Spontaneous Formation of Cushioned Model Membranes Promoted by an Intrinsically Disordered Protein.

In this article, it is shown that by exposing commonly used lipids for biomembrane mimicking studies, to a solution containing the histidine-rich intrinsically disordered protein histatin 5, a protein cushion spontaneously forms underneath the bilayer. The underlying mechanism is attributed to have an electrostatic origin, and it is hypothesized that the observed behavior is due to proton charge fluctuations promoting attractive electrostatic interactions between the positively charged proteins and the anionic surfaces, with concomitant counterion release. Hence, we anticipate that this novel "green" approach of forming cushioned bilayers can be an important tool to mimic the cell membrane without the disturbance of the solid substrate, thereby achieving a further understanding of protein-cell interactions.

Gravimetric tank method to evaluate material-enhanced hydrogen storage by physisorbing materials.

The most common methods to evaluate hydrogen sorption (volumetric and gravimetric) require significant experience and expensive equipment for providing reproducible results. Both methods allow one to measure excess uptake values which are used to calculate the total amount of hydrogen stored inside of a tank as required for applications. Here we propose an easy to use and inexpensive alternative approach which allows one to evaluate directly the weight of hydrogen inside a material-filled test tank. The weight of the same tank filled with compressed hydrogen in the absence of loaded material is used as a reference. We argue that the only parameter which is of importance for hydrogen storage applications is by how much the material improves the total weight of hydrogen inside of the given volume compared to compressed gas. This parameter which we propose to name Gain includes both volumetric and gravimetric characterization of the material; it can be determined directly without knowing the skeletal volume of the material or excess sorption. The feasibility of the Gravimetric Tank (GT) method was tested using several common carbon and Metal Organic Framework (MOF) materials. The best Gain value of ∼12% was found for the Cu-BTC MOF which means that the tank completely filled with this material stores a 12% higher amount of hydrogen compared to H2 gas at the same P-T conditions. The advantages of the GT method are its inexpensive design, extremely simple procedures and direct results in terms of tank capacity as required for industrial applications. The GT method could be proposed as a standard check for verification of the high hydrogen storage capacity of new materials. The GT method is expected to provide even better accuracy for evaluation of a material's performance for storage of denser gases like e.g. CO2 and CH4.

A Molecular Pillar Approach To Grow Vertical Covalent Organic Framework Nanosheets on Graphene: Hybrid Materials for Energy Storage.

Hybrid 2D-2D materials composed of perpendicularly oriented covalent organic frameworks (COFs) and graphene were prepared and tested for energy storage applications. Diboronic acid molecules covalently attached to graphene oxide (GO) were used as nucleation sites for directing vertical growth of COF-1 nanosheets (v-COF-GO). The hybrid material has a forest of COF-1 nanosheets with a thickness of 3 to 15 nm in edge-on orientation relative to GO. The reaction performed without molecular pillars resulted in uncontrollable growth of thick COF-1 platelets parallel to the surface of GO. The v-COF-GO was converted into a conductive carbon material preserving the nanostructure of precursor with ultrathin porous carbon nanosheets grafted to graphene in edge-on orientation. It was demonstrated as a high-performance electrode material for supercapacitors. The molecular pillar approach can be used for preparation of many other 2D-2D materials with control of their relative orientation.

The role of pro-inflammatory S100A9 in Alzheimer's disease amyloid-neuroinflammatory cascade.

Pro-inflammatory S100A9 protein is increasingly recognized as an important contributor to inflammation-related neurodegeneration. Here, we provide insights into S100A9 specific mechanisms of action in Alzheimer's disease (AD). Due to its inherent amyloidogenicity S100A9 contributes to amyloid plaque formation together with Aß. In traumatic brain injury (TBI) S100A9 itself rapidly forms amyloid plaques, which were reactive with oligomer-specific antibodies, but not with Aß and amyloid fibrillar antibodies. They may serve as precursor-plaques for AD, implicating TBI as an AD risk factor. S100A9 was observed in some hippocampal and cortical neurons in TBI, AD and non-demented aging. In vitro S100A9 forms neurotoxic linear and annular amyloids resembling Aß protofilaments. S100A9 amyloid cytotoxicity and native S100A9 pro-inflammatory signaling can be mitigated by its co-aggregation with Aß, which results in a variety of micron-scale amyloid complexes. NMR and molecular docking demonstrated transient interactions between native S100A9 and Aß. Thus, abundantly present in AD brain pro-inflammatory S100A9, possessing also intrinsic amyloidogenic properties and ability to modulate Aß aggregation, can serve as a link between the AD amyloid and neuroinflammatory cascades and as a prospective therapeutic target.

Intercalation of Dyes in Graphene Oxide Thin Films and Membranes.

