Ana Pascual

Broad-Spectrum Antimicrobial Polycarbonate Hydrogels with Fast Degradability

In this study, a new family of broad-spectrum antimicrobial polycarbonate hydrogels has been successfully synthesized and characterized. Tertiary amine-containing eight-membered monofunctional and difunctional cyclic carbonates were synthesized, and chemically cross-linked polycarbonate hydrogels were obtained by copolymerizing these monomers with a poly(ethylene glycol)-based bifunctional initiator via organocatalyzed ring-opening polymerization using 1,8-diazabicyclo[5.4.0]undec-7-ene catalyst. The gels were quaternized using methyl iodide to confer antimicrobial properties. Stable hydrogels were obtained only when the bifunctional monomer concentration was equal to or higher than 12 mol %. In vitro antimicrobial studies revealed that all quaternized hydrogels exhibited broad-spectrum antimicrobial activity against Staphylococcus aureus (Gram-positive), Escherichia coli (Gram-negative), Pseudomonas aeruginosa (Gram-negative), and Candida albicans (fungus), while the antimicrobial activity of the nonquaternized hydrogels was negligible. Moreover, the gels showed fast degradation at room temperature (4-6 days), which makes them ideal candidates for wound healing and implantable biomaterials.

Organic Acid-Catalyzed Polyurethane Formation via a Dual-Activated Mechanism: Unexpected Preference of N-Activation over O-Activation of Isocyanates

A systematic study of acid organocatalysts for the polyaddition of poly(ethylene glycol) to hexamethylene diisocyanate in solution has been performed. Among organic acids evaluated, sulfonic acids were found the most effective for urethane formations even when compared with conventional tin-based catalysts (dibutyltin dilaurate) or 1,8-diazabicyclo[5.4.0]undec-7-ene. In comparison, phosphonic and carboxylic acids showed considerably lower catalytic activities. Furthermore, sulfonic acids gave polyurethanes with higher molecular weights than was observed using traditional catalyst systems. Molecular modeling was conducted to provide mechanistic insight and supported a dual activation mechanism, whereby ternary adducts form in the presence of acid and engender both electrophilic isocyanate activation and nucleophilic alcohol activation through hydrogen bonding. Such a mechanism suggests catalytic activity is a function of not only acid strength but also inherent conjugate base electron density.

Late Holocene pollution in the Gernika estuary (southern Bay of Biscay) evidenced by the study of Foraminifera and Ostracoda

The Arketas pier in the Gernika estuary (southern Bay of Biscay) has during summer periods waters with strong hypoxia (≤1 ml l−1) but curiously bears the richest assemblages of foraminifers and ostracods in the whole estuary. The most abundant species in Arketas are: Ammonia beccarii, Cribroephidium williamsoni, Haynesina germanica and Lobatula lobatula (foraminifers) Loxoconcha elliptica and Leptocythere castanea (ostracods). The benthic foraminifer sub-species A. beccarii tepida exhibits in this estuary three different morphotypes, whose distributions are controlled by changes in the salinity, dissolved oxygen and nutrient content of the waters, and thus could be used as a good indicator of environmental alteration caused by those parameters. To determine whether this environmental alteration is due to natural causes or is anthropogenic, micropalaeontologic and sedimentologic contents of a sediment core 140 cm thick have been analysed. The study of Foraminifera and Ostracoda assemblages, species diversity, and A. beccarii tepida morphotypes allows us to reconstruct the evolution of this part of the estuary over the last 3800 years. To examine anthropogenic effects at this site, we compared the occurrence of heavy metals Pb, As, with the record of A. beccarii tepida morph C in Arketas. The maximum concentration of heavy metals coincides with the maximum occurrence of A. b. tepida morph C, in the 1970s (date calculated according to the estimated rate of sedimentation in this area). This indicates that distribution of A. b. tepida morph C is, at least partially, caused by heavy metal pollution. Nevertheless, the fact that we have found no deformed tests of this taxa in Arketas induces us to think that another factor, such as dysaerobia caused by eutrophization of nutrient inputs in several areas of this estuary, might have been responsible for at least of part of the anomalous shift of A. b. tepida morph C at that time. In recent times, an increase in this anthropogenic activity was evident, reaching its maximum in the 1970s and decreasing from the 1980s. During the late Holocene period (up to 3500 years BP), this site was a middle-outer estuarine settlement, euryhaline with low to moderate salinity. This episode ends with a marine transgressive pulsation. After depositional hiatus of unknown duration, recent sediments suggest a modern palaeogeographic position of Arketas located in a lower estuary environment. The study of A. beccarii through the Holocene sediments of Arketas indicates that dysaerobic/pollution conditions were not a singular event. At the same time, the increase of A. b. tepida morph C were particularly strong over several years of the 20th Century, at precisely the time that a noticeable decrease of richness and diversity of calcareous microfauna is detected in the estuary.

