Electric field strength effects on time-dependent passivation of metal surfaces

This paper presents further results and extensions of our previous point defect model for time-dependent growth of passive oxide films on metal surfaces. Specifically, by accounting for vacancies as material species rather than just holes in the oxide lattice, the model incorporates more plausible expressions for interfacial reactions and associated kinetic rate expressions. We use the model to explore the general effects of varying metal valence and electrolyte pH on passive film growth. Furthermore, we examine key assumptions concerning the thickness dependence of the electric field within the film. When the electric field inside the film remains constant and the rate constant for oxygen vacancy production varies with applied potential, the model predicts trends in thickness versus potential in reasonable agreement with experimental data for a variety of metal/metal oxide systems. This represents a considerable improvement upon the previous ‘high-field’ form of the model which assumed rate constants independent of potential and electric field in the film varying with thickness.     

Fabrication of strong and ultra-lightweight silica-based aerogel materials with tailored properties

Cross-linked silica aerogels are promising, strong, lightweight materials for photolithographic applications. The work presented here details the preparation of ultra-lightweight aerogel materials with tailored properties through the appropriate combination of silica and methacrylate polymer using laser-induced rapid photogelation fabrication technique. For fabrication, an ethanolic solution of hexanediol diacrylate, tetraorthosilicate, Eosin Y and a tertiary amine was prepared. The amounts of reactants were varied to prepare different compositions of aerogel monoliths. The solution was irradiated with a green beam from a low power laser source. The samples, after drying in supercritical ethanol, were characterized using FTIR, BET, SEM, TGA, and a mechanical testing instrument. FTIR data suggests that neither low nor high silica content has an effect on the reactivity of acrylate functionalities during polymer formation. SEM micrographs reveal that variation in silica or polymer content does not produce any phase-separated structures. Instead, uniformly distributed nano-sized polymer–silica structures were obtained for all compositions. Our results suggest that a variety of combinations of mechanical and other properties (such as densities, surface areas, pore sizes, and pore volumes) can be produced through appropriate combination for diverse applications. All these findings provide convincing evidence that the variation of silica and/or polymer content can be used to fabricate aerogels with a variety of properties, which have the depth needed for use in laser-based 3D printing technology of simple or complex structures with nearly any dimensions.     

Graphene quantum dots in alveolar macrophage: uptake-exocytosis,accumulation in nuclei,nuclear responses and DNA cleavage

Background

Given the tremendous potential for graphene quantum dots (QDs) in biomedical applications, a thorough understanding of the interaction of these materials with macrophages is essential because macrophages are one of the most important barriers against exogenous particles. Although the cytotoxicity and cellular uptake of graphene QDs were reported in previous studies, the interaction between nuclei and the internalized graphene QDs is not well understood. We thus systematically studied the nuclear uptake and related nuclear response associated with aminated graphene QDs (AG-QDs) exposure.

Results

AG-QDs showed modest 24-h inhibition to rat alveolar macrophages (NR8383), with a minimum inhibitory concentration (MIC) of 200 μg/mL. Early apoptosis was significantly increased by AG-QDs (100 and 200 μg/mL) exposure and played a major role in cell death. The internalization of AG-QDs was mainly via energy-dependent endocytosis, phagocytosis and caveolae-mediated endocytosis. After a 48-h clearance period, more than half of the internalized AG-QDs remained in the cellular cytoplasm and nucleus. Moreover, AG-QDs were effectively accumulated in nucleus and were likely regulated by two nuclear pore complexes genes (Kapβ2 and Nup98). AG-QDs were shown to alter the morphology, area, viability and nuclear components of exposed cells. Significant cleavage and cross-linking of DNA chains after AG-QDs exposure were confirmed by atomic force microscopy investigation. Molecular docking simulations showed that H-bonding and π-π stacking were the dominant forces mediating the interactions between AG-QDs and DNA, and were the important mechanisms resulting in DNA chain cleavage. In addition, the generation of reactive oxygen species (ROS) (e.g., ?OH), and the up-regulation of caspase genes also contributed to DNA cleavage.

Conclusions

AG-QDs were internalized by macrophages and accumulated in nuclei, which further resulted in nuclear damage and DNA cleavage. It is demonstrated that oxidative damage, direct contact via H-bonding and π-π stacking, and the up-regulation of caspase genes are the primary mechanisms for the observed DNA cleavage by AG-QDs.

     

Structure and properties of clay ceramics for thermal energy storage

In this paper, the structure‐property relationships of a clay ceramic with organic additives (biomass and biochar) are investigated to develop an alternative material for thermal energy storage. The firing transformations were elucidated using X‐ray pair distribution function analysis, differential scanning calorimetry, and scanning electron microscopy. It was found that the biomass increased the porosity, which resulted in a decrease of the specific heat capacity. On the other hand, the biochar remained in the clay ceramic without any interaction with the clay matrix up to 950°C. The specific heat capacity of the clay ceramic increased from 1.20 to 1.49 kJ/kg·K for a 30 wt% addition of biochar. The clay ceramic with a 30 wt% addition of biochar also conserved a high flexural strength of 11.1 MPa compared to that of the clay ceramic without organic additives (i.e., 18.9 MPa). Furthermore, the flexural strength only decreased by 23% after 100 thermal cycles. The crack growth associated with the thermal fatigue was limited by crack bridging and crack trapping. Hence, the current results suggest that clay/biochar ceramics can be as efficient as molten salts in thermal energy storage with the added benefit of an ease of use in the physical form of bricks.     

