Effect of gaseous ozone and light-activated disinfection on the surface hardness of resin-based root canal sealers.

Although root canal instruments remove most of the content from the main root canal space, disinfection or irrigation plays an indispensable role in all areas of the root canal system, especially in parts that are inaccessible by instruments. The originality of this study was to investigate the effect of two novel disinfection techniques on the surface hardness of resin-based endodontic sealers using atomic force microscopy (AFM). Forty extracted single-rooted maxillary central human teeth were prepared and divided into four groups according to treatment methods. The first group was irrigated with saline and served as a control, other groups irrigated with sodium hypochlorite (NaClO); gaseous ozone; and light-activated disinfection (LAD). The groups were divided into two subgroups, according to the obturation method used: subgroup A: gutta-percha and AH plus; and subgroup B: EndoREZ/resin-coated cones. After obturation, atomic force microscopy (AFM) measurement was performed to analyze the surface hardness of the sealers. There was a significant difference between group 1A and group 3A (p < 0.05). Group 3B had the highest surface hardness values that were statistically different (p < 0.05). When disregarding the sealers, the ozone possessed statistically higher surface hardness values than the other groups in all root thirds (p < 0.05). The use of ozone and LAD may alter the surface hardness of resin-based sealers. The use of AFM can be considered an alternative hardness test techonology for sealing material.

Photooxidation of arsenic(III) to arsenic(V) on the surface of kaolinite clay.

As one of the most toxic heavy metals, the oxidation of inorganic arsenic has drawn great attention among environmental scientists. However, little has been reported on the solar photochemical behavior of arsenic species on top-soil. In the present work, the influencing factors (pH, relative humidity (RH), humic acid (HA), trisodium citrate, and additional iron ions) and the contributions of reactive oxygen species (ROS, mainly HO and HO2/O2(-)) to photooxidation of As(III) to As(V) on kaolinite surfaces under UV irradiation (λ=365nm) were investigated. Results showed that lower pH facilitated photooxidation, and the photooxidation efficiency increased with the increase of RH and trisodium citrate. Promotion or inhibition of As(III) photooxidation by HA was observed at low or high dosages, respectively. Additional iron ions greatly promoted the photooxidation, but excessive amounts of Fe(2+) competed with As(III) for oxidation by ROS. Experiments on scavengers indicated that the HO radical was the predominant oxidant in this system. Experiments on actual soil surfaces proved the occurrence of As(III) photooxidation in real topsoil. This work demonstrates that the photooxidation process of As(III) on the soil surface should be taken into account when studying the fate of arsenic in natural soil newly polluted with acidic wastewater containing As(III).

Degradation and mineralization of Bisphenol A (BPA) in aqueous solution using advanced oxidation processes: UV/H2O2 and UV/S2O8(2-) oxidation systems.

This work reports on the removal and mineralization of an endocrine disrupting chemical, Bisphenol A (BPA) at a concentration of 0.22 mM in aqueous solution using inorganic oxidants (hydrogen peroxide, H2O2 and sodium persulfate, Na2S2O8;S2O8(2-)) under UV irradiation at a wavelength of 254 nm and 40 W power (Io = 1.26 × 10(-6) E s(-1)) at its natural pH and a temperature of 29 ± 3 °C. With an optimum persulfate concentration of 1.26 mM, the UV/S2O8(2-) process resulted in ∼95% BPA removal after 240 min of irradiation. The optimum BPA removal was found to be ∼85% with a H2O2 concentration of 11.76 mM. At higher concentrations, either of the oxidants showed an adverse effect because of the quenching of the hydroxyl or sulfate radicals in the BPA solution. The sulfate-based oxidation process could be used over a wider initial pH range of 3-12, but the hydroxyl radical-based oxidation of BPA should be carried out in the acidic pH range only. The water matrix components (bicarbonate, chloride and humic acid) showed higher scavenging effect in hydroxyl radical-based oxidation than that in the sulfate radical-based oxidation of BPA. UV/S2O8(2-) oxidation system utilized less energy (307 kWh/m(3)) EE/O in comparison to UV/H2O2 system (509 kWh/m(3)) under optimum operating conditions. The cost of UV irradiation far outweighed the cost of the oxidants in the process. However, the total cost of treatment of persulfate-based system was much lower than that of H2O2-based oxidation system.

