Isohexide and sorbitol-derived, enzymatically synthesized renewable polyesters with enhanced Tg

Sugar-based polyesters derived from sorbitol and isohexides were obtained via solvent-free enzymatic catalysis. Pendant hydroxyl groups, coming from the sorbitol units, were present along the polyester backbone, whereas the two isohexides, namely, isomannide and isoidide dimethyl ester monomers, were selected to introduce rigidity into the polyester chains. The feasibility of incorporating isomannide as a diol compared to the isoidide dimethyl ester as acyl-donor via lipase-catalyzed polycondensation was investigated. The presence of bicyclic units resulted in enhanced Tg with respect to the parent sorbitol-containing polyester lacking isohexides. The different capability of the two isohexides to boost the thermal properties confirmed the more flexible character provided by the isoidide diester derivative. Solvent-borne coatings were prepared by cross-linking the sugar-based polyester polyols with polyisocyanates. The increased rigidity of the obtained sugar-based polyester polyols led to an enhancement in hardness of the resulting coatings.Peer ReviewedPostprint (author's final draft

Sepulcros campaniformes (no) para muertos: El Alto I y III, Las Cuevas/El Morrón y La Perica (Soria, España)

En este trabajo se trata el reciente descubrimiento de un fenómeno peculiar de gran interés en el Calcolítico campaniforme del Valle de Ambrona (Soria, España), que es la existencia de numerosos túmulos que parecen tumbas pero que no lo son. Algunos contienen incluso ofrendas materiales valiosas (finas cerámicas decoradas, orfebrería de oro) pero no huesos humanos. Esta ausencia no puede atribuirse a factores de preservación diferencial, ya que estos túmulos no se sitúan en suelos ácidos, y de hecho se encuentran fragmentos de fauna en muchos yacimientos de los alrededores. Podríamos interpretarlos, por ello, como testimonios de actividades ceremoniales, que en ocasiones incluirían rituales de comensalidad (en el interior de algunos túmulos se descubrieron recipients rotos intencionadamente). El túmulo se erigiría para señalar y conmemorar en el paisaje tales acontecimientos (¿cenotafios que evocan la muerte de alguien importante lejos de su tierra?) y lugares (localización de rasgos especiales del entorno en sus geografías mitológicas)In this article we will discuss on a peculiar and interesting feature recently discovered in the archaeological record of Copper Age Bell Beakers in the Ambrona Valley (Soria, Spain), that is the existence of barrows which look like tombs but they were not. They even include valuable items (finely decorated pottery, gold jewellery) but no sign of human bones. This absence could not be explained by selective preservation of the materials, since those barrows are not located in acid soils, and faunal remains are usually found in other sites of the same area. We could interpret this special finds as the archaeological testimonies of eventual ceremonial activities, perhaps including commensality rituals (intentionally broken pots are found inside them), being the stone mound the commemoration in the landscape of those important events (a possible cenotaph evoking the death of someone important away from his hometown?) or places (the location of special features of the environment in their mythic geographies

Differential Gene Susceptibility to Sperm DNA Damage: Analysis of Developmental Key Genes in Trout

Palabras clave extraídas de la publicación[EN] Sperm chromatin in mammals is packaged in different blocks associated to protamines (PDNA), histones (HDNA), or nuclear matrix proteins. Differential packaging has been related to early or late transcription and also to differential susceptibility to genotoxic damage. Genes located in the more accessible HDNA could be more susceptible to injuries than those located in PDNA, being potential biomarkers of paternal DNA damage. Fish sperm chromatin organization is much diversified, some species lacking protamines and some others totally depleted of histones. Analyzing genotoxic damage in a species homogeneously compacted with some sperm nuclear basic protein type, could help in deciphering the clues of differential susceptibility to damage. In the present study we analyzed in rainbow trout the differential susceptibility of nine genes to UV irradiation and H2O2 treatment. The absence of histones in the sperm nuclei was confirmed by Western blot. The chromatin fractionation in sensitive and resistant regions to PvuII (presumably HDNA-like and PDNA-like, respectively) revealed that the nine genes locate in the same resistant region. The number of lesions promoted was quantified using a qPCR approach. Location of 8-hydroxyguanosine (8-OHdG) was analyzed by immunocytochemistry and confocal microscopy. UV irradiation promoted similar number of lesions in all the analyzed genes and a homogenous distribution of 8- OHdG within the nuclei. 8-OHdG was located in the peripheral area of the nucleus after H2O2 treatment, which promoted a significantly higher number of lesions in developmental-related genes (8.76-10.95 lesions/10 kb) than in rDNA genes (1.05-1.67 lesions/10 kb). We showed for the first time, that differential susceptibility to damage is dependent on the genotoxic mechanism and relies on positional differences between genes. Sensitive genes were also analyzed in cryopreserved sperm showing a lower number of lesions than the previous treatments and a predominant peripheral distribution of oxidative damage (8-OHdG)SIThis work was supported by the Junta de Castilla y León (Spain) (project LE365A11-2 and EDU/828/2014), the Spanish Ministry of Economy and Competitiveness (project AGL2011-27787) and Fondo Social Europeo. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscrip

