Formation Of Peroxyl Radicals Research Articles

Droplet size dependency and spatial heterogeneity of lipid oxidation in whey protein isolate-stabilized emulsions

Spatiotemporal assessment of lipid and protein oxidation is key for understanding quality deterioration in emulsified food products containing polyunsaturated fatty acids. In this work, we first mechanistically validated the use of the lipid oxidation-sensitive fluorophore BODIPY 665/676 as a semi-quantitative marker for local peroxyl radical formation. Next, we assessed the impact of microfluidic and colloid mill emulsification (respectively producing mono- and polydisperse droplets) on local protein and lipid oxidation kinetics in whey protein isolate (WPI)-stabilized emulsions. We further used BODIPY 581/591 C11 and CAMPO-AFDye 647 as colocalisation markers for lipid and protein oxidation. The polydisperse emulsions showed an inverse relation between droplet size and lipid oxidation rate. Further, we observed less protein and lipid oxidation occurring in similar sized droplets in monodisperse emulsions. This observation was linked to more heterogeneous protein packing at the droplet surface during colloid mill emulsification, resulting in larger inter-droplet heterogeneity in both protein and lipid oxidation. Our findings indicate the critical roles of emulsification methods and droplet sizes in understanding and managing lipid oxidation.

Synthesis of two TiO2-based prodegradant additives and their efficiency in inducing the accelerated photo-oxidation of low-density polyethylene

In this study, two prodegradant additives derived from TiO2 nanoparticles were synthesized and comprehensively characterized through a range of analytic techniques, such as X-ray diffraction (DRX), Fourier Transform Infrared Spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The hydroxyl groups adsorbed on the surface of TiO2 were esterified with biobased arachidonic acid (AA) and cervonic acid (DHA), resulting in levels of functionalization at 13 % and 16 % w/w, respectively. These additives were incorporated into low-density polyethylene (LDPE) films, at concentrations of 1 % and 3 % w/w. The prodegradant efficiency of the additives was subsequently assessed through accelerated UV aging. Following 200 h of exposure, the aged films experienced a loss in molecular weight (Mw) by approximately 95 %, accompanied by carbonyl indexes (CI) measuring 1.8 and 2.0. This high level of degradation observed in the LDPE films denotes an effective degradation mechanism, reliant on the generation of hydroxyl radicals by the TiO2 moiety, upon UV light exposure, and the subsequent abstraction of labile hydrogens within the polyunsaturated sidechain of the additives, resulting in the formation of peroxyl radicals, thereby initiating the swift auto-oxidation of the polyethylene films.

Process for desulfurization and demineralization of low rank coal using oxidation assisted froth floatation technique

This study reports the desulfurization and deashing of Hangu coal by air oxidation assisted froth floatation technique applying performic acid (H2O2+HCOOH) as co-oxidant and Fe ions as catalysts in aqueous solution. This process led to the removal of up to 78.08% of total sulfur (TS) and 50.3% of ash at 60 °C, 30 min, a 2:2 ratio of H2O2+HCOOH (v/v), and 0.10% of Fe ions concentration. The sulfur and ash removal followed Fenton mechanism, wherein hydrogen peroxide (H2O2) dissociated into hydroxyl ions (OH-) and hydroxyl radicals (OH.), facilitated by the dissociation of ferrous ions (Fe2+). The reaction of HCOOH with OH. resulted in the formation of performic acid or peroxyl radical, selectively oxidizing sulfur compounds to sulfone and sulfoxide. In the subsequent phase, coal froth floatation was employed with the addition of surfactant i.e. Triton X-100 (TX-100) and collector i.e. diesel oil (DO), resulting in the removal of up to 49.83% of TS and 43.79% of ash. This was achieved under optimized conditions, specifically with a concentration of 400 ppm solution of TX-100 in the solution and a volume of 0.2 mL for DO. The emulsion of TX-100 and DO for the floatation of coal is a suitable option because TX-100 established polar interactions and hydrogen bonding with the oxidized functionalities of coal, whereas the hydrocarbons of diesel oil get attached to the unoxidized coal matrix through hydrophobic interaction. Onwards, simultaneous oxidation assisted by froth floatation in a two-step batch process at pre-optimized parameters resulted in TS and ash removal of 88.8% and 82.6%, and 62.2% and 39.3% in the froth and tailings, respectively. SEM, FTIR and XRD analyses revealed structural and morphological changes, modifications in chemical functionalities and mineralogical changes in the coal sample. The process can be scaled up for the up-gradation of low grade coal for industrial and power generation purposes.

