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We report on the physicochemical processes and the products of DNA damage involved in Ne-22 ion-beam radiation of hydrated (12 ± 3 H2O/nucleotide) salmon testes DNA at 77 K. Free radicals trapped at 77 K were identified using electron spin resonance (ESR) spectroscopy. The measurement of DNA damage using two different techniques of mass spectrometry revealed the formation of numerous DNA products. Results obtained by ESR spectroscopy showed that as the linear energy transfer (LET) of the ion-beam radiation increases along the beam track, the production of DNA radicals correspondingly increases until just before the Bragg peak is reached. Yields of DNA products along the ion-beam track were in excellent agreement with the radical production. This work is the first to use the combination of ESR spectroscopy and mass spectrometric techniques enabling a better understanding of mechanisms of radiation damage to DNA by heavy ion beams detailing the formation of DNA free radicals and their subsequent products.

Dropping during shipping and handling of liquid biopharmaceutical formulations has long been known to cause protein degradation and aggregation. On the other hand, accidental dropping of freeze-dried protein formulations is generally considered not a major issue for biopharmaceutical quality. Reports of stability and especially the underling degradation mechanism(s) during shipping and handling of freeze-dried protein formulations were rarely seen in literature. In this manuscript, we report an interesting phenomenon in which repeated dropping of freeze-dried monoclonal antibody X (mAb-X) formulation powder resulted in significant protein sub-visible particles (SbVPs) in the reconstituted liquid as determined by the sensitive particle analyzing technique micro-flow imaging (MFI). Free radicals were observed after repeated dropping by electron paramagnetic resonance (EPR). Formation of SbVPs could be partially inhibited by the free radical scavengers methionine and 3-carbamoyl-2,2,5,5-tetramethyl-1-pyrrolidin-yloxy free radical (CTPO). The amount of free radicals and SbVPs was correlated to the sample temperature during dropping. Therefore we propose that the high temperature formed during dropping was probably the root cause for protein aggregation and free radical formation, which could further cause protein aggregation. Our observations suggest that similar to liquid protein formulations, dropping of freeze-dried protein formulations should also be avoided or mitigated.

Photobiomodulation is widely used in clinical practice, and there is increasing interest in using this tool to treat numerous dysfunctions in living organisms. Therefore, this study aimed to verify the action of blue and red light-emitting diode light in cells. Human fibroblast cell line (HFF-1) were irradiated by blue (470 nm) or red (658 nm) light at doses of 4 and 18 J/cm2, respectively. Laboratory analyses were carried out to check for viability, proliferation, cell death, and the formation of reactive oxygen and nitric oxide species. The blue light demonstrated cell protection potential by reducing free radical formation and protecting the cell membrane by decreasing double-stranded DNA strands. On the other hand, the red light showed less potential for cell protection due to the risk of associating more significant nitric oxide formation with increased reactive oxygen species formation, in addition to having a greater amount of extracellular DNA. Cell damage prevention is a potential beneficial effect of blue light at 18 J/cm2. Despite the consolidated effects of red light in treating wounds, there was a potential toxic effect of this wavelength in the doses studied. Given the above, new studies relating these parameters with pathological cells or aggressors that simulate damage may offer results that can better support clinical practice.

OBJECTIVES. The goal of the study was to determine whether reactive oxygen species (ROS) mediates cytomegalovirus (CMV)–induced labyrinthitis. STUDY DESIGN. Murine model of CMV infection. SETTING. University of Utah laboratory. SUBJECTS AND METHODS. Nrf2 knockout mice were inoculated with murine CMV. Auditory brainstem response (ABR) and distortion product otoacoustic emissions (DPOAEs) were then performed on these and uninfected controls. BALB/c mice were inoculated with murine CMV to determine whether a marker for ROS production, dihydroethidium (DHE), is expressed 7 days after inoculation. Finally, 2 antioxidants—D-methionine and ACE-Mg (vitamins A, C, and E with magnesium)—were administered 1 hour before and after infection in inoculated mice for 14 days. Temporal bones were harvested at postnatal day 10 for DHE detection. ABR and DPOAE testing was done at postnatal day 30. Scanning electron microscopy was also performed at postnatal day 30 to evaluate outer hair cell integrity. RESULTS. Nrf2-infected mice had worse hearing than uninfected mice (P < .001). A statistically significant increase in DHE fluorescence was detected in BALB/c-infected mice as compared with uninfected mice 7 days after inoculation. D-methionine- and ACE-Mg-treated mice demonstrated an attenuation of the DHE fluorescence and a significant improvement in ABR and DPOAE thresholds when compared with untreated infected controls (P

Natural antioxidants have received tremendous attention over the last 3 decades. At the same time, the attitude to free radicals is slowly changing, and their signalling role in adaptation to stress has recently received a lot of attention. Among many different antioxidants in the body, taurine (Tau), a sulphur-containing non-proteinogenic β-amino acid, is shown to have a special place as an important natural modulator of the antioxidant defence networks. Indeed, Tau is synthesised in most mammals and birds, and the Tau requirement is met by both synthesis and food/feed supply. From the analysis of recent data, it could be concluded that the direct antioxidant effect of Tau due to scavenging free radicals is limited and could be expected only in a few mammalian/avian tissues (e.g., heart and eye) with comparatively high (>15–20 mM) Tau concentrations. The stabilising effects of Tau on mitochondria, a prime site of free radical formation, are characterised and deserve more attention. Tau deficiency has been shown to compromise the electron transport chain in mitochondria and significantly increase free radical production. It seems likely that by maintaining the optimal Tau status of mitochondria, it is possible to control free radical production. Tau’s antioxidant protective action is of great importance in various stress conditions in human life, and is related to commercial animal and poultry production. In various in vitro and in vivo toxicological models, Tau showed AO protective effects. The membrane-stabilizing effects, inhibiting effects on ROS-producing enzymes, as well as the indirect AO effects of Tau via redox balance maintenance associated with the modulation of various transcription factors (e.g., Nrf2 and NF-κB) and vitagenes could also contribute to its protective action in stress conditions, and thus deserve more attention.

An aerobic multicomponent reaction between monoalkyl-3,3-difluorocyclopropenes, pyridines, and arylthiols has been discovered to afford 3-arylsulfanyl-1-hydroxyindolizines. This reaction proceeds via intermediate C3-free indolizin-1-ols, easily forming free radicals in air. In the presence of arylthiols, potent radical traps, incorporation of arylsulfanyl substituent occurs at the C3 position of indolizin-1-ols by radical recombination. On the contrary, in an inert atmosphere, intermediate 1-hydroxyindolizines react with C- and N-electrophiles in a one-pot fashion. Novel, intensively colored 3-(tropon-2-yl)-indolizin-1-ols and high absorption coefficient 3-(tropolon-5-ylazo)-indolizin-1-ol dyes were synthesized in a multicomponent manner in 50-80% yields. The presence of an O-uncapped indolizin-1-ol moiety modulates the redox properties of the whole molecule, facilitating free radical formation, which is susceptible to further transformations. Three such examples were demonstrated: oxidative recyclization of 3-(2-hydroxyphenylsulfanyl)-indolizin-1-ol, auto-oxidation of substituted 3,3'-biindolizine-1,1'-diol, and diacetoxyiodobenzene (DAIB)-mediated dehydrogenation of 3-(tropolon-5-ylazo)-indolizin-1-ol. The latter reaction affords 3-((4,5-dioxocyclohepta-2,6-dien-1-ylidene)hydrazono)-3H-indolizin-4-ium-1-olate, a mesomeric betaine, strongly absorbing light on the borders of the visible range and showing a solvatochromic effect.