In Vivo Delivery and Activation of Masked Fluorogenic Hydrolase Substrates by Endogenous Hydrolases in C. elegans

Protein expression and localization are often studied in vivo by tagging molecules with green fluorescent protein (GFP), yet subtle changes in protein levels are not easily detected. To develop a sensitive in vivo method to amplify fluorescence signals and allow cell‐specific quantification of protein abundance changes, we sought to apply an enzyme‐activated cellular fluorescence system in vivo by delivering ester‐masked fluorophores to Caenorhabditis elegans neurons expressing porcine liver esterase (PLE). To aid uptake into sensory neuron membranes, we synthesized two novel fluorogenic hydrolase substrates with long hydrocarbon tails. Recombinant PLE activated these fluorophores in vitro. In vivo activation occurred in sensory neurons, along with potent activation in intestinal lysosomes quantifiable by imaging and microplate and partially attributable to gut esterase 1 (GES‐1) activity. These data demonstrate the promise of biorthogonal hydrolases and their fluorogenic substrates as in vivo neuronal imaging tools and for characterizing endogenous C. elegans hydrolase substrate specificities.     

Interfacial delamination of thin-film PTFE (polytetrafluoroethylene) coatings

Interfacial adhesion is a major concern with respect to successful performance of thin polymer films in developing new thin-film processes. Micro-indentation was used to induce interfacial delamination of polytetrafluoroethylene (PTFE) films deposited on glass substrates using hot filament chemical vapour deposition (HFCVD). Film thickness (1, 2, 3, 5, 10 µm) and indentation load (0.5, 0.75, 1, 2, 3 N) effects on the delamination diameter were investigated. A three-dimensional finite element model using shear material failure criterion and cohesive zone model (CZM) was developed to simulate the delamination. A normalized load–delamination radius relationship was obtained to evaluate the interfacial fracture toughness. The experimental observations showed that the delamination diameter depends on film thickness and indentation load. The numerical simulation indicates the delamination diameter depends on film thickness, material properties, and indentation force. The predictions of interfacial fracture toughness for 5- and 10-µm PTFE films are much smaller than those values using Rosenfeld et al.’s equation, which excludes the energy spent during the penetration.     

Towards ecological management of Australian powerline corridor vegetation

Powerline corridor management in Australia has traditionally focused on the complete removal of vegetation using short rotation times due to the perceived fire hazard associated with corridor vegetation. This study assessed vegetation recovery in a powerline corridor, following management, at three sites spanning corridor and forest habitat. Forest and corridor vegetation communities differed significantly between sites and over time. As vegetation recovered, the corridor community became a mix of plants common in the surrounding forest and open areas, changing within the 3-year study from a grass–fern to shrub–sedge community encroached by midstorey species. The current short rotations between management events unnecessarily maintain the corridor in a cycle of degradation, remove resources for native species and may allow introduced grasses and saplings to proliferate in the corridor. Maintaining a shrub layer would help avoid loss of species richness, encourage native species and limit colonisation opportunities of introduced species. Spot spraying emergent saplings and problem plants and mosaic slashing, would keep fire risk low and maintain biodiversity without increasing biomass to dangerous levels.     

Evaluation of web compactness limits for singly and doubly symmetric steel I-girders

This paper presents the results of research aimed at evaluating the web compactness limit for steel I-girders. Specifically, the paper tests the implications of a new web compactness limit equation provided in the 2003 AASHTO LRFD specifications [AASHTO LRFD bridge design specifications. 3rd ed. Washington (DC): AASHTO; 2003 [in press]] versus the web compactness limit in the 2001 AASHTO LRFD specifications [AASHTO LRFD bridge design specifications. 2nd ed. Washington (DC): AASHTO; 1998 [with 2001 interims]] and 1999 AISC LRFD specifications [AISC. Manual of steel construction, load and resistance factor design, Chicago (IL); 2001]. In both the AASHTO and AISC specifications, these limits are required for the nominal moment capacity to equal the plastic moment capacity of the girder, provided other requirements are also satisfied.The origins of the AASHTO [AASHTO LRFD bridge design specifications. 3rd ed. Washington (DC): AASHTO; 2003 [in press]; AASHTO LRFD bridge design specifications. 2nd ed. Washington (DC): AASHTO; 1998 [with 2001 interims]] web compactness limits are presented along with a performance evaluation of these equations. Specifically, resulting moment capacities from a comprehensive suite of finite element analyses are compared to the capacities that the respective limits are intended to provide. Results indicate the AASHTO (2003) web compactness provisions provide a more accurate representation of girder strength than those in the AASHTO (2001) and AISC (1999) Specifications.     

Impacts of Sewers on Groundwater Quality

This paper summarizes the findings of a recent research project on groundwater contamination from leaking sewers, which was completed for the Construction Industry Research and Information Association. Fifty-four incidents were identified in England and Wales from a combined questionnaire survey and literature review. In addition to recorded incidents, the poor quality of many urban groundwaters suggests some effects from leaking sewers. Age is considered to be the most significant characteristic governing leakage from sewers; ground conditions (predominantly aquifer vulnerability) and usage (private versus public ownership) are also important factors relating to the likelihood of groundwater pollution from leaking sewers. Recommended strategies for reducing groundwater contamination include (a) modification of existing criteria for the service performance grading of existing sewers, (b) improved construction of new sewers in appropriate areas, (c) increased groundwater monitoring, and (d) risk assessments for new groundwater sources.