Analysis of polyphenols, anthocyanins and toxic elements in Açaí Juice (Euterpe oleracea Mart.): Quantification and in vivo assessment of the antioxidant capacity of clarified Açaí juice

This study aims to measure the concentration of total polyphenols, anthocyanins and inorganic contaminants (Al, Pb and Ni) in samples of açaí juice collected in the municipalities of Pará and evaluate the in vivo antioxidant capacity of purified açaí juice. Total polyphenols and anthocyanins were determined by UV/Vis spectrophotometry, while inorganic contaminants were measured using Graphite Furnace Atomization Atomic Absorption Spectrometry (GF-AAS) and Flame Atomic Absorption Spectrometry (F-AAS) after microwave-assisted digestion. The in vivo study lasted five days and involved 16 rats divided into four groups. The antioxidant capacity was evaluated through the formation of peroxyl free radicals (ACAP) in rat liver tissue. The average concentrations (mg GAE/DE) of total phenolic compounds averaged 27.34, with individual values ranging from 13.28 to 56.58. The average concentration (mg ANTO/g) of anthocyanins was 7.6, with individual concentrations ranging from 5.52 to 9.75. Contaminant concentrations (mg/kg) ranged from 1.82 to 11.74 for Al, 0.04 to 0.53 for Pb and 0.18 to 0.78 for Ni. The levels of Pb found in the samples may represent a concern to health. Al and Pb induced oxidative stress in the liver tissue, but Euterpe oleracea clarified juice (EOCJ) led to significant antioxidant protection. Animals treated with the highest dose of EOCJ (2.07 g/kg body weight) experienced an approximately five-fold reduction in ACAP compared to the group exposed to the metals (Al and Pb). The findings suggest the need to monitor inorganic contaminants in açaí products as well as the potential benefits of antioxidant compounds against the liver toxicity of Al and Pb.

Differential Remodeling of the Oxylipin Pool After FLASH Versus Conventional Dose-Rate Irradiation In Vitro and In Vivo

The products of lipid peroxidation have been implicated in human diseases and aging. This prompted us to investigate the response to conventional (CONV) versus FLASH irradiation of oxylipins, a family of bioactive lipid metabolites derived from omega-3 or omega-6 polyunsaturated fatty acids through oxygen-dependent non-enzymatic as well as dioxygenase-mediated free radical reactions. Ultrahigh performance liquid chromatography coupled to tandem mass spectrometry was used to quantify the expression of 37 oxylipins derived from eicosatetraenoic, eicosapentaenoic and docosahexaenoic acid in mouse lung and in normal or cancer cells exposed to either radiation modality under precise monitoring of the temperature and oxygenation. Among the 37 isomers assayed, 14-16 were present in high enough amount to enable quantitative analysis. The endpoints were the expression of oxylipins as a function of the dose of radiation, normoxia versus hypoxia, temperature and post-irradiation time. In normal, normoxic cells at 37°C radiation elicited destruction and neosynthesis of oxylipins acting antagonistically on a background subject to rapid remodeling by oxygenases. Neosynthesis was observed in the CONV mode only, in such a way that the level of oxylipins at 5 minutes after FLASH irradiation was 20-50% lower than in non-irradiated and CONV-irradiated cells. Hypoxia mitigated the differential CONV versus FLASH response in some oxylipins. These patterns were not reproduced in tumor cells. Depression of specific oxylipins following FLASH irradiation was observed in mouse lung at 5 min following irradiation, with near complete recovery in 24 hours and further remodeling at one week and two months post-irradiation. Down-regulation of oxylipins was a hallmark of FLASH irradiation specific of normal cells. Temperature effects suggest that this process occurs via diffusion-controlled, bimolecular recombination of a primary radical species upstream from peroxyl radical formation and evoke a major role of the membrane composition and fluidity in response to the FLASH modality.