SUMMARY Loss of moisture in mature seeds of Quercus robur L. was associated with loss of viability, a rise in lipid peroxidation and build-up of free radicals. Radical-initiated damage was largely confined to the embryonic axes as their moisture contents declined to below 47 %. The accumulation of a stable free radical in axial tissue, detected by electron para-magnetic resonance (EPR), was indistinguishable from the EPR response previously shown in a moss on droughting and maize roots on desiccation. A minor higher-field component appeared to represent an intermediate stage in the sequence of free radical reactions associated with loss of water. Using seeds from freshly abscised fruits dried to different moisture contents, protective mechanisms against activated forms of oxygen were monitored in cotyledons and in embryonic axes. The two tissues exhibit distinctly different molecular defences against oxidative attack; that in the cotyledons being predominantly enzymatic, with relatively high and increasing activities of superoxide dismutase and glutathione reductase; that in the axes being largely through the anti-oxidants, ascorbic acid and alpha-tocopherol. We conclude that a decrease in enzymic protection against oxidative attack in the axes, associated with diminishing concentrations of alpha-tocopherol (and depletion of the precursor gamma-tocopherol) as moisture was lost, was directly linked with lipid peroxidation and free radical formation in the axes and that these events taken together may contribute to loss of viability in these recalcitrant seeds.

Numerous reactive oxygen species (ROS) entities exist, and hydrogen peroxide (H2O2) is very key among them as it is well known to possess a stable but poor reactivity capable of generating free radicals. Considered among reactive atoms, molecules, and compounds with electron-rich sites, free radicals emerging from metabolic reactions during cellular respirations can induce oxidative stress and cause cellular structure damage, resulting in diverse life-threatening diseases when produced in excess. Therefore, an antioxidant is needed to curb the overproduction of free radicals especially in biological systems (in vivo and in vitro). Despite the inherent properties limiting its bioactivities, polysaccharides from natural sources increasingly gain research attention given their position as a functional ingredient. Improving the functionality and bioactivity of polysaccharides have been established through degradation of their molecular integrity. In this critical synopsis; we articulate the effects of H2O2 on the degradation of polysaccharides from natural sources. Specifically, the synopsis focused on free radical formation/production, polysaccharide degradation processes with H2O2, the effects of polysaccharide degradation on the structural characteristics; physicochemical properties; and bioactivities; in addition to the antioxidant capability. The degradation mechanisms involving polysaccharide’s antioxidative property; with some examples and their respective sources are briefly summarised.

The effects of low and high frequency ultrasound on the production of volatile compounds along with their derivation and corresponding off-flavours in milk and milk products are discussed in this review. The review will simultaneously discuss possible mechanisms of applied ultrasound and their respective chemical and physical effects on milk components in relation to the production of volatile compounds. Ultrasound offers potential benefits in dairy applications over conventional heat treatment processes. Physical effects enhance the positive alteration of the physicochemical properties of milk proteins and fat. However, chemical effects propagated by free radical generation cause redox oxidations which in turn produce undesirable volatile compounds such as aldehydes, ketones, acids, esters, alcohols and sulphur, producing off-flavours. The extent of volatile compounds produced depends on ultrasonic processing conditions such as sonication time, temperature and frequency. Low frequency ultrasound limits free radical formation and results in few volatile compounds, while high ultrasonic frequency induces greater level of free radical formation. Furthermore, the compositional variations in terms of milk proteins and fat within the milk systems influence the production of volatile compounds. These factors could be controlled and optimized to reduce the production of undesirable volatiles, eliminate off-flavours, and promote the application of ultrasound technology in the dairy field.

The residue lysine 28 (K28) is known to form an important salt bridge that stabilizes the Aβ amyloid structure, and acetylation of lysine 28 (K28Ac) slows the Aβ42 fibrillization rate but does not affect fibril morphology. On the other hand, acetylation of lysine 16 (K16Ac) residue greatly diminishes the fibrillization property of Aβ42 peptide and also affects its toxicity. This is due to the fact that lysine 16 acetylated amyloid beta peptide forms amorphous aggregates instead of amyloid fibrils. This is likely a result of increased hydrophobicity of the K16-A21 region due to K16 acetylation, as confirmed by molecular dynamic simulation studies. The calculated results show that the hydrophobic patches of aggregates from acetylated peptides were different when compared to wild-type (WT) peptide. K16Ac and double acetylated (KKAc) peptide aggregates show significantly higher cytotoxicity compared to the WT or K28Ac peptide aggregates alone. However, the heterogeneous mixture of WT and acetylated Aβ42 peptide aggregates exhibited higher free radical formation as well as cytotoxicity, suggesting dynamic interactions between different species could be a critical contributor to Aβ pathology.

The &beta, amyloid (A&beta, ) peptide plays a key role in the pathogenesis of Alzheimer&rsquo, s disease. The methionine (Met) residue at position 35 in A&beta, C-terminal domain is critical for neurotoxicity, aggregation, and free radical formation initiated by the peptide. The role of Met in modulating toxicological properties of A&beta, most likely involves an oxidative event at the sulfur atom. We therefore investigated the one- or two-electron oxidation of the Met residue of A&beta, 25-35 fragment and the effect of such oxidation on the behavior of the peptide. Bicarbonate promotes two-electron oxidations mediated by hydrogen peroxide after generation of peroxymonocarbonate (HCO4&minus, PMC). The bicarbonate/carbon dioxide pair stimulates one-electron oxidations mediated by carbonate radical anion (CO3&bull, &minus, ). PMC efficiently oxidizes thioether sulfur of the Met residue to sulfoxide. Interestingly, such oxidation hampers the tendency of A&beta, to aggregate. Conversely, CO3&bull, causes the one-electron oxidation of methionine residue to sulfur radical cation (MetS&bull, +). The formation of this transient reactive intermediate during A&beta, oxidation may play an important role in the process underlying amyloid neurotoxicity and free radical generation.