Green and selective polycondensation methods toward linear sorbitol-based polyesters: enzymatic versus organic and metal-based catalysis

Renewable polyesters derived from a sugar alcohol (i.e., sorbitol) were synthesized by solvent-free polycondensation. The aim was to prepare linear polyesters with pendant hydroxyl groups along the polymer backbone. The performance of the sustainable biocatalyst SPRIN liposorb CALB [an immobilized form of Candida antarctica lipase B (CALB); SPRIN technologies] and the organo-base catalyst 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD) were compared with two metal-based catalysts: dibutyl tin oxide (DBTO) and scandium trifluoromethanesulfonate [also known as scandium triflate, Sc(OTf)3]. For the four catalytic systems, the efficiency and selectivity for the incorporation of sorbitol were studied, mainly using 13C and 31P NMR spectroscopies, whereas side reactions, such as ether formation and dehydration of sorbitol, were evaluated using MALDI-TOF-MS. Especially the biocatalyst SPRIN liposorb CALB succeeded in incorporating sorbitol in a selective way without side reactions, leading to close-to-linear polyesters. By using a renewable hydroxyl-reactive curing agent based on l-lysine, transparent and glossy poly(ester urethane) networks were successfully synthesized offering a tangible example of bio-based coatings.Peer ReviewedPostprint (author's final draft

Response of obesity-resistant BALB/c mice to a ketogenic diet

Introduction. The ketogenic diet (KD) is a high-fat, low-carbohydrate diet in which the body undergoes metabolic adjustments that stimulate ketogenesis, thereby increasing circulating ketone bodies. Loss of body weight is attributed to these adjustments, as well as neuroprotective properties. However, the mechanisms involved are still not fully elucidated. That aim of this work was to evaluate the effect of a ketogenic diet on body composition, feeding behavior and glucose metabolism in mice of the BALB/c strain, a mouse model resistant to obesity. Materials and methods. BALB/c mice of both sexes, 12 weeks old, were divided into KD and control groups, which received a ketogenic diet (Research Diets) or standard chow (LabDiet 5001), respectively, for 23 days. Throughout the experiment, body weight gain, water and food intake were measured, whereas body mass index (BMI), the percentage of interscapular, inguinal, and visceral adipose tissue and blood b-hidroxybutyrate levels were measured at the end of the protocol. In addition, glucose tolerance tests were carried out at the beginning and at the end of the experiment. Results. Similar body weight gain (10%) was observed in males and females on KD compared to the control group (p\u3c0.05). However, a higher BMI was observed only in males. The KD group consumed 50% less food in both sexes, whereas water consumption was diminished 25% in males and 50% in females, compared to the control (p= 0.0001). The estimated energy intake was lower (12 Kcal) in males on ketogenic diet, but not in females. Regarding the metabolic state at day 23, in KD mice levels of b-hidroxybutyrate increased to 0.4 mmol/L in males and 0.7 mmol/L in females. Mice of both sexes on KD showed increased inguinal and visceral fat, when compared to the control group on standard chow. At day 23, the glucose tolerance test showed an increase in the area under the curve, indicating impaired glucose tolerance, in both males and females on KD. Conclusions. In obesity-resistant BALB/c mice, the consumption of a ketogenic diet for a short period induces a state of nutritional ketosis accompanied by weight gain, increased fat tissue, and impaired glucose intolerance

