The Space Confinement Approach Using Hollow Graphitic Spheres to Unveil Activity and Stability of Pt‐Co Nanocatalysts for PEMFC

The performance of polymer electrolyte fuel cells is strongly correlated to the electrocatalytic activity and stability. In particular, the latter is the result of an interplay between different degradation mechanisms. The essential high stability, demanded for real applications, requires the synthesis of advanced electrocatalysts that withstand the harsh operation conditions. In the first part of this study, the synthesis of oxygen reduction electrocatalysts consisting of Pt‐Co (i.e., Pt₅Co, Pt₃Co, and PtCo) alloyed nanoparticles encapsulated in the mesoporous shell of hollow graphitic spheres (HGS) is reported. The mass activities of the activated catalysts depend on the initial alloy composition and an activity increase on the order of two to threefold, compared to pure Pt@HGS, is achieved. The key point of the second part is the investigation of the degradation of PtCo@HGS (showing the highest activity). Thanks to pore confinement, the impact of dissolution/dealloying and carbon corrosion can be studied without the interplay of other degradation mechanisms that would induce a substantial change in the particle size distribution. Therefore, impact of the upper potential limit and the scan rates on the dealloying and electrochemical surface area evolution can be examined in detail.     

Individual-based modeling of phytoplankton: evaluating approaches for applying the cell quota model

Present phytoplankton models typically use a population-level (lumped) modeling (PLM) approach that assumes average properties of a population within a control volume. For modern biogeochemical models that formulate growth as a nonlinear function of the internal nutrient (e.g. Droop kinetics), this averaging assumption can introduce a significant error. Individual-based (agent-based) modeling (IBM) does not make the assumption of average properties and therefore constitutes a promising alternative for biogeochemical modeling. This paper explores the hypothesis that the cell quota (Droop) model, which predicts the population-average specific growth or cell division rate, based on the population-average nutrient cell quota, can be applied to individual algal cells and produce the same population-level results. Three models that translate the growth rate calculated using the cell quota model into discrete cell division events are evaluated, including a stochastic model based on the probability of cell division, a deterministic model based on the maturation velocity and fraction of the cell cycle completed (maturity fraction), and a deterministic model based on biomass (carbon) growth and cell size. The division models are integrated into an IBM framework (iAlgae), which combines a lumped system representation of a nutrient with an individual representation of algae. The IBM models are evaluated against a conventional PLM (because that is the traditional approach) and data from a number of steady and unsteady continuous (chemostat) and batch culture laboratory experiments. The stochastic IBM model fails the steady chemostat culture test, because it produces excessive numerical randomness. The deterministic cell cycle IBM model fails the batch culture test, because it has an abrupt drop in cell quota at division, which allows the cell quota to fall below the subsistence quota. The deterministic cell size IBM model reproduces the data and PLM results for all experiments and the model parameters (e.g. maximum specific growth rate, subsistence quota) are the same as those for the PLM. In addition, the model-predicted cell age, size (carbon) and volume distributions are consistent with those derived analytically and compare well to observations. The paper discusses and illustrates scenarios where intra-population variability in natural systems leads to differences between the IBM and PLM models.     

Highly Efficient Semiconductor-Based Metasurface for Photoelectrochemical Water Splitting: Broadband Light Perfect Absorption with Dimensions Smaller than the Diffusion Length

Plasmonics - In this paper, we demonstrate a highly efficient light trapping design that is made of a metal-oxide-semiconductor-semiconductor (nanograting/nanopatch) (MOSSg/p) four-layer design to...     

Use of Agent-Based Modeling To Explore the Mechanisms of Intracellular Phosphorus Heterogeneity in Cultured Phytoplankton

There can be significant intraspecific individual-level heterogeneity in the intracellular P of phytoplankton, which can affect the population-level growth rate. Several mechanisms can create this heterogeneity, including phenotypic variability in various physiological functions (e.g., nutrient uptake rate). Here, we use modeling to explore the contribution of various mechanisms to the heterogeneity in phytoplankton grown in a laboratory culture. An agent-based model simulates individual cells and their intracellular P. Heterogeneity is introduced by randomizing parameters (e.g., maximum uptake rate) of daughter cells at division. The model was calibrated to observations of the P quota of individual cells of the centric diatom Thalassiosira pseudonana, which were obtained using synchrotron X-ray fluorescence (SXRF). A number of simulations, with individual mechanisms of heterogeneity turned off, then were performed. Comparison of the coefficient of variation (CV) of these and the baseline simulation (i.e., all mechanisms turned on) provides an estimate of the relative contribution of these mechanisms. The results show that the mechanism with the largest contribution to variability is the parameter characterizing the maximum intracellular P, which, when removed, results in a CV of 0.21 compared to a CV of 0.37 with all mechanisms turned on. This suggests that nutrient/element storage capabilities/mechanisms are important determinants of intrapopulation heterogeneity.     