The control of bleaching reaction is important in hair bleaching and laundry detergents to ensure quality of the final product. A better understanding of the reaction mechanisms is needed to minimize product failures. 31P NMR-spectroscopy-based spin trap technique was employed to detect and quantify the free radical species that were generated in different bleaching solutions. These solutions contained the key actives in an alkaline hair colorant/bleaching product, an ammonium salt and hydrogen peroxide at pH = 10. Generally, the main radical species detected in hair oxidative coloring or bleaching processes, were hydroperoxyl/superoxide radicals HO2·/O2.-, amino radicals ·NH2 and hydroxyl radicals ·OH. Their amounts showed a variation based on the chemical composition of the bleaching systems and the metal ion content. The generation of free radicals from reactions between transition metal ions, such as copper, and hydrogen peroxide at pH = 10 was evaluated. In the absence of chelating agents, the copper ions generated a significant level of hydroxyl radicals in a Fenton-like reaction with hydrogen peroxide at pH = 10. Besides that, an increase in copper ion content led to an increase of amino radical ·NH2, whereas the concentration of superoxide radical O2·- decreased which was not yet well reported in the previous literature. The effect of chelating agents like ethylenediaminetetraacetic acid (EDTA), tetrasodium-iminodisuccinate (IDS), a mixture of basic amino acids and dicarboxylic acid on free radical formation was investigated in the presence of binary Cu2+-Ca2+ bleaching systems. As expected, in the binary Cu2+-Ca2+ ion system EDTA did not suppress hydroxyl radical formation effectively, but the mixture containing sodium succinate, lysine and arginine reduced hydroxyl radical formation, whereas IDS (nearly) completely inhibited hydroxyl radical formation. The results indicated that each bleaching solution has its characteristic performance and damage profile. Whereas the reactivity can be controlled by the usage of chelating agents.

This study examined to what extent the human cerebral and femoral circulation contribute to free radical formation during basal and exercise-induced responses to hypoxia. Healthy participants (5♂, 5♀) were randomly assigned single-blinded to normoxic (21% O2) and hypoxic (10% O2) trials with measurements taken at rest and 30 min after cycling at 70% of maximal power output in hypoxia and equivalent relative and absolute intensities in normoxia. Blood was sampled from the brachial artery (a), internal jugular and femoral veins (v) for non-enzymatic antioxidants (HPLC), ascorbate radical (A•-, electron paramagnetic resonance spectroscopy), lipid hydroperoxides (LOOH) and low density lipoprotein (LDL) oxidation (spectrophotometry). Cerebral and femoral venous blood flow was evaluated by transcranial Doppler ultrasound (CBF) and constant infusion thermodilution (FBF). With 3 participants lost to follow up (final n = 4♂, 3♀), hypoxia increased CBF and FBF (P = 0.041 vs. normoxia) with further elevations in FBF during exercise (P = 0.002 vs. rest). Cerebral and femoral ascorbate and α-tocopherol consumption (v a) and increased LDL oxidation during hypoxia (P < 0.043-0.049 vs. normoxia) implying free radical-mediated lipid peroxidation subsequent to inadequate antioxidant defense. This was pronounced during exercise across the femoral circulation in proportion to the increase in local O2 uptake (r = -0.397 to -0.459, P = 0.037-0.045) but unrelated to any reduction in PO2. These findings highlight considerable regional heterogeneity in the oxidative stress response to hypoxia that may be more attributable to local differences in O2 flux than to O2 tension.

Honey is known for its wound healing potential. In this study we investigated free radical formation and inhibition in different honeys and the influence on bacterial growth inhibition. alpha-Oxaldehydes and free amino acids were shown to be present in manuka and non-manuka honeys. With electron spin resonance we measured that methylglyoxal (MG) and glyoxal (GO) form different carbon centered radicals under the influence of either hydrogen peroxide or arginine and lysine. These radicals were also formed in a combination of alpha-oxaldehydes and amino acids in artificial honey, which was quantified by the cytochrome C assay. Also, a strong bactericidal activity for MG and GO (minimum concentration 0.6 and 1.25 mM) was shown against different bacterial strains. Interestingly, honeys with a high MG content were shown to be better free radical scavengers for hydroxyl and superoxide radicals, implying a complex mechanism for free radical donation and scavenging in honey.

Grape seeds are a relatively abundant source of oil and bioactive compounds. To use this byproduct, the current work aimed to optimize the ultrasound-assisted extraction (UAE) of grape-seed oil to obtain greater process yield and minimize free radical formation in the oil.; Results: The optimal condition was 15 °C with an ultrasonic wave amplitude of 42 µm, leading to a process yield of 82.9% and content of free radicals of 14.7 × 1017 kg-1 and 3.4 × 1018 kg-1 for samples stored for 7 and 30 days, respectively. No significant differences in fatty acid composition and acidity and iodine values were observed between samples. The oil obtained by ultrasound had greater phenolic compound content and antioxidant activity by ferric reduction than the control sample (without ultrasound application). However, higher content of free radicals and peroxide value was observed.; Conclusion: Sonication improved extraction yield when compared to the process without ultrasound application. Moreover, UAE favored the extraction of phenolic compounds. As it enhanced process yield with the minimum formation of free radicals, UAE is a promising oil-extraction technology. © 2018 Society of Chemical Industry.; © 2018 Society of Chemical Industry.

Increasing studies focus on the degradation of polysaccharides by free radicals. The review mainly provides an overview of degradation of polysaccharides by free radicals generated from hydrogen peroxide (H2O2). Evidence suggests that free radicals generated from H2O2 can be generated by various mechanisms. It broke glycosidic bonds mainly through hydrogen abstraction, causing the degradation of polysaccharides. Its degradation efficiency is affected by many factors, such as the concentration of polysaccharides and H2O2, temperature and pH. In addition, free radical degradation could change the physicochemical and structural properties of polysaccharides, such as water solubility, thermal stability, molecular weight, monosaccharide composition, apparent morphology, and chain conformation, but it had little effects on the primary structure of polysaccharides. Besides, free radical degradation could also improve the bioactivities of polysaccharides, including antioxidant, antitumor and anticoagulant activities.

Polyphenols are reported to have some health benefits, which are link to their antioxidant properties. In the case of ellagic acid (EA), there is evidence that it has free radical scavenger properties and that it is able to form complexes with metal ions. However, information on a possible link between the formation of iron-EA complexes and their interference in Haber-Weiss/Fenton reactions was not yet determined. Thus, the present study investigated the in vitro antioxidant mechanism of EA in a system containing ascorbate, Fe(III) and different iron ligands (EDTA, citrate and NTA). Iron-mediated oxidative degradation of 2-deoxyribose was poorly inhibited (by 12%) in the presence of EA (50 μM) and EDTA. When citrate or NTA - which form weak iron complexes - were used, the 2-deoxyribose protection increased to 89–97% and 45%, respectively. EA also presented equivalent inhibitory effects on iron-mediated oxygen uptake and ascorbyl radical formation. Spectral analyses of iron-EA complexes show that EA removes Fe(III) from EDTA within hours, and from citrate within 1 min. This difference in the rate of iron-EA complex formation may explain the antioxidant effects of EA. Furthermore, the EA antioxidant effectiveness was inversely proportional to the Fe(III) concentration, suggesting a competition with EDTA. In conclusion, the results indicate that EA may prevent in vitro free radical formation when it forms a complex with iron ions.