Gas-Phase Phenyl Radical + O2 Reacts via a Submerged Transition State.

In the gas-phase chemistry of the atmosphere and automotive fuel combustion, peroxyl radical intermediates are formed following O2 addition to carbon-centered radicals which then initiate a complex network of radical reactions that govern the oxidative processing of hydrocarbons. The rapid association of the phenyl radical-a fundamental radical related to benzene-with O2 has hitherto been modeled as a barrierless process, a common assumption for peroxyl radical formation. Here, we provide an alternate explanation for the kinetics of this reaction by deploying double-hybrid density functional theory (DFT), at the DSD-PBEP86-D3(BJ)/aug-cc-pVTZ level of theory, and locate a submerged adiabatic transition state connected to a prereaction complex along the reaction entrance pathway. Using this potential energy scheme, experimental rate coefficients k(T) for the addition of O2 to the phenyl radical are accurately reproduced within a microcanonical kinetic model. This work highlights that purportedly barrierless radical oxidation reactions may instead be modeled using stationary points, which in turn provides insight into pressure and temperature dependence.

Elucidating the mechanism of 1,3-butadiene oxidation with O2: A DFT study

1,3-Butadiene (1,3-C4H6) is a ubiquitous pollutant produced during the combustion of hydrocarbon fuels in engine cylinders. In this study, we delved into the potential energy surface (PES) and rate constant of 1,3-C4H6 employing the density theory (DFT) method and transition state theory (TST). This study comprehensively clarifies the process of O2 oxidation 1,3-C4H6 and its significance on the prediction of combustion dynamic models. Our research reveals that the addition of O2 to the terminal carbon atom of 1,3-C4H6 is the dominant path for addition reactions, leading to the formation of peroxyl radicals. Subsequently, these reactions predominantly yield acrolein and aldehyde groups. Moreover, our data indicates a barrierless and exothermic path for the generation of peroxyl radicals by the O2 addition to the C4H5 radical site. The energy barrier for the dominant path, 1,3-C4H6+H → iC4H5+H2, has been calculated to be 57.6 kJ/mol with a rate constant of 7.89×1010 cm3 mol−1 s−1. This study integrates the kinetic and thermochemical data derived from our targeted reaction system into the updated AramcoMech 3.0. An in-depth analysis reveals the capability of this mechanism to simulate combustion characteristics of 1,3-C4H6, emphasizing its temperature-dependent species profiles. Comparatively, the performance evaluation of the proposed 1,3-C4H6 kinetic mechanism demonstrates its improvement over its predecessor, showing good agreement with experimental results.

Development of an enhanced method for atmospheric carbonyls and characterizing their roles in photochemistry in subtropical Hong Kong

