Rate Of Free Radical Generation Research Articles

Insights on enhancing piezocatalytic performance of Bi2WO6@PDA homojunction from phase coexistence and electron transfer mediators

Piezocatalytic technology with controllable generation of reactive oxygen species (ROS) is emerging in wastewater treatment. This study employed the synergetic regulation of functional surface and phase interface modification to effectively accelerate redox reaction in piezocatalytic process. We anchored the conductive polydopamine (PDA) onto Bi2WO6 (BWO) using template method, in which a small amount of Bi precipitation to induce partial phase transition of BWO from tetragonal to orthorhombic (t/o) in virtue of simple calcination. ROS traceability studies have identified the synergistic relationship between charge separation and transfer. Polarization in two-phase coexistence is intimately modulated by the orthorhombic relative central cation displacement. The orthorhombic phase with large electric dipole moment significantly promotes the generation of piezoresistive effect of intrinsic tetragonal BWO and optimizes the charge distribution. PDA further overcomes the obstruction of carrier migration at the phases interface to accelerate the generation rate of free radicals. Consequently, the superior rhodamine B (RhB) piezocatalytic degradation rate of 0.10 and 0.32 min−1 were delivered by t/o-BWO and t/o-BWO@PDA, respectively. This work reveals a feasible polarization enhancement strategy for the phase coexistence, and flexibly introduces the in-situ synthesized economical polymer conductive unit into the piezocatalysts.

Carbon monoxide neurotoxicity is triggered by oxidative stress induced by ROS production from three distinct cellular sources

Carbon monoxide (CO) poisoning is one of the leading causes of toxic mortality and morbidity. We have studied the generation of reactive oxygen species in cortical neurons in culture in response to toxic doses of CO exposure. Fluorescence microscopy was used to measure the rate of free radical generation, lipid peroxidation, GSH level and also mitochondrial metabolism. We have found that toxic concentrations of CO released from CORM-401 induced mitochondrial depolarisation and inhibition of NADH dependent respiration to a lesser degree than when compared to ischaemia. Energy collapse was not observed within 40 min of CO exposure. We have found that CO induces the generation of reactive oxygen species resulting in lipid peroxidation and a decrease in GSH via three different mechanisms: from mitochondria during the first minutes of CO exposure, from xanthine oxidase at around 20 min exposure due to energy deprivation, and considerable ROS production from NADPH oxidase in the post CO exposure period (re-oxygenation). Inhibition of these different phases with mitochondrial antioxidants, inhibitors of xanthine oxidase, or NADPH oxidase, protected neurons and astrocytes against CO-induced oxidative stress and cell death. The most profound effect was seen during NADPH oxidase inhibition. Thus, oxidative stress has a remarkably significant role in CO-induced neuronal cell death and preventing its occurrence during reoxygenation is of great importance in the consideration of a positive, neurologically protective therapeutic outcome for CO exposed patients.

Effects of olefinic compounds on the thermal transformation for FCC slurry oil: Evolution pattern and mechanism

FCC decant oil was always used as the raw material for the preparation of high-value-added carbonaceous materials. There is little disagreement that the free radical mechanism induces thermal polymerization reactions between reactant molecules and intermediate species, which leads to the formation of carbonaceous mesophase in the early stage of carbonization. Olefinic hydrocarbons were recently found to be widely distributed in FCC decant oil in our previous research, and these chemically active compounds usually possess weak π-bonds in molecules and thus potentially form free radicals easily, which may impact the carbonization performance dramatically. This research investigated the effects of olefinic compounds on the preparation of needle coke from FCC decant oil, as well as the corresponding mechanism in depth combined with the evolution pattern of the intermediate species during liquid carbonization. ESR analyses were adopted to evaluate the variation of the concentration of stable free radicals. Stable free radical concentration varied greatly in diverse polymerizing systems along with the carbonization process. Olefin showed a significant effect on the stable free radical concentration during carbonization. The stable free radical concentration of the polymerizing system derived from FCC decant oil was 3.32 × 1020 spins/g when the reaction time was 4 h. But with 3 wt% addition of 2-vinylnaphthalene and squalene in FCC decant oil, the stable free radical concentration increased to 2.14 × 1021 spins/g and 1.33 × 1021 spins/g, respectively, with the same reaction time. Meanwhile, the olefins conjugated with aromatic rings shown more obvious effect on the generation of free radicals. Olefinic compounds can lead to a high generation rate of free radicals and significantly high stable free radical concentration in the polymerizing system which then promote the formation of disordered carbon materials. Besides, plenty of fine particles appeared between mesophase spheres with the addition of olefinic hydrocarbons, and then impeded the coalescence between mesophase spheres. Effect mechanism for olefin on the development of carbonaceous mesophase was proposed accordingly. In sum, the content of olefinic compounds in raw materials should be limited for reaching the requirements of the synthesis of carbon materials with superior structures, in which the content of olefinic compounds should be less than 1 wt% at least based on the research in this paper.