The role of free radicals can be found in the inflammatory process which is a complex process resulting many human diseases. Inflammations are mainly divided into acute and chronic inflammation depending on various inflammatory processes and cellular mechanisms. In recent years, there has been a great deal of attention to the field of free radical chemistry. Free radicals such as reactive oxygen species (ROS) and reactive nitrogen species (RNS) are generated by our body by various endogenous systems, exposure to different physiochemical conditions or pathological states. The purpose of the present review is to mention the role of free radical formation in the most common inflammatory processes in animals. Continued oxidative stress can lead to chronic inflammation, which in turn could mediate the most chronic diseases including cancer, diabetes, cardiovascular, neurological, and pulmonary diseases. ROS and RNS are well recognized for playing role as deleterious species. ROS and RNS are normally generated by tightly regulated enzymes, such as NO synthase (NOS) and NAD(P)H oxidase isoforms, respectively. The detrimental effect of free radicals causing health damages is termed oxidative stress and nitrosative stress. Overproduction of ROS results in oxidative stress, a deleterious process that can damage cell structures, including lipids, proteins, and DNA.

Co-pyrolysis and steam co-gasification of wheat straw (WS) and lignite coal (LC) were studied in a tube furnace between 700 °C and 900 °C. Synergistic effect in co-pyrolysis is not always apparent. However, with the introduction of H2O vapor, synergetic effect is more obvious. Gas volume generated by co-gasification was higher than the prediction in all cases. Meanwhile, temperature played an important role and had a linear relationship with the excess gas volume when it exceeded 800 °C. These findings can be explained by that sufficient H2O vapor could enhance synergy according raising catalytic effect of alkali and alkaline earth metals (AAEMs), promoting free radical generated and increasing reactivity of half-chars. Moreover, co-gasification of WS and LC with several blending ratios were studied at 850 °C. It found H2O vapor could promote free radical formation stronger with higher ratio of WS during co-gasification, thus showing an enhancing effect on the reactivity of WS-derived chars.

Recently we have reported a qualitative, quantitative and reproducible study of the generation of free radicals as a result of the surface catalytic activity of Fe3O4, Fe2O3, MnFe2O4 and NiFe2O4 nanoparticles as a function of the Fe2+/Fe3+ oxidation state under different pHs (4.8 and 7.4) and temperatures (25 ºC and 40 ºC) condition. These results were contrasted with those obtained from the in vitro experiments in BV2 cells incubated with dextran-coated magneticnanoparticles. Based on these results we affirm that our ferrite magnetic nanoparticles catalyze the formation of free radicals and the decomposition of H2O2 by a ?peroxidase-like? activity. In a comment on this article, Meunier and A. Robert question two points: First they assert that the measured free radicals are not produced by a peroxidase reaction. Also, based on a different normalization method from those reported in our work, they also discuss that the reaction is not catalytic. Here we reply the arguments of the authors about these two points. Fil: Moreno Maldonado, Ana Carolina. Instituto de Nanociencia de Aragón; ; España Fil: Winkler, Elin Lilian. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Raineri Andersen, Mariana. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Toro Cordova, Alfonso. Universidad de Zaragoza; España Fil: Rodriguez, Luis Miguel. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Mojica Pisciotti, Mary Luz. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Vasquez Mansilla, Marcelo. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Tobia, Dina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Nadal, Marcela. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Torres Molina, Teobaldo Enrique. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: de Biasi, Emilio. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Ramos, Carlos Alberto. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Goya, Gerardo Fabian. Universidad de Zaragoza; España Fil: Zysler, Roberto Daniel. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Lima, Enio Junior. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina

Ferrite magnetic nanoparticles (MNPs) have peroxidase-like activity and thus catalyze the decomposition of H2O2-producing reactive oxygen species (ROS). Increasingly important applications of these ferrite MNPs in biology and medicine require that their morphological, physicochemical, and magnetic properties need to be strictly controlled. Usually, the tuning of their magnetic properties is achieved by the replacement of Fe by other 3d metals, such as Mn or Ni. Here, we studied the catalytic activity of ferrite MNPs (MFe2O4, M = Fe2+/Fe3+, Ni, and Mn) with the mean diameter ranging from 10 to 12 nm. Peroxidase-like activity was studied by electron paramagnetic resonance (EPR) using the spin-trap 5,5-dimethyl-1-pyrroline N-oxide at different pHs (4.8 and 7.4) and temperatures (25 and 40 °C). We identified an enhanced amount of hydroxyl (•OH) and perhydroxyl (•OOH) radicals for all samples, compared to a blank solution. Quantitative studies show that [•OH] is the dominant radical formed for Fe3O4, which is strongly reduced with the concomitant oxidation of Fe2+ or its substitution (Ni or Mn). A comparative analysis of the EPR data against in vitro production of ROS in microglial BV2 cell culture provided additional insights regarding the catalytic activity of ferrite MNPs, which should be considered if biomedical uses are intended. Our results contribute to a better understanding of the role played by different divalent ions in the catalytic activity of ferrite nanoparticles, which is very important because of their use in biomedical applications. Fil: Moreno Maldonado, Ana Carolina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina Fil: Winkler, Elin Lilian. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; Argentina Fil: Raineri Andersen, Mariana. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina Fil: Toro Córdova, Alfonso. Universidad de Zaragoza; España Fil: Rodriguez, Luis Miguel. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Mojica Pisciotti, Mary Luz. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina Fil: Vasquez Mansilla, Marcelo. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina Fil: Tobia, Dina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina Fil: Nadal, Marcela. Comisión Nacional de Energía Atómica. Gerencia del Área de Investigación y Aplicaciones No Nucleares. Gerencia de Física. Laboratorio de Resonancias Magnéticas; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Torres Molina, Teobaldo Enrique. Comisión Nacional de Energía Atómica. Gerencia del Área de Investigación y Aplicaciones No Nucleares. Gerencia de Física. Laboratorio de Resonancias Magnéticas; Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: de Biasi, Emilio. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina Fil: Ramos, Carlos A.. Comisión Nacional de Energía Atómica. Gerencia del Área de Investigación y Aplicaciones No Nucleares. Gerencia de Física. Laboratorio de Resonancias Magnéticas; Argentina Fil: Goya, Gerardo Fabian. Universidad de Zaragoza; España Fil: Zysler, Roberto Daniel. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina Fil: Lima, Enio Junior. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina

International audience; The peroxidase-like activity of magnetite and its connection with a neurodegenerative disease such as Alzheimer's disease has been recently questioned by our group, 1 despite claims by Gao et al. 2 Since reproducibility is the essential factor in experimental sciences, the article of Moreno Maldonado et al. on the peroxidase-like activity of magnetite attracted our attention. 3 As a matter of fact this new report is providing additional evidences on the absence of peroxidase activity of magnetite derivatives. The following comments are not a question of semantics, but are driven by the necessity to correctly describe the different possible origins of the oxidative stress involved in many neurodegenerative pathologies.

