Reverse Hierarchy of Alkane Adsorption in Metal–Organic Frameworks (MOFs) Revealed by Immersion Calorimetry

Immersion calorimetry into liquids of different dimensions is a powerful tool to learn about the pore size and shape in nanoporous solids. In general, in the absence of specific interactions with the solid surface, the accessibility of the liquid probe molecule to the inner porosity and the associated enthalpy value decreases with an increase in its kinetic diameter (bulkier molecules have lower accessibility and packing density). Although this is true for the majority of solids (e.g., activated carbons and zeolites), this study anticipates that this is not straightforward in the specific case of metal–organic frameworks (MOFs). The evaluation of different hydrocarbons and their derivatives reveals the presence of reverse selectivity for C6 isomers (2,2-dimethylbutane > 2-methylpentane > n-hexane) in UiO-66 and HKUST-1, whereas size exclusion effects take place in ZIF-8. The immersion calorimetric findings have been compared with vapor adsorption isotherms and computational studies. Monte Carlo simulations suggest that the reverse selectivity in UiO-66 is attributed to the strong confinement of the dibranched hydrocarbons in the small tetragonal cages, whereas the presence of strong interactions with the open metal sites accounts for the preferential adsorption in HKUST-1. These results open the gate toward the application of immersion calorimetry for the prescreening of MOFs to identify in an easy, fast and reliable way interesting characteristics and/or properties such as separation ability, reversed hierarchy, pore-window size, presence of unsaturated metal sites, molecular accessibility, and so on.Authors would like to acknowledge financial support from MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004) and H2020 (MSCA-RISE-2016/NanoMed Project). P.Z.M. is grateful for start-up funds from the University of Sheffield