Physiological and Transcripts Analyses Reveal the Mechanism by Which Melatonin Alleviates Heat Stress in Chrysanthemum Seedlings.

Heat stress limits the growth and development of chrysanthemum seedlings. Although melatonin (MT) has been linked to the heat stress response in plants, research on the underlying molecular mechanisms is scarce. In this study, the regulatory networks of MT on heat stress in chrysanthemum seedlings were explored. Physiological measurements suggested that MT not only reduced malondialdehyde accumulation, hydrogen peroxide content, and superoxide anion free radical generation rate, but also significantly promoted osmotic regulation substance synthesis (proline and soluble protein), antioxidant accumulation (GSH and AsA), and the antioxidant enzyme activities (SOD, POD, CAT, and APX) in chrysanthemum leaves under heat stress. Furthermore, MT increased the fresh weight, dry weight, chlorophyll content, photosynthesis rate, and gas exchange indexes. Further, RNA-seq results revealed 33,497 and 36,740 differentially expressed genes in the S/Con and SMT/ConMT comparisons, respectively. The differences in the comparisons revealed that MT regulated heat shock transcription factors (HSFs) and heat shock proteins (HSPs), and the genes involved in Ca2+ signal transduction (CNGCs and CAM/CMLs), starch and sucrose metabolism (EDGL, BGLU, SuS, and SPS), hormone (PP2Cs, AUX/IAAs, EBFs, and MYC2), chlorophyll metabolism (HEMA and PORA), flavonoid biosynthesis (CHS, DFR, and FNS), and carotenoid biosynthesis (DXPS, GGDP, and PSY). MT effectively improved chrysanthemum seedling heat-resistance. Our study, thus, provides novel evidence of a gene network regulated by MT under heat stress.

Sulfate radicals based heterogeneous peroxymonosulfate system catalyzed by CuO-Fe3O4-Biochar nanocomposite for bisphenol A degradation

Magnetic CuO-Fe3O4-Biochar (CuO-Fe3O4-BC) nanoparticles were successfully synthesized by two steps of coprecipitation and calcination and were characterized as a heterogeneous catalyst to activate peroxymonosulfate for bisphenol A (BPA) degradation. The reaction process and mechanism of heterogeneous catalyst adsorption and synergistic catalytic oxidation for the removal of BPA in CuO-Fe3O4-BC/PMS system were extensively evaluated in view of the practical applications. Results indicated that the addition of CuO achieved a high removal efficiency of BPA in a wide pH range. BPA removal efficiency reached 100 % in 30 min by using 2.0 g/L CuO-Fe3O4-BC and 5 mM PMS at a pH of 9.0, and SO4− played an essential role in the degradation process. The synergistic effect of copper ions and iron ions accelerated the circulation of Fe (II)/Fe (III) and Cu (I)/Cu (II), which improved the electron transfer on the catalyst surface and increased the free radical generation rate. CuO, Fe3O4 and BC achieved a synergistic effect between adsorption and catalysis. The stability and reusability of CuO-Fe3O4-BC/PMS system offer an approach in organic pollutant wastewater treatment since it has great advantages of high removal efficiency, conducting under neutral conditions, energy-saving and avoiding the common issues in traditional Fenton reactions.

Nephroprotective effect of melatonin and L-Ascorbic acid (Vitamin-C) against ampicillin- induced toxicity in Funambulus pennanti