Carbonyl compounds are ubiquitous and play vital roles in tropospheric photochemistry and oxidation capacity, particularly affecting radical cycling and ozone formation. An enhanced method based on ultra-high-performance liquid chromatography and electrospray ionization tandem mass spectrometry was developed to simultaneously quantify 47 carbonyl compounds with carbon (C) numbers from 1 to 13. Applying this new method to samples collected at ground and ship-borne field campaigns, we investigated the abundance, characteristic distribution, and photochemical activity of carbonyl species in the coastal atmosphere of Hong Kong. The total concentration of detected carbonyls ranged from 9.1 to 32.7 ppbv and exhibited distinct spatial variability. In addition to the usual abundant carbonyl species (formaldehyde, acetaldehyde, and acetone), aliphatic saturated aldehydes with C ≥ 5 (particularly hexaldehyde and nonanaldehyde), and di‑carbonyls, exhibit significant abundance and photochemical reactivity in the coastal site and on the sea. The measured carbonyls could contribute to an estimated peroxyl radical formation rate of 1.88–8.43 ppb/h via OH oxidation and photolysis, greatly enhancing oxidation capacity and radical cycling. The ozone formation potential (OFP) estimated from the maximum incremental reactivity (MIR) was dominated (69 %–82 %) by formaldehyde and acetaldehyde, with significant contribution (4 %–13 %) from di‑carbonyls. Furthermore, another dozens of long-chain carbonyls without MIR values, which were typically below detection or not included in the conventional analytical method, would increase the ozone formation rate by an additional 2 %–33 %. Additionally, the glyoxal, methylglyoxal, benzaldehyde and other α, β-unsaturated aldehydes also exhibited considerable contribution to secondary organic aerosol (SOA) formation potential. This study highlights the importance of various reactive carbonyls in the atmospheric chemistry of urban and coastal regions. The newly developed method can effectively characterize more carbonyl compounds and advance our understanding of their roles in photochemical air pollution.

Characterization of triglycerides photooxidation under solar radiations: A stepwise Raman study.

Triglycerides (TGs) are one of the main components of the glycerolipid family. Their main task in cells is to store excess fatty acids. TG energy storage is mainly concentrated in adipocytes. TGs and free fatty acids constitute the majority (57.5%) of the skin surface lipids (SSLs). TGs are essential for the formation of the skin water barrier. This work is the second part of a global study that aims to evaluate the effect of solar radiations on SSLs using vibrational spectroscopy. In the first part of this work, a stepwise characterization of free fatty acids was performed, and different spectral descriptors were used to follow the different structural modifications during the photo-oxidation process, that is hydrogen abstraction, formation of hydroperoxides and peroxyl radicals as primary oxidation products and the formation of aldehydes, ketones, alcohol as secondary products. In this second part, the photo-oxidation of TGs was evaluated using Raman spectroscopy. A decrease in the CH2/CH3 stretching bands ratio that confirmed the hydrogen abstraction, an increase in the 1165/1740cm-1 ((δ(OH) and υ(C-O))/ν(C=O) (ester)) ratio indicated the formation of secondary oxidation products such as hydroperoxides. And finally, an increase in the 1725/1740cm-1 (υ(C=O) (ald.)/υ(C=O) (ester)) ratio and the trans ν(C=C)/cis ν(C=C) ratio highlighted the formation of aldehydes, alcohols, ketone, trans secondary products and others.

Применение Кокарнита у пациенток с ишемической болезнью плаценты в послеродовом периоде

schemic placental disease, which includes such nosological entities as preeclampsia, fetal growth retardation and placental abruption, is commonly the cause of premature labor, which makes it an urgent medical and biological problem. To increase the efficacy of preventive measures, it seems promising to use metabolic therapy, which implies a direct effect on metabolic processes at the tissue and cellular levels. The antioxidant effect of metabolic drugs can reduce the formation of reactive oxygen species and peroxyl radicals in the blood and tissues, and prevent cellular damage. The authors present their experience concerning the use of Cocarnit® metabolic drug, which includes triphosadenine, cocarboxylase, cyanocobalamin and nicotinamide, in complex therapy in the late postpartum period in patients with ischemic placental disease. The use of this drug improves the hemodynamic parameter control, normalizes carbohydrate metabolism, contributes to the rapid restoration of hemoglobin levels in combination with iron preparations, as well as to a softer and faster rehabilitation of female patients in this group, increasing the probability of a favorable outcome in future pregnancy. It should be noted that the preliminary results obtained by the authors require further randomized comparative clinical trials on large samples. KEYWORDS: pregnancy, ischemic placental disease, postpartum period, fetal death, Cocarnit, triphosadenine, cocarboxylase, nicotinamide, cyanocobalamin, metabolic therapy. FOR CITATION: Dobrokhotova Yu.E., Dzhokhadze L.S. Cocarnit in female patients with ischemic placental disease in the postpartum period. Russian Journal of Woman and Child Health. 2023;6(4):385–390 (in Russ.). DOI: 10.32364/2618-8430-2023-6-4-10.

