Synthesis of a Versatile Building Block for the Preparation of 6-N-Derivatized α-Galactosyl Ceramides: Rapid Access to Biologically Active Glycolipids

A concise route to the 6-azido-6-deoxy-α-galactosyl-phytosphingosine derivative 9 is reported. Orthogonal protection of the two amino groups allows elaboration of 9 into a range of 6-N-derivatized α-galactosyl ceramides by late-stage introduction of the acyl chain of the ceramide and the 6-N-group in the sugar head-group. Biologically active glycolipids 6 and 8 have been synthesized to illustrate the applicability of the approach

Efficient harvesting and storage of solar energy of an all-vanadium solar redox flow battery with a MoS2@TiO2 photoelectrode

Solar redox flow batteries constitute an emerging technology that provides a smart alternative for the capture and storage of discontinuous solar energy through the photo-generation of the discharged redox species employed in traditional redox flow batteries. Here, we show that a MoS2-decorated TiO2 (MoS2@TiO2) photoelectrode can successfully harvest light to be stored in a solar redox flow battery using vanadium ions as redox active species in both the catholyte and anolyte, and without the use of any bias. The MoS2@TiO2 photoelectrode achieved an average photocurrent density of ∼0.4 mA cm−2versus 0.08 mA cm−2 for bare TiO2, when tested for the oxidation of V4+ to V5+, attributed to a more efficient light harvesting and charge separation for the MoS2@TiO2 relative to TiO2. The designed solar redox flow cell exhibited an optimal overall solar-to-output energy conversion efficiency (SOEE) of ∼4.78%, which outperforms previously reported solar redox flow batteries. This work demonstrates the potential of the MoS2@TiO2 photoelectrode to efficiently convert solar energy into chemical energy in a solar redox flow battery, and it also validates the great potential of this technology to increase reliability in renewable energies

High-power nitrided TiO2 carbon felt as the negative electrode for all-vanadium redox flow batteries

This work describes the design of an electrode with enhanced performance applied to all-vanadium redox flow batteries (VRFBs). This new electrode consists of a structural porous carbon felt decorated with TiO2 rutile nanoparticles, which has been nitrided using ammonolysis at 900 °C. An outstanding charge and mass transfer over the electrode-electrolyte interface was observed as a consequence of the synergetic effect of N- and O-functionalization over carbon felt (CF) and the partial formation of TiN (metallic conductor) phase. Moreover, this material has not only improved in terms of catalysis towards the V3+/V2+ redox reaction (k0 = 1.6 × 10−3 cm s−1), but also inhibited the hydrogen evolution reaction (HER), which is one of the main causes of imbalances that lead to battery failure. This led to an impressive high-power peak output value up to 700 mW cm−2, as well as work at high current density in galvanostatic conditions (i.e. 150 mA cm−2), exhibiting low ohmic losses (overpotential) and great redox single cell reversibility, with a superior energy efficiency of 71%. An inexpensive, earth abundant and scalable synthesis method to boost VRFBs technology based on nitrided CF@TiO2 is presented, being able to overcome certain constrains, and therefore to achieve high energy and power densities

Investigating the effect of thermal gradients on stress in solid oxide fuel cell anodes using combined synchrotron radiation and thermal imaging

Thermal gradients can arise within solid oxide fuel cells (SOFCs) due to start-up and shut-down, non-uniform gas distribution, fast cycling and operation under internal reforming conditions. Here, the effects of operationally relevant thermal gradients on Ni/YSZ SOFC anode half cells are investigated using combined synchrotron X-ray diffraction and thermal imaging. The combination of these techniques has identified significant deviation from linear thermal expansion behaviour in a sample exposed to a one dimensional thermal gradient. Stress gradients are identified along isothermal regions due to the presence of a proximate thermal gradient, with tensile stress deviations of up to 75Â MPa being observed across the sample at a constant temperature. Significant strain is also observed due to the presence of thermal gradients when compared to work carried out at isothermal conditions

Breakdown of Scaling in the Nonequilibrium Critical Dynamics of the Two-Dimensional XY Model

The approach to equilibrium, from a nonequilibrium initial state, in a system at its critical point is usually described by a scaling theory with a single growing length scale, $\xi(t) \sim t^{1/z}$, where z is the dynamic exponent that governs the equilibrium dynamics. We show that, for the 2D XY model, the rate of approach to equilibrium depends on the initial condition. In particular, $\xi(t) \sim t^{1/2}$ if no free vortices are present in the initial state, while $\xi(t) \sim (t/\ln t)^{1/2}$ if free vortices are present.Comment: 4 pages, 3 figure

Open-circuit dissolution of platinum from the cathode in polymer electrolyte membrane water electrolysers