ABSTRACT Ampicillin is one of the most commonly prescribed antibiotics against intra-renal infections. Prolonged use of ampicillin has been found to be associated with a high rate of free-radical generation and oxidative stress induced nephrotoxicity. In the present study, we report the comparative effects of melatonin and vitamin-C (Vit-C) in ameliorating the biochemical and structural alterations in renal tissues caused by ampicillin sodium. Biochemical parameters such as acid phosphatase (ACP), alkaline phosphatase (ALP), creatinine and urea levels in urine and serum as well as oxidative stress parameters such as superoxide dismutase (SOD) activity, catalase activity, total antioxidant status (TAS%) and lipid peroxidation in the renal cortical tissues were accessed upon treatment of melatonin and Vit-C following ampicillin sodium administration in Funambulus pennanti. Ampicillin treatment increased ACP, ALP, creatinine and urea levels in serum and urine, indicating renal damage. It also induced oxidative stress by increasing lipid peroxidation and decreasing the activity of antioxidative enzymes. However, the exogenous melatonin or Vit-C treatment inhibited ampicillin mediated renal damages. Melatonin or Vit-C pre-treatment significantly decreased ACP, ALP, creatinine, urea, TBARS level and increased SOD, catalase activity and TAS%. Our results suggest that the antibiotic induced nephrotoxicity can be ameliorated by melatonin or Vit-C via reduction of oxidative stress in renal tissues.

Impaired cellular bioenergetics caused by GBA1 depletion sensitizes neurons to calcium overload

Heterozygous mutations of the lysosomal enzyme glucocerebrosidase (GBA1) represent the major genetic risk for Parkinson’s disease (PD), while homozygous GBA1 mutations cause Gaucher disease, a lysosomal storage disorder, which may involve severe neurodegeneration. We have previously demonstrated impaired autophagy and proteasomal degradation pathways and mitochondrial dysfunction in neurons from GBA1 knockout (gba1−/−) mice. We now show that stimulation with physiological glutamate concentrations causes pathological [Ca2+]c responses and delayed calcium deregulation, collapse of mitochondrial membrane potential and an irreversible fall in the ATP/ADP ratio. Mitochondrial Ca2+ uptake was reduced in gba1−/− cells as was expression of the mitochondrial calcium uniporter. The rate of free radical generation was increased in gba1−/− neurons. Behavior of gba1+/− neurons was similar to gba1−/− in terms of all variables, consistent with a contribution of these mechanisms to the pathogenesis of PD. These data signpost reduced bioenergetic capacity and [Ca2+]c dysregulation as mechanisms driving neurodegeneration.

An integrated microwave-ultraviolet catalysis process of four peroxides for wastewater treatment: Free radical generation rate and mechanism

The Advanced Oxidation Processes (AOPs) still require further research in response to ever-increasing standard of reclaimed water reuse and operating environment requirements. In this study, an efficient microwave-ultraviolet catalyzed oxidation system (MW-UV) was successfully developed, and its degradation effect was studied by using activated H2O2, sodium percarbonate (SPC), persulfate (PS), and peroxymonosulfate (PMS) to degrade toxic organic contaminants in wastewater and actual industrial wastewater. It was shown that MW-UV had an exceptionally high capability to react with these four common peroxides to produce reactive radicals (OH and SO4−). This can destroy multiple toxic organic contaminants through nonselective oxidation with a wide range of pH applications, has strong adaptability to anions in bodies of water, and can effectively treat wastewater. The sequence of predominant free radical generation rate by MW-UV was SPC > H2O2 > PS > PMS, with higher generation rate constant than other Fenton processes. The free radical evolution mechanisms for H2O2, SPC, PS, and PMS activation were also investigated. The thermal and non-thermal effects of microwave irradiation have a significant enhancement for UV reactions, and thus the synergy between the MW and UV can effectively activate peroxide. This treatment method could provide scientific basis and reference for degrading toxic organic contaminants in small-scale and limited space wastewater treatment.

Shot noise in radiobiological systems

As a model for human tissue, this report considers the rate of free radical generation in a dilute solution of water in which a beta-emitting radionuclide is uniformly dispersed. Each decay dissipates a discrete quantity of energy, creating a large number of free radicals in a short time within a small volume determined by the beta particle range. Representing the instantaneous dissipated power as a train of randomly-spaced pulses, the time-averaged dissipated power p¯ and rate of free radical generation g¯ are derived. The analogous result in the theory of electrical circuits is known as the shot noise theorem. The reference dose of X-rays Dref producing an identical rate of free radical generation and level of oxidative stress is shown a) to increase with the square root of the absorbed dose, D, and b) to be far larger than D. This finding may have important consequences for public health in cases where the level of shot noise exceeds some noise floor corresponding to equilibrium biological processes. An estimate of this noise floor is made using the example of potassium-40, a beta-emitting radioisotope universally present in living tissue.