Methane hydrate formation in confined nanospace can surpass nature

Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. Here we report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2 degrees C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. The formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelastic neutron scattering experiments and synchrotron X-ray powder diffraction. These findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation).We acknowledge UK Science and Technlology Facilities Council for the provision of beam time on the TOSCA spectrometer (Projects RB1410624 and RB122099) and financial support from the European Commission under the 7th Framework Programme through the 'Research Infrastructures' action of the 'Capacities' Programme (NMI3-II Grant number 283883). J.S.-A. and F.R. acknowledges the financial support from MINECO: Strategic Japanese-Spanish Cooperation Program (PLE2009-0052), Concert Project-NASEMS (PCIN-2013-057) and Generalitat Valenciana (PROMETEO/2009/002). F.R. and J.L.J. thank the financial support from MINECO (MAT2012-38567-C02-01, Consolider Ingenio 2010-Multicat CSD-2009-00050 and SEV-2012-0267). K.K. thanks Grant-in-Aid for Scientific Research (A) (2424-1038), Japan. A.B. and A.U. thank the financial support from MINECO (SEV-2013-0319). J.L.J. and I.P. thank synchrotron ALBA for beamtime availability.Casco, M.; Silvestre Albero, J.; Ramirez-Cuesta, A.; Rey Garcia, F.; Jorda Moret, JL.; Bansode, A.; Urakawa, A.... (2015). Methane hydrate formation in confined nanospace can surpass nature. Nature Communications. 6(6432):1-8. https://doi.org/10.1038/ncomms7432S1866432Sloan, E. D. Jr., & Koh, C. A. Clathrate Hydrates of Natural Gases 3rd edn CRC Press (2007).Gutt, C. et al. The structure of deuterated methane-hydrate. J. Chem. Phys. 113, 4713–4721 (2000).Holbrook, W. S., Hoskins, H., Wood, W. T., Stephen, R. A. & Lizarralde, D. Methane hydrate and free gas on the Blake Ridge from vertical seismic profiling. Science 273, 1840–1843 (1996).Sloan, E. D. Jr., Fundamental principles and applications of natural gas hydrates. Nature 426, 353–363 (2003).Rodríguez-Reinoso, F., Almansa, C. & Molina-Sabio, M. 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Carbon 46, 384–386 (2008).Marsh, H. & Rodríguez-Reinoso, F. Activated Carbon Elsevier (2006).Kubo, T. et al. Diffusion-barrier-free porous carbon monoliths as a new form of activated carbon. ChemSusChem 5, 2271–2277 (2012).Kaneko, K., Itoh, T. & Fujimori, T. Collective interactions of molecules with an interfacial solid. Chem. Lett. 41, 466–475 (2012).Nakamura, M., Ohba, T., Branton, P., Kanoh, H. & Kaneko, K. Equilibrium-time and pore-width dependent hysteresis of water adsorption isotherm on hydrophobic microporous carbons. Carbon 48, 305–308 (2010).Vysniauskas, A. & Bishnoi, P. R. A kinetic study of methane hydrate formation. Chem. Eng. Sci. 38, 1061–1072 (1983).Junhong, Q. & Tianmin, G. Kinetics of methane hydrate formation in pure water and inhibitor containing systems. Chin. J. Chem. Eng 10, 316–322 (2002).Liu, J., Zhou, Y., Sun, Y., Su, W. & Zhou, L. Methane storage in wet carbon of tailored pore sizes. Carbon 49, 3731–3736 (2011).Perrin, A., Celzard, A., Marêché, J. F. & Furdin, G. Methane storage within dry and wet activated carbons: a comparative study. Energy Fuels 17, 1283–1291 (2003).Zhou, L., Liu, L., Su, W., Sun, Y. & Zhou, Y. Progress in studies of natural gas storage with wet adsorbents. Energy Fuels 24, 3789–3795 (2010).Celzard, A. & Marêché, J. F. Optimal wetting of activated carbons for methane hydrate formation. Fuel 85, 957–966 (2006).Webb, E. B. et al. High pressure rheology of hydrate slurries formed from water-in-oil emulsions. Energy Fuels 26, 3504–3509 (2012).Urita, K. et al. Confinement in carbon nanospace-induced production of KI nanocrystals of high-pressure phase. J. Am. Chem. Soc. 133, 10344–10347 (2011).Fujimori, T. et al. Conducting linear chains of sulphur inside carbon nanotubes. Nat. Commun. 4, 2162 (2013).Tse, J. S., Ratcliffe, C. L., Powell, B. M., Sears, V. F. & Handa, Y. P. Rotational and translational motions of trapped methane. Incoherent inelastic neutron scattering of methane hydrate. J. Phys. Chem. 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Immediate vs. deferred switching from a boosted protease inhibitor (PI/r) based regimen to a Dolutegravir (DTG) based regimen in virologically suppressed patients with high cardiovascular risk or Age ≥50 years: final 96 weeks results of NEAT 022 study

Background Both immediate and deferred switching from a ritonavir-boosted protease inhibitor (PI/r)–based regimen to a dolutegravir (DTG)–based regimen may improve lipid profile. Methods European Network for AIDS Treatment 022 Study (NEAT022) is a European, open-label, randomized trial. Human immunodeficiency virus (HIV)–infected adults aged ≥50 years or with a Framingham score ≥10% were eligible if HIV RNA was <50 copies/mL. Patients were randomized to switch from PI/r to DTG immediately (DTG-I) or to deferred switch at week 48 (DTG-D). Week 96 endpoints were proportion of patients with HIV RNA <50 copies/mL, percentage change of lipid fractions, and adverse events (AEs). Results Four hundred fifteen patients were randomized: 205 to DTG-I and 210 DTG-D. The primary objective of noninferiority at week 48 was met. At week 96, treatment success rate was 92.2% in the DTG-I arm and 87% in the DTG-D arm (difference, 5.2% [95% confidence interval, –.6% to 11%]). There were 5 virological failures in the DTG-I arm and 5 (1 while on PI/r and 4 after switching to DTG) in the DTG-D arm without selection of resistance mutations. There was no significant difference in terms of grade 3 or 4 AEs or treatment-modifying AEs. Total cholesterol and other lipid fractions (except high-density lipoprotein) significantly (P < .001) improved both after immediate and deferred switching to DTG overall and regardless of baseline PI/r strata. Conclusions Both immediate and deferred switching from a PI/r to a DTG regimen in virologically suppressed HIV-infected patients ≥50 years old or with a Framingham score ≥10% was highly efficacious and well tolerated, and improved the lipid profile