Analysis of polarized 16 O ( → e , e ′ → p ) observables within the relativistic distorted wave impulse approximation

Recoil nucleon transferred polarization observables in coincidence quasielastic electron scattering are studied within the relativistic distorted wave impulse approximation. Results for response functions and polarization asymmetries are discussed for proton knockout from p 1 ∕ 2 , p 3 ∕ 2 , and s 1 ∕ 2 shells in 16 O . The impact of spinor distortion is examined by comparing the fully relativistic calculation with results obtained by projecting out the negative-energy components. In particular, a careful analysis of effects linked to the description of the bound and scattered relativistic nucleon wave functions is presented. The high sensitivity of some polarization observables to the dynamical enhancement of the lower components, already shown within the relativistic plane wave impulse approximation, is proven to be maintained in the relativistic distorted wave approach. Semi-relativistic approaches based on the effective momentum approximation are also studied. Finally, comparison with experimental data and a brief analysis of effects linked to medium modified form factors is presented.Dirección Genera de Investigación de España (DGI) y Fondos FEDER. BFM2002-03315, BFM2002-03562, FPA2002-04181-C04- 04, y BFM2000-0600Junta de Andalucía, España y Department of Energy de los EE.UU. DE-FC02-94ER4081

Taxonomic descriptions of mantis (MANTODEA) from department of Atlántico, Colombia and comments on their distribution

Se realizó una revisión de caracteres taxonómicos en 98 ejemplares de mántidos depositados en las colecciones biológicas (UARC-135) de la Universidad del Atlántico, con el objetivo de contribuir al conocimiento del orden Mantodea en el territorio colombiano. La identificación de las especies se basó en un análisis exhaustivo de caracteres morfológicos y genitales masculinos de algunos especímenes. Se presentan por primera vez descripciones taxonómicas y apuntes de distribución de 15 especies de mántidos en ecosistemas de bosque seco tropical (Bs-T) del departamento del Atlántico, ampliando de esta forma el conocimiento sobre la diversidad del orden en el Caribe colombiano.Taxonomic revision of 98 mantids specimens stored in the biological collections (UARC-135) from Atlántico University was performed in order to contribute to the knowledge of mantodea order present in Colombia. The species identification was based on a thorough analysis of morphological characters and male genitalia of some specimens. We present for the first time taxonomic descriptions and distribution notes of 15 mantids species in dry tropical forest (Dt-F) ecosystem from Atlántico department, thus expanding knowledge of the Mantodea diversity in the Caribbean region

Formulaciones granulares de baculovirus en combinación con abrillantadores ópticos para su empleo como bioinsecticida

El virus de la poliedrosis nuclear con inclusiones múltiples de Anagrapha falcifera (AfMNPV) es un bioplaguicida con potencial para el control de lepi- dópteros plaga de cultivos en América. Aquí se re- porta la actividad insecticida del AfMNPV contra larvas de Trichoplusia ni, Heliothis virescens y Spodoptera exigua, evaluada por ensayo de gota teñi- da. El AfMNPV producido en H. virescens fue sig- nificativamente menos activo contra H. virescens en comparación con el virus homólogo (HzSNPV). El lote de AfMNPV producido en T. ni fue muy acti- vo contra T. ni, mientras que el obtenido en H. virescens fue menos activo por un logaritmo. La ac- tividad insecticida de AfMNPV contra S. exigua, con todos los lotes producidos, fue muy baja (LC50 > 108 OB/ml). El formulado granular de AfMNPV con lignina en combinación con fagoestimulantes (almidón y harina de maíz, pan molido y germen de trigo) y abrillantadores ópticos (Tinopal UNPA- GX, Blankophor BBU) no afectó su actividad con- tra T. ni y H. virescens. El AfMNPV sin formular perdió actividad de ~1 logaritmo después de almacenarlo por 90 días a 25oC, mientras que el formulado con una humedad de ~10% perdió ~3 logaritmos. El formulado almacenado a 4oC mejoró la estabilidad, conservando ~50% de la activi- dad original (%OAR) después de cuatro meses, y >30% OAR después de ocho meses. Se requieren de más estudios para mejorar la estabilidad duran- te el almacenaje