Gastrointestinal Effects on the Antioxidant and Immunomodulatory Properties of South African Fynbos Honey.

The Fynbos biome, Western Cape Province, South Africa, produces a unique honey from Apis mellifera capensis. The bioactivity of Fynbos (FB1-FB6) honeys and Manuka, unique manuka factor 15+ (MAN UMF15+) honey subjected to simulated in vitro digestion, was compared. The effect of each phase of digestion on the antioxidant properties and nitric oxide- (NO-) associated immunomodulatory effects was determined. The total phenolic content of MAN (UMF15+) was higher than that of FB honeys, and following digestion, the percentage bioaccessibility (BA) was 68.6% and 87.1 ± 27.0%, respectively. With the Trolox equivalent antioxidant capacity assay, the activity of FB1 and FB6 was similar to MAN (UMF15+) but reduced for FB2, FB3, FB4, and FB5 with a %BA of 77.9% for MAN (UMF15+) and 78.2 ± 13.4% for FB. The oxygen radical absorbance capacity of MAN (UMF15+) and FB honeys was similar and unaltered with digestion. In a cellular environment, using colon adenocarcinoma (Caco-2) cells, both undigested and the gastric digested honey reduced 2,2'-azobis-(2-amidinopropane) dihydrochloride- (AAPH-) mediated peroxyl radical formation. In contrast, following gastroduodenal digestion, the formation of reactive oxygen species (ROS) was increased. In murine macrophage (RAW 264.7) cells, all honeys induced different levels of NO which was significantly increased with digestion for MAN (UMF15+) and FB1. In LPS/IFN-γ stimulated RAW 264.7 macrophages, only undigested MAN (UMF15+) effectively reduced NO levels, and with digestion, NO scavenging activity of MAN (UMF15+) was reduced but increased for FB5 and FB6. In a noncellular environment, MAN (UMF15+), FB1, FB2, and FB6 scavenged NO, and with digestion, this activity was maintained. This study has identified that undigested and gastric-digested FB honey has antioxidant properties with strong potential anticancer effects following gastroduodenal digestion, related to ROS formation. MAN (UMF15+) had anti-inflammatory effects which were lost postdigestion, and in contrast, FB5 and FB6 had anti-inflammatory effects postdigestion.

Pristine, carboxylated, and hybrid multi-walled carbon nanotubes exert potent antioxidant activities in in vitro-cell free systems

Multi-walled carbon nanotubes (MWCNTs) are tubular-shaped carbon allotropes, composed of multiple concentric graphene cylinders. The extended systems of conjugated double bonds, that MWCNTs are constituted by, provide them with high electron affinities, enabling them to act as electron donors or acceptors. Consequently, their potential biomedical applications, as synthetic antioxidant agents, are of particular interest. Based on the above, the purpose of the present study was to evaluate the intrinsic antioxidant properties of pristine and carboxylated MWCNTs, as well as of novel hybrid nanocomposites of MWCNTs and inorganic nanoparticles. To this end, after the synthesis and characterization of MWCNTs, their antiradical, reducing, and antigenotoxic properties were assessed in cell-free assays, using a methodological approach that has been recently proposed by our research group. According to our results, most of the tested MWCNTs exhibited strong antioxidant activities. More elaborately, the hybrid material of MWCNTs and ferrous oxide nanoparticles, i.e., CNTs@Fe3O4, showed robust scavenging capacities in all free-radical scavenging assays examined. As regards reducing properties, the pristine MWCNTs, i.e., CNTs-Ref, exhibited the greater electron donating capacity. Finally, in terms of antigenotoxic properties, the hybrid material of MWCNTs and silicon carbide nanoparticles, i.e., CNTs@SiC, exhibited potent ability to inhibit the formation of peroxyl radicals, thus preventing from the oxidative DNA damage. Conclusively, our findings suggest that the MWCNTs of the study could be considered as promising broad-spectrum antioxidants, however, further investigations are required to evaluate their toxicological profile in cell-based and in vivo systems.

