Band 65, Heft 2

Polyunsaturated fatty acids (PUFAs) are functional lipids that have been widely incorporated into several industrial sectors. Apart from animal- and plant-derived origins, oleaginous fungi belonging to Mucorales have been identified as promising alternatives for production of n-3 and n-6 PUFAs. It was found, in Mucorales fungi, that ATP:citrate lyase, acetyl-CoA carboxylase and malic enzyme trigger lipid overproduction, and biosynthesis of PUFA requires membrane-bound desaturases with fatty acyl substrate specificities. Accumulation of PUFAs in the cells is associated not only with the desaturation system, but it is also tightly bound with acyltransferases that facilitate the distribution of newly synthesized PUFA to individual lipid structures. Several physical parameters, such as temperature, aeration, and nutrient regimes, greatly affect either the lipid content or fatty acid composition among different Mucorales species. Conclusive evidence showed that the PUFA production yield of the fungi depends on the environmental control of “oleaginous” enzymes, and on the transcriptional expression of the desaturase genes. These valuable studies provide perspectives with biological rationale for microbial production of economically important lipids.

The quantitative structure-retention relationship (QSRR) was used to predict Kováts retention indices of forty-three volatile olefins on the chemically bonded stationary phase, containing 1,4,8,11-tetraazacycloteradecane (cyclam) complexes of copper(II) chloride. Retention indices were correlated with eleven descriptors derived from structures of olefins optimised using the molecular mechanics force field calculations (MM2). Descriptors were generated with the use of quantitative structure-activity relationships (QSAR), semi-empirical Austin Model 1 methods (AM1), and obtained from physicochemical databases. Five well-correlated models were built, with predictive coefficients of determination (R 2) values of 0.993 and 0.995. The dielectric energy (DE) descriptor was identified as being as important as the polarizability (P) descriptor in the process of separation of unsaturated olefins on stationary phases containing metal complexes. The DE index proved to be decisive in distinguishing between the geometric cis and trans isomers of the tested compounds.

A piece of fused-silica fibre coated with silica modified with ketamine-groups was used as a solidphase microextraction (SPME) fibre and its efficiency in the qualitative and quantitative analysis of volatile organic compounds released from coloured overprinting on DVDs was evaluated. The effect of the parameters that can affect the SPME procedure, such as extraction time, extraction temperature, desorption temperature, was investigated to determine the analytical performance of this novel fibre in the qualitative and quantitative analyses of organic compounds. The optimised procedure was applied to the qualitative and quantitative analyses of organic compounds released from coloured overprinting on DVDs. The limit of detection of 4-methoxyphenol (mequinol) was 88 × 10−3 μg mL−1, while the limit of quantification (LOQ) was calculated as ten times the baseline noise, i.e. 3.1 × 10−1 μg mL−1. The proposed fibre was used successfully for preconcentration of the volatile organic compounds from the gaseous phase of DVD samples.

The kinetics of continuous citric acid (CA) fermentation, using two acetate-negative mutants of Yarrowia lipolytica (Wratislavia AWG7 and Wratislavia 1.31) with long-term cell recycle, were investigated at a dilution rate (D) of 0.011 h−1. The capacity of the mutants to produce CA from raw glycerol under steady state conditions was compared. The process involving the Wratislavia AWG7 strain showed that this strain was a better producer of CA than the Wratislavia 1.31 strain in this regime. In steady state, the concentration of CA in the effluent was constant and amounted to 116 g dm−3. This corresponded to a volumetric CA production rate of 1.3 g dm−3 h−1. A stable high-level production of CA was maintained for over 400 h of operation. The Wratislavia AWG7 strain employed remained highly stable throughout the experiment and demonstrated good viability, high genetic and phenotypic stability over the long-term continuous fermentation process.

Gamma-linolenic acid (GLA, C18:3Δ6,9,12) is an n-6 polyunsaturated fatty acid (PUFA) that has been used for the alleviation and treatment of a number of symptoms and diseases. Increasing GLA demand has led to a search for alternative producers and potential strategies for GLA production. Based on the successful performance of Hansenula polymorpha, a methylotrophic yeast, as a “cell factory” for the production of valuable bioproducts, a bioprocess development approach was implemented for GLA production in the recombinant yeast carrying the mutated Δ6-desaturase gene of Mucor rouxii. Using a substrate-feeding strategy under glycerol-limited conditions, the physical-chemical variables during the fed-batch fermentation of the recombinant H. polymorpha were optimised for GLA production through response surface methodology using a Box-Behnken design. The medium composition, including yeast extract and trace elements, and dissolved oxygen tension (DOT) were targeted. We found that DOT was the most effective variable for enhancing GLA yield. These results also suggest that the optimum conditions for GLA production are 28 % saturation of DOT, 1 g L−1 of yeast extract and 3.6 mL L−1 of the Pichia trace metals 1 (PTM1).

