RESUMEN
Solution-phase racemization drives the evolution of single chirality in the solid phase by the "chiral amnesia" process first described by Viedma. The current investigations lay the basis for a better understanding of the mechanism of the solid-phase deracemization by uncoupling the chemical rate processes associated with the interconversion of enantiomers in the solution phase from the physical processes associated with solution-solid phase transfer via dissolution and reaccretion of molecules onto crystals. In addition, the enantiomer concentration profiles presented in this work, together with an analytical treatment of the racemization process in the presence of excess enantiopure solid, unequivocally reconfirm the validity of the Meyerhoffer double solubility rule for systems under solution racemization conditions.
Asunto(s)
Amidas/química , Ácido Aspártico/química , Compuestos de Bencilo/química , Glicina/análogos & derivados , Soluciones/química , Cristalografía , Glicina/química , Estructura Molecular , Solubilidad , EstereoisomerismoRESUMEN
The inexorable evolution of solid-phase single chirality is demonstrated for the first time for a proteinogenic amino acid. Enantioenrichment is observed both under attrition-enhanced conditions and without the aid of particle grinding. Differences in the form of the conversion profiles for the process under the two sets of conditions provide suggestions concerning the mechanism of the transformation.
Asunto(s)
Aminoácidos/química , Proteínas/química , Estructura Molecular , EstereoisomerismoRESUMEN
A borehole drilling campaign has allowed the study of a former littoral lagoon located next to the harbour city of Cartagena in South-East Spain (close to the Sierra de Cartagena polymetallic ore deposits). This lagoon, which developed during the Holocene, was first a shallow sedimentary marine environment and later evolved into a swampy semi-endorheic basin named "Almarjal" (after the Arab term from the fourteenth century). The lagoon eventually dried out and at present forms part of the substratum of the modern sector of the city urban area. The basin representative sediments are sapropelic black silty facies forming a continuous sedimentary archive, accounting for more than 8000 years of depositional phenomena. The geochemical study of these sediments, together with their absolute calibrated dating by 14C, allows definition of successive stages of mining and metallurgical activities in the area. In turn, this information provides a more comprehensive perspective regarding metal pollution, particularly lead contamination during different periods of the Recent Prehistory and the Classical Age. The results indicate that the beginning of contamination by lead and other heavy metals occurred as early as 4500 years ago, when the Final Chalcolithic period was taking place in the South-East of the Iberian Peninsula. This finding provides further insights regarding the debate on the origins of lead mining and metallurgy in SE Spain.
Asunto(s)
Monitoreo del Ambiente , Sedimentos Geológicos , Ciudades , Europa (Continente) , Humanos , Metales Pesados , Minería , EspañaRESUMEN
A real amplification of an initial enantiomeric excess can be detected when two amino acids are sublimed at high temperature, even if one of the components is a racemic compound that does not convert into a conglomerate by sublimation.
Asunto(s)
Aminoácidos/química , Calor , Difracción de Polvo , Estereoisomerismo , Difracción de Rayos XRESUMEN
A straightforward unprecedented sublimation protocol that reveals both conversion of a racemic compound into a racemic conglomerate and subsequent enantioenrichment has been developed for the proteinogenic amino acid valine. The phenomenon has been observed in closed and open systems, providing insight into asymmetric amplification mechanisms under presumably prebiotic conditions.
Asunto(s)
Valina/química , Cromatografía Líquida de Alta Presión , Estereoisomerismo , Difracción de Rayos XRESUMEN
Fossil evidence from the Iberian Peninsula is essential for understanding Neandertal evolution and history. Since 2000, a new sample approximately 43,000 years old has been systematically recovered at the El Sidrón cave site (Asturias, Spain). Human remains almost exclusively compose the bone assemblage. All of the skeletal parts are preserved, and there is a moderate occurrence of Middle Paleolithic stone tools. A minimum number of eight individuals are represented, and ancient mtDNA has been extracted from dental and osteological remains. Paleobiology of the El Sidrón archaic humans fits the pattern found in other Neandertal samples: a high incidence of dental hypoplasia and interproximal grooves, yet no traumatic lesions are present. Moreover, unambiguous evidence of human-induced modifications has been found on the human remains. Morphologically, the El Sidrón humans show a large number of Neandertal lineage-derived features even though certain traits place the sample at the limits of Neandertal variation. Integrating the El Sidrón human mandibles into the larger Neandertal sample reveals a north-south geographic patterning, with southern Neandertals showing broader faces with increased lower facial heights. The large El Sidrón sample therefore augments the European evolutionary lineage fossil record and supports ecogeographical variability across Neandertal populations.