Sequential reduction-oxidation for photocatalytic degradation of tetrabromobisphenol A: kinetics and intermediates.

C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC-MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N(2)-saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO(2) system by changing the reaction atmospheres.

A study of hydrogen peroxide chemistry and photochemistry in tea stain solution with relevance to clinical tooth whitening.

OBJECTIVE: Tooth whitening using hydrogen peroxide is a complex process, and there is still some controversy about the roles of pH, temperature, chemical activators, and the use of light irradiation. In this work the basic interactions between whitening agents and stain molecules are studied in simple solutions, thus avoiding the physics of diffusion and light penetration in the tooth to give clarity on the basic chemistry which is occurring. METHOD: The absorbance of tea stain solution at 450 nm was measured over a period of 40 min, with various compositions of whitening agent added (including hydrogen peroxide, ferrous gluconate and potassium hydroxide) and at the same time the samples were subjected to blue light (465 nm) or infra-red light (850 nm) irradiation, or alternatively they were heated to 37°C. RESULTS: It is shown that the reaction rates between chromogens in the tea solution and hydrogen peroxide can be accelerated significantly using ferrous gluconate activator and blue light irradiation. Infra red irradiation does not increase the reaction rate through photochemistry, it serves only to increase the temperature. Raising the temperature leads to inefficiency through the acceleration of exothermic decomposition reactions which produce only water and oxygen. CONCLUSION: By carrying out work in simple solution it was possible to show that ferrous activators and blue light irradiation significantly enhance the whitening process, whereas infra red irradiation has no significant effect over heating. The importance of controlling the pH within the tooth structure during whitening is also demonstrated.

Novel imazethapyr detoxification applying advanced oxidation processes.

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O3), and hydrogen peroxide tied to UV-irradiation (H2O2/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O3/UV), ozonation joined to titanium dioxide photo-catalysis (TiO2/UV+O3), sole photo-catalysis (TiO2/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO2/UV+H2O2) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.

Cytotoxic activity of guaiazulene on gingival fibroblasts and the influence of light exposure on guaiazulene-induced cell death.

Guaiazulene (GA) is widely used as a natural ingredient in many health care products and solutions. Although it has been reported to have interesting biological effects, GA and azulene derivatives have been proven to be cytotoxic against normal human cells and human tumor cells; moreover, guaiazulene has shown photomutagenic properties on bacterial strains. Therefore, we evaluated and compared the cytotoxicity of GA at different concentrations on human gingival fibroblast (HGF) cell cultures under normal conditions and under UV irradiation (UV-A dose: 6.4 J/cm(2)). The compound tested was found to significantly reduce cell viability (dose-dependent trend, IC(50) 72.1 µM), decrease protein procollagen α1 type I synthesis, a marker for HGF protein, and COL1A1 mRNA expression. The cytotoxic effects were accompanied by activation of an intrinsic apoptotic pathway, studied using transmission electron microscopy (TEM) and caspase-3 activation. The light exposure of the cell culture treated decreased GA-induced cell death (IC(50) 128.9 µM), suggesting a photoprotective effect due to the photodegradation of the toxic agent, guaiazulene. Furthermore, the products of the photodegradation reaction of GA proved not to be toxic against HGFs.

Chemoprotective effect of N-acetylcysteine (NAC) on cellular oxidative damages and apoptosis induced by nano titanium dioxide under UVA irradiation.