GC-MS methods for metabolic profiling of microbial fermentation products of dietary polyphenols in human and in vitro intervention studies

Flavonoids, a subclass of polyphenols, are major constituents of many plant-based foods and beverages, including tea, wine and chocolate. Epidemiological studies have shown that a flavonoid-rich diet is associated with reduced risk of cardiovascular diseases. The majority of the flavonoids survive intact until they reach the colon where they are then extensively metabolized into smaller fragments. Here, we describe the development of GC-MS-based methods for the profiling of phenolic microbial fermentation products in urine, plasma, and fecal water. Furthermore, the methods are applicable for profiling products obtained from in vitro batch culture fermentation models. The methods incorporate enzymatic deconjugation, liquid-liquid extraction, derivatization, and subsequent analysis by GC-MS. At the level of individual compounds, the methods gave recoveries better than 80% with inter-day precision being better than 20%, depending on the matrix. Limits of detection were below 0.1mug/ml for most phenolic acids. The newly developed methods were successfully applied to samples from human and in-vitro intervention trials, studying the metabolic impact of flavonoid intake. In conclusion, the methods presented are robust and generally applicable to diverse biological fluids. Its profiling character is useful to investigate on a large scale the gut microbiome-mediated bioavailability of flavonoids.     

Equivalent Porous Media (EPM) Simulation of Groundwater Hydraulics and Contaminant Transport in Karst Aquifers

Karst aquifers have a high degree of heterogeneity and anisotropy in their geologic and hydrogeologic properties which makes predicting their behavior difficult. This paper evaluates the application of the Equivalent Porous Media (EPM) approach to simulate groundwater hydraulics and contaminant transport in karst aquifers using an example from the North Coast limestone aquifer system in Puerto Rico. The goal is to evaluate if the EPM approach, which approximates the karst features with a conceptualized, equivalent continuous medium, is feasible for an actual project, based on available data and the study scale and purpose. Existing National Oceanic Atmospheric Administration (NOAA) data and previous hydrogeological U. S. Geological Survey (USGS) studies were used to define the model input parameters. Hydraulic conductivity and specific yield were estimated using measured groundwater heads over the study area and further calibrated against continuous water level data of three USGS observation wells. The water-table fluctuation results indicate that the model can practically reflect the steady-state groundwater hydraulics (normalized RMSE of 12.4%) and long-term variability (normalized RMSE of 3.0%) at regional and intermediate scales and can be applied to predict future water table behavior under different hydrogeological conditions. The application of the EPM approach to simulate transport is limited because it does not directly consider possible irregular conduit flow pathways. However, the results from the present study suggest that the EPM approach is capable to reproduce the spreading of a TCE plume at intermediate scales with sufficient accuracy (normalized RMSE of 8.45%) for groundwater resources management and the planning of contamination mitigation strategies.     

Generation and characterization of inner photoreceptor-specific enhancer-trap lines using a novel piggyBac-Gal4 element in Drosophila

The Drosophila inner photoreceptors R7 and R8 are responsible for color vision and their differentiation starts at the third instar larval stage. Only a handful of genes with R7 or R8-cell-specific expression are known. We performed an enhancer-trap screen using a novel piggyBac transposable element, pBGay, carrying a Gal4 sequence under the control of the P promoter to identify novel genes expressed specifically in R7 or R8 cells. From this screen, three lines were analyzed in detail: piggyBac^AC109 and piggyBac^AC783 are expressed in R8 cells and piggyBac^AC887 is expressed in R7 cells at the third instar larval stage and pupal stages. Molecular analysis showed that the piggyBac elements were inserted into the first intron of CG14160 and CG7985 genes and the second intron of unzipped. We show the expression pattern in the developing eye imaginal disc, pupal retina as well as the adult retina. The photoreceptor-specific expression of these genes is reported for the first time and we propose that these lines are useful tools for studying the development of the visual system.     

Drosophila crumbs is required to inhibit light-induced photoreceptor degeneration

Mutations in the human transmembrane protein CRB1 are associated with severe forms of retinal dystrophy, retinitis pigmentosa 12 (RP12), and Leber's congenital amaurosis (LCA). The Drosophila homolog, crumbs, is required for polarity and adhesion in embryonic epithelia and for correct formation of adherens junctions and proper morphogenesis of photoreceptor cells. Here, we show that mutations in Drosophila crumbs result in progressive, light-induced retinal degeneration. Degeneration is prevented by expression of p35, an inhibitor of apoptosis, or by reduction of rhodopsin levels through a vitamin A-deficient diet. In the dark, rhabdomeres survive but exhibit morphogenetic defects. We demonstrate that it is the extracellular portion of the Crumbs protein that is essential to suppress light-induced programmed cell death, while proper morphogenesis depends on the intracellular part. We conclude that human and Drosophila Crumbs proteins are functionally conserved to prevent light-dependent photoreceptor degeneration. This experimental system is now ideally suited to study the genetic and molecular basis of RP12- and LCA-related retinal degeneration.