Intercalation of dyes into thin multilayered graphene oxide (GO) films was studied by neutron reflectivity and X-ray diffraction. Methylene blue (MB) penetrates the interlayer space of GO in ethanol solution and remains intercalated after the solvent evaporation, as revealed by the expansion of the interlayer lattice and change in chemical composition. The sorption of MB by thin GO films is found to be significantly stronger compared to the sorption of Crystal violet (CV) and Rose bengal (RB). This effect is attributed to the difference in the geometrical shape of planar MB and essentially nonflat CV and RB molecules. Graphite oxides and restacked GO films are found to exhibit different methylene blue (MB) sorptions. MB sorption by precursor graphite oxide and thin spin-coated films of GO is significantly stronger compared to freestanding micrometer-thick membranes prepared by vacuum filtration. Nevertheless, the sorption capacity of GO membranes is sufficient to remove a significant part of the MB from diluted solutions tested for permeation in several earlier studies. High sorption capacity results in strong modification of the GO structure, which is likely to affect permeation properties of GO membranes. Therefore, MB is not suitable for testing size exclusion effects in the permeation of GO membranes. It is not only hydration or solvation diameter but also the exact geometrical shape of molecules that needs to be taken into account considering size effects for penetration of molecules between GO layers in membrane applications.

Effect of nonionic and amphoteric surfactants on salivary pellicles reconstituted in vitro.

Surfactants are important components of oral care products. Sodium dodecyl sulfate (SDS) is the most common because of its foaming properties, taste and low cost. However, the use of ionic surfactants, especially SDS, is related to several oral mucosa conditions. Thus, there is a high interest in using non-ionic and amphoteric surfactants as they are less irritant. To better understand the performance of these surfactants in oral care products, we investigated their interaction with salivary pellicles i.e., the proteinaceous films that cover surfaces exposed to saliva. Specifically, we focused on pentaethylene glycol monododecyl ether (C12E5) and cocamidopropyl betaine (CAPB) as model nonionic and amphoteric surfactants respectively, and investigated their interaction with reconstituted salivary pellicles with various surface techniques: Quartz Crystal Microbalance with Dissipation, Ellipsometry, Force Spectroscopy and Neutron Reflectometry. Both C12E5 and CAPB were gentler on pellicles than SDS, removing a lower amount. However, their interaction with pellicles differed. Our work indicates that CAPB would mainly interact with the mucin components of pellicles, leading to collapse and dehydration. In contrast, exposure to C12E5 had a minimal effect on the pellicles, mainly resulting in the replacement/solubilisation of some of the components anchoring pellicles to their substrate.

A comparison between the structures of reconstituted salivary pellicles and oral mucin (MUC5B) films.

HYPOTHESIS: Salivary pellicles i.e., thin films formed upon selective adsorption of saliva, protect oral surfaces against chemical and mechanical insults. Pellicles are also excellent aqueous lubricants. It is generally accepted that reconstituted pellicles have a two-layer structure, where the outer layer is mainly composed of MUC5B mucins. We hypothesized that by comparing the effect of ionic strength on reconstituted pellicles and MUC5B films we could gain further insight into the pellicle structure. EXPERIMENTS: Salivary pellicles and MUC5B films reconstituted on solid surfaces were investigated at different ionic strengths by Force Spectroscopy, Quartz Crystal Microbalance with Dissipation, Null Ellipsometry and Neutron Reflectometry. FINDINGS: Our results support the two-layer structure for reconstituted salivary pellicles. The outer layer swelled when ionic strength decreased, indicating a weak polyelectrolyte behavior. While initially the MUC5B films exhibited a similar tendency, this was followed by a drastic collapse indicating an interaction between exposed hydrophobic domains. This suggests that mucins in the pellicle outer layer form complexes with other salivary components that prevent this interaction. Lowering ionic strength below physiological values also led to a partial removal of the pellicle inner layer. Overall, our results highlight the importance that the interactions of mucins with other pellicle components play on their structure.

Fabrication of microporous layer - free hierarchical gas diffusion electrode as a low Pt-loading PEMFC cathode by direct growth of helical carbon nanofibers.

Improving interfacial contact between each component in the proton exchange membrane fuel cell (PEMFC) can lead to a significant increase in power density and Pt utilization. In this work, the junction between the catalyst layer and gas diffusion layer (GDL) is greatly enhanced through direct attachment of helical carbon nanofibers, giving rise to a hierarchical structure within the electrical interconnections. The alternative novel GDL is produced by spraying a thin layer of Pd2C60 precursor on commercial carbon paper, followed by chemical vapor deposition growth resulting in a surface morphology of well-attached nanofibers surrounding the microfibers present in the commercial carbon paper. Subsequent solvothermal deposition of platinum nanoparticles allowed evaluation of its suitability as gas diffusion electrode in cathodic H2/O2 PEMFC environment. A combination of lowered charge transfer resistance and enhanced Pt-utilization is attributed to its unique wire-like appearance and its robust properties. The fabricated microporous layer - free GDL is suitable for relatively aggressive membrane electrode assembly fabrication procedures and is produced by industrially favorable techniques, rendering it capable of efficiently supporting small amounts of precious metal catalyst nanoparticles in various PEM applications.