Platinum is the state-of-the-art catalyst for hydrogen evolution in polymer electrolyte membrane (PEM) water electrolysers; however, its stability has only been characterized to a limited extent in situ. This study measures platinum dissolving from the cathode during intermittent operation of a 3-electrode PEM electrolyser cell, using a differential pulse voltammetry technique that provided detection limits for platinum of less than 2 ng L−1. Water samples were periodically taken during on-off current cycling, and during periods of open-circuit voltage (OCV) platinum dissolution was detected when the cathode potential rose above 0.85 V NHE due to diffusion of oxygen from the anode. This reached a maximum dissolution rate at the highest cathode potential of 1.02 V NHE, and gradually decayed over a 90 h period. The average total amount of platinum dissolved per 90 h OCV period was estimated to be 152 ng cm−2 or 0.005% of the initial electrode catalyst mass. The dissolution mechanism was predicted to be the same as that occurring in PEM fuel cell cathodes, although being kinetically hindered in PEM electrolysers by the slow diffusion of oxygen from the anode to the cathode

The origin of overpotential in lithium-mediated nitrogen reduction

The verification of the lithium-mediated nitrogen reduction system in 2019 has led to an explosion in the literature focussing on improving the metrics of faradaic efficiency, stability, and activity. However, while the literature acknowledges the vast intrinsic overpotential for nitrogen reduction due to the reliance on in situ lithium plating, it has thus far been difficult to accurately quantify this overpotential and effectively analyse further voltage losses. In this work, we present a simple method for determining the Reversible Hydrogen Electrode (RHE) potential in the lithium-mediated nitrogen reduction system. This method allows for an investigation of the Nernst equation and reveals sources of potential losses. These are namely the solvation of the lithium ion in the electrolyte and resistive losses due to the formation of the solid electrolyte interphase. The minimum observed overpotential was achieved in a 0.6 M LiClO4, 0.5 vol% ethanol in tetrahydrofuran electrolyte. This was −3.59 ± 0.07 V vs. RHE, with a measured faradaic efficiency of 6.5 ± 0.2%. Our method allows for easy comparison between the lithium-mediated system and other nitrogen reduction paradigms, including biological and homogeneous mechanisms

Towards a mechanistic understanding of particle shrinkage during biomass pyrolysis via synchrotron X-ray microtomography and in-situ radiography

Accurate modelling of particle shrinkage during biomass pyrolysis is key to the production of biochars with specific morphologies. Such biochars represent sustainable solutions to a variety of adsorption-dependent environmental remediation challenges. Modelling of particle shrinkage during biomass pyrolysis has heretofore been based solely on theory and ex-situ experimental data. Here we present the first in-situ phase-contrast X-ray imaging study of biomass pyrolysis. A novel reactor was developed to enable operando synchrotron radiography of fixed beds of pyrolysing biomass. Almond shell particles experienced more bulk shrinkage and less change in porosity than did walnut shell particles during pyrolysis, despite their similar composition. Alkaline pretreatment was found to reduce this difference in feedstock behaviour. Ex-situ synchrotron X-ray microtomography was performed to study the effects of pyrolysis on pore morphology. Pyrolysis led to a redistribution of pores away from particle surfaces, meaning newly formed surface area may be less accessible to adsorbates

Dehydropeptide supramolecular hydrogels and nanostructures as potential peptidomimetic biomedical materials

Supramolecular peptide hydrogels are gaining increased attention, owing to their potential in a variety of biomedical applications. Their physical properties are similar to those of the extracellular matrix (ECM), which is key to their applications in the cell culture of specialized cells, tissue engineering, skin regeneration, and wound healing. The structure of these hydrogels usually consists of a di- or tripeptide capped on the N-terminus with a hydrophobic aromatic group, such as Fmoc or naphthalene. Although these peptide conjugates can offer advantages over other types of gelators such as cross-linked polymers, they usually possess the limitation of being particularly sensitive to proteolysis by endogenous proteases. One of the strategies reported that can overcome this barrier is to use a peptidomimetic strategy, in which natural amino acids are switched for non-proteinogenic analogues, such as D-amino acids, β-amino acids, or dehydroamino acids. Such peptides usually possess much greater resistance to enzymatic hydrolysis. Peptides containing dehydroamino acids, i.e., dehydropeptides, are particularly interesting, as the presence of the double bond also introduces a conformational restraint to the peptide backbone, resulting in (often predictable) changes to the secondary structure of the peptide. This review focuses on peptide hydrogels and related nanostructures, where α,β-didehydro-α-amino acids have been successfully incorporated into the structure of peptide hydrogelators, and the resulting properties are discussed in terms of their potential biomedical applications. Where appropriate, their properties are compared with those of the corresponding peptide hydrogelator composed of canonical amino acids. In a wider context, we consider the presence of dehydroamino acids in natural compounds and medicinally important compounds as well as their limitations, and we consider some of the synthetic strategies for obtaining dehydropeptides. Finally, we consider the future direction for this research area.This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding of CQUM (UID/QUI/00686/2019). FCT, FEDER, PORTUGAL2020 and COMPETE2020 are also acknowledged for funding under research project PTDC/QUI-QOR/29015/2017 (POCI-01-0145-FEDER-029015)