Mesoporous mixed Nb2O5-ZrO2 catalysts for dehydration of glucose into 5-hydroxymethylfurfural

Biomass is the world’s most important renewable carbon source, whose major component, carbohydrates, can be valorized by transformation into biofuels and high value-added chemicals. Among the latter, 5-hydroxymethylfurfural (HMF), obtained by C6 carbohydrates dehydration, is a versatile and key intermediate for the production of a large spectrum of biobased chemicals. Different catalytic systems have been evaluated for HMF production, mostly based on heterogeneous catalysis as alternative to the use of conventional mineral acids [1]. Moreover, niobium oxide has shown interesting properties as acid catalyst for dehydration of sugars [2-3]. On the other hand, the high surface area and large pore size of mesoporous solids make them suitable for many catalytic processes. In the present work, the dehydration of glucose to HMF has been evaluated by using different mesoporous mixed Nb2O5-ZrO2 in a biphasic water–Methyl Isobutyl Ketone (MIBK) solvent system to avoid the HMF degradation. Different experimental parameters, such as reaction temperature and time, as well as the addition of CaCl2 have been studied in order to maximize the HMF yield.N2 adsorption-desorption isotherms have corroborated the mesostructured character of catalysts, being all isotherms of Type IV according to the IUPAC classification. BET surface area decreases for catalysts with higher Zr content (Table 1). Likewise, pore volume and average pore diameter values diminish after Zr incorporation. Concerning the acid properties, a clear correlation between Nb and acidity can be observed, in such a way that total acidity, as deduced from NH3-TPD, decreases when the Zr content rises, and consequently the amount of Nb is reduced.These mesoporous Nb-Zr catalysts have been tested in the dehydration of glucose to HMF at 175 ºC under batch operation in aqueous solution, using MIBK as co-solvent. It can be observed that both glucose conversion and HMF yield increase with the Nb content, being maximum (90% and 36%, respectively) after 90 minutes for Nb2O5. This trend changes when CaCl2 is added to the reaction medium, improving the catalytic performance of mixed oxides and ZrO2, but Nb2O5 maintains similar results than without salt addition. This could be justified by the interaction between CaCl2 and Lewis acid sites, since zirconium oxide possesses a higher amount of this acid sites type.

Lower Aptian Comparative Stratigraphy of the Basco-Cantabrian Region (Spain) and Eastern Cordillera (Colombia): implications for local factors in the depositional record of Oceanic Anoxic Event 1a (OAE-1a)

An important episode of carbon sequestration, Oceanic Anoxic Event 1a (OAE-1a), characterizes the Lower Aptian worldwide, and is mostly known from deeper-water settings. The present work of two Lower Aptian deposits, Madotz (N Spain) and Curití Quarry (Colombia), is a multiproxy study that includes fossil assemblages, microfacies, X-ray diffraction bulk and clay mineralogy, elemental analyses (major, minor, trace elements), Rock-Eval pyrolysis, biomarkers, inorganic and organic carbon content, and stable carbon isotopes. The results provide baseline evidence of the local and global controlling environmental factors influencing OAE-1a in shallow-water settings. The data also improve our general understanding of the conditions under which organic-carbon-rich deposits accumulate. The sequence at Madotz includes four intervals (Unit 1; Subunits 2a, 2b and 2c) that overlap the times prior to, during and after the occurrence of OAE-1a. The Lower Unit 1(3m thick) is essentially siliciclastic, and Subunit 2a (20m) contains Urgonian carbonate facies that document abruptly changing platform conditions prior to OAE-1a. Subunit 2b (24.4 m) is a mixed carbonate-siliciclastic facies with orbitolinid-rich levels that coincides with OAE-1a δ13C stages C4-C6, and is coeval with the upper part of the Deshayesites forbesi ammonite zone. Levels with pyrite and the highest TOC values (0.4-0.97%), interpreted as accumulating under suboxic conditions, and are restricted to δ13C stages C4 and C5. The best development of the suboxic facies is at the level representing the peak of the transgression. Subunit 2c, within δ13C stage C7, shows a return of the Urgonian facies. The 23.35-m section at Curití includes a 6.3-m interval at the base of the Paja Formation dominated by organic-rich marlstones and shales lacking benthic fossils and bioturbation, with TOC values as high as 8.84%. The interval overlies a level containing reworked and phosphatized assemblages of middle Barremian to lowest Aptian ammonites. The range of values and the overall pattern of the δ13Corg (-22.05‰ to -20.47‰) in the 6.3m-interval is comparable with Lower Aptian δ13C stage C7. Thus, conditions of oxygen depletion at this site also occurred after Oceanic Anoxic Event-1a, which developed between carbon isotope stages C3 and C6. Both sites, Madotz and Curití, attest to the importance of terrigenous and nutrient fluxes in increasing OM productivity that led to episodic oxygen deficiency.

