to be consistent with the structure of the Hofmann-T d-type clathrates.

Gaussian analysis of bands between 500 cm−1 and 600 cm−1 attributed to the $$ \tilde \nu $$ as (Cu4O) stretching vibration of the tetrahedral Cu4O core in Cu4OBrnCl(6−n)(4-Mepy)4 (n = 0–6) complexes showed two bands, symmetry reduction of the T 2 mode of vibration towards the A 1 and E modes and vibrational coupling with an R-sensitive in-plane pyridine ring bending. The Cu-O bond is considered as vibrationally coupled with the Cu-N bond and the pyridine ring through the donor-acceptor vibrational coupling and the corresponding equilibrium charge distribution. The linear correlation between $$ \tilde \nu $$ as(Cu4O) and the number of bromides in Cu4OBrnCl(6−n)(4-Mepy)4 complexes was used for the estimation of partial charges on the 4-Mepy ligands which were positive for the prevailing donors and negative for the prevailing acceptors thus evoking a π-back bonding between the Cu(II) atoms and the 4-Mepy ligands. Correlations involving selected bond lengths and bond angles in the molecular structure of the Cu4OCl6(4-Mepy)4 complex with four symmetrically independent molecules present in the unit cell indicate a symmetry reduction of the T 2 mode of vibration and the π-back bonding between the Cu(II) atoms and the 4-Mepy ligands.

From a series of pentanuclear, heterobimetallic complexes of the general composition [{Ln(H2O)n}2{Ni(dto)2}3] · xH2O, four complexes (Ln = Gd(III) with n = 4; Ln = Dy(III), Ho(III), or Er(III), with n = 5; x = 9–12; dto = 1,2-dithiooxalate) were studied due to their large magnetic moments (up to 14.65 B.M.). The magnetic properties of these complete series were measured at room temperature and the temperature dependent magnetic properties of the complexes Gd2Ni3, Dy2Ni3, Ho2Ni3, and Er2Ni3 were studied at room temperature down to 1.8 K. Whereas the intramolecular metal-metal distances were rather long (Ni1-Ni2: 11.0–11.5 Å; Ln-Ni: 6.0–6.3 Å), relatively short intermolecular metal-metal distances (Ni1-Ni2′: 3.5 Å; Er-Er′: 6.0 Å) were found in the crystal lattice, giving rise to weak intermolecular metal-metal interactions. These weak spin interactions were also supported by the EPR spectrum of a powdered sample of the diamagnetically undiluted Gd2Ni3 complex.

Iron(III)-5-fluorosalicylic acid systems were investigated in water by pH potentiometry combined with UV-VIS spectrophotometry. The data revealed that stable aquated mono-, bis-, and tris(5-fluorosalicylato) iron(III) complexes are formed together with their monohydroxo and dihydroxo analogues. The stability constants of all present iron(III) species were calculated. Based on pH and the metal: ligand ratio dependent distribution of the species, electronic absorption spectra of the complexes in the visible region were obtained. Redox stability was monitored as an ability to undergo both spontaneous and photoinduced reduction of iron(III) to iron(II). Complexes do not undergo any redox changes when in dark neither in methanol nor in water. While aqueous solutions of complexes are stable under the influence of incident visible radiation, steady-state irradiation of the methanolic systems by visible light led to photoreduction of iron(III) to iron(II), the quantum yield of iron(II) photoformation was determined.

In order to investigate the effect of presence of well defined nano-sized inorganic particles on the molecular mobility a conformation statistics of polymer chains, well defined polystyrene (PS) and poly(methyl methacrylate) (PMMA) macromolecules containing polyhedral oligomeric silsesquioxanes nanoparticles (POSS) were synthesized by copper-mediated atom transfer radical polymerization (ATRP). Two approaches were used for the synthesis — the first involves POSS as the initiator of ATRP; the second way considers an addition of POSS to the polymer (prepared by ATRP) with an appropriate functional group. Kinetics of polymerization was determined using common analytical methods and it was compared to the polymerizations initiated by low-molecular weight initiators, regarding the polymerization rate, initiation efficiency and polydispersity of the polymer. Efficiency of the initiation with POSS-containing initiators was low, causing remnants of inseparable free POSS in polymer. The second approach bypassed these disadvantages —POSS is connected to the polymer through a pending allyl group using the very efficient hydrosilylation reaction.

