Graphene as an Electron Shuttle for Silver Deoxidation: Removing a Key Barrier to Plasmonics and Metamaterials for SERS in the Visible

The role of graphene in enabling deoxidation of silver nanostructures, thereby contributing to enhance plasmonic properties and to improve the temporal stability of graphene/silver hybrids for both general plasmonic and meta‐materials applications, as well as for surface enhanced Raman scattering (SERS) substrates, is demonstrated. The chemical mechanism occurring at the graphene–silver oxide interface is based on the reduction of silver oxide triggered by graphene that acts as a shuttle of electrons and as a kind of catalyst in the deoxidation. A mechanism is formulated, combining elements of electron transfer, role of defects in graphene, and electrochemical potentials of graphene, silver, and oxygen. Therefore, the formulated model represents a step forward from the simple view of graphene as barrier to oxygen diffusion proposed so far in literature. Single layer graphene grown by chemical vapor deposition is transferred onto silver thin films, a periodic silver fishnet structure fabricated by nanoimprint lithography, and onto silver nanoparticle ensembles supporting a localized surface plasmon resonance in the visible range. Through the study of these nanostructured graphene/Ag hybrids, the effectiveness of graphene in preventing and reducing oxidation of silver plasmonic structures, keeping silver in a metallic state over months at air exposure, is demonstrated. The enhanced and stable plasmonic properties of the silver‐fishnet/graphene hybrids are evaluated through their SERS response for detecting benzyl mercaptane.     

Fabrication of co‐continuous poly(ε‐caprolactone)/polyglycolide blend scaffolds for tissue engineering

The apparent inability of a single biomaterial to meet all the requirements for tissue engineering scaffolds has led to continual research in novel engineered biomaterials. One method to provide new materials and fine‐tune their properties is via mixing materials. In this study, a biodegradable powder blend of poly(ε‐caprolactone) (PCL), polyglycolide (PGA), and poly(ethylene oxide) (PEO) was prepared and three‐dimensional interconnected porous PCL/PGA scaffolds were fabricated by combining cryomilling and compression molding/polymer leaching techniques. The resultant porous scaffolds exhibited co‐continuous morphologies with ～50% porosity. Mean pore sizes of 24 and 56 μm were achieved by varying milling time. The scaffolds displayed high mechanical properties and water uptake, in addition to a remarkably fast degradation rate. The results demonstrate the potential of this fabrication approach to obtain PCL/PGA blend scaffolds with interconnected porosity. In general, these results provide significant insight into an approach that will lead to the development of new composites and blends in scaffold manufacturing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42471.     

Effect of particle size on arsenic bioaccessibility in gold mine tailings of Nova Scotia

Tailings samples from the Goldenville and Montague abandoned gold mines in Nova Scotia, Canada were subjected to bioaccessibility tests to examine the effects of the choice of particle size fraction on the bioaccessibility of arsenic. The proportion of finer grains (< 150 μm) in this sample set varied from 6.0 to 66 wt.%. Samples were sieved to < 250, < 150, and < 45 μm particle size fractions. The arsenic bioaccessibility ranged from less than 1.0 to 48%, but no systematic variation was observed (p > 0.13) precluding the association of greater percent arsenic bioaccessibility with a specific particle size fraction, method or site. On the other hand, the highest bioaccessible arsenic concentrations (up to 5200 mg kg^− 1) were consistently observed in samples sieved to the < 45 μm particle size, for both the physiologically based extraction test and a glycine-buffered bioaccessibility method (in 89 and 87% of samples tested, respectively). This was due to higher total arsenic concentrations in the same particle size fraction. Grain maps obtained by X-ray absorption spectroscopy indicate that samples with the highest percent arsenic bioaccessibility contain amorphous pentavalent arsenic distributed throughout the sample as well as grains coated with pentavalent arsenic. Arsenic bioaccessibilities lower than 10% were found in samples with encapsulated arsenopyrite and some grains composed primarily of pentavalent arsenic. The < 45 μm particle size fraction appears to yield conservative (protective) estimates of the bioaccessible dose of arsenic, but wide variations exist in particle size distribution and arsenic bioaccessibility between samples. As well, sieving to < 45 μm may exclude potentially relevant particles by restricting the study to an average particle size that is smaller than the average size of particles found on human hands, and may unduly influence the resulting bioaccessibility measurements.     

