Direct Hydroxylation of Phenol to Dihydroxybenzenes by H2O2 and Fe-based Metal-Organic Framework Catalyst at Room Temperature

A semi-crystalline iron-based metal-organic framework (MOF), in particular Fe-BTC, that contained 20 wt.% Fe, was sustainably synthesized at room temperature and extensively characterized. Fe-BTC nanopowders could be used as an efficient heterogeneous catalyst for the synthesis of dihydroxybenzenes (DHBZ), from phenol with hydrogen peroxide (H2O2), as oxidant under organic solvent-free conditions. The influence of the reaction temperature, H2O2 concentration and catalyst dose were studied in the hydroxylation performance of phenol and MOF stability. Fe-BTC was active and stable (with negligible Fe leaching) at room conditions. By using intermittent dosing of H2O2, the catalytic performance resulted in a high DHBZ selectivity (65%) and yield (35%), higher than those obtained for other Fe-based MOFs that typically require reaction temperatures above 70◦C. The long-term experiments in a fixed-bed flow reactor demonstrated good Fe-BTC durability at the above conditionsThe authors thank the financial support by Consejo Nacional de Ciencia y Tecnología (CONACYT) for the grant number 764635 and the project 256296; and to TNM for the supporting project 5627.19.P. Also, to the Spanish Ministerio de Ciencia, Innovación y Universidades (MICINN) and FEDER program (EU) through the projects: CTM2016-76454-R (MICINN) and RTI2018-095052-B-I00 ((MCIU/AEI/FEDER, UE

Hydroelastic effects during the fast lifting of a disc from a water surface

Here we report the results of an experimental study where we measure the hydrodynamic force acting on a plate which is lifted from a water surface, suddenly starting to move upwards with an acceleration much larger than gravity. Our work focuses on the early stage of the plate motion, when the hydrodynamic suction forces due to the liquid inertia are the most relevant ones. Besides the force, we measure as well the acceleration at the centre of the plate and the time evolution of the wetted area. The results of this study show that, at very early stages, the hydrodynamic force can be estimated by a simple extension of the linear exit theory by Korobkin (J. Fluid Mech., vol. 737, 2013, pp. 368–386), which incorporates an added mass to the body dynamics. However, at longer times, the measured acceleration decays even though the applied external force continues to increase. Moreover, high-speed recordings of the disc displacement and the radius of the wetted area reveal that the latter does not change before the disc acceleration reaches its maximum value. We show in this paper that these phenomena are caused by the elastic deflection of the disc during the initial transient stage of water exit. We present a linearised model of water exit that accounts for the elastic behaviour of the lifted body. The results obtained with this new model agree fairly well with the experimental results

Stellarator Optimization Using a Distributed Swarm Intelligence-Based Algorithm

The design of enhanced fusion devices constitutes a key element for the development of fusion as a commercial source of energy. Stellarator optimization presents high computational requirements because of the complexity of the numerical methods needed as well as the size of the solution space regarding all the possible configurations satisfying the characteristics of a feasible reactor. The size of the solution space does not allow to explore every single feasible configuration. Hence, a metaheuristic approach is used to achieve optimized configurations without evaluating the whole solution space. In this paper we present a distributed algorithm that mimics the foraging behaviour of bees. This behaviour has manifested its efficiency in dealing with complex problems

CD44-high neural crest stem-like cells are associated with tumour aggressiveness and poor survival in neuroblastoma tumours

BACKGROUND: Neuroblastoma is a paediatric tumour originated from sympathoadrenal precursors and characterized by its heterogeneity and poor outcome in advanced stages. Intra-tumoral cellular heterogeneity has emerged as an important feature in neuroblastoma, with a potential major impact on tumour aggressiveness and response to therapy. CD44 is an adhesion protein involved in tumour progression, metastasis and stemness in different cancers; however, there has been controversies about the significance of CD44 expression in neuroblastoma and its relationship with tumour progression. METHODS: We have performed transcriptomic analysis on patient tumour samples studying the outcome of patients with high CD44 expression. Adhesion, invasion and proliferation assays were performed in sorted CD44high neuroblastoma cells. Tumoursphere cultures have been used to enrich in undifferentiated stem-like cells and to asses self-renewal and differentiation potential. We have finally performed in vivo tumorigenic assays on cell line-derived or Patient-derived xenografts. FINDINGS: We show that high CD44 expression is associated with low survival in high-grade human neuroblastoma, independently of MYCN amplification. CD44 is expressed in a cell population with neural crest stem-like features, and with the capacity to generate multipotent, undifferentiated tumourspheres in culture. These cells are more invasive and proliferative in vitro. CD44 positive cells obtained from tumours are more tumorigenic and metastatic, giving rise to aggressive neuroblastic tumours at high frequency upon transplantation. INTERPRETATION: We describe an unexpected intra-tumoural heterogeneity within cellular entities expressing CD44 in neuroblastoma, and propose that CD44 has a role in neural crest stem-like undifferentiated cells, which can contribute to tumorigenesis and malignancy in this type of cancer. FUNDING: Research supported by grants from the "Asociación Española contra el Cáncer" (AECC), the Spanish Ministry of Science and Innovation SAF program (SAF2016-80412-P), and the European Research Council (ERC Starting Grant to RP).Spanish Ministry of Science and Innovation SAF program (SAF2016-80412-P

