Abstract: The irreversible release of the lattice oxygen in layered cathodes is one of the major degradation mechanisms of lithium ion batteries, which accounts for a number of battery failures including the voltage/capacity fade, loss of cation ions and detachment of the primary particles, etc. Oxygen release is generally attributed to the stepwise thermodynamic controlled phase transitions from the layered to spinel and rock salt phases. Here, we report a strong kinetic effect from the mobility of cation ions, whose migration barrier can be significantly modulated by the phase epitaxy at the degrading interface. It ends up with a clear oxygen release heterogeneity and completely different reaction pathways between the thin and thick areas, as well as the interparticle valence boundaries, both of which widely exist in the mainstream cathode design with the secondary agglomerates. This work unveils the origin of the heterogenous oxygen release in the layered cathodes. It also sheds light on the rational design of cathode materials with enhanced oxygen stability by suppressing the cation migration.

Abstract: Urban environments typically exhibit large atmospheric pollution variation, in both space and time. In contrast to traditional monitoring networks suffering from a limited spatial coverage, mobile platforms enable personalized high-resolution monitoring, providing valuable insights into personal atmospheric pollution exposure, and the identification of potential pollution hotspots. This study evaluated personal cyclist exposure to UFPs, BC and heavy metals whilst commuting near Antwerp, Belgium, by performing mobile measurements with wearable black carbon (BC) and ultrafine particle (UFP) instruments. Loaded micro-aethalometer filterstrips were chemically analysed and the inhaled pollutant dose determined from the exhibited heart rate. Considerable spatial pollutant variation was observed along the travelled routes, with distinct contributions from spatial factors (e.g. traffic intersections, urban park and market) and temporary events. On average 300% higher BC, 20% higher UFP and changing elemental concentrations are observed along the road traffic route (RT), when compared to the bicycle highway route (BH). Although the overall background pollution determines a large portion of the experienced personal exposure (in this case 53% for BC and 40% for UFP), cyclists can influence their personal atmospheric pollution exposure, by selecting less exposed commuting routes. Our results, hereby, strengthen the body of evidence in favour of further policy investments in isolated bicycle infrastructure.

Abstract: This paper conducts a meta-analysis of 32 electricity demand response programs in the residential sector to understand whether their success is dependent on specific characteristics. The paper analyses several regression models using various combinations of variables that capture the designs of the programs and the socio-economic conditions in which the programs are implemented. The analysis reveals that demand response programs are more likely to succeed in highly urbanized areas, in areas where economic growth rates are high, and in areas where the renewable energy policy is favorable. These findings provide useful guidance in determining where and how to implement future demand response programs.

Abstract: Despite modern therapeutic advances, the survival prospects of pancreatic cancer patients remain poor, due to chemoresistance and dysregulated oncogenic kinase signaling networks. We applied a novel kinome activitymapping approach using biological peptide targets as phospho-sensors to identify vulnerable kinase de­pendencies for therapy sensitization by physical plasma. Ser/Thr-kinome specific activity changes were mapped upon induction of ferroptotic cell death in pancreatic tumor cells exposed to reactive oxygen and nitrogen species of plasma-treated water (PTW). This revealed a broad kinome activity response involving the CAMK, the AGC and CMGC family of kinases. This systems-level kinome network response supports stress adaptive switches between chemoresistant anti-oxidant responses of Kelch-like ECH-associated protein 1 (KEAP1)/Heme Oxy­genase 1 (HMOX1) and ferroptotic cell death sensitization upon suppression of Nuclear factor (erythroid derived 2)-like 2 (NRF2) and Glutathione peroxidase 4 (GPX4). This is further supported by ex vivo experiments in the chicken chorioallantoic membrane assay, showing decreased GPX4 and Glutathione (GSH) expression as well as increased lipid peroxidation, along with suppressed BxPC-3 tumor growth in response to PTW. Taken all together, we demonstrate that plasma treated water-derived oxidants sensitize pancreatic cancer cells to fer­roptotic cell death by targeting a NRF2-HMOX1-GPX4 specific kinase signaling network.

