Formation and inhibition of N-nitrosodiethanolamine in cosmetics under pH, temperature, and fluorescent, ultraviolet, and visual light.

N-nitrosodiethanolamine (NDELA), a type of nitrosamine, is a possible human carcinogen that may form in cosmetic products. The aim of this study was to examine the formation and inhibition of NDELA through chemical reactions of secondary amines including mono-ethanolamine, di-ethanolamine (DEA), and tri-ethanolamine (TEA), and sodium nitrite (SN) under varying conditions such as pH, temperature, and fluorescent, ultraviolet (UV), and visual light (VIS) using liquid chromatography-mass spectroscopy. In a mixture of TEA and SN under acidic conditions pH 2, residual NDELA concentrations rose significantly under various storage conditions in the following order: 50°C > 40°C > UV (2 W/m2) > VIS (4000 lux) > fluorescent light > 25°C > 10°C. In a mixture of DEA and SN under the same acidic pH 2 conditions, NDELA formation was significantly elevated in the following order: UV (2 W/m2) > VIS (4000 lux) > 50°C > 40°C > fluorescent light > 25°C > 10°C. Inhibition of NDELA formation by d-mannitol, vitamin C (Vit C), or vitamin E (Vit E) was determined under varying conditions of pH, temperature, and fluorescent, UV, and VIS. At high concentrations of 100 or 1000 µg/ml, Vit E significantly decreased residual NDELA compared with control levels under acidic pH 2, but not under basic pH 6. Among various antioxidants, Vit E reacted more effectively with many nitrosating agents such as nitrate and nitrite found in cosmetic products. Therefore, to reduce NDELA, it is recommended that cosmetics be stored under cool/amber conditions and that Vit E or Vit C inhibitors of nitrosation be optimally added to cosmetic formulations at concentrations between 100 and 1000 µg/ml.

Nitrite-induced photo-oxidation of thiol and its implications in smog toxicity to the eye: prevention by ascorbate.

Studies have been conducted on nitrite-induced oxidation of corneal thiols and reduced glutathione (GSH). Oxidation of GSH in the presence of nitrite (NaNO2) was minimal in the dark. Exposure of GSH to UV (365 nm) in the presence of nitrite substantially accelerated this oxidation; only < 10% of the original GSH remained at the end of 20 minutes. A similar Thiol depletion was observed in the case of corneal epithelial extracts irradiated with UV in the presence of the nitrite. Nitrite is therefore considered to be a potent phototoxicant with possible pathophysiological implications to the external eye tissues. Ascorbate was found to be effective in preventing thiol oxidation, suggesting the possibility of preventing nitrogen oxide-based smog irritation to the eye by this physiologically compatible antioxidant.

Photochemical generation of nitric oxide from nitro-containing compounds: possible relation to vascular photorelaxation phenomena.

We examined the production of nitric oxide (NO) from various nitro-containing compounds (500 microM and 100 microM solutions in Krebs buffer, pH 7.4). Sealed vials containing solutions of NaNO2, N-nitro-L-arginine, 4-nitrophenol, BAY K 8644, or N-nitro-L-arginine methyl ester were stored in the dark, under normal room light, or were exposed to ultraviolet light (365 nm), for 30 min (24 degrees C). NO was measured in the vial headspace after 30 min, using a sensitive assay previously established in our laboratory. Production of NO was found to be dependent on the intensity of light exposure for all compounds, and the highest degree of light-induced production of NO was found for NaNO2 and BAY K 8644 solutions. Since NO is a relaxant of smooth muscle, these results help explain the increased sensitivity to relaxation by UV light of vascular and other types of smooth muscle in the presence of NaNO2, BAY K 8644 and N-nitro-L-arginine, as observed by other investigators.

Mutagenicity of photochemical reaction products of polycyclic aromatic hydrocarbons with nitrite.

Six kinds of polycyclic aromatic hydrocarbons (PAHs) were subjected to ultraviolet light irradiation with nitrite for 1, 4, 8 and 24 h, and the irradiated samples were tested for mutagenicity towards Salmonella typhimurium TA 98, TA 100 and TA 1538. Irradiated samples of pyrene, fluoranthene and benzo[a]pyrene showed marked mutagen responses towards TA 98 and TA 1538, especially in the absence of S9 mix. The direct-acting mutagenic activity of these samples, showing high activities at 1-8 h, decreased greatly with the development of irradiation. Further, these direct-acting mutagens were mostly present in the neutral fraction. On the other hand, the mutagenicity of the irradiated sample of 5,6-benzoquinoline was high both with and without S9 mix, and was mostly present in the basic fraction because of its authentic characteristic. There was no correlation between the yield of 1-nitropyrene and the mutagenic activity of the photochemical reaction product of pyrene with nitrite. Further studies by TLC separation suggested that a considerable number of direct-acting mutagens formed in this experiment were more polar than nitrated PAH such as 1-nitropyrene.