We demonstrate the use of Scanning Electron microscopy (SEM) in combination with Surface Plasmon Resonance (SPR) to probe and verify the formation of amyloid and its morphology on an SPR chip. SPR is a technique that measures changes in the immobilized weight on the chip surface and is frequently used to probe the formation and biophysical properties of amyloid structures. In this context it is of interest to also monitor the morphology of the formed structures. The SPR chip surface is made of a layer of gold, which represent a suitable material for direct analysis of the surface using SEM. The standard SPR chip used here (CM5-chip, GE Healthcare, Uppsala, Sweden) can easily be disassembled and directly analyzed by SEM. In order to verify the formation of amyloid fibrils in our experimental conditions we analyzed also in-solution produced structures by using Transmission Electron Microscopy (TEM). For further details and experimental findings, please refer to the article published in Journal of Molecular Biology, (Brännström K. et al., 2018) [1].

Fibril formation of the amyloid-β peptide (Aβ) follows a nucleation-dependent polymerization process and is associated with Alzheimer's disease. Several different lengths of Aβ are observed in vivo, but Aβ1-40 and Aβ1-42 are the dominant forms. The fibril architectures of Aβ1-40 and Aβ1-42 differ and Aβ1-42 assemblies are generally considered more pathogenic. We show here that monomeric Aβ1-42 can be cross-templated and incorporated into the ends of Aβ1-40 fibrils, while incorporation of Aβ1-40 monomers into Aβ1-42 fibrils is very poor. We also show that via cross-templating incorporated Aβ monomers acquire the properties of the parental fibrils. The suppressed ability of Aβ1-40 to incorporate into the ends of Aβ1-42 fibrils and the capacity of Aβ1-42 monomers to adopt the properties of Aβ1-40 fibrils may thus represent two mechanisms reducing the total load of fibrils having the intrinsic, and possibly pathogenic, features of Aβ1-42 fibrils in vivo. We also show that the transfer of fibrillar properties is restricted to fibril-end templating and does not apply to cross-nucleation via the recently described path of surface-catalyzed secondary nucleation, which instead generates similar structures to those acquired via de novo primary nucleation in the absence of catalyzing seeds. Taken together these results uncover an intrinsic barrier that prevents Aβ1-40 from adopting the fibrillar properties of Aβ1-42 and exposes that the transfer of properties between amyloid-β fibrils are determined by their path of formation.

Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an approach to modulate the electronic structure of iron phosphide (FeP). The Fe vacancies were produced by chemical leaching of Mg that was introduced into FeP as "sacrificial dopant". The obtained Fe-vacancy-rich FeP nanoparticulate films, which were deposited on Ti foil, show excellent HER activity compared to pristine FeP and Mg-doped FeP, achieving a current density of 10 mAcm(-2) at overpotentials of 108 mV in 1 m KOH and 65 mV in 0.5 m H2SO4, with a near-100% Faradaic efficiency. Our theoretical and experimental analyses reveal that the improved HER activity originates from the presence of Fe vacancies, which lead to a synergistic modulation of the structural and electronic properties that result in a near-optimal hydrogen adsorption free energy and enhanced proton trapping. The success in catalytic improvement through the introduction of cationic vacancy defects has not only demonstrated the potential of Fe-vacancy-rich FeP as highly efficient, earth abundant HER catalyst, but also opens up an exciting pathway for activating other promising catalysts for electrochemical water splitting.

The development of efficient, durable, and inexpensive hydrogen evolution electrodes remains a key challenge for realizing a sustainable H-2 fuel production via electrocatalytic water splitting. Herein, nickel-iron phosphide porous films with precisely controlled metal content were synthesized on Ti foil using a simple and scalable two-step strategy of spray-pyrolysis deposition followed by low-temperature phosphidation. The nickel-iron phosphide of an optimized Ni:Fe ratio of 1:4 demonstrated excellent overall catalytic activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4, achieving current densities of -10 and -30 mA cm(-2) at overpoteritials of 101 and 123 mV, respectively, with a Tafel slope of 43 mV dec(-1). Detailed analysis obtained by X-ray diffraction, electron microscopy, electrochemistry, and X-ray photoelectron spectroscopy revealed that the superior overall HER activity of nickel iron phosphide as compared to nickel phosphide and iron phosphide was a combined effect of differences in the morphology (real surface area) and the intrinsic catalytic properties (electronic structure). Together with a long-term stability and a near-100% Faradaic efficiency, the nickel-iron phosphide electrodes produced in this study provide blueprints for large-scale H-2 production.

