Background: Advanced Oxidation Processes (AOPs) are the water treatment techniques that are commonly used forthe decomposition of the non-biodegradable organic pollutants. However, some pollutants are electron deficient and thus resistant to attack by reactive oxygen species (e.g.
View Article and Find Full Text PDFThe mechanism of high-energy radiation induced degradation of perfluorooctanoate anion (PFOA, CFCOO) was investigated in aqueous solutions. Identification and quantification of transient species was performed by pulse radiolysis and of final products by gas and ion chromatography, electrochemical method using fluoride ion-selective electrode and ESI-MS after γ-radiolysis. Experimental data were further supported by kinetic simulations and quantum mechanical calculations.
View Article and Find Full Text PDFIn this work, the feasibility of sterilizing a water suspension of poly-3-hexylthiophene nanoparticles (P3HT-NPs) is investigated using ionizing radiation, either γ-rays or high-energy electrons (e-beam). It is found that regardless of the irradiation source, the size, polydispersity, aggregation stability, and morphology of the NPs are not affected by the treatment. Furthermore, the impact of ionizing radiation on the physicochemical properties of NPs at different absorbed radiation doses (10-25 kGy) and dose rates (kGy time ) is evaluated through different spectroscopic techniques.
View Article and Find Full Text PDFThe reaction of hydroxyl radical (HO) with DNA produces many primary reactive species and many lesions as final products. In this study, we have examined the optical spectra of intermediate species derived from the reaction of HO with a variety of single- and double-stranded oligodeoxynucleotides and ct-DNA in the range of 1 μs to 1 ms by pulse radiolysis using an Intensified Charged Coupled Device (ICCD) camera. Moreover, we applied our published analytical protocol based on an LC-MS/MS system with isotopomeric internal standards to enable accurate and precise measurements of purine lesion formation.
View Article and Find Full Text PDFThe photoreduction by amines and N-phenylglycine, NPG, of six styrylquinoxalin-2(1 H)-ones derivatives substituted in the styryl moiety, R-SQ, was studied by using flash photolysis. The photoreaction is initiated via a single electron transfer from the electron donor (amines or NPG) to R-SQ excited triplet state, R-SQ*, with the formation of a triplet state radical ion pair or a charge transfer exciplex, [CRIP/CTE]. These species live longer than the respective R-SQ* and have very similar transient spectra.
View Article and Find Full Text PDFThe monitoring of Advanced Oxidation/Reduction Processes (AO/RPs) for the evaluation of the yield and mechanisms of decomposition of perfluorinated compounds (PFCs) is often a more difficult task than their determination in the environmental, biological or food samples with complex matrices. This is mostly due to the formation of hundreds, or even thousands, of both intermediate and final products. The considered AO/RPs, involving free radical reactions, include photolytic and photocatalytic processes, Fenton reactions, sonolysis, ozonation, application of ionizing radiation and several wet oxidation processes.
View Article and Find Full Text PDFA shape-persistent molecule, featuring four bipyridinium units, has been synthesized that upon reduction undergoes intermolecular pimerization because of the rigid architecture of the molecule. The pimerization process has been investigated by a variety of techniques, such as absorption measurements, EPR spectroscopy, as well as gamma and pulse radiolysis, and compared with the behavior of a model compound. Computational studies have also been performed to support the experimental data.
View Article and Find Full Text PDFThe most important contributions of radiation chemistry to some selected technological issues related to water-cooled reactors, reprocessing of spent nuclear fuel and high-level radioactive wastes, and fuel evolution during final radioactive waste disposal are highlighted. Chemical reactions occurring at the operating temperatures and pressures of reactors and involving primary transients and stable products from water radiolysis are presented and discussed in terms of the kinetic parameters and radiation chemical yields. The knowledge of these parameters is essential since they serve as input data to the models of water radiolysis in the primary loop of light water reactors and super critical water reactors.
