Scavenging of Cation Radicals of the Visual Cycle Retinoids by Lutein, Zeaxanthin, Taurine, and Melanin.

In the retina, retinoids involved in vision are under constant threat of oxidation, and their oxidation products exhibit deleterious properties. Using pulse radiolysis, this study determined that the bimolecular rate constants of scavenging cation radicals of retinoids by taurine are smaller than 2 × 107 M-1s-1 whereas lutein scavenges cation radicals of all three retinoids with the bimolecular rate constants approach the diffusion-controlled limits, while zeaxanthin is only 1.4-1.6-fold less effective. Despite that lutein exhibits greater scavenging rate constants of retinoid cation radicals than other antioxidants, the greater concentrations of ascorbate in the retina suggest that ascorbate may be the main protectant of all visual cycle retinoids from oxidative degradation, while α-tocopherol may play a substantial role in the protection of retinaldehyde but is relatively inefficient in the protection of retinol or retinyl palmitate. While the protection of retinoids by lutein and zeaxanthin appears inefficient in the retinal periphery, it can be quite substantial in the macula. Although the determined rate constants of scavenging the cation radicals of retinol and retinaldehyde by dopa-melanin are relatively small, the high concentration of melanin in the RPE melanosomes suggests they can be scavenged if they are in proximity to melanin-containing pigment granules.

COVID-19 and the ethnicity link - is there a photochemical link?

A hypothesis is proposed to explain the increased detrimental effect of COVID-19 for Black, Asian and Minority Ethnic (BAME) men and women compared to Caucasian individuals. This is based on the differing photochemistry of phaeomelanin in fair skin and eumelanin in dark/black skin. It is suggested that a range of reactive oxygen species, including, singlet oxygen and the superoxide radical anion, derived via direct photolysis of phaeomelanin, may escape the melanocyte and cause subsequent damage to the SARS-CoV-2 virus. It is further suggested that (large) carbon and sulphur peroxy radicals, from oxygen addition to radicals formed by carbon-sulphur bond cleavage, may assist via damage to the cell membranes. It is also speculated that light absorption by phaeomelanin and the subsequent C-S bond cleavage, leads to release of pre-absorbed reactive oxygen species, such as singlet oxygen and free radicals, which may also contribute to an enhanced protective effect for fair-skinned people.

School formation characteristics and stimuli based modeling of tetra fish.

Self-organizing motion is an important yet inadequately understood phenomena in the field of collective behavior. For birds flocks, insect swarms, and fish schools, group behavior can provide a mechanism for defense against predators, better foraging and mating capabilities and increased hydro/aerodynamic efficiency in long-distance migration events. Although collective motion has received much scientific attention, more work is required to model and understand the mechanisms responsible for school initiation and formation, and information transfer within these groups. Here we investigate schooling of black tetra (Gymnocorymbus ternetzi) fish triggered by startle stimuli in the form of approaching objects. High-speed video and tagging techniques were used to track the school and individual members. We then measured several variables including reaction times, group formation shapes, fish velocity, group density, and leadership within the group. These data reveal three things: (1) information propagates through the group as a wave, indicating that each fish is not reacting individually to the stimulus, (2) the time taken for information to transfer across the group is independent of group density, and (3) information propagates across large groups faster than would be expected if the fish were simply responding to the motion of their nearest neighbor. A model was then built wherein simulated fish have a simple 'stimuli/escape' vector based on a hypothetical field of vision. The model was used to simulate a group of individual fish with initial conditions, size, and stimuli similar to the biological experiments. The model revealed similar behavior to the biological experiments and provide insights into the observed patterns, response times, and wave speeds.

Cavitation clusters in lipid systems - Ring-up, bubble population, and bifurcated streamer lifetime.

The processing of oils is vital to their ultimate use within the food industry. Control over the physical properties of such materials could be achieved through the application of high-intensity ultrasound (HIU). However, the exact mechanism, centred upon acoustic cavitation, is currently unclear. To investigate the cavitation environment in oils further, the ring-up of a HIU source in an oil media is studied in the presence and absence of a pre-existing bubble population. High-speed imaging and acoustic measurements within the system is demonstrated to be extremely useful in characterising the dynamics present under non steady-state conditions. The behaviour of the clusters generated in the first 1000 ms under these conditions is shown to be significantly different depending on the bubble population. A bifurcated streamer (BiS), originating from a unique bi-cluster event, is only observable in the presence of a bubble population during the ring-up process to higher cluster orders. In addition, the lifetime of this BiS event is highly temperature dependent and is shown to be a good marker for the viscosity of the oil employed.