Oxygen evolution catalysts (OEC) are often employed on the surface of photoactive, semiconducting photoanodes to boost their kinetics and stability during photoelectrochemical water oxidation. However, the necessity of using optically transparent OEC to avoid parasitic light absorption by the OEC under front-side illumination is often neglected. Here, we show that furnishing the surface of a WO3 photoanode with suitable loading of FeOOH as a transparent OEC improved the photocurrent density by 300% at 1 V versus RHE and the initial photocurrent-to-O-2 Faradaic efficiency from similar to 70 to similar to 100%. The data from the photo-voltammetry, electrochemical impedance, and gas evolution measurements these improvements were a combined result of reduced hole-transfer resistance for water oxidation, minimized surface recombination of charge carriers, and improved stability against photocorrosion of WO3. We demonstrate the utility of transparent FeOOH-coated W(O)3 in a solar-powered, tandem water-splitting device by combining it with a double-junction Si solar cell and a Ni-Mo hydrogen evolution catalyst. This device performed at a solar-to-hydrogen conversion efficiency of 1.8% in near-neutral K2SO4 electrolyte.

Stable and efficient oxygen evolution reaction (OER) catalysts for the oxidation of water to dioxygen in highly acidic media are currently limited to expensive noble metal (Ir and Ru) oxides since presently known OER catalysts made of inexpensive earth-abundant materials generally suffer anodic corrosion at low pH. In this study, we report that a mixed-polymorph film comprising maghemite and hematite, prepared using spray pyrolysis deposition followed by low-temperature annealing, showed a sustained OER rate (>24 h) corresponding to a current density of 10 mA cm−2 at an initial overpotential of 650 mV, with a Tafel slope of only 56 mV dec−1 and near-100% Faradaic efficiency in 0.5 M H2SO4 (pH 0.3). This performance is remarkable, since iron (III) oxide films comprising only maghemite were found to exhibit a comparable intrinsic activity, but considerably lower stability for OER, while films of pure hematite were OER-inactive. These results are explained by the differences in the polymorph crystal structures, which cause different electrical conductivity and surface interactions with water molecules and protons. Our findings not only reveal the potential of iron (III) oxide as acid-stable OER catalyst, but also highlight the important yet hitherto largely unexplored effect of crystal polymorphism on electrocatalytic OER performance.

Earth-abundant cobalt-doped hematite thin-film electrocatalysts were explored for acidic water oxidation. The strategically doped hematite produced a stable geometric current density of 10 mA cm(-2) for up to 50 h at pH 0.3, as a result of Co-enhanced intrinsic catalytic activity and charge transport properties across the film matrix.

Hydrated clay minerals that are common to Earth’s atmosphere and terrestrial and aquatic environments can form gels that host saline solutions. Using cryogenic electron microscopy and vibration spectroscopy, we show that saline gels of montmorillonite frozen at < −90 °C host elongated hexagonal ice (Ih) microcrystals embedded in a network of honeycomb micropores. Freezing segregates salts into walls of aggregated clay nanoparticles sharing face-to-face contacts. Above ∼ −50 °C, clay gels that are sufficiently dense (≫10 g/L) and flexible (Na-exchanged montmorillonite) also host the cryosalt mineral hydrohalite (NaCl·2H2O), either co-existing or entirely replacing Ih in the gels. Hydrohalite does not form in gels of low-density (<10 g/L) or rigid (Ca-exchange montmorillonite) clay particles. These results suggest that hydrohalite forms in expandable clay gels that are sufficiently dense and flexible to retain saline solutions within their walls, possibly through interparticle capillary and hydration forces. These forces effectively oppose water diffusion to growing ice microcrystals within micropores, thus prolonging the lifetime of hydrohalite within these hydrated clay gels. Our findings tie the fate of ice and cryosalt nucleation and growth to the water-retention capability of expandable clay gels.