Abstract: Clathrate hydrates gained significant attention as a viable option for large-scale storage of natural gas, primarily methane (CH4). Unlike employing the nanoconfinement for enhancing the nucleation sites and hydrate growth as in the porous materials, whose synthesis is often associated with high costs and poor batch reproducibility, a new approach for promoting CH4 hydrates using pure water (H2O) in an unstirred reactor packed with stainless steel beads (SSB) was proposed in this fundamental work, where the interstitial space between the beads was exploited for enhanced hydrate growth. SSB of two diameters, 5 mm and 2 mm, were used as. a packed bed to investigate their effects on CH4 hydrate formation at 273.65 K, 275.65 K, and 277.65 K with an initial pressure of 6 MPa. The thermal conductivity of SSB packing potentially aided hydrate growth by expelling the hydration heat, while, the results also revealed that driving force has a substantial impact on the rate of CH4 hydrate formation and gas uptake. The experiments conducted in both 5 mm and 2 mm SSB packed bed reactors showed a maximum gas uptake of 0.147 mol CH4/mol H2O at 273.65 K with water to hydrate conversion of 84.42% with no significant variation. The results established the promotion effect on the kinetics of CH4 hydrate formation in the unstirred reactor packed with 2 mm SSB due to the availability of more interstitial space offering multiple nucleation sites for CH4 hydrate by providing a larger specific surface area for H2O-CH4 reaction. Experiments with varying H2O content were also performed and the results showed that the water to hydrate conversion and rate of hydrate formation could be enhanced at a lower H2O content in a packed bed reactor. This study demonstrates that the use of costly or intricate porous materials can be made redundant, by exploiting the interstitial voids in packing of cheap and widely available SSB as a promising alternative material for enhancing the kinetics of artificial CH4 hydrate synthesis.

Abstract: Methane (CH4) clathrate hydrates have gained much attention in the ever-growing search for novel energy storage methods; however, they are currently limited due to their poor water-to-hydrate conversions and slow formation kinetics. To surmount these bottlenecks, significant research has been centered on the design of novel methods (porous media). In this vein, the present work explores two hydrophobic mesoporous solids, an alkyl-grafted mesoporous silica (SBA-15 C8) and a periodic mesoporous organosilica (Ring-PMO), in their ability to promote CH4 clathrates. Both materials have shown to facilitate CH4 clathrate formation at mild operating conditions (6 MPa and 269–276 K). The study revealed that the maximal CH4 storage capacities are strongly linked to the critical/optimal quantity of water in the system which was determined to be at 130% and 200% of the pore volume for SBA-15 C8 and Ring-PMO, respectively. Up to 90% and 95% of the maximum water-to-hydrate conversions were achieved in 90 min at the lowest experimental temperature and critical water content for SBA-15 C8 and Ring-PMO, respectively. At these conditions, SBA-15 C8 and Ring-PMO showed a maximum gas uptake of 98.2 and 101.2 mmol CH4/mol H2O, respectively. Both the materials exhibited no chemical or morphological changes post-clathrate formations (characterized using FT-IR, N2 sorption, XRD, and TEM), inferring their viability as clathrate promoters for multiple cycles. An integrated multistep model was considered adequate for representing the hydrate crystallization kinetics and fits well with the experimental kinetic data with a low average absolute deviation in water-to-hydrate conversions among the three distinct kinetic models analyzed. Overall, the results from this study demonstrate hydrophobic porous materials as effective promoters of CH4 clathrates, which could make clathrate-based CH4 storage and transport technology industrially viable.

Abstract: There is convincing evidence for a scaling relationship between leaf dry weight (DW) and leaf surface area (A) for broad-leaved plants, and most estimates of the scaling exponent of DW vs. A are greater than unity. However, the scaling relationship of leaf fresh weight (FW) vs. A has been largely neglected. In the present study, we examined whether there is a statistically strong scaling relationship between FW and A and compared the goodness of fit to that of DW vs. A. Between 250 and 520 leaves from each of 12 bamboo species within 2 genera (Phyllostachys and Pleioblastus) were investigated. The reduced major axis regression protocols were used to determine scaling relationships. The fit for the linearized scaling relationship of FW vs. A was compared with that of DW vs. A using the coefficient of determination (i.e., r2). A stronger scaling relationship between FW and A than that between DW and A was observed for each of the 12 bamboo species investigated. Among the 12 species examined, five had significantly smaller scaling exponents of FW vs. A compared to those of DW vs. A; only one species had a scaling exponent of FW vs. A greater than that of DW vs. A. No significant difference between the two scaling exponents was observed for the remaining 6 species. Researchers conducting future studies might be well advised to consider the influence of leaf fresh weight when exploring the scaling relationships of foliar biomass allocation patterns.