Results of the experimental research on gas hold-up, power consumption for liquid phase and gas—liquid systems, and on residence time of the gas bubbles are presented in the paper for an agitated vessel with a turbine impeller. Distilled water or aqueous solutions of NaCl were used as the liquid phase. Air was dispersed into liquid as the gas phase. The studies were carried out in an agitated vessel of the inner diameter D = 0.634 m. Tubular baffles of the diameter of 0.7D, consisting of 24 vertical tubes of the diameter of 0.016D, were located inside a flat-bottomed tank. Turbines with six blades and the pitch of 90°, 60°, or 45°, respectively, were used for agitation. Measurements were carried out in the range of good dispersion of gas bubbles in the liquid within the turbulent regime of the liquid flow. Effects of the gas bubbles capability to coalesce on the gas hold-up, residence time of the gas bubbles, and power consumption were analyzed. Results of the power consumption (P G-L/P o = f 1(Kg, Fr)) and gas hold-up (φ= f 2(Kg, We, Y)) were approximated mathematically, using Eqs. (5) and (6), respectively. In Eq. (6), parameter Y was introduced in order to describe the influence of the bubbles capability to coalesce on the gas hold-up. The results of the study show that power consumption does not depend on the capability of bubbles to coalesce, but the pitch of the turbine impeller affects the power characteristics in such a physical system significantly. However, the residence time of the gas phase in agitated liquid depends on the pitch of the impeller blade and on the capability of bubbles to coalesce.

Activated sewage sludge samples obtained from two different waste water treatment plants were investigated by thermogravimetric analysis. Due to a very high content of water in the sludge samples, these had to be dried at 160°C in an electrical oven in order to remove all adsorbed water. To ensure pyrolysis conditions, nitrogen atmosphere was applied. The pyrolysis decomposition process was carried out in the temperature range from ambient temperature to 900°C at three different heating rates: 2 K min−1, 5 K min−1, 10 K min−1. TGA and DTG curves of the decomposition processes were obtained. Temperature of onset decomposition, final temperature of decomposition, maximum decomposition rate, and decomposition temperature were determined by thermogravimetric analysis for both sludge samples used. The main decomposition process takes place at temperatures in the range from 230°C to 500°C. Above this temperature, there are only small changes in the mass loss which are often attributed to the decomposition of carbonates present in the sewage sludge samples. To determine the apparent kinetic parameters such as the activation energy and the preexponential factor, the so called Friedman isoconversional method was used. Because of the requirements of this method, initial and final parts of the decomposition process, where crossings of the decomposition lines occurred, were cut off. Obtained dependencies of the apparent activation energies and preexponential factors as a function of conversion were used backwards to calculate the modeled decomposition process of sewage sludge and the experimental data were in good accordance with the data obtained by simulation.

The paper presents results of an experimental analysis of the transport phenomena at the vicinity of the wall of an unbaffled agitated vessel with an eccentrically located impeller. Distributions of the transport coefficients were experimentally studied using an electrochemical method within the turbulent regime of the Newtonian liquid flow. Measurements were carried out in an agitated vessel with the inner diameter T = 0.3 m. Liquid height in the vessel was equal to the inner diameter, H = T. The agitated vessel was equipped with a Rushton or a Smith turbine or an A 315 impeller. Eccentricity of the impeller shaft was varied from 0 to 0.53. Local values of the dimensionless shear rate, shear stress, dynamic velocity and friction coefficient were integrated numerically for the whole surface area of the cylindrical wall of the vessel. Averaged values of these quantities were correlated with the impeller eccentricity and modified Reynolds number. The proposed Eqs. (5)–(8), with the coefficients given in Table 2, have no equivalent in open literature concerning this subject. Distributions of the shear rate, γ/n, and friction coefficient, f, at the vicinity of the cylindrical wall of the unbaffled vessel equipped with eccentric Rushton or Smith turbine or A 315 impeller are very uneven and they depend significantly on the impeller eccentricity, e/R. Maximum local values of these variables are located on the wall section closest to the impeller blades. From among the tested impellers, the greatest effects of the impeller eccentricity, e/R, and the liquid turbulence (described by the modified Reynolds number Re P,M) on the averaged dimensionless shear rate (γ/n)m and friction coefficient, f m, are found for the radial-flow Rushton turbine located eccentrically in an unbaffled agitated vessel.