Anti- and pro-oxidative mechanisms comparing the macular carotenoids zeaxanthin and lutein with other dietary carotenoids - a singlet oxygen, free-radical in vitro and ex vivo study.

The interactions of dietary carotenoids, and particularly the xanthophylls in the macula, with singlet oxygen and three different oxy-radicals, (hydroxyl radical, nitrogen dioxide and the superoxide radical anion) are compared using pulsed laser and γ-techniques. The results give possible molecular mechanisms for the switch from anti-oxidant (protection) by carotenoids to pro-oxidant (damage) by carotenoids. The participation of oxygen in radical mechanisms in the presence of different carotenoids is compared for the different radicals. It is shown that the mechanistic role of oxygen differs very significantly for anti-/pro-oxidation by hydroxyl radicals when compared to nitrogen dioxide. Lutein was found to be an extremely good cell protector against hydroxyl radicals at all oxygen concentrations, including under physiological conditions.

The Benefits and Risks of Certain Dietary Carotenoids that Exhibit both Anti- and Pro-Oxidative Mechanisms-A Comprehensive Review.

Carotenoid pigments, particularly ß-carotene and lycopene, are consumed in human foodstuffs and play a vital role in maintaining health. ß-carotene is known to quench singlet oxygen and can have strong antioxidant activity. As such, it was proposed that ß-carotene might reduce the risk of cancer. Epidemiological studies found inverse relationships between cancer risk and ß-carotene intake or blood levels. However, clinical trials failed to support those findings and ß-carotene supplementation actually increased lung cancer incidence in male smokers. Early experimental animal studies found dietary ß-carotene inhibited UV-induced skin cancers. Later studies found that ß-carotene supplementation exacerbated UV-carcinogenic expression. The discrepancies of these results were related to the type of diet the animals consumed. Lycopene has been associated with reduced risk of lethal stage prostate cancer. Other carotenoids, e.g., lutein and zeaxanthin, play a vital role in visual health. Numerous studies of molecular mechanisms to explain the carotenoids' mode of action have centered on singlet oxygen, as well as radical reactions. In cellular systems, singlet oxygen quenching by carotenoids has been reported but is more complex than in organic solvents. In dietary ß-carotene supplement studies, damaging pro-oxidant reactivity can also arise. Reasons for this switch are likely due to the properties of the carotenoid radicals themselves. Understanding singlet oxygen reactions and the anti-/pro-oxidant roles of carotenoids are of importance to photosynthesis, vision and cancer.

How vision governs the collective behaviour of dense cycling pelotons.

In densely packed groups demonstrating collective behaviour, such as bird flocks, fish schools or packs of bicycle racers (cycling pelotons), information propagates over a network, with individuals sensing and reacting to stimuli over relatively short space and time scales. What remains elusive is a robust, mechanistic understanding of how sensory system properties affect interactions, information propagation and emergent behaviour. Here, we show through direct observation how the spatio-temporal limits of the human visual sensory system govern local interactions and set the network structure in large, dense collections of cyclists. We found that cyclists align in patterns within a ± 30° arc corresponding to the human near-peripheral visual field, in order to safely accommodate motion perturbations. Furthermore, the group structure changes near the end of the race, suggesting a narrowing of the used field of vision. This change is consistent with established theory in psychology linking increased physical exertion to the decreased field of perception. Our results show how vision, modulated by arousal-dependent neurological effects, sets the local arrangement of cyclists, the mechanisms of interaction and the implicit communication across the group. We furthermore describe information propagation phenomena with an analogous elastic solid mechanics model. We anticipate our mechanistic description will enable a more detailed understanding of the interaction principles for collective behaviour in a variety of animals.

Scavenging of Retinoid Cation Radicals by Urate, Trolox, and α-, ß-, γ-, and δ-Tocopherols.

