•5CQA was selective towards DPPH, HO, and O2− in the ESR measurements.•The HAT, RAF, SPLET, and SET-PT mechanisms were investigated.•Thermodynamic approach included the O2−, HOO, HO, and DPPH radical ...species.•Mechanisms of all antioxidative paths of 5CQA and HO were studied for the first time.•HAT, RAF (neutral and acidic media), and SPLET (basic media) are likely pathways.
Although chlorogenic acid (5CQA) is an important ingredient of various foods and beverages, mechanisms of its antioxidative action have not been fully clarified. Besides electron spin resonance experiment, this study includes thermodynamic and mechanistic investigations of the hydrogen atom transfer (HAT), radical adduct formation (RAF), sequential proton loss electron transfer (SPLET), and single electron transfer – proton transfer (SET-PT) mechanisms of 5CQA in benzene, ethanol, and water solutions. The calculations were performed using the M06-2X/6-311++G(d,p) level of theory and CPCM solvation model. It was found that SET-PT is not a plausible antioxidative mechanism of 5CQA. RAF pathways are faster, but HAT yields thermodynamically more stable radical products, indicating that in acidic and neutral media 5CQA can take either HAT or RAF pathways. In basic environment (e.g. at physiological pH) SPLET is the likely antioxidative mechanism of 5CQA with extremely high rate.
Modern communication standards, such as 5G new radio (5G NR), require a high speed decoder for highly irregular quasi-cyclic low density parity check (QC-LDPC) codes. A widely used approach in ...QC-LDPC decoders is a layered decoding schedule which processes the parity check matrix in parts, thus providing faster convergence. However, pipelined layered decoding architecture suffers from data hazards that reduce the throughput. This paper presents a novel architecture, which can facilitate any QC-LDPC decoding without stall cycles caused by pipeline hazards. The decoder conveniently incorporates both the layered and the flooding schedules in cases when hazards occur. The paper also presents the genetic algorithm based optimization of the decoding schedule for better signal-to-noise ratio (SNR) performance. The proposed architecture enables insertion of a large number of pipeline stages, thus providing high operating frequency. As a case study, the FPGA implementation for WiMAX, DVB-S2X, and 5G NR provided coded throughput of up to 1.77 Gbps, 4.32 Gbps, and 4.92 Gbps at 10 iterations, respectively. The results show a strong throughput increase of 30%-109% compared with the conventional layered decoder for 5G NR for the same SNR performance. The decoder provides highly efficient utilization of resources when compared with the state-of-the-art solutions.
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•Conformational analysis of delphinidin, pelargonidin and malvin was performed.•OH and NO antiradical activity was examined theoretically and experimentally.•EPR measurements proved ...Dp, Pg and Mv was selective towards hydroxyl radical.•EPR measurements proved Dp, Pg and Mv was not selective towards nitric oxide.•Molecules investigated reacted with hydroxyl radical via HAT and SPLET mechanisms.
Naturally occurring flavonoids, delphinidin, pelargonidin and malvin, were investigated experimentally and theoretically for their ability to scavenge hydroxyl and nitric oxide radicals. Electron spin resonance (ESR) spectroscopy was used to determine antiradical activity of the selected compounds and M05-2X/6-311+G(d,p) level of theory for the calculation of reaction enthalpies related to three possible mechanisms of free radical scavenging activity, namely HAT, SET-PT and SPLET. The results obtained show that the molecules investigated reacted with hydroxyl radical via both HAT and SPLET in the solvents investigated. These results point to HAT as implausible for the reaction with nitric oxide radical in all the solvents investigated. SET-PT also proved to be thermodynamically unfavourable for all three molecules in the solvents considered.
Filozofija sporta. Nastanak i razvoj jedne discipline “Philosophy of Sport. Emergence and Development of a Discipline” was published in 2021 by Pergamena publishing house, and it represents the ...author’s attempt to answer some fundamental questions regarding the philosophy of sport, which were previously left unanswered in literature. Questions such as: When was it that the foundations of the philosophy of sport were set? What are the crucial points in the development of this discipline? What are all the themes that the philosophy of sports deals with, and its most important concepts? What are the possible directions for further development of this discipline? The author provides the answers to these and many other questions in his work, which is presented on more than 300 B5 pages.
