Nitrogen Oxides Ozonation as a Method for NOx Emission Abatement

Attempts to develop new technologies of reduction of NO_x emission are still carried out all around the world. However, most of them as literature survey suggests is focused on NO_x emission control from power plants and mobile vehicles. Fewer investigations are conducted on the NO_x emission abatement from the chemical industry. One of the relatively new approaches is the application of ozone injection into exhaust gas stream followed by an absorption process. Ozone is used to transform NO_x to higher nitrogen oxides that are more soluble in water, and therefore the higher yield of nitric acid is expected. The main objective of this article is to present results of our studies in which the effectiveness of the ozonation process, as well as the dependence of the conversion rate and the selectivities of NO ozonation into NO₂, N₂O₅ and HNO₃ on the residence time of reagents in the reactor space were studied. Results of laboratory investigations were confirmed during ozonation experiments with real exhaust gases from a nitric acid pilot plant in Fertilizers Research Institute in Pulawy, Poland.     

MicroRNAs and Extracellular Vesicles as Distinctive Biomarkers of Precocious and Advanced Stages of Breast Cancer Brain Metastases Development

Triple negative breast cancer presents higher mortality and poorer survival rates than other breast cancer (BC) types, due to the proneness to brain metastases formation, which are usually diagnosed at advanced stages. Therefore, the discovery of BC brain metastases (BCBM) biomarkers appears pivotal for a timely intervention. With this work, we aimed to disclose microRNAs (miRNAs) and extracellular vesicles (EVs) in the circulation as biomarkers of BCBM formation. Using a BCBM animal model, we analyzed EVs in plasma by nanoparticle tracking analysis and ascertained their blood-brain barrier (BBB) origin by flow cytometry. We further evaluated circulating miRNAs by RT-qPCR and their brain expression by in situ hybridization. In parallel, a cellular model of BCBM formation, combining triple negative BC cells and BBB endothelial cells, was used to differentiate the origin of biomarkers. Established metastases were associated with an increased content of circulating EVs, particularly of BBB origin. Interestingly, deregulated miRNAs in the circulation were observed prior to BCBM detection, and their brain origin was suggested by matching alterations in brain parenchyma. In vitro studies indicated that miR-194-5p and miR-205-5p are expressed and released by BC cells, endothelial cells and during their interaction. These results highlight miRNAs and EVs as biomarkers of BCBM in early and advanced stages, respectively.     

Proton Binding Is Part of Protein Relaxation of Flash-Excited Reaction Center from Photosynthetic Bacteria Rhodobacter sphaeroides

In the first part of this work, a brief review is presented of the recent knowledge of charge stabilization processes in flash-excited reaction center protein from photosynthetic bacteria Rhodobacter sphaeroides. The adaptation of the protein to charge separation is comprised of different manifestations of protein relaxation including proton binding at the late phase. In the second part, a unique method, comparative measurement of prompt and millisecond-delayed fluorescence of the bacteriochlorophyll dimer of the reaction center protein is used to determine the free energy levels of the charge-separated states with respect to that of the excited singlet state of the dimer: −910 ± 20 meV and −970 ± 20 meV were measured at pH 8.0 for reaction centers in the absence and presence of secondary quinone, respectively. The pH-dependence of the energetics of charge stabilization due to light-induced proton binding is described in reaction centers with and without secondary quinone activity. The range of free-energy change between pH 11 and pH 5 was −65 meV with a single (alkaline) inflection point (no active secondary quinone) and −175 meV with an additional (acidic) inflection point (active secondary quinone). The conclusions from fluorescence data agreed well with pH-dependence of integrated proton uptake (a model-independent method) and with calculations based on interaction of quinones with four key amino acid residues. The enthalpy and entropy parts of the free-energy changes were determined from van't Hoff analysis of the delayed fluorescence and compared with data of other methods. It is concluded that the charge stabilization including proton binding is a highly enthalpy-driven process.     