Leading individual features of antioxidant systematically classified by the ORAC assay and its single electron transfer and hydrogen atom transfer reactivities; analyzing ALS therapeutic drug Edaravone

Many natural compounds mop up radicals and limit radical reactions and may prove useful in reducing or preventing oxidative stress-related diseases in vivo. Several assays have been developed to measure antioxidant or anti-radical activity. Here, we measured the anti-radical activities of representative antioxidants using different assays. The oxygen radical absorption capacity (ORAC) assay has two mechanistic stages. We classified antioxidant behavior using two characteristic values thought to be related to the two stages — peroxyl radical formation time (lag time) and fluorescein annihilation rate (kobs) — by applying Voronoi polyhedral division. We focused on four class-representative antioxidants, Trolox ®, vitamin C, l-cysteine, and 2,6-di‑tert‑butyl‑p-cresol, and compared their characteristic activities with those of edaravone. Our analysis indicates that edaravone is in the same group as cysteine and may function via a similar mechanism. Our results suggest that analyzing lag time and kobs is a useful method to characterize antioxidants.

Proton-Sensitive Free-Radical Dimer Evolution Is a Critical Control Point for the Synthesis of Δ2,2′-Bibenzothiazines

The mechanism of the acid-dependent interring dehydrogenation in the conversion of the single-bonded 3-phenyl-2H-1,4-benzothiazine dimer 2 to the Δ2,2′-bi(2H-1,4-benzothiazine) scaffold of red hair pigments is disclosed herein. Integrated chemical oxidation and oxygen consumption experiments, coupled with electron paramagnetic resonance (EPR) analyses and DFT calculations, allowed the identification of a key diprotonated free-radical intermediate, which was implicated in a remarkable oxygen-dependent chain process via peroxyl radical formation and evolution to give the Δ2,2′-bi(2H-1,4-benzothiazine) dimer 3 by interring dehydrogenation. The critical requirement for strongly acidic conditions was rationalized for the first time by the differential evolution channels of isomeric peroxyl radical intermediates at the 2- versus 3-positions. These results offer for the first time a rationale to expand the synthetic scope of the double interring dehydrogenation pathway for the preparation of novel symmetric double-bond bridged captodative heterocycles.

The Effects of Dietary Inclusion of Bilberry and Walnut Leaves in Laying Hens' Diets on the Antioxidant Properties of Eggs.

Simple SummaryEggs are considered common dietary sources of n-3 polyunsaturated fatty acids (PUFA), but they are susceptible to quality deterioration. In order to reduce oxidation, the best strategy is the addition of antioxidants to hens’ diets. Walnut and bilberry co-products, rich in phenolic compounds, are produced in agricultural industries, and are a valuable source of antioxidants for animal nutrition. The dietary inclusion of bilberry and walnut leaves as natural sources of antioxidants in poultry diets led to the accumulation of nutrients with antioxidant activity in the egg yolk, and the susceptibility of the yolk to lipid peroxidation during storage improved. The results of the present study showed that including bilberry and walnut leaves in laying hens’ diets enhanced the oxidative stability of the egg yolk and retarded the lipid peroxidation process during storage.The purpose of this study was to examine the effects of dietary inclusion of walnut and bilberry leaves (WL and BL), as sources of natural antioxidants in poultry diets, on the enrichment of antioxidant nutrients in the egg yolk and on the susceptibility of the yolk to lipid peroxidation during storage. The experiment was conducted on 32-week-old TETRA SL LL laying hens, which were assigned to three dietary treatments with 30 birds each. Each treatment was replicated 10 times with three chicks per replicate pen. Experimental dietary treatments differed from control diet (C) by addition of 0.5% BL supplement or 1% WL supplement. The phytoadditives were not significant contributors to the productive parameters. The addition of BL and WL in laying hens’ diets significantly increased the total polyphenol content, and the zinc, lutein and zeaxanthin concentrations in the egg yolks. In regards to the oxidative stability parameters, a significant decrease in the concentrations of primary oxidation products formed in the egg yolk of experimental groups was seen, proving an efficient inhibition effect of the phytoadditives on peroxyl radical formation. A significant correlation was observed between primary oxidation products and total polyphenol content of the egg yolks, where zinc, lutein and zeaxanthin are the bioactive compounds that inhibit the formation of secondary oxidation products.