Tes Kaines diathekes apanta = Noui Testamenti omnia.

Texto en griego clásico

Harnessing bacterial signals for suppression of biofilm formation in the nosocomial fungal pathogen Aspergillus fumigatus

Faced with the continued emergence of antibiotic resistance to all known classes of antibiotics, a paradigm shift in approaches toward antifungal therapeutics is required. Well characterized in a broad spectrum of bacterial and fungal pathogens, biofilms are a key factor in limiting the effectiveness of conventional antibiotics. Therefore, therapeutics such as small molecules that prevent or disrupt biofilm formation would render pathogens susceptible to clearance by existing drugs. This is the first report describing the effect of the Pseudomonas aeruginosa alkylhydroxyquinolone interkingdom signal molecules 2-heptyl-3-hydroxy-4-quinolone and 2-heptyl-4-quinolone on biofilm formation in the important fungal pathogen Aspergillus fumigatus. Decoration of the anthranilate ring on the quinolone framework resulted in significant changes in the capacity of these chemical messages to suppress biofilm formation. Addition of methoxy or methyl groups at the C5–C7 positions led to retention of anti-biofilm activity, in some cases dependent on the alkyl chain length at position C2. In contrast, halogenation at either the C3 or C6 positions led to loss of activity, with one notable exception. Microscopic staining provided key insights into the structural impact of the parent and modified molecules, identifying lead compounds for further development.

Láser Q-Switched en el manejo de ocronosis exógena: revisión sistemática de la literatura

Antecedentes: La ocronosis Exógena (OE) es una enfermedad subdiagnosticada y de difícil manejo (1). El láser Q-Switched (QS) surge como una alternativa para el tratamiento de esta (2). Objetivo: Describir las características de los pacientes, del láser QS y los desenlaces en el tratamiento de OE. Métodos: Se realizó una búsqueda de la literatura en las bases PubMed, Embase, PMC, Scielo, Elselvier, BMJ Case Reports, Journal of Medical Case Reports, Cases Journal e International Medical Case Reports Journal, desde enero del 2000 a marzo del 2016, pacientes con ocronosis exógena, 18 a 70 años, tratados con láser QS. Los artículos fueron evaluados mediante la herramienta de evaluación de validez y valor educativo de reportes de caso descrito por Pierson (3). Resultados: Se encontraron 256 artículos, 63 fueron seleccionados: 28 repetidos y 31 no cumplieron criterios de inclusión. Se escogieron 4 artículos que reportan 12 casos de pacientes con ocronosis exógena diagnosticada mediante estudio histopatológico y tratada con láser QS. Discusión: Hay poca experiencia con el láser QS en OE. En la práctica clínica se usa para tatuajes y patologías pigmentarias dérmicas con resultados satisfactorios. El pigmento dérmico en OE y la corta duración de pulso de láser QS, podrían ser el pilar de tratamiento para OE. Conclusión: El láser QS puede ser útil para el tratamiento en OE, con nivel de evidencia 3 y grado de recomendación D. Se sugiere realizar estudios clínicos con mayor grado de evidencia.

Design and characterization of polymorphs and co-crystals of organic molecular semiconductors

In the last decades, organic semiconductors have attracted attention due to their possible employment in solution-processed optoelectronic and electronic devices. One of the advantages of solution processing is the possibility to process into flexible substrates at low cost. Organic molecular materials tend to form polymorphs, which can exhibit very different properties. In most cases, the control of the crystal structure is decisive to maximize the performance of the final device. Although organic electronics have progressed a lot, n-type organic semiconductors still lag behind p-type, presenting challenges such as air instability and poor solubility. NDI derivatives are promising candidates for applications in organic electronics due to their characteristics. Recently, the structure-properties relationship and the polymorphism of these molecules have gained attention. In the first part of this thesis, NDI-C6 thermal behavior was extensively explored which revealed two different behaviors depending on the annealing process. This study allowed to define the stability ranking of the NDI-C6 bulk forms and to determine the crystal structure of Form γ at 54°C. Additionally, the polymorphic and thermal behavior of thin films of NDI-C6 was also explored. It was possible to isolate pure Form α, Form β, Form γ and a new metastable Form ε. It was also possible to determine the stability ranking of the phases in thin films. OFETs were fabricated having different polymorphs as active layer, unfortunately the performance was not ideal. During the second part of this thesis, core-chlorinated NDIs with fluoroalkyl chains were studied. Initially, the focus was on the polymorphism of CF3-NDI that revealed a solvate form with a very interesting molecular arrangement suggesting the possibility to form charge transfer co-crystals. In the last part of the thesis, the synthesis and characterization of CT co-crystal with different NDI derivatives, and acceptor and as donor BTBT and ditBu-BTBT were explored.