Platinum nanoparticles inhibit antioxidant effects of vitamin C via ascorbate oxidase-mimetic activity.

The development and application of nanomaterials as consumer products including food, drugs, and cosmetics are rapidly expanding. However, interactions between these novel materials and other chemical components of consumer products have not been thoroughly studied. Here, by using electron spin resonance techniques, we compared the effects of Au, Ag, and Pt nanoparticles (NPs) on the antioxidant activity of vitamin C (sodium l-ascorbate, NaA).

Facet Energy versus Enzyme-like Activities: The Unexpected Protection of Palladium Nanocrystals against Oxidative Damage.

To develop nanomaterials as artificial enzymes, it is necessary to better understand how their physicochemical properties affect their enzyme-like activities. Although prior research has demonstrated that nanomaterials exhibit tunable enzyme-like activities depending on their size, structure, and composition, few studies have examined the effect of surface facets, which determine surface energy or surface reactivity. Here, we use electron spin-resonance spectroscopy to report that lower surface energy {111}-faceted Pd octahedrons have greater intrinsic antioxidant enzyme-like activity than higher surface energy {100}-faceted Pd nanocubes.

Crossover between Anti- and Pro-oxidant Activities of Graphene Quantum Dots in the Absence or Presence of Light.

Graphene quantum dots (GQDs), zero-dimensional carbon materials displaying excellent luminescence properties, show great promise for medical applications such as imaging, drug delivery, biosensors, and novel therapeutics. A deeper understanding of how the properties of GQDs interact with biological systems is essential for these applications. Our work demonstrates that GQDs can efficiently scavenge a number of free radicals and thereby protect cells against oxidative damage.

Enhancement of Paramagnetic Relaxation by Photoexcited Gold Nanorods.

Electron spin resonance (ESR) spectroscopy was used to investigate the switchable, light-dependent effects of gold nanorods (GNRs) on paramagnetic properties of nitroxide spin probes. The photoexcited GNRs enhanced the spin-spin and spin-lattice relaxations of nitroxide spin probes. It was shown that molecular oxygen plays the key role in this process.

Platinum Nanoparticles: Efficient and Stable Catechol Oxidase Mimetics.

Although enzyme-like nanomaterials have been extensively investigated over the past decade, most research has focused on the peroxidase-like, catalase-like, or SOD-like activity of these nanomaterials. Identifying nanomaterials having oxidase-like activities has received less attention. In this study, we demonstrate that platinum nanoparticles (Pt NPs) exhibit catechol oxidase-like activity, oxidizing polyphenols into the corresponding o-quinones.

Composition Directed Generation of Reactive Oxygen Species in Irradiated Mixed Metal Sulfides Correlated with Their Photocatalytic Activities.

The ability of nanostructures to facilitate the generation of reactive oxygen species and charge carriers underlies many of their chemical and biological activities. Elucidating which factors are essential and how these influence the production of various active intermediates is fundamental to understanding potential applications of these nanostructures, as well as potential risks. Using electron spin resonance spectroscopy coupled with spin trapping and spin labeling techniques, we assessed 3 mixed metal sulfides of varying compositions for their abilities to generate reactive oxygen species, photogenerate electrons, and consume oxygen during photoirradiation.

FD&C Yellow No. 5 (tartrazine) degradation via reactive oxygen species triggered by TiO2 and Au/TiO2 nanoparticles exposed to simulated sunlight.

When exposed to light, TiO2 nanoparticles (NPs) become photoactivated and create electron/hole pairs as well as reactive oxygen species (ROS). We examined the ROS production and degradation of a widely used azo dye, FD&C Yellow No. 5 (tartrazine), triggered by photoactivated TiO2 NPs.

Unraveling the enhanced photocatalytic activity and phototoxicity of ZnO/metal hybrid nanostructures from generation of reactive oxygen species and charge carriers.