Combined spectroscopic (UV/visible, MS and EPR), electrochemical (CV) and theoretical approaches were used to evaluate the relevant interactions of morin and quercetin, as well as their respective ...iron(III) complexes with DPPH, tempone, hydroxyl and superoxide radicals. The results on iron complexation specify the stoichiometry and the relevant structural forms entering the chelation of the molecules. The spectroscopic DPPH assay shows better antioxidant activity of quercetin and its iron complex both in terms of EC(50) values and stoichiometry. The results of 2-deoxyribose degradation suggest that antioxidant activities of morin and quercetin may originate from their combined effect of iron chelation and radical scavenging. The distinctive difference in the EPR spectra of morin and quercetin radicals suggests different positions of the radical centers which may account for different sequences of their activities towards investigated radicals. Activity ranking of quercetin and morin, established by cyclic voltammetry, confirms their activity sequence obtained by EPR results and is also in agreement with the results of conformational analysis. The equilibrium geometries, optimized with the M052X functionals and 6-311G(d,p) basis set, predict structural modifications between the ligand molecules in the free state and in the complex structures. The arguments gained through experimental results can also be rationalized in terms of overall molecular geometry and structural features governing antioxidant behavior i.e. substitution pattern of the ring B.
Naturally occurring flavonoid molecules, i.e. fisetin (2-(3,4-dihydroxyphenyl)-3,7-dihydroxychromen-4-one) and baicalein (5,6,7-trihydroxy-2-phenyl-4 H -chromen-4-one), have been investigated ...experimentally and theoretically for their ability to scavenge hydroxyl and superoxide anion radicals. The reaction enthalpies for the reaction of fisetin and baicalein with selected radical species, related to three mechanisms of free radical scavenging activity (HAT, SET-PT and SPLET), are calculated using the M05-2X/6-311+G(d,p) model. The calculated energy requirements indicated the preferred radical scavenging mechanisms in polar protic and aprotic solvents.
An ion chromatographic method is described for the quantification of the simple alkyl amines: methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA) and ...triethylamine (TEA), in the ambient atmosphere. Limits of detection (3σ) are in the tens of pmol range for all of these amines, and good resolution is achieved for all compounds except for TMA and DEA. The technique was applied to the analysis of time-integrated samples collected using a micro-orifice uniform deposition impactor (MOUDI) with ten stages for size resolution of particles with aerodynamic diameters between 56 nm and 18 μm. In eight samples from urban and rural continental airmasses, the mass loading of amines consistently maximized on the stage corresponding to particles with aerodynamic diameters between 320 and 560 nm. The molar ratio of amines to ammonium (R3NH+/NH4+) in fine aerosol ranged between 0.005 and 0.2, and maximized for the smallest particle sizes. The size-dependence of the R3NH+/NH4+ ratio indicates differences in the relative importance of the processes leading to the incorporation of amines and ammonia into secondary particles. The technique was also used to make simultaneous hourly online measurements of amines in the gas phase and in fine particulate matter using an Ambient Ion Monitor Ion Chromatograph (AIM-IC). During a ten day campaign in downtown Toronto, DMA, TMA + DEA, and TEA were observed to range from below detection limit to 2.7 ppt in the gas phase. In the particle phase, MAH+ and TMAH+ + DEAH+ were observed to range from below detection limit up to 15 ng m−3. The presence of detectable levels of amines in the particle phase corresponded to periods with higher relative humidity and higher mass loadings of nitrate. While the hourly measurements made using the AIM-IC provide data that can be used to evaluate the application of gas-particle partitioning models to amines, the strong size-dependence of the R3NH+/NH4+ ratio indicates that using bulk measurements may not be appropriate.
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