The chemoprotective effect of N-acetylcysteine (NAC), a sulfhydryl-containing antioxidant, on nano titanium dioxide (nano-TiO(2)) induced oxidative stress and apoptosis in human keratinocyte (HaCaT) cells was assessed. HaCaT cells were pretreated with NAC followed by treatment with 200 µg/ml nano-TiO(2), then exposed to ultraviolet A (UVA, 365 nm) for 1 h and cultured for 24 h. Intracellular reactive oxygen species (ROS) and nitric oxide (NO) formation, mitochondrial membrane potential (MMP), apoptosis and the content of the lipid peroxidation product malondialdehyde (MDA) were measured. Keratin 6 (K6) mRNA expression was also analyzed. The results showed that NAC strongly inhibited ROS and NO production in nano-TiO(2) treated cells. The extent of lipid peroxidation was also decreased in the presence of NAC. In addition, NAC suppressed nano-TiO(2) induced apoptosis and increased K6 mRNA expression. The results indicated that NAC could prevent oxidative stress and apoptosis induced by nano-TiO(2) in HaCaT cells.

Preparation and photocatalytic performance of Fe (III)-amidoximated PAN fiber complex for oxidative degradation of azo dye under visible light irradiation.

Polyacrylonitrile (PAN) fiber was modified with hydroxylamine hydrochloride to introduce amidoxime groups onto the fiber surface. These amidoxime groups were used to react with Fe (III) ions to prepare Fe (III)-amidoximated PAN fiber complex, which was characterized using SEM, XRD, FTIR, XPS, DMA, and DRS respectively. Then the photocatalytic activity of Fe-AO-PAN was evaluated in the degradation of a typical azo dye, C. I. Reactive Red 195 in the presence of H(2)O(2) under visible light irradiation. Moreover, the effect of the Fe content of Fe-AO-PAN on dye degradation was also investigated. The results indicated that Fe (III) ions can crosslink between the modified PAN fiber chains by the coordination of Fe (III) ions with the amino nitrogen atoms and hydroxyl oxygen atoms of the amidoximation groups to form Fe (III)-amidoximated PAN fiber complex, and the Fe content of which is mainly determined by Fe (III) ions and amidoximation groups. Fe (III)-amidoximated PAN fiber complex is found to be activated in the visible light region. Moreover, Fe (III)-amidoximated PAN fiber complex shows the catalytic activity for dye degradation by H(2)O(2) at pH=6.0 in the dark, and can be significantly enhanced by increasing light irradiation and Fe content, therefore, it can be used as a new heterogeneous Fenton photocatalyst for the effective decomposition of the dye in water. In addition, ESR spectra confirm that Fe (III)-amidoximated PAN fiber complex can generate more OH radicals from H(2)O(2) under visible light irradiation, leading to dye degradation. A possible mechanism of photocatalysis is proposed.

A role for DNA-mediated charge transport in regulating p53: Oxidation of the DNA-bound protein from a distance.

Charge transport (CT) through the DNA base pairs provides a means to promote redox reactions at a remote site and potentially to effect signaling between molecules bound to DNA. Here we describe the oxidation of a cell-cycle regulatory protein, p53, from a distance through DNA-mediated CT. A consensus p53 binding site as well as three DNA promoters regulated by p53 were synthesized containing a tethered DNA photooxidant, anthraquinone. Photoinduced oxidation of the protein occurs from a distance; introduction of an intervening CA mismatch, which inhibits DNA-mediated CT, prevents oxidation of p53. DNA-mediated oxidation is shown to promote dissociation of p53 from only some promoters, and this sequence-selectivity in oxidative dissociation correlates with the biological regulation of p53. Under severe oxidative stress, effected here through oxidation at long range, p53 dissociates from a promoter that activates DNA repair as well as the promoter for the negative regulator of p53, Mdm2, but not from a promoter activating cell-cycle arrest. Mass spectrometry results are consistent with disulfide bond formation in p53 upon DNA-mediated oxidation. Furthermore, DNA-bound p53 oxidation is shown in vivo by up-regulation of p53 and subsequent irradiation in the presence of a rhodium photooxidant to give a new p53 adduct that can be reversed with thiol treatment. This DNA-mediated oxidation of p53 parallels that seen by treating cells with hydrogen peroxide. These results indicate a unique mechanism using DNA-mediated CT chemistry by which p53 activity on different promoters may be controlled globally under conditions of oxidative stress.

