Unexpected one-pot synthesis of highly conjugated pentacyclic diquinoid compounds

A new class of pentacyclic diquinoid compounds has been synthesized with a facile one-pot reaction of two molecules of 2-hydroxynaphthoquinone and 1-bromoalkanes in the presence of ferrocene. These molecules were isolated as enol tautomers that exhibit intramolecular hydrogen bond and extended electronic conjugation as proved by the intense absorption spectrum with a broad band between 400 and 600 nm. The spectroscopic and electrochemical characterization of this new class of compounds has been performed. One of the synthesized diquinoid derivatives showed a significant cytotoxicity with IC50 values of 25−50 μM against Cisplatin-Resistant SKOV3 and colon carcinoma SW480 cell lines. The results of our study provide a valuable tool to a one-pot synthesis of highly conjugated polyquinones, analogous to important biological systems, with significant antitumoral activity

Humin Formation on SBA-15-pr-SO3H Catalysts during the Alcoholysis of Furfuryl Alcohol to Ethyl Levulinate: Effect of Pore Size on Catalyst Stability, Transport, and Adsorption

Herein, the alcoholysis of furfuryl alcohol in a series of SBA-15-pr-SO3H catalysts with different pore sizes is reported. Elemental analysis and NMR relaxation/diffusion methods show that changes in pore size have a significant effect on catalyst activity and durability. In particular, the decrease in catalyst activity after catalyst reuse is mainly due to carbonaceous deposition, whereas leaching of sulfonic acid groups is not significant. This effect is more pronounced in the largest-pore-size catalyst C3, which rapidly deactivates after one reaction cycle, whereas catalysts with a relatively medium and small average pore size (named, respectively, C2 and C1) deactivate after two reaction cycles and to a lesser extent. CHNS elemental analysis showed that C1 and C3 experience a similar amount of carbonaceous deposition, suggesting that the increased reusability of the small-pore-size catalyst can be attributed to the presence of SO3H groups mostly present on the external surface, as corroborated by results on pore clogging obtained by NMR relaxation measurements. The increased reusability of the C2 catalyst is attributed to a lower amount of humin being formed and, at the same time, reduced pore clogging, which helps to maintain accessible the internal pore space

Características fisiológicas de sementes de trevo-alexandrino e trevo-vesiculoso e necessidade de escarificação.

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Rapa Nui (Easter Island) Rano Raraku crater lake basin: Geochemical characterization and implications for the Ahu-Moai Period

Rano Raraku, the crater lake constrained by basaltic tuff that served as the primary quarry used to construct the moai statues on Rapa Nui (Easter Island), has experienced fluctuations in lake level over the past centuries. As one of the only freshwater sources on the island, understanding the present and past geochemical characteristics of the lake water is critical to understand if the lake could have been a viable freshwater source for Rapa Nui. At the time of sampling in September 2017, the maximum lake depth was ~1 m. The lake level has substantially declined in the subsequent years, with the lake drying almost completely in January 2018. The lake is currently characterized by highly anoxic conditions, with a predominance of ammonium ions on nitrates, a high concentration of organic carbon in the water-sediment interface and reducing conditions of the lake, as evidenced by Mn/Fe and Cr/V ratios. Our estimates of past salinity inferred from the chloride mass balance indicates that it was unlikely that Rano Raraku provided a viable freshwater source for early Rapa Nui people. The installation of an outlet pipe around 1950 that was active until the late 1970s, as well as grazing of horses on the lake margins appear to have significantly impacted the geochemical conditions of Rano Raraku sediments and lake water in recent decades. Such impacts are distinct from natural environmental changes and highlight the need to consider the sensitivity of the lake geochemistry to human activities

High-accuracy methodology for the integrative restoration of archaeological teeth by using reverse engineering techniques and rapid prototyping

The reconstruction of the original morphology of bones and teeth after sampling for physicochemical (e.g., radiocarbon and uranium series dating, stable isotope analysis, paleohistology, trace element analysis) and biomolecular analyses (e.g., ancient DNA, paleoproteomics) is appropriate in many contexts and compulsory when dealing with fossil human remains. The reconstruction protocols available to date are mostly based on manual re-integration of removed portions and can lead to an imprecise recovery of the original morphology. In this work, to restore the original external morphology of sampled teeth we used computed microtomography (microCT), reverse engineering (RE), computer-aided design (CAD) and rapid prototyping (RP) techniques to fabricate customized missing parts. The protocol was tested by performing the reconstruction of two Upper Palaeolithic human teeth from the archaeological excavations of Roccia San Sebastiano (Mondragone, Caserta, southern Italy) and Riparo I of Grotte Verdi di Pradis (Clauzetto, Pordenone, north-eastern Italy) (RSS2 and Pradis 1, respectively), which were sampled for physicochemical and biomolecular analyses. It involved a composite procedure consisting in: a) the microCT scanning of the original specimens; b) sampling; c) the microCT scanning of the specimens after sampling; d) the reconstruction of the digital 3D surfaces of the specimens before and after sampling; e) the creation of digital models of the missing/sampled portions by subtracting the 3D images of the preserved portions (after the sampling) from the images of the intact specimens (before the sampling) by using reverse engineering techniques; f) the prototyping of the missing/sampled portions to be integrated; g) the painting and application of the prototypes through the use of compatible and reversible adhesives. By following the proposed protocol, in addition to the fabrication of a physical element which is faithful to the original, it was possible to obtain a remarkable correspondence between the contact surfaces of the two portions (the original and the reconstructed one) without having to resort to any manipulation/adaptation of either element

The impact of socioeconomic and phenotypic traits on self-perception of ethnicity in Latin America

Self-perception of ethnicity is a complex social trait shaped by both, biological and non-biological factors. We developed a comprehensive analysis of ethnic self-perception (ESP) on a large sample of Latin American mestizos from five countries, differing in age, socio-economic and education context, external phenotypic attributes and genetic background. We measured the correlation of ESP against genomic ancestry, and the influence of physical appearance, socio-economic context, and education on the distortion observed between both. Here we show that genomic ancestry is correlated to aspects of physical appearance, which in turn affect the individual ethnic self-perceived ancestry. Also, we observe that, besides the significant correlation among genomic ancestry and ESP, specific physical or socio-economic attributes have a strong impact on self-perception. In addition, the distortion among ESP and genomic ancestry differs across age ranks/countries, probably suggesting the underlying effect of past public policies regarding identity. Our results indicate that individuals’ own ideas about its origins should be taken with caution, especially in aspects of modern life, including access to work, social policies, and public health key decisions such as drug administration, therapy design, and clinical trials, among others