Abstract: Current cross-sectional methodologies measuring climate change impacts assume that regions at the same latitude face a similar climate response and therefore have the same adaptive capacity. This paper proves that assumption to be erroneous in the European Union. It does so by ameliorating the Ricardian methodology by restricting which farmers (and therefore which adaptation options) are allowed in the dataset. In doing so, a comparative Ricardian methodology is suggested that makes it possible to examine, for the first time, how the climate responsiveness of a region changes if adaptive capacity changes. The paper combines climate, soil, geographic, socio-economic, and farm-level data in a linear mixed-effect model and examines whether Eastern and Western Europe have the same climate responses and how these responses change if regional adaptive capacity increases. The paper concludes that both regions currently have a significantly different climate response, but that if Eastern Europe were to implement the same adaptation options as Western Europe, it could avoid a large decrease in land value and even benefit from climate change depending on the climate scenario.

Abstract: Understanding the folding and stability of membrane proteins is of great importance in protein science. Recently, osmolytes and ionic liquids (ILs) are increasingly being used as drug delivery systems in the biopharmaceutical industry. However, the stability of membrane proteins in the presence of osmolytes and ILs is not yet fully understood. Besides, the effect of oxidative stress on membrane proteins with osmolytes or ILs has not been investigated. Therefore, we studied the influence of osmolytes and ILs as co-solvents on the stability of a model membrane protein (i.e., Bacteriorhodopsin in purple membrane of Halobacterium salinarum), using UV–Vis spectroscopy and molecular dynamics (MD) simulations. The MD simulations allowed us to determine the flexibility and solvent accessible surface area (SASA) of Bacteriorhodopsin protein in the presence and/or absence of cosolvents, as well as to carry out principal component analysis (PCA) to identify the most important movements in this protein. In addition, by means of UV–Vis spectroscopy we studied the effect of oxidative stress generated by cold atmospheric plasma on the stability of Bacteriorhodopsin in the presence and/or absence of co-solvents. This study is important for a better understanding of the stability of proteins in the presence of oxidative stress.

Abstract: NADPH oxidases 1 (NOX1) derived reactive oxygen species (ROS) play an important role in the progression of cancer through signaling pathways. Therefore, in this paper, we demonstrate the effect of cold atmospheric plasma (CAP) on the structural changes of Noxa1 SH3 protein, one of the regulatory subunits of NOX1. For this purpose, firstly we purified the Noxa1 SH3 protein and analyzed the structure using X-ray crystallography, and subsequently, we treated the protein with two types of CAP reactors such as pulsed dielectric barrier discharge (DBD) and Soft Jet for different time intervals. The structural deformation of Noxa1 SH3 protein was analyzed by various experimental methods (circular dichroism, fluorescence, and NMR spectroscopy) and by MD simulations. Additionally, we demonstrate the effect of CAP (DBD and Soft Jet) on the viability and expression of NOX1 in A375 cancer cells. Our results are useful to understand the structural modification/oxidation occur in protein due to reactive oxygen and nitrogen (RONS) species generated by CAP.