Retinoids are present in human tissues exposed to light and under increased risk of oxidative stress, such as the retina and skin. Retinoid cation radicals can be formed as a result of the interaction between retinoids and other radicals or photoexcitation with light. It has been shown that such semi-oxidized retinoids can oxidize certain amino acids and proteins, and that α-tocopherol can scavenge the cation radicals of retinol and retinoic acid. The aim of this study was to determine (i) whether ß-, γ-, and δ-tocopherols can also scavenge these radicals, and (ii) whether tocopherols can scavenge the cation radicals of another form of vitamin A-retinal. The retinoid cation radicals were generated by the pulse radiolysis of benzene or aqueous solution in the presence of a selected retinoid under oxidizing conditions, and the kinetics of retinoid cation radical decays were measured in the absence and presence of different tocopherols, Trolox or urate. The bimolecular rate constants are the highest for the scavenging of cation radicals of retinal, (7 to 8) × 109 M-1·s-1, followed by retinoic acid, (0.03 to 5.6) × 109 M-1·s-1, and retinol, (0.08 to 1.6) × 108 M-1·s-1. Delta-tocopherol is the least effective scavenger of semi-oxidized retinol and retinoic acid. The hydrophilic analogue of α-tocopherol, Trolox, is substantially less efficient at scavenging retinoid cation radicals than α-tocopherol and urate, but it is more efficient at scavenging the cation radicals of retinoic acid and retinol than δ-tocopherol. The scavenging rate constants indicate that tocopherols can effectively compete with amino acids and proteins for retinoid cation radicals, thereby protecting these important biomolecules from oxidation. Our results provide another mechanism by which tocopherols can diminish the oxidative damage to the skin and retina and thereby protect from skin photosensitivity and the development and/or progression of changes in blinding retinal diseases such as Stargardt's disease and age-related macular degeneration (AMD).

Singlet Oxygen and Free Radical Reactions of Retinoids and Carotenoids-A Review.

We report on studies of reactions of singlet oxygen with carotenoids and retinoids and a range of free radical studies on carotenoids and retinoids with emphasis on recent work, dietary carotenoids and the role of oxygen in biological processes. Many previous reviews are cited and updated together with new data not previously reviewed. The review does not deal with computational studies but the emphasis is on laboratory-based results. We contrast the ease of study of both singlet oxygen and polyene radical cations compared to neutral radicals. Of particular interest is the switch from anti- to pro-oxidant behavior of a carotenoid with change of oxygen concentration: results for lycopene in a cellular model system show total protection of the human cells studied at zero oxygen concentration, but zero protection at 100% oxygen concentration.

Cavitation clusters in lipid systems - surface effects, local heating and streamer formation.

Cavitation clusters and streamers are characterised in lipid materials (specifically sunflower oil) and compared to water systems. The lipid systems, which are important in food processing, are studied with high-speed camera imaging, laser scattering and pressure measurements. In these oils, clusters formed at an aged (roughened) tip of the sound source (a piston like emitter, PLE) are shown to collapse with varied periodicity in relation to the drive amplitude employed. A distinct streamer (an area of increased flow emanating from the cavitation cluster) is seen in the lipid media which is collimated directly away from the tip of the PLE source whereas in water the cavitation plume is visually less distinct. The velocity of bubbles in the lipid streamer near the cluster on the order of 10 m s-1. Local heating effects, within the streamer, are detected using a dual thermocouple measurement at extended distances. Viscosity, temperature and the outgassing within the oils are suggested to play a key role in the streamer formation in these systems.

Disease-associated prion protein in neural and lymphoid tissues of mink (Mustela vison) inoculated with transmissible mink encephalopathy.

