Selenomethionine: A Pink Trojan Redox Horse with Implications in Aging and Various Age-Related Diseases

Selenium is an essential trace element. Although this chalcogen forms a wide variety of compounds, there are surprisingly few small-molecule organic selenium compounds (OSeCs) in biology. Besides its more prominent relative selenocysteine (SeCys), the amino acid selenomethionine (SeMet) is one example. SeMet is synthesized in plants and some fungi and, via nutrition, finds its way into mammalian cells. In contrast to its sulfur analog methionine (Met), SeMet is extraordinarily redox active under physiological conditions and via its catalytic selenide (RSeR’)/selenoxide (RSe(O)R’) couple provides protection against reactive oxygen species (ROS) and other possibly harmful oxidants. In contrast to SeCys, which is incorporated via an eloquent ribosomal mechanism, SeMet can enter such biomolecules by simply replacing proteinogenic Met. Interestingly, eukaryotes, such as yeast and mammals, also metabolize SeMet to a small family of reactive selenium species (RSeS). Together, SeMet, proteins containing SeMet and metabolites of SeMet form a powerful triad of redox-active metabolites with a plethora of biological implications. In any case, SeMet and its family of natural RSeS provide plenty of opportunities for studies in the fields of nutrition, aging, health and redox biology.

Pyrite Oxidation Controlled Siderophile Element Accumulation on the K-Pg Boundary at El Kef, Tunisia

<p>In a transformative contribution, Alvarez et al. (1980) discovered the iridium anomaly at several K-Pg boundary locations that they attributed to an extraterrestrial impact that triggered the end-Cretaceous extinction. The absence of a suitable mechanism by which to concentrate siderophile elements in the boundary clay drove the argument for an extraterrestrial origin of the iridium. They made the observation that fallout from a fireball would be expected to create a uniform distribution of Ir in the clay layer and puzzled over the scale of lateral variation in Ir observed even then. A detailed global study of the siderophile element (Ru, Rh, Pd, Ir, Pt Au) distribution at the K-Pg boundary found non-chondritic patterns concluding that some post-depositional process(es) must have affected the elemental distribution (Goderis et al., 2015). Such processes would mobilize siderophile elements into the surrounding strata. Here, we applied laser ablation ICP-MS, a microanalytical technique, to investigate the distribution of 60 elements, with an emphasis on the siderophile elements, in a vertical transect at the K-Pg boundary at El Kef, Tunisia, to search for elemental transport in or out of the K-Pg clay layer. The K-Pg boundary at El Kef consists of irregular mixed layers of clay, goethite and gypsum with marls above and below. The siderophile elements are concentrated in the goethite-rich component with a distinctly terrestrial crust pattern, albeit super-enriched, with prominent negative Pt anomalies indicative of deposition from an oxidized solution. The Fe/Se ratio indicates an origin of the goethite by oxidation of sedimentary pyrite. Iron oxyhydroxides are effective substrates for the binding of trace metal oxyanions from solution. The extreme enrichment of siderophile elements reflects long-term concentration of siderophile elements from percolating oxidized groundwaters at El Kef. The sulfuric acid produced by pyrite oxidation was neutralized by calcium carbonate in the marls to form gypsum. Selenium (normally a sulfur analog) is undetectable in the El Kef gypsum endmember (Se/S~0), unlike marine gypsum, supporting a formation by pyrite oxidation. This observation potentially explains the ubiquitous non-chondritic siderophile patterns observed globally and the variable Ir enrichments that puzzled geochemists since Alvarez et al. (1980). In view of this observation, siderophile element enrichment in the K-Pg layer can no longer be taken as unambiguous evidence of an extraterrestrial impact.</p>

Different Oxidation Pathways of 2-Selenouracil and 2-Thiouracil, Natural Components of Transfer RNA

Sulfur- and selenium-modified uridines present in the wobble position of transfer RNAs (tRNAs) play an important role in the precise reading of genetic information and tuning of protein biosynthesis in all three domains of life. Both sulfur and selenium chalcogens functionally operate as key elements of biological molecules involved in the protection of cells against oxidative damage. In this work, 2-thiouracil (S2Ura) and 2-selenouracil (Se2Ura) were treated with hydrogen peroxide at 1:0.5, 1:1, and 1:10 molar ratios and at selected pH values ranging from 5 to 8. It was found that Se2Ura was more prone to oxidation than its sulfur analog, and if reacted with H2O2 at a 1:1 or lower molar ratio, it predominantly produced diselenide Ura-Se-Se-Ura, which spontaneously transformed to a previously unknown Se-containing two-ring compound. Its deselenation furnished the major reaction product, a structure not related to any known biological species. Under the same conditions, only a small amount of S2Ura was oxidized to form Ura-SO2H and uracil (Ura). In contrast, 10-fold excess hydrogen peroxide converted Se2Ura and S2Ura into corresponding Ura-SeOnH and Ura-SOnH intermediates, which decomposed with the release of selenium and sulfur oxide(s) to yield Ura as either a predominant or exclusive product, respectively. Our results confirmed significantly different oxidation pathways of 2-selenouracil and 2-thiouracil.

Semithiobambus[6]uril is a transmembrane anion transporter

Bambus[6]uril analogs are excellent anion binders but only the sulfur analog is also an effective anion transporter capable of polarizing lipid membranes through selective anion uniport.