1-Phenylethanol can be produced by biotransformation of acetophenone using microorganisms. The next step is the separation of biomass from the fermentation solution (e.g. using microfiltration) and then the separation of the product. Membrane extraction was studied in the presented work for this purpose. Equilibria of acetophenone and 1-phenylethanol in the equilibrium system solute-organic solvent-water were investigated for three different organic solvents (heptane, toluene, ethyl acetate). On the basis of this investigation, extraction kinetics of both solutes from the model aqueous solution to the heptane organic phase, using a hollow fiber membrane module, were studied. To simulate the extraction kinetics, mathematical model of an experimental parallel flow hollow fiber contactor is presented and verified using experimental values with good agreement. Extraction kinetics for the investigated organic solvents were simulated and compared using the verified mathematical model and the chosen membrane extraction parameters.

Steady state analysis of a combined hybrid process consisting of a reactive distillation column, pervaporation unit, and a distillation column is presented. This process configuration was first presented by Steinigeweg and Gmehling (2004) for the transesterification of methyl acetate and butanol to butyl acetate and methanol. This system is characteristic for its low reaction rate and complex phase equilibrium. Steinigeweg and Gmehling (2004) have shown that the combination of reactive distillation and pervaporation is favourable since conversions close to 100 % can be reached with a reasonable size of the reactive section in the reactive distillation column. The aim of this paper is to show that although high conversion can be achieved, very complicated steady state behaviour must be expected. The presented analysis is based on mathematical modelling of a process unit, where the steady-state analysis, including continuation and bifurcation analyses, was used. Multiple steady states were predicted for the studied system; three steady states with conversions higher than 98 %. However, not all predicted steady states met the maximal allowed temperature condition in the reactive section (catalyst maximal operation temperature of 393 K). The presence of multiple steady states reduces the operability and controllability of the reactive distillation column during its start-up and during the occurrence of any variation of operating parameters because the system can be shifted from one steady state to another one (concurrent exceeding the maximal allowed temperature) with unwanted consequences, e.g. production loss. Therefore, design and subsequent operation of such a complicated system is an ambitious task requiring knowledge of any possible system behaviour.

Experimental verification of our previous numerical simulation of wall effects on the terminal falling velocity of spherical particles moving slowly along the axis of a cylindrical vessel filled with a Carreau model fluid is presented. Dependences of the wall correction factor F W on the sphere to tube ratio d/D and on the dimensionless Carreau model parameters m, Λ, and η r were obtained using a finite element method. Calculated data of the wall correction factor were compared with the results of our new falling sphere experiments. The experiments were carried out in six types of cylindrical Perspex columns (16 mm, 21 mm, 26 mm, 34 mm, 40 mm, and 90 mm in diameter) filled with aqueous solutions of polymers exhibiting different degrees of shear thinning and elasticity. Seventeen types of spherical particles (1–8 mm in diameter) made of glass, ceramics, steel, lead, and tungsten carbide were used for the drop tests. Measurements of the liquid flow curves, primary normal stress differences, oscillatory, creep and recovery, stress relaxation, and stress growth tests were carried out on the rheometer Haake MARS (Thermo Scientific). A good agreement between numerically and experimentally obtained F W data was found.

The results of studies concerning two- and three-phase systems in an agitated vessel are presented. The aim of our research was to investigate the effect of the physical properties of the liquid phase on the value of the volumetric gas-liquid mass transfer coefficient in mechanically agitated gas-liquid and gas-solid-liquid systems. Our experimental studies were conducted in a vessel with an internal diameter of 0.288 m. The flat bottom vessel, equipped with four baffles, was filled with liquid up to a height equal to the inner diameter. The liquid volume was 0.02 m3. Three high-speed impellers of a diameter equal to 0.33 of the vessel diameter were used: Rushton turbine (RT), Smith turbine (CD 6), or A 315 impeller. The measurements were carried out in coalescing and non-coalescing systems. Distilled water and aqueous solutions of an electrolyte (sodium chloride) of two different concentrations were used as the liquid phase. The gas phase was air. In the three-phase system, particles of sea sand were used as solid phase. The measurements were conducted at five different gas-flow rates and three particle loadings. Volumetric gas-liquid mass transfer coefficients were measured using the dynamic method. The presence and concentration of an electrolyte strongly affected the value of the gas-liquid mass transfer coefficient in both two- and three-phase systems. For all agitators used, significantly higher k l a coefficient values were obtained in the 0.4 kmol m−3 and 0.8 kmol m−3 aqueous NaCl solutions compared with the data for a coalescing system (with distilled water as the liquid phase). The k l a coefficient did not exhibit a linear relationship with the electrolyte concentration. An increase in the sodium chloride concentration from 0.4 kmol m−3 to 0.8 kmol m−3 caused a considerable decrease in the volumetric mass transfer coefficient in both the two-phase and three-phase systems. It was concluded that the mass transfer processes improved at a certain concentration of ions; however, above this concentration no further increase in k l a could be achieved.