Ring opening polymerization of macrolactones using amines as initiators

The ring opening polymerization (ROP) of these macrolactones mediated by alcohols as initiators and organic and metal-based catalysts has been reported before with satisfactory results [4,5]. In the present work, the polymerization of these macrolactones has been studied using amines as initiators. The ROP of both PDL and 6HDL was carried out in bulk at 100 oC using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as organocatalyst. Distinct types of amines were tested as initiators for the ROP of these macrolactones. The copolymerization reaction was also studied by ROP of PDL and 6HDL with an oligo-polyethylene glycol bis(3-aminopropyl) terminated and an amino-ended homopolypeptide (poly(¿-benzyl a,Lglutamate) as initiator.Postprint (published version

Diversidad mitocondrial en el nor-occidente de venezuela. implicaciones para probables rutas migratorias prehispánicas

RESUMEN La utilidad del ADN mitocondrial (ADNmt) para determinar afinidad genética entre grupos indígenas contemporáneos e inferir sobre migraciones, ha sido demostrada; pero la imposibilidad de estudiar grupos prehispánicos extintos, limita las inferencias sobre migraciones en esa época. El mestizaje en poblaciones neoamericanas ha sido caracterizado por uniones entre hombres europeos y mujeres indígenas, permitiendo detectar en la población contemporánea haplogrupos mitocondriales amerindios que informan sobre poblaciones extintas. Para conocer los linajes femeninos en el occidente de Venezuela, se estudiaron los haplogrupos del ADNmt a partir de RFLP, en una muestra de 193 individuos con antepasados procedentes del occidente de Venezuela, 81 del Estado Lara (Barquisimeto) y 112 de tres pueblos del Estado Falcón (Macu-quita=25, Macanillas=29 y Churuguara=58). Se comparó la distribución de haplogrupos entre las poblaciones y se estimó el mestizaje por línea femenina en ellas. Se comparó la distribución de cuatro haplogrupos indígenas con otras regiones de América. Se observa que en las cuatro poblaciones predominan haplogrupos amerindios, seguidos de los africanos. Al comparar la fracción indígena con el resto de América encontramos que Macanillas, Lara y Churuguara se asemejan a grupos de Amazonas y Suramérica, mientras que Macuquita a Aruba. Esto sugiere una diversidad genética importante en esa zona como probable ruta de paso hacia el sur y el Caribe; además refleja vínculos genéticos importantes entre grupos prehispánicos de Aruba y los de la Península de Paraguaná. Evidencias arqueológicas soportan estos postulados. Se recomienda aumentar la muestra y realizar análisis de secuencias para un nivel mayor de precisión. Palabras clave: ADN mitocondrial, haplogrupos, población venezolana, grupos indígenas. ABSTRACT Mitocondrial DNA (mtDNA) has been widely used to study genetic relationships between contemporary Amerindian groups and to infer ancestral migration movements; however inferences about migration routes of prehispanic extinct groups are difficult. Admixture of Neoamerican groups has been characterized by unions between European males and Amerindian females. This allows the identification in present populations of Amerindian mitocondrial haplogroups which give information on ancestral groups. In order to investigate female lineages present in western Venezuela, RFLP haplogroups from mtDNA were obtained from 193 individuals with grandparents from this region, 81 from the State of Lara (Barquisimeto) and 112 from 3 towns of the State of Falcon (Macuquita=25; Macanilla=29 and Churuguara=58). Comparison of haplogroup distributions between groups was performed, and admixture estimates based on female lineages were obtained. The distribution of four Amerindian haplogroups was compared with those of other populations from the American Continent. In our four samples Amerindian haplogroups predominate, followed by those of African origin. In the comparison of the mtDNA Amerindian fraction with other populations we find that Macanillas, Lara and Churuguara are similar to South American and Amazonian groups whilst Macuquita is similar to groups from Aruba. Our findings suggest an important genetic diversity in this region, explained by migration routes to and from the south and the Caribean. They also suggest genetic relationship between prehispanic groups from Aruba and those from the Paraguaná peninsula, which have been inferred by archeological evidences. An increase in sample size and analysis of sequences for more precision is recommended. Key words: Mitocondrial DNA, haplogroups, Venezuelan population, Amerindians