The First Occurrence in the Fossil Record of an Aquatic Avian Twig-Nest with Phoenicopteriformes Eggs: Evolutionary Implications

Background We describe the first occurrence in the fossil record of an aquatic avian twig-nest with five eggs in situ (Early Miocene Tudela Formation, Ebro Basin, Spain). Extensive outcrops of this formation reveal autochthonous avian osteological and oological fossils that represent a single taxon identified as a basal phoenicopterid. Although the eggshell structure is definitively phoenicopterid, the characteristics of both the nest and the eggs are similar to those of modern grebes. These observations allow us to address the origin of the disparities between the sister taxa Podicipedidae and Phoenicopteridae crown clades, and traces the evolution of the nesting and reproductive environments for phoenicopteriforms. Methodology/Principal Findings Multi-disciplinary analyses performed on fossilized vegetation and eggshells from the eggs in the nest and its embedding sediments indicate that this new phoenicopterid thrived under a semi-arid climate in an oligohaline (seasonally mesohaline) shallow endorheic lacustine environment. High-end microcharacterizations including SEM, TEM, and EBSD techniques were pivotal to identifying these phoenicopterid eggshells. Anatomical comparisons of the fossil bones with those of Phoenicopteriformes and Podicipediformes crown clades and extinct palaelodids confirm that this avian fossil assemblage belongs to a new and basal phoenicopterid. Conclusions/Significance Although the Podicipediformes-Phoenicopteriformes sister group relationship is now well supported, flamingos and grebes exhibit feeding, reproductive, and nesting strategies that diverge significantly. Our multi-disciplinary study is the first to reveal that the phoenicopteriform reproductive behaviour, nesting ecology and nest characteristics derived from grebe-like type strategies to reach the extremely specialized conditions observed in modern flamingo crown groups. Furthermore, our study enables us to map ecological and reproductive characters on the Phoenicopteriformes evolutionary lineage. Our results demonstrate that the nesting paleoenvironments of flamingos were closely linked to the unique ecology of this locality, which is a direct result of special climatic (high evaporitic regime) and geological (fault system) conditions.

Distribution and annual variations ofLoxoconcha elliptica in the Gernika estuary (Bay of Biscay)

Abstract The high number of individuals of the ostracode Loxoconcha elliptica appear in the Gernika estuary (Bay of Biscay), has made it possible to carry out a study on the said species. In accordance with its annual distribution, it has been possible to differentiate two zones in the estuary: That of the head with abundant especimens, and the mouth which is lacking in them. Also, a greater number of individuals were observed on the right bank than on the left one. Therefore, the presence of this ostracode indicates the separation of the estuarine and marine environments. When analyzing the relation existing between the aforesaid organism and the physico-chemical factors of the environment, as well as its life cycle, it can be proved that Loxoconcha elliptica is able to supply information about the prevailing environmental conditions and characteristics (substratum, currents, oxygen etc) and contribute information to paleoecological studies (changes of the water masses through time).

ASOCIACIONES DE OSTRÁCODOS DEL MIOCENO TEMPRANO-MEDIO DE LOMA NEGRA (BARDENAS REALES DE NAVARRA, CUENCA DEL EBRO): EVOLUCIÓN PALEOAMBIENTAL DE UN MEDIO LACUSTRE

Abstract. LOWER—MIDDLE MIOCENE OSTRACOD ASSEMBLAGES OF LOMA NEGRA (BARDENAS REALES DE NAVARRA, EBRO BASIN): PALAEOENVIRONMENTAL EVOLUTION OF A LACUSTRINE SYSTEM. The palaeoenvironmental evolution of the Loma Negra section (Bardenas Reales de Navarra, Ebro Basin) during the lower—middle Miocene, is studied for the first time. The paleoenvironmental interpretation is based on the recovered ostracod assemblages and the sedimentology. The lower part of this section is composed by red, yellow and grey mudstones, and with Paralimnocythere sp. as the most abundant ostracod taxon. The lithological features and the faunistic assemblage allows the interpretation of a paleoenvironment with the development of shallow water bodies with stagnant, warm and fresh to oligohaline waters in distal alluvial flood plains for this section. The presence of some sandstone levels where the most abundant ostracod species is Cyclocypris laevis (Müller) marks punctual higher energy events inside this alluvial system and the presence of more saline waters. The upper part of the section is formed by grey limestones with interbedded fine grey mudstones. In this interval, Pseudocandona parallela Müller is the most abundant ostracod species, indicating the development of a stable lacustrine system with water currents, and temperate to cold and oligohaline to mesohaline waters. The transition between the alluvial and the lacustrine systems shows a gradual evolution.