Localized extinction of an arboreal desert lizard caused by habitat fragmentation

We adopted a species' perspective for predicting extinction risk in a small, endemic, and strictly scansorial lizard (Urosaurus nigricaudus), in an old (∿60. year) and highly fragmented (8% habitat remaining) agricultural landscape from the Sonoran Desert, Mexico. We genotyped 10. microsatellite loci in 280 individuals from 11 populations in fragmented and continuous habitat. Individual dispersal was restricted to less than 400. m, according to analyses of spatial autocorrelation and spatially explicit Bayesian assignment methods. Within this scale, continuous areas and narrow washes with native vegetation allowed high levels of gene flow over tens of kilometers. In the absence of the native vegetation, cleared areas and highways were identified as partial barriers. In contrast, outside the scale of dispersal, cleared areas behaved as complete barriers, and surveys corroborated the species went extinct after a few decades in all small (less than 45. ha), isolated habitat fragments. No evidence for significant loss of genetic diversity was found, but results suggested fragmentation increased the spatial scale of movements, relatedness, genetic structure, and potentially affected sex-biased dispersal. A plausible threshold of individual dispersal predicted only 23% of all fragments in the landscape were linked with migration from continuous habitat, while complete barriers isolated the majority of fragments. Our study suggested limited dispersal, coupled with an inability to use a homogeneous and hostile matrix without vegetation and shade, could result in frequent time-delayed extinctions of small ectotherms in highly fragmented desert landscapes, particularly considering an increase in the risk of overheating and a decrease in dispersal potential induced by global warming. © 2012 Elsevier Ltd.Peer Reviewe

Artificial diet sandwich reveals subsocial behavior in the coffee berry borer Hypothenemus hampei (Coleoptera: Curculionidae: Scolytinae)

An artificial diet sandwich, consisting of coffee berry borer artificial diet within two glass plates, has been developed to elucidate the behaviour of the coffee berry borer, an insect that in nature spends most of its life cycle inside the coffee berry. Various types of behaviour have been observed for the first time, including gallery construction, oviposition, gallery blocking, mating and most remarkably, subsocial tasks such as maternal sanitation and tending of eggs and larvae. This observational technique is a breakthrough for studies and manipulations of the coffee berry borer's social behaviour and could be applicable to other bark beetles, consequently yielding important insights into the origin of parental care in scolytine beetles

Tectonic implications of paleontologic dating of Cretaceous-Danian sections of Eastern Cuba

The sedimentary rocks intercalated in volcanic and metavolcanic sections of Mayarí-Baracoa and Sierra del Purial Mountains (Eastern Cuba), yielded Cretaceous through Danian microfossils. In the Mayarí Mountains the Téneme Fm consists of basalts and hyaloclastites with minor intercalations of well-bedded foliated limestone and shaly limestone that in the type area contain a Turonian or early Coniacian planktonic foraminifera assemblage. In the Morel area (Moa-Baracoa massif), back-arc pillow basalts with ribbon cherts include a late Turonian or Coniacian limestone bed intercalated with interbedded organic-rich calcareous shales near the top. The upper part of the Coniacian (?)-Campanian Santo Domingo Fm crops out west of Moa and it consists of finegrained well-bedded volcaniclastic rocks with two intercalated lenses of coarse-grained impure biocalcirudites to biocalcarenites. These rocks yielded a mixed penecontemporaneous planktonic and benthonic microfossil assemblage attributed to the lower part of the late Campanian (Globotruncanita calcarata Zone). At Sierra del Purial, crystalline limestones embedded within the metavulcano-sedimentary Río Baracoa section (Purial metamorphic complex) yielded Campanian microfossils. The Maastrichtian Yaguaneque (=Cañas) limestones crop out extensively in both Mayarí-Baracoa and Purial Mountains. All the formations previously mentioned unconformably overlie and tectonically intermingle with the late Maastrichtian-early Danian clastic rocks of the Mícara and La Picota Fms. Our new dates demonstrate that in the Greater Antilles the PIA (Primitive Island Arc-tholeiite) recorded by the Téneme Fm would be Late Cretaceous in age in opposition to the Lower Cretaceous age proposed for the PIA basalts. The protolith of the Purial metamorphic complex is probably Maastrichtian-early Danian, but certainly Campanian and older in age. This fact suggests that the metamorphism that affected the Purial rocks took place probably in the late Maastrichtian and was coeval with the detachment, exhumation and emplacement of mafic-ultramafic thrust-sheet bodies. This event recorded in Eastern Cuba/Western Hispaniola and Guatemala might have been related to the insertion of thick oceanic ridges into the subduction zone