View Article and Find Full Text PDFHydrophobic room-temperature ionic liquids (ILs) hold promise as replacements for molecular diluents for processing of used nuclear fuel as well as for the development of alternative separations processes, provided that the solvent can be made resistant to ionizing radiation. We demonstrate that 1-benzylpyridinium cations are uniquely suited as radiation resistant cations due to the occurrence of charge delocalization in both their reduced and oxidized forms in the ILs. It is suggested that the excess electron and hole in the latter ILs are stabilized through the formation of π-electron sandwich dimers that are analogous to the well-known dimer radical cations of aromatic molecules.
View Article and Find Full Text PDFPhotoreduction of 7H-benzo[e]perimidin-7-one (3-AOIA, A1) and its 2-methyl derivative (2-Me-3-AOIA, A2) by non-H-donating amines (1,4-diazabicyclo[2.2.2]octane [DABCO]; 2,2,6,6-tetramethylpiperidine [TMP]), and a hydrogen-donating amine (triethylamine [TEA]), has been studied in deaerated neat acetonitrile solutions using laser flash photolysis (LFP) and steady-state photolysis.
View Article and Find Full Text PDFOn time scales of a nanosecond or less, radiolytically-generated excess electrons in ionic liquids undergo solvation processes and reactions that determine all subsequent chemistry and the accumulation of radiolytic damage. Using picosecond pulse radiolysis detection methods, we observed and quantified the solvation response of the electron in 1-methyl-1-butyl-pyrrolidinium bis (trifluoromethylsulfonyl)amide and used it to understand electron scavenging by a typical solute, duroquinone.
View Article and Find Full Text PDFThe thermostability of glucose oxidase entrapped in silica gel obtained by sol-gel method was studied by thermostimulated fluorescence of FAD at pH 5 and 7 and compared with that of the native enzyme in the solution and at the presence of ethanol. The unfolding temperatures were found to be lower for the enzyme immobilised in gel as compared with the native enzyme but higher as for the enzyme at the presence of ethanol. In gel, the thermal denaturation of glucose oxidase is independent on pH while in solution the enzyme is more stable at pH 5.
View Article and Find Full Text PDFEstrogen receptors, similarly as other nuclear receptors, are transcription factors, which after binding to a proper ligand (17beta-estradiol, estron or estriol) are capable of regulating transcription of target genes. Due to the functions that estrogens play in the regulation of reproduction, development of the mammary gland, growth and differentiation of cells, estrogen receptors and their genes are considered as candidate markers for production and functional traits in farm animals. Known are two isoforms of the estrogen receptor-alpha and beta.
View Article and Find Full Text PDFDue to the variant functions that estrogens play in the regulation of reproduction, development of the mammary gland, growth and differentiation of cells, estrogen receptors and their genes are considered as a candidates for the markers of production and functional traits in farm animals, including cattle. In the earliest study, a 2853-bp bovine ER gene 5'-region was PCR amplified and sequenced. Moreover, for the first time, a polymorphism was described within 5' region of the bovine ERalpha gene--A/G transition lying upstream at position 2591 from acceptor splice site +85, possibly within its promoter--which could be recognized with RFLP-BglI.
View Article and Find Full Text PDFPairing of a Keggin or Lindqvist polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation is shown to yield the first members of a new family of ionic liquids (ILs). Detailed characterization of one of them, an ambient-temperature "liquid POM" comprising the Lindqvist salt of the trihexyl(tetradecyl) phosphonium cation, by voltammetry, viscometry, conductimetry, and thermal analysis indicates that it exhibits conductivity and viscosity comparable to those of the one previously described inorganic-organic POM-IL hybrid but with substantially improved thermal stability.
View Article and Find Full Text PDFThe pairing of selected polyoxometalate (POM) anions with appropriate tetraalkylphosphonium cations is shown to yield an original family of ionic liquids, among them an ambient-temperature "liquid POM".
View Article and Find Full Text PDFDue to the functions that estrogens play in the regulation of reproduction, development of the mammary gland, growth and differentiation of cells, estrogen receptors and their genes are considered candidates for the markers of production and functional traits in farm animals, including cattle. In the present study, on the basis of the sequences of the human, ovine, and porcine ER genes, available in the GenBank database, sets of PCR primers were designed and used to amplify the bovine ERalpha gene 5'-region. Seven overlapping fragments of the 5' region of the bovine ERalpha gene were amplified and then sequenced.
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