Guía docente de Química Inorgánica Avanzada (2010-2011)

Esta guía docente de la asignatura Química Inorgánica Avanzada (de cuarto de Químicas) incluye: descriptor, objetivos y programa, datos matrícula, contenidos teóricos y prácticos y bibliografía

p53 prevents entry into mitosis with uncapped telomeres.

Telomeres are protected by capping structures consisting of core protein complexes that bind with sequence specificity to telomeric DNA. In their absence, telomeres trigger a DNA damage response, materialized in accumulation at the telomere of damage response proteins, e.g., phosphorylated histone H2AX (gammaH2AX), into telomere-dysfunction-induced foci. Telomere uncapping occurs transiently in every cell cycle in G2, following DNA replication, but little is known about how protective structures are reassembled or whether this process is controlled by the cell-cycle surveillance machinery. Here, we report that telomere capping is monitored at the G2/M transition by the p53/p21 damage response pathway. Unlike their wild-type counterparts, human and mouse cells lacking p53 or p21 progress into mitosis prematurely with persisting uncapped telomeres. Furthermore, artificially uncapped telomeres delay mitotic entry in a p53- and p21-dependent manner. Uncapped telomeres that persist in mitotic p53-deficient cells are shorter than average and religate to generate end-to-end fusions. These results suggest that a p53-dependent pathway monitors telomere capping after DNA replication and delays G2/M progression in the presence of unprotected telomeres. This mechanism maintains a cell-cycle stage conducive for capping reactions and prevents progression into stages during which uncapped telomeres are prone to deleterious end fusions

Hyperspectral LCTF-based system for classification of decay in mandarins caused by Penicillium digitatum and Penicillium italicum using the most relevant bands and non-linear classifiers

[EN] Green mold (Penicillium digitatum) and blue mold (Penicillium italicum) are important sources of postharvest decay affecting the commercialization of mandarins. These fungi infections produce enormous economic losses in mandarin production if early detection is not carried out. Nowadays, this detection is performed manually in dark chambers, where the fruit is illuminated by ultraviolet light to produce fluorescence, which is potentially dangerous for humans. This paper documents a new methodology based on hyperspectral imaging and advanced machine-learning techniques (artificial neural networks and classification and regression trees) for the segmentation and classification of images of citrus free of damage and affected by green mold and blue mold. Feature selection methods are used in order to reduce the dimensionality of the hyperspectral images and determine the 10 most relevant. Neural Networks were used to segment the hyperspectral images. Result's achieved using classifiers based on decision trees show an accuracy of around 93% in the problem of decay classification.This work was partially funded by the University of Valencia through project UV-INV-AE11-41271 and by the Instituto Nacional de Investigacion y Tecnologia Agraria y Alimentaria de Espana (INIA) through research projects RTA2012-00062-C04-01 and RTA2012-00062-C04-03Gomez-Sanchis, J.; Blasco, J.; Soria-Olivas, E.; Lorente, D.; Escandell-Montero, P.; Martinez-Martinez, JM.; Martinez-Sober, M.... (2013). Hyperspectral LCTF-based system for classification of decay in mandarins caused by Penicillium digitatum and Penicillium italicum using the most relevant bands and non-linear classifiers. Postharvest Biology and Technology. 82:76-86. https://doi.org/10.1016/j.postharvbio.2013.02.011S76868