Free radicals in thermally treated chloramphenicol were examined by electron paramagnetic resonance (EPR) spectroscopy. The parameters and shape of EPR spectra were analysed and free radical concentrations were obtained in the tested drug samples. Chloramphenicol was thermally sterilized at pharmacopeia conditions: 100 °C (120 min). Sterilization was also carried out at different conditions, 110 °C (60 min) and 120 °C (30 min), for comparison with pharmacopeia settings. Microbiological analysis was performed on the samples to confirm sterility. The aim of this work was to determine the concentration of free radicals in chloramphenicol following thermal sterilization at pharmacopeia conditions and compare this with other sets of conditions [110 °C (60 min) and 120 °C (30 min)]. The best conditions of thermal sterilization are determined as those that kill microorganisms and produce the lowest amounts of free radicals in this drug. It was concluded that the optimal temperatures and times for the thermal sterilization of chloramphenicol are 100 °C and 120 min and 110 °C and 60 min. A temperature of 120 °C coupled with a heating time of 30 min was rejected for thermal sterilization because of the high amount of free radicals produced by the drug samples.

Adaptations of living organisms to the environment are formed and manifested at different levels, from molecular to biocoenotic. Nowadays, the metabolic antioxidant system (AOS) is considered the key part of the process of adaptation; its activation is considered a general response of biota to the negative effect of the environment. The usage of AOS components as biomarkers of the stress condition in hydrobionts has good prospects; it is actively applied in the monitoring of aquatic ecosystems. Here, the kinetics of the free radical formation in various zoobenthic species from the Yenisei River (amphipods, oligochaetes, leeches, and chironomids) and in the amphipods from the Us River (a small mountain river, the Yenisei tributary) is analyzed. The parameters of kinetics of radical formation were registered in vitro in the homogenates of hydrobionts tissues under the initiation of the oxidative stress by the hydrogen peroxide using luminol-dependent chemoluminescence. In amphipods, unlike other invertebrates, the antioxidative activity is characterized by two chemiluminescent peaks. In addition, the kinetics of free radical elaboration has interspecific and agerelated variability in amphipods. In Gmelinoides fasciatus Stebb., the peak of the free radical elaboration and their total number significantly exceeded these parameters for Gammarus sp. and Eulimnogammarus viridis Dybowsky in a 60-min period. The increase of the production of free radicals in E. viridis and Gammarus sp. and its decrease in G. fasciatus were age-dependent. A significantly higher production of free radicals has been registered in G. fasciatus and E. viridis inhabiting the zone of elevated anthropogenic load in the Yenisei River.

The use of particulate titanium dioxide (TiO2) as an active sunscreen ingredient has raised concerns about potential risks from TiO2-mediated free radical formation. To date, remediation attempts have concentrated on reducing the yield of free radical generation by TiO2 upon sunlight exposure. The problem with this approach is that given the band gap in TiO2, production of radical and the ensuing reactive oxygen species (ROS) is completely normal. Our strategy is based on a nontoxic, biocompatible shell that neutralizes the free radicals by scavenging them with natural antioxidants before they exit the particle. The new lignin@TiO2 composites preserve the scattering and absorption properties of TiO2 because the particles retain their nanoscale dimensions as preferred by the cosmetic industry. Although the target properties for photocatalysis and sun-protection applications are opposite, we argue that exactly the same knowledge is required to optimize either one.

SummaryThe ‘holy grail’ in radiation oncology is to improve the outcome of radiation therapy (RT) with a radiosensitizer—a systemic chemical/biochemical agent that additively or synergistically sensitizes tumor cells to radiation in the absence of significant toxicity. Similar to the oxygen effect, in which DNA bases modified by reactive oxygen species prevent repair of the cellular radiation damage, these compounds in general magnify free radical formation, leading to the permanent “fixation” of the resultant chemical change in the DNA structure. The purpose of this review is to present the origin story of the radiosensitizer, RRx-001, which emerged from the aerospace industry. The activity of RRx-001 as a chemosensitizer in multiple tumor types and disease states including malaria, hemorrhagic shock and sickle cell anemia, are the subject of future reviews.

Tamoxifen is the most prescribed anticancer oral drug for increasing overall survival and decreasing recurrence and the risk of contralateral disease. However, some side effects, such as endometrial and liver tumors, thromboembolic disorders, and drug resistance, are associated with long-term tamoxifen treatment. We assessed the hematologic and organ toxicity after oral administration of three different doses of nanotamoxifen formulations. We also performed biodistribution studies of Technetium-99m (99mTc)-nanotamoxifen after intravenous administration. The results demonstrated that nanotamoxifen was well-tolerated, with no adverse effect on biochemical parameters of blood and at the cellular level. Nitric oxide (NO) levels indicated no free radical formation. Oral nanotamoxifen is well-tolerated, with no hepatic or renal toxicity. Intravenous nanotamoxifen has potential to escape the liver, and is known for producing the harmful metabolite 4-hydroxytamoxifen (4OH-tamoxifen), which can cause uterine cancer.

A novel visible light responsive metal–organic framework (MOF) with a pillared-layer structure has been constructed from photoactive anthracene derived bipyridine. The as-prepared MOF was studied by single crystal X-ray diffraction, steady-state fluorescence, and electron paramagnetic resonance and so on. Studies reveal the visible light induced free radical formation of the bipyridine pillars in the MOF structure. Consequently, the promising photocatalytic reaction of atom transfer radical polymerization for methacrylate monomers was performed upon the utilization of the MOF material as a photosensitizer to reduce the copper catalyst via electron transfer. It has been demonstrated that the reaction shows characteristics of controlled radical polymerization and the prepared polymers show narrow molecular weight distributions and high retention of chain-end activities. Moreover, the photopolymerization can be easily manipulated by light switching.

Silk fibroin determines the perseverance of silk-based materials. The samples of silk fibroin were pretreated combined alkali/urea system with rapid freezing in liquid nitrogen. The structural changes of unpretreated and pretreated silk fibroins were investigated by XRD, SAXS and FTIR. The results indicate that part of the amorphous region was transformed into silk-II crystalline structure, and the radius of gyration decreased due to the folding of molecular chains by hydrogen bonds. The free radicals of unpretreated and pretreated silk fibroin induced by electron beam irradiation were studied by electron spin resonance (ESR). The results indicate that the radical concentration increased by 10 times at 25 kGy and attained 8.04*1019 spins·g−1 at 50 kGy after pretreatment, which is comparable to the saturated radical concentration of unpretreated silk fibroin above 200 kGy. And the half-life time of free radicals is 10 times longer than that of the unpretreated samples. The higher stability of the free radicals is considered to be related to the protein structure changes induced by pretreatment and this can provide convenience for silk irradiation grafting. The new pretreatment method may provide inspiration for designing protein structures to regulate free radical formation.