Is a vegan or a vegetarian diet associated with the microbiota composition in the gut? Results of a new cross-sectional study and systematic review

Abstract

It is assumed that diet influences the composition of gut microbiota, which in turn may affect human health status. This systematic review aimed to summarize associations of a vegan or vegetarian diet with the composition of microbiota. A literature search was conducted in PubMed and Embase for eligible human studies with vegan or vegetarian diets as an exposure and microbiota composition as an outcome in healthy adults. Furthermore, data from our cross-sectional study with vegan participants were included. Out of sixteen included studies, six investigated the association between gut microbiota composition in both vegans and in vegetarians, six in vegans and four studies in vegetarians compared to omnivores, respectively. Among 5 different phyla, 28 families, 96 genera and 177 species, Bacteroides, Bifidobacterium and Prevotella were the most reported genera, followed by the species Prevotella copri, Faecalibacterium prausnitzii and Escherichia coli in all diets. No consistent association between a vegan diet or vegetarian diet and microbiota composition compared to omnivores could be identified. Moreover, some studies revealed contradictory results. This result could be due to high microbial individuality, and/or differences in the applied approaches. Standardized methods with high taxonomical and functional resolutions are needed to clarify this issue.     

Does it make sense to modify tropical cyclones? A decision-analytic assessment

Recent dramatic increases in damages caused by tropical cyclones (TCs) and improved understanding of TC physics have led DHS to fund research on intentional hurricane modification. We present a decision analytic assessment of whether it is potentially cost-effective to attempt to lower the wind speed of TCs approaching South Florida by reducing sea surface temperatures with wind-wave pumps. Using historical data on hurricanes approaching South Florida, we develop prior probabilities of how storms might evolve. The effects of modification are estimated using a modern TC model. The FEMA HAZUS-MH MR3 damage model and census data on the value of property at risk are used to estimate expected economic losses. We compare wind damages after storm modification with damages after implementing hardening strategies protecting buildings. We find that if it were feasible and properly implemented, modification could reduce net losses from an intense storm more than hardening structures. However, hardening provides "fail safe" protection for average storms that might not be achieved if the only option were modification. The effect of natural variability is larger than that of either strategy. Damage from storm surge is modest in the scenario studied but might be abated by modification.     

Parade Game: Impact of Work Flow Variability on Trade Performance

The Parade Game illustrates the impact work flow variability has on the performance of construction trades and their successors. The game consists of simulating a construction process in which resources produced by one trade are prerequisite to work performed by the next trade. Production-level detail, describing resources being passed from one trade to the next, illustrates that throughput will be reduced, project completion delayed, and waste increased by variations in flow. The game shows that it is possible to reduce waste and shorten project duration by reducing the variability in work flow between trades. Basic production management concepts are thus applied to construction management. They highlight two shortcomings of using the critical-path method for field-level planning: The critical-path method makes modeling the dependence of ongoing activities between trades or with operations unwieldy and it does not explicitly represent variability. The Parade Game can be played in a classroom setting either by hand or using a computer. Computer simulation enables students to experiment with numerous alternatives to sharpen their intuition regarding variability, process throughput, buffers, productivity, and crew sizing. Managers interested in schedule compression will benefit from understanding work flow variability's impact on succeeding trade performance.     

Motion Analysis by Random Sampling and Voting Process

In computer vision, motion analysis is a fundamental problem. Applying the concepts of congruence checking in computational geometry and geometric hashing, which is a technique used for the recognition of partially occluded objects from noisy data, we present a new random sampling approach for the estimation of the motion parameters in two- and three-dimensional Euclidean spaces of both a completely measured rigid object and a partially occluded rigid object. We assume that the two- and three-dimensional positions of the vertices of the object in each image frame are determined using appropriate methods such as a range sensor or stereo techniques. We also analyze the relationships between the quantization errors and the errors in the estimation of the motion parameters by random sampling, and we show that the solutions obtained using our algorithm converge to the true solutions if the resolution of the digitalization is increased.     