Effect of Ca2 + species with different modes of occurrence on direct liquefaction of a calcium-rich lignite

Low-rank coals concurrently contain organically bound alkali and alkaline earth metals (AAEM species) and discrete mineral matters. In this work, the influences of exchangeable calcium cations and discrete calcium salts on direct liquefaction of a Ca2+-rich lignite were investigated. The raw coal was partially demineralized by ammonium acetate solution and certain amounts of Ca2+ were loaded into the demineralized coal (DMC) by ion-exchanged or physical mixing method separately. The amount of exchangeable Ca2+ and -COOH groups were finely correlated by FTIR spectra. Temperature programmed liquefaction of various samples was performed to obtain the product distributions. Experimental results of liquefaction demonstrate that exchangeable Ca2+ present in coal are adverse to direct liquefaction process and Ca2+ loaded by physical mixing method have less detrimental effects on the oil yield compared with the exchangeable ones. The reason could be attributed to that exchangeable Ca2+ accelerate generation of CO2 and free radical fragments through coal pyrolysis, which enhance the unbalance between generation rate of free radicals and that of their combination with hydrogen donors, and eventually results in the formation of tetrahydrofuran-insoluble portion (THFISP). Therefore, oil generation during liquefaction of the lignite is mainly inhibited by exchangeable Ca2+ and the influences of discrete calcium salts are negligible.

Computational modelling of a photocatalytic UV-LED reactor with internal mass and photon transfer consideration

Photocatalytic breakdown of organic pollutants was modelled and experimentally validated using phenol as probe molecule and UV-LEDs as the radiation source. A nanocrystalline TiO2 film was immobilized in a quartz continuous parallel plate reactor and illuminated by an array of 88 LEDs, each emitting 375nm radiation. The degradation of phenol in steady state conditions was recorded for different irradiances and a pseudo first order reaction rate constant was obtained for this process. The rate constant was found to be of the order of 10−4s−1. A computational fluid dynamics (CFD) coupled with reaction model for the studied reactor was developed. The model considers the catalyst coating as a porous medium instead of a surface. It accounts for the mass transfer and light penetration within the immobilized catalyst. The model has one degree of freedom which was validated for different light intensities and flow rates. The degree of freedom in the model can be defined as “rate of free radical generation” and the unit is molL−1s−1. This variable was experimentally coupled by a linear relation to the irradiance on the catalyst coating. Photonic efficiency of the system was also investigated. A photonic efficiency range of 0.44–1.4% was obtained at light intensities of 2000 and 200μWcm−2, respectively. The model and the data obtained are scalable and applicable to different reactors. Comparison of photonic efficiencies obtained, show that the immobilized TiO2 reactor has similar efficiency to referred works which considered slurry reactors.

Toxicity evaluation of β‐diketone antibiotics on the development of embryo‐larval zebrafish (Danio rerio)

This study evaluated the effects of β-diketone antibiotics (DKAs) on the development of embryo-larval zebrafish (Danio rerio). When exposure to DKAs, developmental malformations, such as hatching delay, curved body axis, pericardial edema, uninflated swim bladder and yolk sac edema, were observed at 120 h postfertilization (hpf). The estimated 120 hpf nominal concentrations of no observed effect concentration and lowest observed effect concentration for DKAs were 18.75 and 37.50 mg/L, respectively, suggesting that DKAs have much lower toxicity than other persistent pollutants. Following DKA exposure, embryonic heart rates were significantly reduced as compared to the controls at 48 and 60 hpf. The peak bending motion frequency appeared 1 h earlier than in control embryos. The 2.34 and 9.38-mg/L treatment groups had a higher basal swim rate than control groups at 120 hpf in both light and light-to-dark photoperiod experiments. The occurrence of high speed swim rates was enhanced approximately threefold to sevenfold in the 2.34 and 9.38 mg/L treatments compared to the control. Glutathione (GSH) concentrations in the 2.34 and 9.38-mg/L treatments were significantly higher than the control at 72 hpf, suggesting that GSH production was induced at the end of the hatching period. When exposed to DKAs, zebrafish superoxide dismutase enzyme (SOD) activities were significantly inhibited in the early embryonic period, demonstrating that the clearing ability in zebrafish was lower than the generation rate of free radicals. In summary, the combined DKAs were developmentally toxic to zebrafish in their early life stages and had the ability to impair individual behaviors that are of great importance in the assessment of their ecological fitness.

