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Vascular relaxation to nitroglycerin (glyceryl trinitrate; GTN) requires its bioactivation by mechanisms that remain controversial. We report here that glyceraldehyde-3-phosphate dehydrogenase (GAPDH) catalyzes the release of nitrite from GTN. In assays containing dithiothreitol (DTT) and NAD+, the GTN reductase activity of purified GAPDH produces nitrite and 1,2-GDN as the major products. A vmax of 2.6 nmol min−1 mg−1 was measured for nitrite production by GAPDH from rabbit muscle and a GTN KM of 1.2 mM. Reductive denitration of GTN in the absence of DTT results in dose- and time-dependent inhibition of GAPDH dehydrogenase activity. Disulfiram, a thiol-modifying drug, inhibits both the dehydrogenase and GTN reductase activity of GAPDH, while DTT or tris(2-carboxyethyl)phosphine reverse the GTN-induced inhibition. Incubation of intact human erythrocytes or hemolysates with 2 mM GTN for 60 min results in 50% inhibition of GAPDH’s dehydrogenase activity, indicating that GTN is taken up by these cells and that the dehydrogenase is a target of GTN. Thus, erythrocyte GAPDH may contribute to GTN bioactivation.

Oxybenzone (OXB) is one of the most widely employed sunscreen ingredients, yet its allowed load is limited to a maximum of 6% reflecting the frequency with which adverse effects are reported. From a spectroscopic point of view, OXB has excellent absorption properties in both the UVB and UVA regions. We propose that zeolite encapsulation can lead to a sunscreen composite ingredient, that we describe as a supramolecular sunscreen, that will retain the excellent spectroscopic properties of OXB, while preventing contact between the skin and the active ingredient. OXB is very photostable, with the only photodegradative pathway observed being the monophotonic photoejection of electrons that leads to trace yields of phenoxyl radicals; this trace reaction is so minor that it cannot be detected from the recovery of unreacted OXB following UV exposure. Solution, as well as powder and in vitro studies of the supramolecular sunscreen, demonstrate that the protective properties of OXB are totally preserved when encapsulated in zeolite NaY.

Fluorescein (2-(6-hydroxy-3-oxo-(3H)-xanthen-9-yl)benzoic acid) has been prepared inside the pores of zeolite-Y via ship-in-a-bottle synthesis. Fluorescein, whose dimensions prevent it from entering through the ∼7 A windows of the faujasite zeolite used, was prepared by the acid-catalyzed reaction of resorcinol and phthalic anhydride. In this article we report initial spectroscopic data as well as an example of the usefulness of these fluorescence-labeled nanoparticles for imaging applications such as confocal fluorescence microscopy. Encapsulated fluorescein shows a remarkable increase in photostability.

Methyl triazone (4,4′,4″-[1,3,5-triazine-2,4,6-triyltriimino]tris-trimethyl benzoate) has been included in mesoporous MCM-41 (Mobil's composition of matter-41) silica, and its fluorescence emission has been compared in solution and in the solid state. Although inclusion does not affect significantly the absorption properties, a fluorescence emission shift and a behavior similar to the solid state has been observed by increasing the loading. It is believed that this observation reflects molecular aggregation inside the MCM-41 channels. The potential of formulations of this type for sunscreen applications is discussed.

The phototoxic and photoallergic effects of the once popular UV sunscreen p-aminobanzoic acid are related, in part, to its ability to sensitize the formation of singlet oxygen as well as other reactive oxygen species. In this work we demonstrate that the sunscreen-photoinduced inactivation of a model protein, horseradish peroxidase, is reduced by approximately a factor of three when the sunscreen is encaspsulated in zeolite sodium Y. These results provide evidence that using the technology of zeolite encapsulation to prepare a supramolecular sunscreen that minimizes the skin contact of active ingredients may reduce the adverse effects of "naked" sunscreens on biological systems. These radiation-induced effects, unfortunately, frequently accompany the desirable UV-screening role of these products. These results provide an important benchmark for the use of zeolite encapsulation as a means of improving the safety of UV sunscreens for topical application.

Oxytocin (OT; Cys-Tyr-Ile-Gln-Asn-Cys-Pro-leu-Gly), a posterior pituitary peptide hormone, is characterized by a Cys1-Cys6 disulfide bond in its stable, isolated state. This paper describes a simple, one-step method for the production of OT in its reduced, dithiol form (OT dithiol), free of reducing agent. The effects of temperature, pH, and metal-ion chelators on the autoxidation of OT dithiol were examined to establish if this form is likely to persist under biological conditions. It was found that OT dithiol has a half-life of 1.8h with respect to reformation of OT disulfide at 37 degrees C and pH 6.9 in the presence of the copper chelators, DTPA and neocuproine. S-Nitrosation of OT dithiol by acidified nitrite at pH 3.0 was examined by absorption spectroscopy and HPLC-UV-MS, which revealed that both singly and doubly S-nitrosated OT are formed. These results suggest novel chemical aspects to OT signaling, the biological implications of which are discussed here.