In situ ESR response to temperature evolution of styrene/dibenzoyl peroxide/Di‐TEMPO biradical system

The initial stage of the di‐TEMPO (N,N′‐bis(4‐(2,2,6,6‐tetramethylpiperidin‐1‐yloxyl))diaminobutane) controlled radical polymerization of styrene was investigated by electron spin resonance (ESR) method in a temperature range of 300–410 K. Processes corresponding to three subsequent temperature subranges 300–360, 360–375, and 375–410 K have been discussed. The decrease of concentration of the di‐TEMPO biradicals is faster than for the TEMPO monoradicals in the range 370–390 K. The reduced mobility of capping groups is postulated to be responsible for the differences between TEMPO monoradical and di‐TEMPO biradical mediators. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparative risk assessment of residential radon exposures in two radon-prone areas, ?tei (Romania) and Torrelodones (Spain)

Radon and radon progeny are present indoors, in houses and others dwellings, representing the most important contribution to dose from natural sources of radiation. Most studies have demonstrated an increased risk of lung cancer at high concentration of radon for both smokers and nonsmokers. The work presents a comparative analysis of the radon exposure data in the two radon-prone areas, ?tei, Transylvania, (Romania), in the near of old Romanian uranium mines and in the granitic area of Torrelodones town, Sierra de Guadarrama (Spain). Measurements of indoor radon were performed in 280 dwellings (Romania) and 91 dwellings (Spain) by using nuclear track detectors, CR 39. The highest value measured in ?tei area was 2650 Bq m^− 3 and 366 Bq m^− 3 in the Spanish region. The results are computed with the BEIR VI report estimates using the age-duration model at an exposure rate below 2650 Bq m^− 3. We used the EC Radon Software to calculate the lifetime lung cancer death risks for individuals groups in function of attained age, radon exposures and tobacco consumption. A total of 233 lung cancer deaths were observed in the ?tei area for a period of 13 years (1994-2006), which is 116.82% higher than expected from the national statistics. In addition, the number of deaths estimated for the year 2005 is 28, which is worth more than 2.21 times the amount expected by authorities. In comparison, for Torrelodones was rated a number of 276 deaths caused by lung cancer for a period of 13 years, which is 2.09 times higher than the number expected by authorities. For the year 2005 in the Spanish region were reported 32 deaths caused by pulmonary cancer, the number of deaths exceeding seen again with a factor of 2.10 statistical expectations. This represents a significantly evidence that elevated risk can strongly be associated with cumulated radon exposure.     

A Theoretical Study of the Half-Sandwich Silicon(II) Cation [(Me<Subscript>5</Subscript>C<Subscript>5</Subscript>)Si]<Superscript>+</Superscript> and of the Cationic Complex [(Me<Subscript>5</Subscript>C<Subscript>5</Subscript>)Si (DME)]<Superscript>+</Superscript>

Ab-initio calculations have been performed for the half-sandwich cation [(Me₅C₅)Si]⁺ and its DME complex [(Me₅C₅)Si(DME)]⁺. For these cations, the ground state energies, the complexation energy, the frontier orbitals, the vertical singlet-triplet excitation energies, and the natural atomic charges have been calculated. In both cations, the “lone-pair” at silicon does not represent the HOMO. The nature of the weak dative O → Si bond can best be described in terms of electrostatic and attractive dispersion interactions. The DME coordination destabilizes the cluster orbitals and slightly enhances the positive charge at silicon.     

Biomass productivity and phytoremediation potential of Salix alba and Salix viminalis

The aim of this work was to determine selected Salix clones’ capacities for biomass production and accumulation of heavy metal ions. Determination of the relationship between sorption of metals and biomass productivity was a further purpose of this study. Eight Salix viminalis cultivars and one Salix alba cultivar were analyzed. The taxa characterized by greatest biomass production were S. alba var. Chermesina and S. viminalis ‘1056’ (respectively 6.8 and 4.3 kg of fresh mass per shrub per year).The results have revealed significant differences among clones. The clones most effective in accumulating all five metals were S. viminalis ‘1154’ and ‘1054’. The studied Salix population was significantly diverse as regards accumulation efficiency. The differences between the highest and lowest heavy metal content in extreme clones were for: Cd 84%, Cu 90%, Hg 167%, Pb 190% and Zn 36%. At the same time, significant differences were observed in Salix structure. The greatest cellulose content was observed in S. viminalis ‘Sprint’ (49.69%) and the lowest in S. viminalis ‘1059’ (42.09%).     