An effective way for promoting photocatalytic activity of a semiconductor is deposition of noble metal nanoparticles (NPs) onto it. In this paper, we deposited Ag and Pd onto ZnO NPs to form ZnO/Ag and ZnO/Pd hybrid nanostructures. It was found that both Ag and Pd nanocomponents can greatly enhance the photocatalytic activity and phototoxicity of ZnO toward human skin cells.

Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides.

Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS)-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase), and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances.

Mechanistic characterization of titanium dioxide nanoparticle-induced toxicity using electron spin resonance.

Titanium dioxide nanoparticles (TiO(2) NPs) are one of the most widely used nanomaterials that have been manufactured worldwide and applied in different commercial realms. The well-recognized ability of TiO(2) to promote the formation of reactive oxygen species (ROS) has been extensively studied as one of the important mechanisms underlying TiO(2) NPs toxicity. As the "gold standard" method to quantify and identify ROS, electron spin resonance (ESR) spectroscopy has been employed in many studies aimed at evaluating TiO(2) NPs safety.

Electron spin resonance spectroscopy for the study of nanomaterial-mediated generation of reactive oxygen species.

Many of the biological applications and effects of nanomaterials are attributed to their ability to facilitate the generation of reactive oxygen species (ROS). Electron spin resonance (ESR) spectroscopy is a direct and reliable method to identify and quantify free radicals in both chemical and biological environments. In this review, we discuss the use of ESR spectroscopy to study ROS generation mediated by nanomaterials, which have various applications in biological, chemical, and materials science.

Photogenerated charge carriers and reactive oxygen species in ZnO/Au hybrid nanostructures with enhanced photocatalytic and antibacterial activity.

Semiconductor nanostructures with photocatalytic activity have the potential for many applications including remediation of environmental pollutants and use in antibacterial products. An effective way for promoting photocatalytic activity is depositing noble metal nanoparticles (NPs) on a semiconductor. In this paper, we demonstrated the successful deposition of Au NPs, having sizes smaller than 3 nm, onto ZnO NPs.

Enzyme-mimetic effects of gold@platinum nanorods on the antioxidant activity of ascorbic acid.

Au@Pt nanorods were prepared by growing platinum nanodots on gold nanorods. Using electron spin resonance (ESR), we determined that the mechanisms for oxidation of ascorbic acid (AA) by Au@Pt nanorods and ascorbic acid oxidase (AAO) were kinetically similar and yielded similar products. In addition we observed that Au@Pt nanorods were stable with respect to temperature and pH.

Updates on chemical and biological research on botanical ingredients in dietary supplements.

Increased use of dietary supplements is a phenomenon observed worldwide. In the USA, more than 40% of the population recently reported using complementary and alternative medicines, including botanical dietary supplements. Perceptions that such dietary supplements are natural and safe, may prevent disease, may replace prescription medicines, or may make up for a poor diet, play important roles in their increased use.

Single-walled carbon nanotubes alter cytochrome c electron transfer and modulate mitochondrial function.

Single-walled carbon nanotubes (SWCNTs) are broadly used for various biomedical applications such as drug delivery, in vivo imaging, and cancer photothermal therapy due to their unique physiochemical properties. However, once they enter the cells, the effects of SWCNTs on the intracellular organelles and macromolecules are not comprehensively understood. Cytochrome c (Cyt c), as a key component of the electron transport chain in mitochondria, plays an essential role in cellular energy consumption, growth, and differentiation.

Intrinsic catalytic activity of Au nanoparticles with respect to hydrogen peroxide decomposition and superoxide scavenging.

Gold nanoparticles have received a great deal of interest due to their unique optical and catalytic properties and biomedical applications. Developing applications as well as assessing associated risks requires an understanding of the interactions between Au nanoparticles (NPs) and biologically active substances. In this paper, electron spin resonance spectroscopy (ESR) was used to investigate the catalytic activity of Au NPs in biologically relevant reactions.

Mechanisms of the pH dependent generation of hydroxyl radicals and oxygen induced by Ag nanoparticles.

Many of the chemical and biological effects of silver nanoparticles (Ag NPs) are attributed to the generation of reactive oxygen species (ROS). ESR spectroscopy was used to provide direct evidence for generating ROS during decomposition of H(2)O(2) assisted by Ag NPs. Hydroxyl radical formation was observed under acidic conditions and was accompanied by dissolution of Ag NPs.