Attempts to develop new technologies of NOx (NO + NO2) emission reduction are still carried out all around the world. One of the relatively new approaches is the application of ozone injection into the exhaust gas stream followed by the absorption process. Ozone is used to transform NOx to higher nitrogen oxides which yield nitric acid with better effectiveness. The main objective of this paper was to study the influence of mole ratio (MR) O3/NO used in the ozonation process of NOx on the effectiveness of NOx oxidation to higher oxides. The ozonation process was carried out in a flow reactor for concentrations of nitric oxide in the range of 1.5 × 10−5−7.7 × 10−5 mol dm−3 and varying O3/NO mole ratios. Measurements were conducted with the use of a FTIR spectrometer. The results obtained prove that for MR higher than 1, the oxidation effectiveness of nitric oxides generally reaches 95 %, whereas for MR higher than 2, oxidation of NOx to higher nitrogen oxides is completed.

Samples of iron catalysts of various specific surface areas for ammonia synthesis underwent nitriding with ammonia in a tubular reactor where continuous thermogravimetric measurement and measurements of hydrogen concentration in the gaseous phase were simultaneously performed. The nitriding process was performed under atmospheric pressure at 475°C. It was observed that, along with an increase in the mean size of iron nano-crystallites, the minimum nitriding potential (at which the iron nitriding reaction is initiated) of the gaseous phase also increased. The degree of nitriding of the catalyst samples increased with the increase in the mean size of iron crystallites. On the basis of the values of nitriding potential, nano-crystallite size distributions can be determined.

In the present work, the effect of individual additives calculated as molar fractions of Sb2O3 and CeO2 (x Sb 2O3 range: 0.03–0.08 %, x CeO 2 range: 0.05–0.14 %), on the phase composition, phase transformation, and optical properties of photostable rutile titanium dioxide was studied using selective leaching method, ICP-AES technique, XRD method, spectrophotometric analysis and S BET measurements. The starting material was hydrated titanium dioxide. It was observed that the addition of Sb2O3 to TiO2 did not influence the anatase-rutile phase transformation, but increasing the CeO2 addition caused a decrease in the rutilization degree. Thus, CeO2 acted as an inhibitor of the TiO2 phase transformation. Sb2O3 addition to TiO2 presumably caused the formation of a co-phase of Sb with Ti. Cerium formed a separate phase, CeO2, and reacted partly with titanium, probably creating co-phase, Ce0.8Ti0.2O2. Comparing the colour of modified rutile titanium dioxide according to the type of the additive introduced, it was found that TiO2 with CeO2 had higher brightness but lower white tone values when compared with TiO2 modified with Sb2O3. The relative lightening power and grey tone of the modified TiO2 were higher in TiO2 modified with Sb2O3. The values of the photocatalytic activity measured in all TiO2 samples modified either with Sb2O3 or CeO2 were very similar and varied around the value of 21.

Melt dispersion technique was investigated for carnauba wax microparticles production. Microbeads with spherical shape and narrow size distribution were produced. The main objective of this study was to investigate the effect of significant process variables (initial wax concentration, stirring speed, stirring time, and surfactants) on sphericity, size distribution, and morphological properties of wax microparticles. Optimal conditions were evaluated on the basis of particle size distribution and visual analysis. Surface morphology of microparticles was characterized by scanning electron microscopy (SEM). Effects of process conditions on the size distribution of particles were evaluated by sieve analysis. Main purpose of these investigations was to apply optimized parameters to aroma encapsulation for their use in food and feed industry.