The influence of surface-applied original and enzymatically-modified sugar beet pectin on strength properties of fluting, coating base paper, and core board was investigated. The effect was compared with the application of commercial strength-increasing agents. With increasing the polymer uptake, measured strength of paper increased. Original sugar beet pectin increased the strength properties of papers, at the same uptake of polymer, to a higher extent than oxidised potato starch or modified grain flour, while the effect of enzymatically-modified sugar beet pectin was the lowest. For the same increase of paper strength, a several times higher uptake of enzymatically-modified sugar beet pectin was required when compared with the original pectin, oxidised potato starch, or modified grain flour.

In the effort to improve the performance of hydroxylapatite (HA) in removing lead ions from aqueous solutions, millimeter-sized granules with 50 % porosity were synthesized. Such HA particles, after drying at 100°C, or heating at 800°C or 1100°C, exhibited the specific surface areas of 50 m2 g−1, 25 m2 g−1, and 5 m2 g−1, respectively. It was found that heavy metal sorption capacity of HAs can be related to their surface area. Non-calcined granules were difficult to handle and easy to crush. Hardened granules showed heavy metal absorption on their outer surfaces. Absorption capacity of sintered HA particles towards lead was lower but adsorbed lead ions were spread inside the porous structure of HA granules more evenly. Under flow conditions, lead ions were captured by HA at a rate of 0.5 mg g−1 min−1. Small lead phosphate aggregates were released from the HA sorbent together with calcium ions. Size of the aggregates depended on the lead concentration and ranged from 1–50 μm in diameter; the aggregates could be removed by ultrafiltration. Results show that porous hardened HA granules can be used as an efficient phosphate source for the immobilization of lead ions from aqueous media. Organic ligands tend to interfere with the water purification procedure.

One-pot synthesis of aryl-14H-dibenzo[a,j]xanthene and 1,8-dioxo-octahydroxanthene derivatives using montmorillonite K10 as reusable eco-friendly catalyst under solvent-free conditions is described.

Plant-originated cyclopolypeptide (XIII) was synthesized by coupling of dipeptide Boc-l-asn(bzh)-l-phe-OH and tetrapeptide gly-l-leu-l-ala-l-tyr-OMe followed by cyclization of a linear hexapeptide segment. Structure elucidation of XIII was done on basis of detailed spectral analysis including FTIR, 1H NMR, 13C NMR, FAB MS and elemental analysis. From the results of pharmacological screening, it was concluded that XIII possesses high cytotoxic activity against DLA and EAC cell lines with CTC50 values of 15.1 μM and 18.6 μM, and potent antimicrobial activity against pathogenic fungi C. albicans with MIC of 6 μg mL−1. Moreover, XIII possesses moderate anthelmintic activity against earthworms M. konkanensis, P. corethruses, and Eudrilus sp. at 2 mg mL−1 dose level.

The title compound is the first example of N,N′-diethylnicotinamidium, [denaH]+, salt which has been characterized by X-ray analysis and IR spectra. [denaH]ClO4 was obtained from the reaction mixture prepared from N,N′-diethylnicotinamide (dena) and Fe(ClO4)3 in ethanol without any addition of HClO4. The proton required for protonation of dena is produced by hydrolysis of aquairon(III) cations. In the crystal structure, cations and anions are held together by ionic interactions. The cations are linked to each other by pyridinium-carbonyl N-H⋯O=C hydrogen bonds and an infinite linear chain along axis a is formed.