Single- and Two-Electron Reduction of Nitroaromatic Compounds by Flavoenzymes: Mechanisms and Implications for Cytotoxicity

Nitroaromatic compounds (ArNO₂) maintain their importance in relation to industrial processes, environmental pollution, and pharmaceutical application. The manifestation of toxicity/therapeutic action of nitroaromatics may involve their single- or two-electron reduction performed by various flavoenzymes and/or their physiological redox partners, metalloproteins. The pivotal and still incompletely resolved questions in this area are the identification and characterization of the specific enzymes that are involved in the bioreduction of ArNO₂ and the establishment of their contribution to cytotoxic/therapeutic action of nitroaromatics. This review addresses the following topics: (i) the intrinsic redox properties of ArNO₂, in particular, the energetics of their single- and two-electron reduction in aqueous medium; (ii) the mechanisms and structure-activity relationships of reduction in ArNO₂ by flavoenzymes of different groups, dehydrogenases-electrontransferases (NADPH:cytochrome P-450 reductase, ferredoxin:NADP(H) oxidoreductase and their analogs), mammalian NAD(P)H:quinone oxidoreductase, bacterial nitroreductases, and disulfide reductases of different origin (glutathione, trypanothione, and thioredoxin reductases, lipoamide dehydrogenase), and (iii) the relationships between the enzymatic reactivity of compounds and their activity in mammalian cells, bacteria, and parasites.     

Comparative Study of Reactive Dyes Oxidation by H2O2/UV,H2O2/UV/Fe2+ and H2O2/UV/Fe° Processes

The decolorization and mineralization of two reactive dyes C.I. Reactive Blue 4 (RB 4) and C.I. Reactive Blue 268 (RB 268) were studied using various advanced oxidation processes (AOPs) such as H₂O₂/UV, H₂O₂/UV/Fe²⁺, and the H₂O₂/UV/Fe°. All processes were performed within a laboratory-scale photo-reactor setup. The experimental results were assessed in terms of absorbance (A) and total organic carbon (TOC) reduction. The main degradation products were identified by high resolution gas chromatography/high resolution mass spectrometry analyses. The results of our study demonstrated that the additions of moderate concentrations of H₂O₂ and Fe catalyst during the AOPs evidently increased the decolorization efficiencies within the first few minutes of the processing time (5–10 min) for both tested dyes, and prolonged irradiation does not necessarily significantly improve decolorization. On contrary, TOC removal rate increased with the processing time and with the addition of the catalyst from 40–50% up to 70–80% at defined experimental conditions. All the tested AOPs were very successful methods for RB 268 decolorization, having very complex structure and much higher molecular weight compared to the dye RB 4. This is important from both economic and ecological points of view.     

‘Green’ synthesis and optical properties of silver–chitosan complexes and nanocomposites

Silver nanoparticles were synthesized in a chitosan biopolymer by an in situ ‘green’ chemical procedure, using d-glucose as the reducing agent. The reaction intermediates (silver–chitosan complexes) as well as the obtained nanocomposites were investigated using transmission electron microscopy, UV–vis, FTIR and photoluminescence spectroscopy. The theoretical analysis of the UV–vis absorption of the Ag–chitosan complexes suggested that the significant contribution to the complex spectrum arises from clusters of silver containing 4–9 atoms. The absorption spectrum of the nanocomposite exhibited a strong surface plasmon resonance band at 406 nm. The photoluminescence behavior of the pure chitosan, the silver–chitosan complexes and the nanocomposites were discussed in terms of morphology and silver weight content.     

Effect of sodium bicarbonate solution on methyltrimethoxysilane-derived silica aerogels dried at ambient pressure

Here we present an economical ambient pressure drying method of preparing monolithic silica aerogels from methyltrimethoxysilane precursor while using sodium bicarbonate solution as the exchanging solvent. We prepared silica aerogels with a density and a specific surface area of 0.053 g∙cm⁻³ and 423 m²∙g⁻¹, respectively. The average pore diameter of silica aerogels is 23 nm as the pore specific volume is 1.11 cm³∙g⁻¹. Further, the contact angle between water droplet and the surface of silica aerogels in specific condition can be as high as 166°, which indicates a super-hydrophobic surface of aerogels.     