Antioxidant Activity Evaluation Assay Based on Peroxide Radicals Generation and Potentiometric Measurement

A new version of potentiometric evaluation of antioxidant activity in biological liquids, food, drinks, and so forth, based on the mediator system combined with the free radicals generation has been proposed. A radical initiator, 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH), and K3[Fe(CN)6]/K4[Fe(CN)6] as a mediator system were used. Interactions of the mediator system with radicals, radicals with antioxidants, and erythrocytes have been investigated. The correlation coefficient between the data obtained in the presence and the absence of AAPH equals 0.98. In addition, the possibility to determine a free radical generation rate by using the mediator system has been demonstrated.

Clotrimazole enhances lysis of human erythrocytes induced by t-BHP

Clotrimazole (CLT) is an antifungal and antimalarial agent also effective as a Gardos channel inhibitor. In addition, CLT possesses antitumor properties. Recent data provide evidence that CLT forms a complex with heme (hemin), which produces a more potent lytic effect than heme alone. This study addressed the effect of CLT on the lysis of normal human erythrocytes induced by tert-butyl hydroperoxide (t-BHP). For the first time, it was shown that 10 μM CLT significantly enhanced the lytic effect of t-BHP on erythrocytes in both Ca 2+-containing and Ca 2+-free media, suggesting that the effect is not related to Gardos channels. CLT did not affect the rate of free radical generation, the kinetics of GSH degradation, methemoglobin formation and TBARS generation; therefore, we concluded that CLT does not cause additional oxidative damage to erythrocytes treated with t-BHP. It is tempted to speculate that CLT enhances t-BHP-induced changes in erythrocyte volume and lysis largely by forming a complex with hemin released during hemoglobin oxidation in erythrocytes: the CLT–hemin complex destabilizes the cell membrane more potently than hemin alone. If so, the effect of CLT on cell membrane damage during free-radical oxidation may be used to increase the efficacy of antitumor therapy.

The Role of External and Matrix pH in Mitochondrial Reactive Oxygen Species Generation

Reactive oxygen species (ROS) generation in mitochondria as a side product of electron and proton transport through the inner membrane is important for normal cell operation as well as development of pathology. Matrix and cytosol alkalization stabilizes semiquinone radical, a potential superoxide producer, and we hypothesized that proton deficiency under the excess of electron donors enhances reactive oxygen species generation. We tested this hypothesis by measuring pH dependence of reactive oxygen species released by mitochondria. The experiments were performed in the media with pH varying from 6 to 8 in the presence of complex II substrate succinate or under more physiological conditions with complex I substrates glutamate and malate. Matrix pH was manipulated by inorganic phosphate, nigericine, and low concentrations of uncoupler or valinomycin. We found that high pH strongly increased the rate of free radical generation in all of the conditions studied, even when ΔpH = 0 in the presence of nigericin. In the absence of inorganic phosphate, when the matrix was the most alkaline, pH shift in the medium above 7 induced permeability transition accompanied by the decrease of ROS production. ROS production increase induced by the alkalization of medium was observed with intact respiring mitochondria as well as in the presence of complex I inhibitor rotenone, which enhanced reactive oxygen species release. The phenomena revealed in this report are important for understanding mechanisms governing mitochondrial production of reactive oxygen species, in particular that related with uncoupling proteins.

Efficacy of Metmyoglobin and Hemin as a Catalyst of Lipid Peroxidation Determined by Using a New Testing System

A new quantitative approach to investigate the capability of iron heme complexes (HEM), metmyoglobin and hemin, to catalyze lipid peroxidation was elaborated. The oxidation of methyl linoleate in micellar solutions was used as a testing model. The key point was the determination of the rate of free radical generation, RIN, calculated from the rate of oxygen consumption. The HEM catalytic activity was characterized by two independent parameters: by reactivity and by its resistance to degradation. Both parameters were found to be pH-dependent. The reactivity was expressed as the effective rate constant for the reaction of HEM with lipid hydroperoxide. The resistance to degradation was characterized by the rate of the decrease in RIN with time and also by the regeneration coefficient, which shows how many active free radicals can be generated by one molecule of HEM. Both Hemin and metMB were found to be very effective catalysts even at nanomolar concentrations. The effective regeneration of active forms of HEM was observed. The catalytic activity of HEM was rapidly reduced with time. The kinetic scheme of the process under consideration was suggested, and this was applied for kinetic computer simulations.