Photocytotoxicity in human dermal fibroblasts elicited by permanent makeup inks containing titanium dioxide.

Titanium dioxide (TiO2) is a pigment widely used in decorative tattoo and permanent makeup inks. However, little is known about the risks associated with its presence in these products. We have developed an in vitro assay to identify inks containing TiO2 that are cytotoxic and/or photocytotoxic.

Comparison of metabolism-mediated effects of pyrrolizidine alkaloids in a HepG2/C3A cell-S9 co-incubation system and quantification of their glutathione conjugates.

1. Toxicity of pyrrolizidine alkaloids (PAs) largely depends on their metabolic activation by hepatic enzymes, including cytochrome P450s, to become chemically reactive pyrrolic derivatives. These then spontaneously release the esterifying acids to generate carbonium ions that form covalent adducts with cellular nucleophiles to exhibit toxicity.

Evaluation of accelerated UV and thermal testing for benzene formation in beverages containing benzoate and ascorbic acid.

Under certain conditions, benzene can form in beverages containing benzoic and ascorbic acids. The American Beverage Assn. (ABA) has published guidelines to help manufacturers mitigate benzene formation in beverages.

The scavenging of reactive oxygen species and the potential for cell protection by functionalized fullerene materials.

We demonstrated that three different types of water-soluble fullerenes materials can intercept all of the major physiologically relevant ROS. C(60)(C(COOH)(2))(2), C(60)(OH)(22), and Gd@C(82)(OH)(22) can protect cells against H(2)O(2)-induced oxidative damage, stabilize the mitochondrial membrane potential and reduce intracellular ROS production with the following relative potencies: Gd@C(82)(OH)(22)> or =C(60)(OH)(22)>C(60)(C(COOH)(2))(2). Consistent with their cytoprotective abilities, these derivatives can scavenge the stable 2,2-diphenyl-1-picryhydrazyl radical (DPPH), and the reactive oxygen species (ROS) superoxide radical anion (O(2)(*-)), singlet oxygen, and hydroxyl radical (HO(*)), and can also efficiently inhibit lipid peroxidation in vitro.

Photodecomposition of vitamin A and photobiological implications for the skin.

Vitamin A (retinol), an essential human nutrient, plays an important role in cellular differentiation, regulation of epidermal cell growth and normal cell maintenance. In addition to these physiological roles, vitamin A has a rich photochemistry. Photoisomerization of vitamin A, involved in signal transduction for vision, has been extensively investigated.

Physiological role of retinyl palmitate in the skin.

The skin is similar to other organs in how it absorbs, stores, and metabolizes vitamin A. However, because of the anatomical location of skin and the specialized physiological roles it plays, there are ways in which the skin is rather unique. The stratified structure of the epidermis results from the orchestration of retinoid-influenced cellular division and differentiation.

Photoirradiation of retinyl palmitate in ethanol with ultraviolet light--formation of photodecomposition products, reactive oxygen species, and lipid peroxides.

We have previously reported that photoirradiation of retinyl palmitate (RP), a storage and ester form of vitamin A (retinol), with UVA light resulted in the formation of photodecomposition products, generation of reactive oxygen species, and induction of lipid peroxidation. In this paper, we report our results following the photoirradiation of RP in ethanol by an UV lamp with approximately equal UVA and UVB light. The photodecomposition products were separated by reversed-phase HPLC and characterized spectroscopically by comparison with authentic standards.

Levels of retinyl palmitate and retinol in the stratum corneum, epidermis, and dermis of female SKH-1 mice topically treated with retinyl palmitate.

Retinyl esters are the storage form of vitamin A in skin, and retinyl palmitate (RP) accounts for the majority of the retinyl esters endogenously formed in skin. RP is also obtained exogenously through the topical application of cosmetic and skin care products that contain RP. There is limited information on the penetration and distribution of RP and vitamin A within the stratified layers of the skin.