Impact of phosphatidylcholine and phosphatidylethanolamine on the oxidative stability of stripped peanut oil and bulk peanut oil

Effect of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) on oxidation stability of stripped peanut oil (SPO) and bulk peanut oil (BPO) was investigated by EPR. Impact of commercial lecithin and cephalin on BPO oxidation was also studied. PC < 1000 ppm could not affect SPO oxidation but obviously accelerated oxidation above 1000 ppm. PE acted as antioxidant below 250 ppm, had no effect at 500 and 1000 ppm but behaved prooxidative properties above 2500 ppm. It suggested that there was a threshold value for PC and PE to act as prooxidant in SPO, which above the CMC yet not just at the CMC. PC (500 ppm) and PE (100–500 ppm) decreased BPO oxidation rate through reducing the formation of peroxyl and carbon-centered radicals. 250, 500 ppm PC from lecithin and 100, 250 ppm PE from cephalin possessed antioxidant abilities in BPO during Schaal oven test, demonstrating the results obtained with EPR.

Conservation Issues of Modern Oil Paintings: A Molecular Model on Paint Curing.

The 20th and 21st century oil paintings are presenting a range of challenging conservation problems that can be distinctly different from those noted in paintings from previous centuries. These include the formation of vulnerable surface "skins" of medium and exudates on paint surfaces, efflorescence, unpredictable water and solvent sensitivity, and incidence of paint dripping which can occur within a few years after the paintings were completed. Physicochemical studies of modern oil paints and paintings in recent years have identified a range of possible causal factors for the noted sensitivity of painting surfaces to water and protic solvents, including the formation of water-soluble inorganic salts and/or the accumulation of diacids at the paint surface, which are oxidation products of the oil binder. Other studies have investigated the relationship between water sensitivity and the degree of hydrolysis of the binder, the proportions of free fatty and dicarboxylic acids formed, as well as the relative content of free metal soaps. Thus far, data indicate that the qualitative and quantitative composition of the nonpolymerized fractions of the oil binder cannot be solely or directly related to the solvent sensitivity of the paint film. Conclusions therefore indicate that the polymeric network, formed upon the curing of the oil, plays a fundamental role, suggesting that water sensitivity, at least in some cases, may be related to the poor development and/or polar nature of the formed polymeric network rather than the composition of the nonpolymerized fractions. Poorly developed polymeric networks, in combination with the migration of polar fractions, i.e., dicarboxylic and hydroxylated fatty acids toward the paint surface, can be related to other degradation phenomena, including the separation and migration of the paint binder which can lead to the presence of observable skins of medium as well as the more alarming phenomenon of liquefying or dripping oil paints. It is thus crucial to understand the molecular composition of these paints and their physicochemical behavior to aid the further development of appropriate conservation and preservation strategies, as the risks currently associated with surface cleaning treatments and other conservation procedures can be unacceptably high. This Account reviews the relationships between the degradation phenomena associated with modern oil paintings and the chemical composition of the oil binder and proposes a molecular model for the development of water sensitivity and other noted degradation phenomena. It is suggested that water sensitivity (and possibly other degradation phenomena) is a consequence of processes that take place upon curing, and in particular to the rate of formation and decomposition of alkoxyl and peroxyl radicals. These reactions are strongly dependent on the type of oil present, the ambient environmental conditions, and the chemical and physical nature of the pigments and additives present in the paint formulation. When the curing environment is oxidizing, the chemistry of peroxyl radicals dominates the reaction pathways, and oxidative decomposition of the paint film overwhelms cross-linking reactions.