Transmissible spongiform encephalopathies (TSEs) are diagnosed by immunodetection of disease-associated prion protein (PrP(d)). The distribution of PrP(d) within the body varies with the time-course of infection and between species, during interspecies transmission, as well as with prion strain. Mink are susceptible to a form of TSE known as transmissible mink encephalopathy (TME), presumed to arise due to consumption of feed contaminated with a single prion strain of ruminant origin. After extended passage of TME isolates in hamsters, two strains emerge, HY and DY, each of which is associated with unique structural isoforms of PrP(TME) and of which only the HY strain is associated with accumulation of PrP(TME) in lymphoid tissues. Information on the structural nature and lymphoid accumulation of PrP(TME) in mink is limited. In this study, 13 mink were challenged by intracerebral inoculation using late passage TME inoculum, after which brain and lymphoid tissues were collected at preclinical and clinical time points. The distribution and molecular nature of PrP(TME) was investigated by techniques including blotting of paraffin wax-embedded tissue and epitope mapping by western blotting. PrP(TME) was detected readily in the brain and retropharyngeal lymph node during preclinical infection, with delayed progression of accumulation within other lymphoid tissues. For comparison, three mink were inoculated by the oral route and examined during clinical disease. Accumulation of PrP(TME) in these mink was greater and more widespread, including follicles of rectoanal mucosa-associated lymphoid tissue. Western blot analyses revealed that PrP(TME) accumulating in the brain of mink is structurally most similar to that accumulating in the brain of hamsters infected with the DY strain. Collectively, the results of extended passage in mink are consistent with the presence of only a single strain of TME, the DY strain, capable of inducing accumulation of PrP(TME) in the lymphoid tissues of mink but not in hamsters. Thus, mink are a relevant animal model for further study of this unique strain, which ultimately may have been introduced through consumption of a TSE of ruminant origin.

Interactions of dietary carotenoids with singlet oxygen (1O2) and free radicals: potential effects for human health.

The dietary carotenoids provide photoprotection to photosynthetic organisms, the eye and the skin. The protection mechanisms involve both quenching of singlet oxygen and of damaging free radicals. The mechanisms for singlet oxygen quenching and protection against free radicals are quite different - indeed, under some conditions, quenching of free radicals can lead to a switch from a beneficial anti-oxidant process to damaging pro-oxidative situation. Furthermore, while skin protection involves ß-carotene or lycopene from a tomato-rich diet, protection of the macula involves the hydroxyl-carotenoids (xanthophylls) zeaxanthin and lutein. Time resolved studies of singlet oxygen and free radicals and their interaction with carotenoids via pulsed laser and fast electron spectroscopy (pulse radiolysis) and the possible involvement of amino acids are discussed and used to (1) speculate on the anti- and pro-oxidative mechanisms, (2) determine the most efficient singlet oxygen quencher and (3) demonstrate the benefits to photoprotection of the eye from the xanthophylls rather than from hydrocarbon carotenoids such as ß-carotene.

Reduction of oxidized guanosine by dietary carotenoids: a pulse radiolysis study.

Time-resolved pulse radiolysis investigations reported herein show that the carotenoids ß-carotene, lycopene, zeaxanthin and astaxanthin (the last two are xanthophylls--oxygen containing carotenoids) are capable of both reducing oxidized guanosine as well as minimizing its formation. The reaction of the carotenoid with the oxidized guanosine produces the radical cation of the carotenoid. This behavior contrasts with the reactions between the amino acids and dietary carotenoids where the carotenoid radical cations oxidized the amino acids (tryptophan, cysteine and tyrosine) at physiological pH.

Prooxidant and antioxidant behaviour of usnic acid from lichens under UVB-light irradiation--studies on human cells.

Natural compounds which can behave as antioxidants and protect against UV-radiation may well have medical and cosmetic value. Usnic acid, which can be obtained from lichens offer such a potential. The latter is one of the best known and reviewed compounds present in lichens and exhibits many properties of value such as antibiotic, antitumor and UV-filter-effects. We report studies of the potential antioxidant and prooxidant activity of usnic acid extracted from Xanthoparmelia farinosa (Vainio) using a human lymphocyte cell line (Jurkat-cells) under UV-B-irradiation. Cell survival and cell metabolism were determined using different conditions such as usnic acid concentration and UVB dose. Compared to the controls the cells incubated with usnic acid in concentrations of 1 x 10(-8) and 1 x 10(-6) M showed a higher cell survival and a normal metabolism under low doses of UVB-light up to 0.1 J/cm(2). When both higher UVB doses (up to 14 J/cm(2)) and higher concentrations of usnic acid (1 x 10(-4) M) where used, the opposite effect was observed. It is concluded that these effects are due to bifunctional (a switch of) anti-oxidative-pro-oxidative behaviour of usnic acid under UV-B-irradiation.

Ovine progressive pneumonia virus capsid antigen as found in CD163- and CD172a-positive alveolar macrophages of persistently infected sheep.