Free radical plays an important role in catalytic reactions. However, until recently, seldom article discussed the formation and trapping of free radical in catalytic reduction of nitric oxide (NO). For the first time, free–radical formation and its influence on the catalytic activity were investigated by Electron Paramagnetic Resonance. A metal–organic framework (MF) removed 97.59% of NO at 400 °C. This activity was higher than that (72.94%) of an activated carbon–supported catalyst (AC), although surface area of AC (1000.662 m2/g) surpassed MF (3.129 m2/g). When molecular of NO interacted with MF, carbon dioxide anion and hydroxyl radicals were formed. Under same conditions, no free radical was detected in AC. Mass Spectrum further revealed that above radicals were derived from structure of MF. As a result, the enhanced performance of MF was attributed to formations of free radicals, which increased the catalytic activity in return. The main result of this work helps us to obtain a comprehensive understanding of nitric–oxide reduction by carbon reductant.

Dye decolouring peroxidases (DyPs) are the most recent class of heme peroxidase to be discovered. On reacting with H2 O2 , DyPs form a high-valent iron(IV)-oxo species and a porphyrin radical (Compound I) followed by stepwise oxidation of an organic substrate. In the absence of substrate, the ferryl species decays to form transient protein-bound radicals on redox active amino acids. Identification of radical sites in DyPs has implications for their oxidative mechanism with substrate. Using a DyP from Streptomyces lividans, referred to as DtpA, which displays low reactivity towards synthetic dyes, activation with H2 O2 was explored. A Compound I EPR spectrum was detected, which in the absence of substrate decays to a protein-bound radical EPR signal. Using a newly developed version of the Tyrosyl Radical Spectra Simulation Algorithm, the radical EPR signal was shown to arise from a pristine tyrosyl radical and not a mixed Trp/Tyr radical that has been widely reported in DyP members exhibiting high activity with synthetic dyes. The radical site was identified as Tyr374, with kinetic studies inferring that although Tyr374 is not on the electron-transfer pathway from the dye RB19, its replacement with a Phe does severely compromise activity with other organic substrates. These findings hint at the possibility that alternative electron-transfer pathways for substrate oxidation are operative within the DyP family. In this context, a role for a highly conserved aromatic dyad motif is discussed.

Engineered viruses are finding an increasing number of applications in basic, translational research and materials science. Genetic and chemical engineering of capsids represents a key point for tailoring the properties of viral particles, but the synthetic efforts and limits accompanying these processes still hinder their usability. Here, a single-step highly selective biocatalytic functionalization approach is described, providing a general platform for virus-acrylate hybrid particles. The tobacco mosaic virus (TMV) and the bacteriophage M13 have been successfully modified via laccase induced free radical formation on the tyrosine residues through single electron oxidation as the initiating step and the free radicals subsequently react with acrylate-based monomers. This new approach can be extended to other biomolecular assemblies with surface exposed tyrosine residues, when the introduction of new functionalities is desired.

Background Human skin protects the body from external damage, pathogens and oxidative stress factors such as ultraviolet (UV) radiation. Excessive exposure to UV radiation can lead to increased production of free radicals and hence to skin damage such as inflammation, premature skin ageing and skin cancer. Besides UV, the visible and near infrared (NIR) regions are also a source of radical production. Half of all free radicals are induced by the visible + NIR region of the solar spectrum in people with skin types I-III, but data on the effects in people with skin types IV-VI are missing. Objectives This in vivo pilot study addressed the distribution of radical production in skin types IV and V during irradiation in the UV, visible and NIR spectral regions, comparing the first results with those of skin type II. Methods The measurements were performed in vivo using L-band electron paramagnetic resonance spectroscopy and the spin probe PCA. Results In skin types IV-V most radicals were induced in the visible + NIR region, followed by the NIR and UV regions of the sun spectrum. Significantly (P ≤ 0·05) more radicals were induced in skin types IV-V than in type II during NIR irradiation, whereas skin types IV-V exhibited significantly less UV-induced radicals (P ≤ 0·01) than skin type II. Conclusions All spectral regions (UV, visible and NIR) cause free radical formation in skin types II and IV-V. After 4 min of solar-simulated exposure (UV-NIR), the radical formation in skin types IV-V is 60% of that in skin type II. Therefore people with darker skin types also need solar protection.

Background Flavoring chemicals, or flavorants, have been used in electronic cigarettes (e-cigarettes) since their inception; however, little is known about their toxicological effects. Free radicals present in e-cigarette aerosols have been shown to induce oxidative stress resulting in damage to proliferation, survival, and inflammation pathways in the cell. Aerosols generated from e-liquid solvents alone contain high levels of free radicals but few studies have looked at how these toxins are modulated by flavorants. Objectives We investigated the effects of different flavorants on free radical production in e-cigarette aerosols. Methods Free radicals generated from 49 commercially available e-liquid flavors were captured and analyzed using electron paramagnetic resonance (EPR). The flavorant composition of each e-liquid was analyzed by gas chromatography mass spectroscopy (GCMS). Radical production was correlated with flavorant abundance. Ten compounds were identified and analyzed for their impact on free radical generation. Results Nearly half of the flavors modulated free radical generation. Flavorants with strong correlations included β-damascone, δ-tetradecalactone, γ-decalactone, citral, dipentene, ethyl maltol, ethyl vanillin, ethyl vanillin PG acetal, linalool, and piperonal. Dipentene, ethyl maltol, citral, linalool, and piperonal promoted radical formation in a concentration-dependent manner. Ethyl vanillin inhibited the radical formation in a concentration dependent manner. Free radical production was closely linked with the capacity to oxidize biologically-relevant lipids. Conclusions Our results suggest that flavoring agents play an important role in either enhancing or inhibiting the production of free radicals in flavored e-cigarette aerosols. This information is important for developing regulatory strategies aimed at reducing potential harm from e-cigarettes.

Detection of free radicals in biological systems is challenging due to their short half-lives. We have applied electron spin resonance (ESR) spectroscopy combined with spin traps using the probes PBN ( N-tert -butyl-α-phenylnitrone) and DMPO (5,5-dimethyl-1-pyrroline N -oxide) to assess free radical formation in the human pathogen Staphylococcus aureus treated with a bactericidal antibiotic, vancomycin or ciprofloxacin. While we were unable to detect ESR signals in bacterial cells, hydroxyl radicals were observed in the supernatant of bacterial cell cultures. Surprisingly, the strongest signal was detected in broth medium without bacterial cells present and it was mitigated by iron chelation or by addition of catalase, which catalyzes the decomposition of hydrogen peroxide to water and oxygen. This suggests that the signal originates from hydroxyl radicals formed by the Fenton reaction, in which iron is oxidized by hydrogen peroxide. Previously, hydroxyl radicals have been proposed to be generated within bacterial cells in response to bactericidal antibiotics. We found that when S. aureus was exposed to vancomycin or ciprofloxacin, hydroxyl radical formation in the broth was indeed increased compared to the level seen with untreated bacterial cells. However, S. aureus cells express catalase, and the antibiotic-mediated increase in hydroxyl radical formation was correlated with reduced katA expression and catalase activity in the presence of either antibiotic. Therefore, our results show that in S. aureus , bactericidal antibiotics modulate catalase expression, which in turn influences the formation of free radicals in the surrounding broth medium. If similar regulation is found in other bacterial species, it might explain why bactericidal antibiotics are perceived as inducing formation of free radicals.

