Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C=O over C=C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C=O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes

Structural and Functional Analysis of Laninamivir and its Octanoate Prodrug Reveals Group Specific Mechanisms for Influenza NA Inhibition

The 2009 H1N1 influenza pandemic (pH1N1) led to record sales of neuraminidase (NA) inhibitors, which has contributed significantly to the recent increase in oseltamivir-resistant viruses. Therefore, development and careful evaluation of novel NA inhibitors is of great interest. Recently, a highly potent NA inhibitor, laninamivir, has been approved for use in Japan. Laninamivir is effective using a single inhaled dose via its octanoate prodrug (CS-8958) and has been demonstrated to be effective against oseltamivir-resistant NA in vitro. However, effectiveness of laninamivir octanoate prodrug against oseltamivir-resistant influenza infection in adults has not been demonstrated. NA is classified into 2 groups based upon phylogenetic analysis and it is becoming clear that each group has some distinct structural features. Recently, we found that pH1N1 N1 NA (p09N1) is an atypical group 1 NA with some group 2-like features in its active site (lack of a 150-cavity). Furthermore, it has been reported that certain oseltamivir-resistant substitutions in the NA active site are group 1 specific. In order to comprehensively evaluate the effectiveness of laninamivir, we utilized recombinant N5 (typical group 1), p09N1 (atypical group 1) and N2 from the 1957 pandemic H2N2 (p57N2) (typical group 2) to carry out in vitro inhibition assays. We found that laninamivir and its octanoate prodrug display group specific preferences to different influenza NAs and provide the structural basis of their specific action based upon their novel complex crystal structures. Our results indicate that laninamivir and zanamivir are more effective against group 1 NA with a 150-cavity than group 2 NA with no 150-cavity. Furthermore, we have found that the laninamivir octanoate prodrug has a unique binding mode in p09N1 that is different from that of group 2 p57N2, but with some similarities to NA-oseltamivir binding, which provides additional insight into group specific differences of oseltamivir binding and resistance

Distinguishing freezing and thawing dark energy models through measurements of the fine-structure constant

Mapping the behaviour of dark energy is a pressing task for observational cosmology. Phenomenological classification divides dynamical dark energy models into freezing and thawing, depending on whether the dark energy equation of state is approaching or moving away from w = p/ρ = −1. Moreover, in realistic dynamical dark energy models the dynamical degree of freedom is expected to couple to the electromagnetic sector, leading to variations of the fine-structure constant α. We discuss the feasibility of distinguishing between the freezing and thawing classes of models with current and forthcoming observational facilities and using a parametrisation of the dark energy equation of state, which can have either behaviour, introduced by Mukhanov as fiducial paradigm. We illustrate how freezing and thawing models lead to different redshift dependencies of α, and use a combination of current astrophysical observations and local experiments to constrain this class of models, improving the constraints on the key coupling parameter by more than a factor of two, despite considering a more extended parameter space than the one used in previous studies. We also briefly discuss the improvements expected from future facilities and comment on the practical limitations of this class of parametrisations. In particular, we show that sufficiently sensitive data can distinguish between freezing and thawing models, at least if one assumes that the relevant parameter space does not include phantom dark energy models

Cumulative climatic stressors strangles marine aquaculture: Ancillary effects of COVID 19 on Spanish mariculture

Marine aquaculture takes advantage of marine ecosystem services to produce goods that can be relevant from a food security point of view. However, this activity is subject to multiple stressors as the ones exerted by global climate change. Local stressed conditions due to environmental drivers may be exacerbated by the COVID19 pandemic crisis. In this paper we analyze the pre-COVID-19 situation in two Spanish regions with the highest aquaculture production, Galicia and the Valencian Community. The incidence of storms, heat waves and mussel farming closure were analyzed, and surveys were used to define the perception of producers in terms of economic problems derived from COVID-19 and synergistic environmental concerns. Also the temporal trend of mussel production was analyzed. Spanish marine aquaculture has been intensively subjected to climatic stressors that made it more vulnerable to COVID-19, showing some weakness in terms of production as can be seen in mussel production and fresh consumption. Anyway, extensive aquaculture and aquaculture developed by Integrated Multi-Trophic Aquaculture (IMTA) was reported as somewhat more resilient to the impact of COVID-19. In order to ensure the environmental and economic sustainability of marine aquaculture - under a future uncertain pandemic scenario – our outcomes underline the need for more resilient adaptation programs and recovery plans taking into account the climate change effects

Engineering covalent organic frameworks in the modulation of photocatalytic degradation of pollutants under visible light conditions

Mixtures of triphenylamine (TPA) and phenyl phenothiazine (PTH) fragments have been incorporated into a series of extended polyimine structures that have been applied in the photodegradation of pollutants of different nature under visible light irradiation. Results obtained revealed that materials containing PTH as the sole photoactive unit resulted in the most active photocatalytic material in the degradation of polybrominated diphenyl ether-1 and Sudan Red III. In contrast, the covalent organic framework containing only TPA acted as the best photocatalyst for the degradation of Methylene Blue. These different trends are related to the versatility of PTH moiety to trigger both photoredox and energy transfer processes, while TPA is only an effective energy transfer catalyst.Financial support was provided by the European Research Council (ERC-CoG, contract number: 647550), Spanish Government (PID2019-110637RB-I00, RTI2018-095038-B-I00 and RTI2018-095622-B-I00), “Comunidad de Madrid” and European Structural Funds (S2018/NMT-4367). It was also funded by the CERCA Program/Generalitat de Catalunya. ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706). Alberto López-Magano thanks to UAM for FPI-UAM predoctoral fellowship