Regulation of lipid peroxidation and ferroptosis in diverse species.

Lipid peroxidation is the process by which oxygen combines with lipids to generate lipid hydroperoxides via intermediate formation of peroxyl radicals. Vitamin E and coenzyme Q10 react with peroxyl radicals to yield peroxides, and then these oxidized lipid species can be detoxified by glutathione and glutathione peroxidase 4 (GPX4) and other components of the cellular antioxidant defense network. Ferroptosis is a form of regulated nonapoptotic cell death involving overwhelming iron-dependent lipid peroxidation. Here, we review the functions and regulation of lipid peroxidation, ferroptosis, and the antioxidant network in diverse species, including humans, other mammals and vertebrates, plants, invertebrates, yeast, bacteria, and archaea. We also discuss the potential evolutionary roles of lipid peroxidation and ferroptosis.

Propagation of free-radical reactions in concentrated protein solutions

The reactions of proteins with biologically relevant oxidants have been widely studied, although most of the work has been performed in diluted homogenous solutions conditions that differ from those in intracellular environments. Cellular compartments represent highly crowded milieu in which high concentrations of biomolecules are present, unspecific intermolecular interactions are promoted, and physicochemical properties of constituents are modified. In this work, we propose that the high concentration at which proteins are present inside cells favours radical oxidative reactions between polypeptides which propagate in an oxygen-dependent process similar to membrane lipid peroxidation. The results presented herein show that highly concentrated solutions of bovine serum albumin (BSA) exposed to peroxynitrite, or metmyoglobin/H2O2, initiate the formation and propagation of protein peroxyl radicals, as evidenced by oxygen consumption, fluorescence spectroscopy, chemiluminescence, and electron paramagnetic resonance studies. Moreover, peroxyl radicals are capable of converting nitrite to nitrogen dioxide, which can oxidise amino acid residues to further assist radical-mediated protein oxidation. In addition, we also show that nitrone spin traps stop these propagation reactions in proteins, in line with the previously reported antioxidant role of these compounds in vivo. In summary, our results suggest that in crowded environments such as cellular compartments radical chain reactions propagate protein oxidative damage, highlighting a previously under recognised mechanism of cellular nitroxidative stress.

Study on relationship of total bilirubin with acute coronary syndrome (ACS) and associated risk factors

Background: Cardiovascular risk factors for ACS are on the rise in people of Indian origin and ACS is now the leading cause of death. More recent evidence suggests that bilirubin is a potent physiological antioxidant that may provide important protection against atherosclerosis and inflammation. Substantial evidence has documented that the development of CAD involves lipid oxidation and formation of oxygen radicals as atherosclerosis and inflammation are associated with formation of oxygen and peroxyl radicals. Keep of these points in mind, the present study was undertaken to find relation between Serum Bilirubin and Acute Coronary Syndrome.Methods: The present descriptive cross-sectional study conducted at A.J Institute of Medical Sciences and Research Centre, Mangaluru from October 2016 to April 2017. A detailed history, general physical examination, systemic examination and investigations was performed on all patients who fulfill the inclusion criterion and age &gt;18yrs, both sexes who are admitted in CCU.Results: Hypertension had statistically significant correlation with ACS. All risk factors were more associated with STEMI compared to unstable angina or NSTEMI. On Correlation of LDL and Total leucocyte count with bilirubin both were statistically significant when compared to bilirubin levels.Conclusions: The study showed an inverse correlation of bilirubin with ACS, which in shows fact that bilirubin acts as an antioxidant and has cardioprotective action and patients with ACS have lower levels of bilirubin. This can use as a factor for screening individuals who have high risk for ACS and preventive strategies applied in them before the onset of overt ACS.