Free radicals in synthetic melanin and melanin from Sepia officinalis were studied by electron paramagnetic resonance (EPR) spectroscopy. The effect of time of ultraviolet (UV) irradiation on free radicals in these melanins was tested. The samples were exposed to UV during 15, 30, and 60 minutes. EPR spectra were measured with microwaves from an X-band (9.3 GHz) in the range of microwave power of 2.2–70 mW. The performed EPR examinations indicate that high concentrations (~1021–1022 spin/g) of o-semiquinone free radicals with g factors of 2.0039–2.0045 exist in all the tested samples. For nonirradiated samples, free radical concentration was higher in natural melanin than in synthetic melanin. UV irradiation caused the increase of free radical concentrations in synthetic melanin samples and this effect depends on the time of irradiation. The largest free radical formation in the both melanins was obtained for 60 min of UV irradiation. Free radical concentrations after the UV irradiation of melanins during 30 min were lower than during irradiation by 15 min, and probably this effect was the result of recombination of the radiatively formed free radicals. EPR lines of the tested samples broadened with increasing microwave power, so these lines were homogeneously broadened. The two types of melanins differed in the time of spin-lattice relaxation processes. Slower spin-lattice relaxation processes exist in melanin from Sepia officinalis than in synthetic melanin. UV irradiation did not change the time of spin-lattice relaxation processes in the tested melanins. The performed studies confirmed the usefulness of EPR spectroscopy in cosmetology and medicine.

Electron paramagnetic resonance (EPR) spectroscopy was used to examine insulins interactions with free radicals. Human recombinant DNA insulins of three groups were studied: short-acting insulin (Insuman Rapid); intermediate-acting insulins (Humulin N, Insuman Basal), and pre-mixed insulins (Humulin M3, Gensulin M50, Gensulin M40, Gensulin M30). The aim of an X-band (9.3GHz) study was comparative analysis of antioxidative properties of the three groups of human insulins. DPPH was used as a stable free radical model. Amplitudes of EPR lines of DPPH as the paramagnetic free radical reference, and DPPH interacting with the individual tested insulins were compared. For all the examined insulins kinetics of their interactions with free radicals up to 60 min were obtained. The strongest interactions with free radicals were observed for the short-acting insulin - Insuman Rapid. The lowest interactions with free radicals were characteristic for intermediate-acting insulin - Insuman Basal. The pre-mixed insulins i.e. Humulin M3 and Gensulin M50 revealed the fastest interactions with free radicals. The short acting, intermediate acting and premixed insulins have been found to be effective agents in reducing free radical formation in vitro and should be further considered as potential useful tools in attenuation of oxidative stress in diabetic patients.

Purpose : An ex vivo method for detection of free radicals and their neutralization by aqueous tea in human normal lymphocytes and MEC-1 leukemia cells under ultraviolet (UV) irradiation was investigated. Materials and methods : This method is based on the electron paramagnetic resonance (EPR) spectroscopy spin-trapping technique. 5-tert-butoxycarbonyl 5-methyl-1-pyrroline N-oxide (BMPO) was used as the spin trap. Normal human lymphocytes and leukemia cells were exposed to UVB radiation (290 – 315 nm) at 47.7 and 159 mJ/cm 2 and to UVA radiation (315 – 400 nm) at 53.7 J/cm 2 . Results : No signifi cant radical production at 47.7 mJ/cm 2 UVB dose in both cell lines was observed. In normal cells, free radical production was observed at 159 mJ/cm 2 UVB and 53.7 J/cm 2 UVA doses. However, both UV sources did not signifi cantly produce free radicals in leukemia cells. A radical scavenging property of tea extracts (black, green, sage, rosehip) was observed in normal lymphocytes after both UVB and UVA exposure. In leukemia cells, the intensities of EPR signals produced in BMPO with tea extracts were found to be increased substantially after UVA exposure. Conclusion : These results showed that UV radiation induced free radical formation in normal human lymphocytes and indicated that tea extracts may be useful as photoprotective agents for them. On the other hand, tea extracts facilitated free radical production in leukemia cells.

The integrated microwave with Mn/γ-Al2O3 and ozone was employed to oxidize elemental mercury (Hg0) in simulated flue gas. Hg0 oxidation efficiency in the integrated system attained 92.2%. Mn/γ-Al2O3 catalyst was characterized by XRD, XPS, FT-IR, SEM. XPS spectra indicate the formation of a stable mercuric oxide species (HgO) from mercury oxidation. Ozone molecules in air could enhance free radical formation. Hg0 was oxidized to HgO in the presence of ozone and free radical. The coupling role between ozone and radical on mercury oxidation was formed. Microwave catalytic oxidation of elemental mercury reaction with the Mn/γ-Al2O3 catalyst follows Langmuir–Hinshelwood kinetics.

The ever-evolving market of electronic cigarettes (e-cigarettes) presents a challenge for analyzing and characterizing the harmful products they can produce. Earlier we reported that e-cigarette aerosols can deliver high levels of reactive free radicals; however, there are few data characterizing the production of these potentially harmful oxidants. Thus, we have performed a detailed analysis of the different parameters affecting the production of free radical by e-cigarettes. Using a temperature-controlled e-cigarette device and a novel mechanism for reliably simulating e-cigarette usage conditions, including coil activation and puff flow, we analyzed the effects of temperature, wattage, and e-liquid solvent composition of propylene glycol (PG) and glycerol (GLY) on radical production. Free radicals in e-cigarette aerosols were spin-trapped and analyzed using electron paramagnetic resonance. Free radical production increased in a temperature-dependent manner, showing a nearly 2-fold increase between 100 and 300 °C under constant-temperature conditions. Free radical production under constant wattage showed an even greater increase when going from 10 to 50 W due, in part, to higher coil temperatures compared to constant-temperature conditions. The e-liquid PG content also heavily influenced free radical production, showing a nearly 3-fold increase upon comparison of ratios of 0:100 (PG:GLY) and 100:0 (PG:GLY). Increases in PG content were also associated with increases in aerosol-induced oxidation of biologically relevant lipids. These results demonstrate that the production of reactive free radicals in e-cigarette aerosols is highly solvent dependent and increases with an increase in temperature. Radical production was somewhat dependent on aerosol production at higher temperatures; however, disproportionately high levels of free radicals were observed at ≥100 °C despite limited aerosol production. Overall, these findings suggest that e-cigarettes can be designed to minimize exposure to these potentially harmful products.