Stable DNA-protein cross-links are products of DNA charge transport in a nucleosome core particle.

DNA-protein cross-links (DPCs) in nucleosome core particles (NCPs), the fundamental building block of chromatin, arise during times of cellular oxidative stress. These lesions are expected to be detrimental to the cell due to interference with processes like chromatin remodeling, transcription, DNA replication, and epigenetic marking. However, much is still unknown about the mechanisms leading to the formation of DPCs in NCPs, and the exact sites of these lesions in chromatin have not been delineated. During DNA charge transport (CT), an oxidant leads to the formation of a guanine radical cation (G*+) which then becomes mobile and migrates away from the initial site of damage. Since previous studies have established that reactions between a G*+ and some amino acids lead to DPC formation in both DNA-peptide and DNA-protein complexes, we hypothesized that DNA CT could lead to DPC formation within NCPs. To test this hypothesis, we studied DNA CT reactions in NCPs reconstituted with DNA containing (i) the 601 NCP positioning sequence and (ii) 14 bp of a linker DNA with a covalently attached anthraquinone (AQ) photooxidant. Collectively, the results from Western blotting, EMSAs, and DNA footprinting reactions lead to the conclusion that AQ-initiated DNA CT is responsible for DNA-H3 cross-linking in one specific region of these NCPs. Furthermore, these DPCs are stable for days at 37 degrees C, indicating that DNA CT in chromatin can lead to long-lived DNA lesions which the cell must somehow find and excise.

Photochemical damage of the retina.

Visual perception occurs when radiation with a wavelength between 400 and 760 nm reaches the retina. The retina has evolved to capture photons efficiently and initiate visual transduction. The retina, however, is vulnerable to damage by light, a vulnerability that has long been recognized. Photochemical damage has been widely studied, because it can cause retinal damage within the intensity range of natural light. Photochemical lesions are primarily located in the outer layers at the central region of the retina. Two classes of photochemical damage have been recognized: Class I damage, which is characterized by the rhodopsin action spectrum, is believed to be mediated by visual pigments, with the primary lesions located in the photoreceptors; whereas Class II damage is generally confined to the retinal pigment epithelium. The action spectrum peaks in the short wavelength region, providing the basis for the concept of blue light hazard. Several factors can modify the susceptibility of the retina to photochemical damage. Photochemical mechanisms, in particular mechanisms that arise from illumination with blue light, are responsible for solar retinitis and for iatrogenic retinal insult from ophthalmological instruments. Further, blue light may play a role in the pathogenesis of age-related macular degeneration. Laboratory studies have suggested that photochemical damage includes oxidative events. Retinal cells die by apoptosis in response to photic injury, and the process of cell death is operated by diverse damaging mechanisms. Modern molecular biology techniques help to study in-depth the basic mechanism of photochemical damage of the retina and to develop strategies of neuroprotection.

Disinfection of Pythium-infested recirculation water by UV-oxidation technology.

Selective disinfection against Pythium aphanidermatum in recirculation water was tested with UV-irradiation and with UV-oxidation technology with the objective to reduce the electrical energy consumption per cubic meter treated water. UV-oxidation technology is based on injection of hydrogen peroxide in recirculation water, just before passage along a UV-lamp, thus creating hydroxyl radicals. Pythium aphanidermatum was applied artificially to recirculation water from tomatoes, grown, in rockwool and coconut fibre. Other parameters in this study were pH and transmission value (T10) of the infested recirculation water. Results indicated that the recommended UV-C dose of 100 mJ/cm2 for elimination of fungal pathogens in general can be lowered in case recirculation water is infected with Pythium aphanidermatum only. When UV-oxidation technology was applied with 1 mmol hydrogen peroxide per litre recirculation water, the UV-C dose could be reduced even more in comparison with merely UV irradiation.