In situ detection of ovine progressive pneumonia virus (OPPV) and the phenotypic identification of the cells that harbor OPPV have not been described for the OPPV-affected tissues, which include lung, mammary gland, synovial membranes of the carpal joint, and choroid plexus of the brain. In this study, the authors first developed a single enzyme-based automated immunohistochemical (IHC) analysis for detection of OPPV capsid antigen (CA) on OPPV-affected tissues, using 2 anti-CAEV CA monoclonal antibodies, 5A1 and 10A1, and 2 enzyme-based IHC systems. Out of 10 naturally and persistently OPPV-infected ewes, OPPV CA was detected in intercellular regions of the carpal synovial membrane of 1 ewe, in cells resembling alveolar macrophages and pulmonary interstitial macrophages in lung tissue of 3 ewes, and in mammary alveolar cells of 1 ewe. Furthermore, dual enzyme-based automated IHC analyses revealed that OPPV CA was predominantly detected in CD172a- or CD163-positive alveolar macrophages of the lungs and mammary gland. That anti-inflammatory (CD163) and downregulatory (CD172a) types of alveolar macrophage harbor OPPV CA leads to the possibility that during persistent infection with OPPV, the host alveolar macrophage might serve to limit inflammation while OPPV persists undetected by the host adaptive immune response in the lung and mammary gland.

Lichens--photophysical studies of potential new sunscreens.

Fundamental photophysical properties have been obtained for six polyaromatics, calycine, usnic acid, vicanicine, 1-Cl-pannerine and epiphorelic acids I and II, extracted from Antarctic lichens--potential future sunscreens. None of the lichen compounds produced a measurable amount of triplet states and the singlet oxygen quantum yield was also very low ranging from 0.003 to 0.06. However, three exhibited triplet energy levels which may be above that of thymine. The radical cations of calycine and usnic acid were generated via pulse radiolysis and were observed to be quenched by vitamin C, vitamin E and Trolox.

The carbonate radical: its reactivity with oxygen, ammonia, amino acids, and melanins.

The carbonate radical (CO 3 (*-)) is of importance in biology and chemistry. We used pulse radiolysis to generate the CO 3 (*-) radical and show there is no reaction with oxygen. However, in the presence of ammonia the CO 3 (*-) radical is removed by NO (*), which itself arises from the scavenging of NH 2 (*) by oxygen, and the mechanism of this process is reported. The CO 3 (*-) radical shows complex decay patterns in the presence of ammonia, which can be understood as a balance between the radical-radical reaction CO 3 (*-) + CO 3 (*-) and CO 3 (*-) + NH 2 (*) (the amino radical). Also, we report reactivity with glycine and alanine and with melanin models. The CO 3 (*-) reacts with both dopa-melanin (DM, a model of black eumelanin) and with cysteinyl-dopa-melanin (CDM, a model of red/blond phaeomelanin). However, the reaction rate constant is much higher with CDM than with DM.

Direct observation of NH2* reactions with oxygen, amino acids, and melanins.

We report the direct observation of the quenching of the weakly absorbing transient due to the amino radical by oxygen and, hence determine, by a totally direct method, the corresponding rate constant (k = (1.1 +/- 0.1) x 10(9) dm3 mol(-1) s(-1)). We also report the rate constants for the reactions of the amino radical with several amino acids and models of black eumelanin and blond/red phaeomelanin. These reactions lead to a mechanism, based on free radicals, that can explain why ammonia is useful in commercial hair (melanin) bleaching, avoiding excessive amino acid (hair protein) damage.

Studies of carotenoid one-electron reduction radicals.

The relative reduction potentials of a variety of carotenoids have been established by monitoring the reaction of carotenoid radical anion (CAR1(*-)) with another carotenoid (CAR2) in hexane and benzene. This order is consistent with the reactivities of the carotenoid radical anions with porphyrins and oxygen in hexane. In addition, investigation of the reactions of carotenoids with reducing radicals in aqueous 2% Triton-X 100, such as carbon dioxide radical anion (CO2(*-)), acetone ketyl radical (AC(*-)) and the corresponding neutral radical (ACH(*)), reveals that the reduction potentials for beta-carotene and zeaxanthin lie in the range -1950 to -2100 mV and those for astaxanthin, canthaxanthin and beta-apo-8'-carotenal are more positive than -1450 mV. This illustrates that the presence of a carbonyl group causes the reducing ability to decrease. The radical cations have been previously shown to be strong oxidising agents and we now show that the radical anions are very strong reducing agents.