Mitochondrial free radical generation and lifespan control in the fungal aging model Podospora anserina

In the filamentous fungus Podospora anserina a central role of mitochondria in the control of aging has been repeatedly demonstrated. Interestingly, impairments in cytochrome c oxidase (COX) activity induce an enhancement in the expression of the quinol-oxygen alternative oxidoreductase (AOX) correlating with an extension of lifespan. This effect is thought to be determined by a reduction of the free radical generation in mitochondria. In the current investigation we have analyzed the electron transport chain composition of P. anserina and the superoxide generation rate in wild type s and in mutant grisea, a long-lived mutant with complex IV deficiency. Here we report that, similarly to other fungi, mitochondrial respiration in P. anserina is a combination of standard and alternative routes. A switch in the COX/AOX respiration balance affects the mitochondrial free radical generation. Lower mitochondrial rates of superoxide generation were found in the long-lived mutant, supporting the central role of mitochondrial free radical generation in the lifespan control of P. anserina. The question of how the activity of the alternative respiratory pathway influences the rate of free radical generation in P. anserina mitochondria is discussed.

Minireview: The Role of Oxidative Stress in Relation to Caloric Restriction and Longevity

Reduction of caloric intake without malnutrition is one of the most consistent experimental interventions that increases mean and maximum life spans in different species. For over 70 yr, caloric restriction has been studied, and during the last years the number of investigations on such nutritional intervention and aging has dramatically increased. Because caloric restriction decreases the aging rate, it constitutes an excellent approach to better understand the mechanisms underlying the aging process. Various investigations have reported reductions in steady-state oxidative damage to proteins, lipids, and DNA in animals subjected to restricted caloric intake. Most interestingly, several investigations have reported that these decreases in oxidative damage are related to a lowering of mitochondrial free radical generation rate in various tissues of the restricted animals. Thus, similar to what has been described for long-lived animals in comparative studies, a decrease in mitochondrial free radical generation has been suggested to be one of the main determinants of the extended life span observed in restricted animals. In this study we review recent reports of caloric restriction and longevity, focusing on mitochondrial oxidative stress and the proposed mechanisms leading to an extended longevity in calorie-restricted animals.

Dietary Restriction at Old Age Lowers Mitochondrial Oxygen Radical Production and Leak at Complex I and Oxidative DNA Damage in Rat Brain

Previous studies in mammalian models indicate that the rate of mitochondrial reactive oxygen species ROS production and the ensuing modification of mitochondrial DNA (mtDNA) link oxidative stress to aging rate. However, there is scarce information concerning this in relation to caloric restriction (CR) in the brain, an organ of maximum relevance for ageing. Furthermore, it has never been studied if CR started late in life can improve those oxidative stress-related parameters. In this investigation, rats were subjected during 1 year to 40% CR starting at 24 months of age. This protocol of CR significantly decreased the rate of mitochondrial H(2)O(2) production (by 24%) and oxidative damage to mtDNA (by 23%) in the brain below the level of both old and young ad libitum-fed animals. In agreement with the progressive character of aging, the rate of H(2)O(2) production of brain mitochondria stayed constant with age. Oxidative damage to nuclear DNA increased with age and this increase was fully reversed by CR to the level of the young controls. The decrease in ROS production induced by CR was localized at Complex I and occurred without changes in oxygen consumption. Instead, the efficiency of brain mitochondria to avoid electron leak to oxygen at Complex I was increased by CR. The mechanism involved in that increase in efficiency was related to the degree of electronic reduction of the Complex I generator. The results agree with the idea that CR decreases aging rate in part by lowering the rate of free radical generation of mitochondria in the brain.

The effects of manganese doping on UVA absorption and free radical generation of micronised titanium dioxide and its consequences for the photostability of UVA absorbing organic sunscreen components.

The effect of manganese doping on the free radical generation rate, free radical scavenging and UVA absorption properties of micronised sunscreen grade titania has been studied with respect to enhancement of the UVA photostability of test sunscreen formulations containing the organic UVA absorber Parsol 1789. Manganese doping has been shown to increase the UVA:UVB absorption ratio of titania, reduce free radical generation rates by over 90%, and provide free radical scavenging behaviour. Adding manganese-doped titania to a test formulation incorporating Parsol 1789 shows that manganese doping increases UVA attenuation stability by up to 3 times the amount achieved by comparable commercial undoped titania materials. HPLC data shows this to be related to an improved stabilisation of the organic sunscreen components. Manganese doped titania shows improved efficacy over undoped titania in sunscreen formulations containing organic UV absorbers.