Self-Assembly Nanoparticles of Natural Bioactive Abietane Diterpenes

Different approaches have been reported to enhance penetration of small drugs through physiological barriers; among them is the self-assembly drug conjugates preparation that shows to be a promising approach to improve activity and penetration, as well as to reduce side effects. In recent years, the use of drug-conjugates, usually obtained by covalent coupling of a drug with biocompatible lipid moieties to form nanoparticles, has gained considerable attention. Natural products isolated from plants have been a successful source of potential drug leads with unique structural diversity. In the present work three molecules derived from natural products were employed as lead molecules for the synthesis of self-assembled nanoparticles. The first molecule is the cytotoxic royleanone 7α-acetoxy-6β-hydroxyroyleanone (Roy, 1) that has been isolated from hairy coleus (Plectranthus hadiensis (Forssk.) Schweinf). ex Sprenger leaves in a large amount. This royleanone, its hemisynthetic derivative 7α-acetoxy-6β-hydroxy-12-benzoyloxyroyleanone (12BzRoy, 2) and 6,7-dehydroroyleanone (DHR, 3), isolated from the essential oil of thicket coleus (P. madagascariensis (Pers.) Benth.) were employed in this study. The royleanones were conjugated with squalene (sq), oleic acid (OA), and/or 1-bromododecane (BD) self-assembly inducers. Roy-OA, DHR-sq, and 12BzRoy-sq conjugates were successfully synthesized and characterized. The cytotoxic effect of DHR-sq was previously assessed on three human cell lines: NCI-H460 (IC₅₀ 74.0 ± 2.2 µM), NCI-H460/R (IC₅₀ 147.3 ± 3.7 µM), and MRC-5 (IC₅₀ 127.3 ± 7.3 µM), and in this work Roy-OA NPs was assayed against Vero-E6 cells at different concentrations (0.05, 0.1, and 0.2 mg/mL). The cytotoxicity of DHR-sq NPs was lower when compared with DHR alone in these cell lines: NCI-H460 (IC₅₀ 10.3 ± 0.5 µM), NCI-H460/R (IC₅₀ 10.6 ± 0.4 µM), and MRC-5 (IC₅₀16.9 ± 0.5 µM). The same results were observed with Roy-OA NPs against Vero-E6 cells as was found to be less cytotoxic than Roy alone in all the concentrations tested. From the obtained DLS results, 12BzRoy-sq assemblies were not in the nano range, although Roy-OA NP assemblies show a promising size (509.33 nm), Pdl (0.249), zeta potential (−46.2 mV), and spherical morphology from SEM. In addition, these NPs had a low release of Roy at physiological pH 7.4 after 24 h. These results suggest the nano assemblies can act as prodrugs for the release of cytotoxic lead molecules.     

Fetal Immunomodulatory Environment Following Cartilage Injury—The Key to CARTILAGE Regeneration?

Fetal cartilage fully regenerates following injury, while in adult mammals cartilage injury leads to osteoarthritis (OA). Thus, in this study, we compared the in vivo injury response of fetal and adult ovine articular cartilage histologically and proteomically to identify key factors of fetal regeneration. In addition, we compared the secretome of fetal ovine mesenchymal stem cells (MSCs) in vitro with injured fetal cartilage to identify potential MSC-derived therapeutic factors. Cartilage injury caused massive cellular changes in the synovial membrane, with macrophages dominating the fetal, and neutrophils the adult, synovial cellular infiltrate. Correspondingly, proteomics revealed differential regulation of pro- and anti-inflammatory mediators and growth-factors between adult and fetal joints. Neutrophil-related proteins and acute phase proteins were the two major upregulated protein groups in adult compared to fetal cartilage following injury. In contrast, several immunomodulating proteins and growth factors were expressed significantly higher in the fetus than the adult. Comparison of the in vitro MSCs proteome with the in vivo fetal regenerative signature revealed shared upregulation of 17 proteins, suggesting their therapeutic potential. Biomimicry of the fetal paracrine signature to reprogram macrophages and modulate inflammation could be an important future research direction for developing novel therapeutics.