Abstract: While the microstructure of a metal is well-known to affect its equilibrium hydrogen uptake and therefore the hydriding thermodynamics, microstructural effects on the hydriding kinetics are much less documented. Moreover, for thin film systems, such microstructural effects are difficult to separate from the internal stress effect, since most defects generate internal stresses. Such a decoupling has been achieved in this paper for nanocrystalline Pd thin film model systems through the use of a high-resolution, in-situ curvature measurement set-up during Pd deposition, annealing and hydriding. This set-up allowed producing Pd thin films with similar internal stress levels but significantly different microstructures. This was evidenced from detailed defect statistics obtained by transmission electron microscopy, which showed that the densities of grain boundaries, dislocations and twin boundaries have all been lowered by annealing. The same set-up was then used to study the hydriding equilibrium and kinetic behaviour of the resulting films at room temperature. A full quantitative analysis of their hydriding cycles showed that the rate constants of both the adsorption- and absorption-limited kinetic regimes were strongly affected by microstructure. Defect engineering was thereby shown to increase the rate constants for hydrogen adsorption and absorption in Pd by a factor 40 and 30, respectively. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Abstract: In the recent advances towards more sustainable global energy supply, H2 is a possible alternative for large scale energy storage. In this view, Liquid Organic Hydrogen Carriers (LOHC) are a class of molecules that allow for easier long term energy storage compared to conventional H2 technologies. CFD simulations were used to showcase the hydrodynamics of the dehydrogenation of a LOHC in a new reactor unit, via a cold flow mock-up study. This reactor was designed to allow for a swirling motion of the liquid carrier material, favouring the removal of H2 gas from the flow and forcing the equilibrium of the reaction towards dehydrogenation, as well as to keep the catalyst particles in motion. The CFD simulations were validated qualitatively with experimental operation of the reactor, in a system with identical dimensionless numbers (Reynolds and Stokes), in order to use less costly products during the prototyping phase.

Abstract: The impact of graphene reinforcement on the mechanical properties of metals has been a subject of intense investigation over the last decade in surface applications to mitigate the impact of tribological loadings or for strengthening purposes when dispersed into a bulk material. Here, the effect on the plastic indentation response of a single graphene layer grown on copper is analyzed for two configurations: one with graphene at the surface, the other with graphene sandwiched under a 100 nm thick copper cap layer. Nanoindentation under both displacement and load control conditions show both earlier and shorter pop-in excursions compared to systems without graphene. Atomic force microscopy reveals much smoother pile-ups with no slip traces in the presence of a surface graphene layer. The configuration with the intercalated graphene layer appears as an ideal elementary system to address bulk hardening mechanisms by indentation testing. Transmission electron microscopy (TEM) cross-sections below indents show more diffuse and homogeneous dislocation activity in the presence of graphene. 3D dislocation dynamics simulations allow unraveling of the origin of these 3D complex phenomena and prove that the collective dislocation mechanisms are dominantly controlled by the strong back stress caused by the graphene barrier. These results provide a quantitative understanding of the impact of graphene on dislocation mechanisms for both surface and bulk applications, but with an impact that is not as large as anticipated from other studies or general literature claims.

Abstract: Biomass fast pyrolysis has been considered one of the best alternatives for the thermal conversion of biomass into bio-oil. This work introduces a new reactor technology for biomass fast pyrolysis, the Gas-Solid Vortex Reactor (GSVR), to obtain high bio-oil yields. The GSVR was designed to decrease the residence time of the pyrolysis vapors; thus, the secondary cracking reactions are reduced, to enhance the segregation of the char and the unreacted biomass and to improve the heat transfer rate. Biomass fast pyrolysis experiments have been carried out for the first time in a Gas-Solid Vortex Reactor (GSVR) at 773 K, using softwood (pine) and hardwood (poplar) as feedstock. Char yields as low as 10 wt. % in the GSVR were comparable to those reported for the same feedstocks processed in conventional fluidized bed reactors. The yields of non-condensable gases in the range of 15–17 wt. % were significantly lower than those reported for other commonly used biomass fast pyrolysis reactors. Two-dimensional gas chromatography (GC × GC) revealed noticeable differences at the molecular level between the bio-oils from the GSVR and bio-oils from other reactors. The aromatics in the pine bio-oil consist almost entirely (85 wt. %) of guaiacols. For poplar bio-oils no predominant group of aromatics was found, but phenolics, syringols, and catechols were the most pronounced. The experimental results highlight the advantages of the GSVR for biomass pyrolysis, reaching stable operation in around 60 s, removing the formed char selectively during operation, and enabling fast entrainment of pyrolysis vapors. Results indicate a great potential for increasing yield and selectivity towards guaiacols in softwood (e.g., pine) bio-oil. Likewise, decreasing pyrolysis temperature could increase the yield of guaiacols and syringols in hardwood (e.g., poplar) bio-oil.