Anticorrosive polyurethane paints with nano- and microsized phosphates

Two types of phosphate fillers (nanosized aluminum phosphate and microsized aluminum–zinc phosphate) were tested as anticorrosive fillers in 2 K solvent-borne polyurethane paints based on commercial acrylic resin with OH groups and an isophorone diisocyanate-type hardener. Three coating compositions containing commercial fillers (mica/quartz, TiO₂, wollastonite, talc) and also mentioned nanosized aluminum phosphate or microsized aluminum–zinc phosphate were prepared using a pearl-mill as well as a laboratory dissolver, applied onto a steel substrate and cured at room temperature for 14 days. An influence of the type and content of a phosphate filler on properties of polyurethane paints and coatings has been investigated. Incorporation of nanosized aluminum phosphate into coating compositions increases their viscosity while cured paints exhibit reduced adhesion to steel substrates. The results of corrosion tests in a salts spray chamber as well as immersion in an aqueous NaCl solution indicated that the paint system with 9.8 wt.% of applied nanofiller had similar protective properties to a polyurethane coat containing a higher dose (i.e. 15.6 wt.%) of commercial microsized aluminum–zinc phosphate.     

The effect of the surface nanostructure and composition on the antiwear properties of zirconia–titania coatings

This study describes the preparation, surface imaging and tribological properties of titania coatings modified by zirconia nanoparticles agglomerated in the form of island-like structures on the titania surface. Titania coatings and titania coatings with embedded zirconia nanoparticles were prepared by the sol–gel spin coating process on silicon wafers. After deposition the coatings were heat-treated at 500 °C or 1000 °C. The natural tendency of nanoparticles to form agglomerates was used to build separated island-like structures unevenly distributed over the titania surface having the size of 1.0–1.2 μm. Surface characterization of coatings before and after frictional tests was performed by atomic force microscopy (AFM) and optical microscopy. Zirconia nanoparticles were imaged with the use of transmission electron microscopy (TEM). The tribological properties were evaluated with the use of microtribometer operating in ambient air at technical dry friction conditions under normal load of 80 mN. It was found that nanocomposite coatings exhibit lower coefficient of friction (CoF) and considerably lower wear compared to titania coating without nanoparticles. The lowering of CoF is about 40% for coatings heated at 500 °C and 33% for the coatings heated at 1000 °C. For nanocomposites the wear stability was enhanced by a factor of 100 as compared to pure titania coatings. We claim that enhanced tribological properties are closely related to the reduction of the real contact area, lowering of the adhesive forces in frictional contacts and increasing of the composite hardness. The changes in materials composition in frictional contact has secondary effect.     

Synthesis,Biological Activity and Molecular Docking Studies of Novel Nicotinic Acid Derivatives

In our research, we used nicotinic acid as a starting compound, which was subjected to a series of condensation reactions with appropriate aldehydes. As a result of these reactions, we were able to obtain a series of twelve acylhydrazones, two of which showed promising activity against Gram-positive bacteria (MIC = 1.95–15.62 µg/mL), especially against Staphylococcus epidermidis ATCC 12228 (MIC = 1.95 µg/mL). Moreover, the activity of compound 13 against the Staphylococcus aureus ATCC 43300 strain, i.e., the MRSA strain, was MIC = 7.81 µg/mL. Then, we subjected the entire series of acylhydrazones to a cyclization reaction in the acetic anhydride, thanks to which we were able to obtain twelve new 3-acetyl-2,5-disubstituted-1,3,4-oxadiazoline derivatives. Obtained 1,3,4-oxadiazolines were also tested for antimicrobial activity. The results showed high activity of compound 25 with a 5-nitrofuran substituent, which was active against all tested strains. The most promising activity of this compound was found against Gram-positive bacteria, in particular against Bacillus subtilis ATCC 6633 and Staphylococcus aureus ATCC 6538 (MIC = 7.81 µg/mL) and ATCC 43300 MRSA strains (MIC = 15.62 µg/mL). Importantly, the best performing compounds did not show cytotoxicity against normal cell lines. It seems practical to use some of these compounds or their derivatives in the future in the prevention and treatment of infections caused by some pathogenic or opportunistic microorganisms.