A “green” laser (e.g. Nd:YAG, λ = 532 nm) together with the red dye Rose Bengal (RB) have been used for photochemical tissue bonding (PTB). It has been reported that irradiation of RB with light at 532 nm produces free radicals. For tissue bonding with a Nd:YAG laser it has been proposed that the free radicals than crosslink the tissue collagen and lead to the closing of the surgical incisions. RB is also a red solution and it is possible that RB absorbs the photons delivered from the laser and converts them into heat with a measurable local temperature increase. It is possible that the mechanism for PTB is not only caused by free radical formation but also by a temperature increase in the tissue. In the present study we measured the local tissue temperature with a micro thermometer during irradiation with a Nd:YAG laser before and after RB was applied. For the present laser settings “tissue painting” with RB lead to a temperature increase resulting in tissue coagulation and charring. PTB was also studied for RB with a free radical scavenger, vitamin C. No significant difference in bonding strength was found for RB alone and for RB together with a free radical scavenger. In case no RB was applied no tissue bonding occurred. Bonding strength was quantified using the leakage seal test

This chapter discusses the role of free radicals with respect to their initiation of oxidative damage to biomolecular systems. It examines the role of a wide variety of enzymes in the generation of free radicals in biological systems, including various membrane-bound enzymes, cytosolic enzymes, and organelle enzymes, as well as the role of redox and photochemical and ionizing radiation in free radical formation in an extracellular milieu. The pathways, products, and impacts of a number of enzyme-induced reactions are described for biological systems.

Low-density lipoprotein (LDL) oxidation is the primary event in atherosclerosis, and LDL lipoperoxidation leads to modifications in apolipoprotein B-100 (apo B-100) and lipids. Intermediate species of lipoperoxidation are known to be able to generate amino acid-centered radicals. Thus, we hypothesized that lipoperoxidation intermediates induce protein-derived free radical formation during LDL oxidation. Using DMPO and immuno-spin trapping, we detected the formation of protein free radicals on LDL incubated with Cu(2+) or the soybean lipoxidase (LPOx)/phospholipase A2 (PLA2). With low concentrations of DMPO (1mM), Cu(2+) dose-dependently induced oxidation of LDL and easily detected apo B-100 radicals. Protein radical formation in LDL incubated with Cu(2+) showed maximum yields after 30 min. In contrast, the yields of apo B-100 radicals formed by LPOx/PLA2 followed a typical enzyme-catalyzed kinetics that was unaffected by DMPO concentrations of up to 50mM. Furthermore, when we analyzed the effect of antioxidants on protein radical formation during LDL oxidation, we found that ascorbate, urate, and Trolox dose-dependently reduced apo B-100 free radical formation in LDL exposed to Cu(2+). In contrast, Trolox was the only antioxidant that even partially protected LDL from LPOx/PLA2. We also examined the kinetics of lipid radical formation and protein radical formation induced by Cu(2+) or LPOx/PLA2 for LDL supplemented with α-tocopherol. In contrast to the potent antioxidant effect of α-tocopherol on the delay of LDL oxidation induced by Cu(2+), when we used the oxidizing system LPOx/PLA2, no significant protection was detected. The lack of protection of α-tocopherol on the apo B-100 and lipid free radical formation by LPOx may explain the failure of vitamin E as a cardiovascular protective agent for humans.

In the present work, β-carotene antioxidant was incorporated in two different lipid nanoaggregates, bicelles and bicosomes, and its effectiveness against free radical formation in porcine skin in vitro was determined using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) spin trap and Electron Paramagnetic Resonance spectroscopy (EPR). Bicelles are discoidal nanostructures formed by self-assembly of phospholipids dispersed in aqueous solution. Bicosomes emerge as a strategy to stabilize and protect bicelles encapsulating these nanostructures in liposomes. Results from Dynamic Light Scattering (DLS) and cryo Transmission Electron Microscopy (cryo-TEM) demonstrated a slight modification in the size of both systems when β-carotene was incorporated. EPR revealed that after skin irradiation both systems presented free radical scavenging activity. This activity was statistically significant for bicosomes containing β-carotene. Differences regarding this scavenging activity between bicelles and bicosomes would probably be due to the different interaction of both systems with the skin. In this study, six different radicals were identified in skin spectra: two originated from oxygen centred radicals (primary/secondary and tertiary alkoxyl radicals) and another from carbon-centred radicals. Additionally, the presence of 5,5-dimethyl-2-oxo-pyrroline-1-hydroxyl (DMPO-OH), 5,5-dimethyl-2-oxo-pyrroline-1-hydrogen (DMPO-H) adducts and aminoxyl radicals (RR′NO˙) were detected. Considering these results, bicelles and bicosomes could be useful lipid systems for future dermopharmaceutical applications.

The effects of water-filtered infrared-A (wIRA) and of convective heat on viability, inflammation, inducible free radicals and antioxidative power were investigated in natural and viable skin using the ex vivo Bovine Udder System (BUS) model. Therefore, skin samples from differently treated parts of the udder of a healthy cow were analyzed using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) test, by prostaglandin E2 (PGE2) measurement and by electron spin resonance (ESR) spectroscopy. Neither cell viability, the inflammation status, the radical status or the antioxidative defence systems of the skin were significantly affected by wIRA applied within 30 min by using an irradiance of 1900 W m(-2) which is of relevance for clinical use, but which exceeded the maximum solar IR-A irradiance at the Earth's surface more than 5 times and which resulted in a skin surface temperature of about 45 °C without cooling and of about 37 °C with convective cooling by air ventilation. No significant effects on viability and on inflammation were detected when convective heat was applied alone under equivalent conditions in terms of the resulting skin surface temperatures and exposure time. As compared with untreated skin, free radical formation was almost doubled, whereas the antioxidative power was reduced to about 50% after convective heating to about 45 °C.

AimsArterial hypoxaemia stimulates free radical formation. Cellular studies suggest this may be implicated in coagulation activation though human evidence is lacking. To examine this, an observational study was designed to explore relationships between systemic oxidative stress and haemostatic responses in healthy participants exposed to inspiratory hypoxia.ResultsActivated partial thromboplastin time and international normalised ratio were measured as routine clinical biomarkers of coagulation and ascorbate free radical (A•−) as a direct global biomarker of free radical flux. Six hours of hypoxia activated coagulation, and increased formation of A•−, with inverse correlations observed against oxyhaemoglobin saturation.ConclusionsThis is the first study to address the link between free radical formation and coagulation in vivo. This ‘proof-of-concept’ study demonstrated functional associations between hypoxaemia and coagulation that may be subject to redox activation of the intrinsic pathway. Further studies are required to identify precisely which intrinsic factors are subject to redox activation.