Utilisation of waste heat from exhaust gases of drying process

Nowadays a lot of low-grade heat is wasted from the industry through the off- and flue-gasses with different compositions. These gases provide the sensitive heat with utilisation potential and latent heat with the components for condensation. In this paper, process integration methodology has been applied to the partly condensed streams. A hot composite curve that represents the gas mixture cooling according to equation of state for real gases was drawn to account the gas-liquid equilibrium. According to the pinch analysis methodology, the pinch point was specified and optimal minimal temperature difference was determined. The location of the point where gas and liquid phases can be split for better recuperation of heat energy within heat exchangers is estimated using the developed methodology. The industrial case study of tobacco drying process off-gasses is analysed for heat recovery. The mathematical model was developed by using MathCad software to minimise the total annualised cost using compact plate heat exchangers for waste heat utilisation. The obtained payback period for the required investments is less than six months. The presented method was validated by comparison with industrial test data.

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4-Hydroxynonenal Modulates Blood–Brain Barrier Permeability In Vitro through Changes in Lipid Composition and Oxidative Status of Endothelial Cells and Astrocytes

Blood brain barrier (BBB) is a dynamic interface responsible for proper functioning of brain, but also a major obstacle for effective treatment of neurological diseases. Increased levels of free radicals, in high ferrous and high lipid content surrounding, induce lipid peroxidation, leading to production of 4-hydroxynonenal (HNE). HNE modifies all key proteins responsible for proper brain functioning thus playing a major role in the onset of neurological diseases. To investigate HNE effects on BBB permeability, we developed two in vitro BBB models–‘physiological’ and ‘pathological’. The latter mimicked HNE modified extracellular matrix under oxidative stress conditions in brain pathologies. We showed that exogenous HNE induce activation of antioxidative defense systems by increasing catalase activity and glutathione content as well as reducing lipid peroxide levels in endothelial cells and astrocytes of ‘physiological’ model. While in ‘pathological’ model, exogenous HNE further increased lipid peroxidation levels of endothelial cells and astrocytes, followed by increase in Nrf2 and glutathione levels in endothelial cells. At lipid composition level, HNE caused increase in ω3 polyunsaturated fatty acid (PUFA) level in endothelial cells, followed by decrease in ω3 PUFA level and increase in monounsaturated fatty acid level in astrocytes. Using these models, we showed for the first time that HNE in ‘pathological’ model can reduce BBB permeability.     

Chemometric evaluation of binary mixtures of alginate and polysaccharide biopolymers as carriers for microencapsulation of green tea polyphenols

In this study principal component analysis and artificial neural networks were used to evaluate the potential of using binary mixtures of sodium alginate and other polysaccharide biopolymers as the carriers for microencapsulation of green tea bioactive compounds. Using binary mixtures of alginate and adjunct biopolymers increased the particle size (from 722 to 1344 µm) and textural parameters of the microbeads. Chemometric techniques revealed the combination of biopolymers and their ratio as the main factors influencing the encapsulation performance. The combination of alginate with hydroxypropyl methylcellulose and locust bean gum enabled to retain the highest (-)-epigallocatechin gallate and caffeine contents, the highest total phenols encapsulation efficiency, and their most retarded release in water, confirming these as the best delivery systems of polyphenol-type active compounds and signifying their potent food applications.     

Second order derivative spectrophotometric method for determination of vitamin C content in fruits,vegetables and fruit juices

A second-order derivative UV spectrophotometric method for determination of vitamin C [ascorbic acid (AA)] content in a variety of natural samples is described. The method is based on the measurement of a peak–baseline amplitude in the second derivative of the AA spectrum at 267.5 nm. The following corresponding regression equation was obtained within the concentration range 2×10^-5 to 1×10^-4 M AA (3.5–17.6 g/cm³ AA) in 1.0 M HCl solution: ²D_267.5=2.420×10⁴ c+0.025; the correlation coefficient was 0.9993 and the detection limit 4.2×10^-6 M. The results obtained by analysing 21 different species of fruits, vegetables and juices indicated a possibility for a more extensive application of the proposed method. This method is rapid, simple and requires no pretreatment of the analysed material, which makes it suitable for routine analyses. The reliability of the method was confirmed by comparative determinations with the generally accepted 2,6-dichloroindophenol method.     

Turbogenerator end-winding leakage inductance calculation using a 3-D analytical approach based on the solution of Neumann Integrals

An analytical technique that can be effectively used for the calculation of the end-winding leakage inductance of a turbogenerator has been presented. It is based on a three-dimensional geometric model of the end-winding region in which each coil is modeled as a set of serially connected straight filaments. The calculation of the mutual inductance of the end coils is based on the multiple solutions of the Neumann integral. The method also accounts for the influence of stator core iron on the end-winding leakage inductance by using the method of images. The results of the calculations have been compared with the measured values of the leakage inductance for 247-MVA turbogenerator manufactured by KONCAR Generators and Motors Inc., Zagreb, Croatia. The principle of the end-winding leakage inductance calculation described herein can be effectively used for other types of machines and windings as well.