Multilayered intercalation of 1-octanol into Brodie graphite oxide.

Multilayered intercalation of 1-octanol into the structure of Brodie graphite oxide (B-GO) was studied as a function of temperature and pressure. Reversible phase transition with the addition/removal of one layer of 1-octanol was found at 265 K by means of X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC). The same transition was observed at ambient temperature upon a pressure increase above 0.6 GPa. This transition was interpreted as an incongruent melting of the low temperature/high pressure B-GO intercalated structure with five layers of 1-octanol parallel to GO sheets (L-solvate), resulting in the formation of a four-layered structure that is stable under ambient conditions (A-solvate). Vacuum heating allows the removal of 1-octanol from the A-solvate layer by layer, while distinct sets of (00l) reflections are observed for three-, two-, and one-layered solvate phases. Step by step removal of the 1-octanol layers results in changes of distance between graphene oxide planes by ∼4.5 Å. This experiment proved that both L- and A-solvates are structures with layers of 1-octanol parallel to GO planes. Unusual intercalation with up to five distinct layers of 1-octanol is remarkably different from the behaviour of small alcohol molecules (methanol and ethanol), which intercalate B-GO structure with only one layer under ambient conditions and a maximum of two layers at lower temperatures or higher pressures. The data presented in this study make it possible to rule out a change in the orientation of alcohol molecules from parallel to perpendicular to the GO planes, as suggested in the 1960s to explain larger expansion of the GO lattice due to swelling with larger alcohols.

Structure of graphene oxide membranes in solvents and solutions.

The change of distance between individual graphene oxide sheets due to swelling is the key parameter to explain and predict permeation of multilayered graphene oxide (GO) membranes by various solvents and solutions. In situ synchrotron X-ray diffraction study shows that swelling properties of GO membranes are distinctly different compared to precursor graphite oxide powder samples. Intercalation of liquid dioxolane, acetonitrile, acetone, and chloroform into the GO membrane structure occurs with maximum one monolayer insertion (Type I), in contrast with insertion of 2-3 layers of these solvents into the graphite oxide structure. However, the structure of GO membranes expands in liquid DMSO and DMF solvents similarly to precursor graphite oxide (Type II). It can be expected that Type II solvents will permeate GO membranes significantly faster compared to Type I solvents. The membranes are found to be stable in aqueous solutions of acidic and neutral salts, but dissolve slowly in some basic solutions of certain concentrations, e.g. in NaOH, NaHCO3 and LiF. Some larger organic molecules, alkylamines and alkylammonium cations are found to intercalate and expand the lattice of GO membranes significantly, e.g. up to ∼35 Šin octadecylamine/methanol solution. Intercalation of solutes into the GO structure is one of the limiting factors for nano-filtration of certain molecules but it also allows modification of the inter-layer distance of GO membranes and tuning of their permeation properties. For example, GO membranes functionalized with alkylammonium cations are hydrophobized and they swell in non-polar solvents.

Hydrogen storage in high surface area graphene scaffolds.

Using an optimized KOH activation procedure we prepared highly porous graphene scaffold materials with SSA values up to 3400 m(2) g(-1) and a pore volume up to 2.2 cm(3) g(-1), which are among the highest for carbon materials. Hydrogen uptake of activated graphene samples was evaluated in a broad temperature interval (77-296 K). After additional activation by hydrogen annealing the maximal excess H2 uptake of 7.5 wt% was obtained at 77 K. A hydrogen storage value as high as 4 wt% was observed already at 193 K (120 bar H2), a temperature of solid CO2, which can be easily maintained using common industrial refrigeration methods.

Delamination of graphite oxide in a liquid upon cooling.

Graphite oxide (GO) in liquid acetonitrile undergoes a transition from an ordered phase around ambient temperature to a gel-like disordered phase at temperatures below 260 K, as demonstrated by in situ X-ray diffraction. The stacking order of GO layers is restored below the freezing point of acetonitrile (199 K). The reversible swelling transition between a stacked crystalline phase and an amorphous delaminated state observed upon cooling provides an unusual example of increased structural disorder at lower temperatures. The formation of the gel-like phase is attributed to the thermo-responsive conformational change of individual GO flakes induced by stronger solvation. Scanning force microscopy demonstrates that GO flakes deposited onto a solid substrate from acetonitrile dispersions at a temperature below 260 K exhibit corrugations and wrinkling which are not observed for the flakes deposited at ambient temperature. The thermo-responsive transition between the delaminated and stacked phases reported here can be used for sonication-free dispersion of graphene oxide, micro-container applications, or the preparation of new composite materials.