Results of spectroscopic investigations related to complex compositions of 3-substituted derivatives of pentane-2,4-dione (β-diketonate) complexes with chosen d- and f-metal ions are presented. Ligands 3-allylacetylacetone (3all-acac) and 3-benzylacetylacetone (3ben-acac) were prepared and used for the complexation study with Cu(II), Co(II), Nd(III), and Ho(III) metal ions. Based on the absorption spectra of lanthanide ions in their hypersensitive transitions, with the use of computer assisted target factor analysis (CAT) and absorption spectra of the ligands with Cu(II) and Co(II), the verification of complex compositions and the determination of their stability constants were achieved. In case of Nd(III) and Ho(III) complexes with β-diketone ligands, absorption of their maxima were studied in the range of hypersensitive transitions 4 I 9/2 → 4 F 7/2 + 4 S 3/2 (λ max ∼ 734 nm and 748 nm) for Nd(III) and in the range of 435–465 nm, corresponding to the hypersensitive transition 5 G 6 → 5 I 8 (λ max ∼ 450 nm), for Ho(III).

Extraction experiments are presented dealing with the partition of Cu(II) complexes of 1-alkyl-2-methylimidazoles, 1-alkyl-2-ethylimidazoles, 1-alkyl-2-propylimidazoles, 1-alkyl-2-butylimidazoles, and 1-alkyl-2-pentylimidazoles (where alkyl = ethyl, butyl, hexyl) between water and an immiscible organic solvent (chloroform, methylene chloride, 2-ethylhexanol, isoamyl alcohol, benzyl alcohol, methyl propyl ketone, and toluene). It has been shown that the partition ratios of Cu(II) complexes are dependent on the donor number (DN) of the solvent and the partition ratios increase distinctly with their increase in DN.

Transport of sulphuric acid in the presence of zinc sulphate through the anion-exchange membrane Neosepta-AFN (Astom Corporation, Japan) was studied in a two-compartment counter-current dialyzer with single passes at steady state. The following characteristics were used to characterize the dialysis process: recovery yield of acid, rejection coefficient of salt, and permeability coefficient of the membrane. In case of the H2SO4 + ZnSO4 mixture, permeability of the membrane was quantified by four phenomenological coefficients which are functions of acid and salt concentrations in the feed. They were determined by numerical integration of differential equations describing the concentration profiles of both components in both compartments, which was combined with an optimizing procedure.

Research into the interactions of small molecules (ligands) with DNA is a very important field of biochemistry. A ligand interacts with a DNA structure in many ways, depending on the structural features of the ligand (the presence of rings, substituent groups, length of bonds, etc.) or nucleic acid (number and association of strands, base sequence etc.). This study reports on an investigation of the preferential binding of arylstilbazolium ligands to a four-stranded DNA. For this purpose, an equilibrium dialysis was used. Equilibrium dialysis is a versatile method which enables many DNA structures to be investigated at the same time. A dozen different DNA structures of (single-stranded, double-stranded (duplex), triple-stranded (triplex), and four-stranded (tetraplex)) were involved in experiments with each ligand. Following the dissociation of DNA-ligand complexes by SDS, the concentration of the ligand bound was calculated from fluorescence and absorbance calibration curves. As a result, the amount of the ligand bound was directly related to the ligand-binding affinity. Equilibrium dialysis was used as a powerful tool to indicate which of the arylstilbazolium ligands investigated was the best therapeutic agent targeting G-quadruplex. Arylstilbazolium derivatives demonstrated strong interactions with the DNA samples used in the assay. The most interesting finding was a selective, preferential binding of anthryl derivative to c-MYC DNA (c-MYC is a DNA sequence that appears in an oncogene). Furthermore, as this derivative binds preferentially to one of the triplexes investigated, it can find an application in the TFO-triplex forming oligonucleotides which are used in gene therapy.

A heterogeneous sandwich immunoassay of ferritin on a poly(dimethylsiloxane) microfluidic chip is proposed. An undemanding “prepolymerization technique” based on wet treatment of a phosphor bronze substrate was used for the microchip fabrication. Receptor rabbit antibodies were immobilized via passive sorption directly on microchannel walls. After the incubation of ferritin samples, secondary biotinylated antibodies were introduced. A solution of avidin molecules labeled by fluorescein isothiocyanate was finally added into the microchannels. Lamp-based fluorescence detection of the immunocomplex was then carried out. Dynamic detection range of the method was in the interval from 100 ng mL−1 to 10 μg mL−1.