Mechanical and electrical properties of single-walled carbon nanotubes synthesized by chemical vapor deposition

Despite the tremendous application potentials of carbon nanotubes (CNTs) proposed by researchers in the last two decades, efficient experimental techniques and methods are still in need for controllable production of CNTs in large scale, and for conclusive characterizations of their properties in order to apply CNTs in high accuracy engineering. In this dissertation, horizontally well-aligned high quality single-walled carbon nanotubes (SWCNTs) have been successfully synthesized on St-cut quartz substrate by chemical vapor deposition (CVD). Effective radial moduli (Eradial) of these straight SWCNTs have been measured by using well-calibrated tapping mode and contact mode atomic force microscopy (AFM). It was found that the measured Eradial decreased from 57 to 9 GPa as the diameter of the SWCNTs increased from 0.92 to 1.91 nm. The experimental results were consistent with the recently reported theoretical simulation data. The method used in this mechanical property test can be easily applied to measure the mechanical properties of other low-dimension nanostructures, such as nanowires and nanodots. The characterized sample is also an ideal platform for electrochemical tests. The electrochemical activities of redox probes Fe(CN)63-/4-, Ru(NH3) 63+, Ru(bpy)32+ and protein cytochrome c have been studied on these pristine thin films by using aligned SWCNTs as working electrodes. A simple and high performance electrochemical sensor was fabricated. Flow sensing capability of the device has been tested for detecting neurotransmitter dopamine at physiological conditions with the presence of Bovine serum albumin. Good sensitivity, fast response, high stability and anti-fouling capability were observed. Therefore, the fabricated sensor showed great potential for sensing applications in complicated solution.^

Pollination, Herbivory, and Habitat Fragmentation: Their Effects on the Reproductive Fitness of Angadenia berteroi, a Native Perennial Plant of the South Florida Pine Rocklands

Angadenia berteroi is a tropical perennial subshrub of the pine rocklands with large yellow flowers that set very few fruits. My dissertation seeks to elucidate the factors that affect the reproductive fitness of Angadenia berteroi a native species of the south Florida pine rocklands. I provide novel information on the pollination biology of this native species. I also assess the effects of herbivory on growth and the reproductive success of A. berteroi. Finally, I elucidate how habitat fragmentation and quality are correlated with reproductive fitness of this native perennial plant. Using a novel experimental approach, I determined the most effective pollinator group. I used nylon fishing line of widths corresponding to proboscis diameter of the major groups of visitors to examine pollen removal and deposition. In the field, I estimated visitation frequency and efficacy of each pollinator type. Using potted plants, I exposed flowers to single visit from different types of pollinators to measure fruit set. I performed artificial defoliation with scissors on plants growing in the greenhouse to assess the effects of defoliation before flowering as well as during flowering. Additionally, I used structural equation modelling (SEM) to elucidate how A. berteroi reproductive fitness was affected by habitat fragmentation and quality. My experiments provide evidence that Angadenia berteroi is specialized for bee pollination; though butterflies, skippers and others also visit its flowers, A. berteroi is exclusively pollinated by two native bees of the South Florida pine rocklands . This research also demonstrated that herbivory by the oleander moth may have direct and indirect effects on Angadenia berteroi growth and reproductive success. The SEM results suggested that habitat quality (litter depth and subcanopy cover) may favor reproduction in native species of the South Florida pine rocklands that are properly maintained by periodic fires and exotic control. Insights from this threatened and charismatic species may provide impetus to properly manage remaining pine rocklands in South Florida for this and other endemic understory species.

Improving performance of a permeable reactive barrier in the degradation of trichloroethylene using ultrasound

The impact of ultrasound on improving the performance of a granular iron Permeable Reactive Barrier (PRB) in the degradation of Trichloroethylene (TCE) was evaluated. Two treatment columns made of clear Plexiglas with a height of 1ft and a diameter of 2 inches and filled with granular iron were used. One was fitted with 25Khz ultrasound probes. A solution of TCE was run through at constant flow rate. Samples obtained from the column at different residence times before and after sonication were analyzed for concentrations of TCE and used to generate concentration profiles to obtain rate constants, which were compared. An improvement of 23.4% in the reaction rate of TCE degradation was observed after sonication of the iron media suggesting that ultrasound may contribute to improving the performance of PRBs in the degradation of TCE in contaminated groundwater.

A mathematical model for the maneuvering simulation of a propelled SPAR vessel

To predict the maneuvering performance of a propelled SPAR vessel, a mathematical model was established as a path simulator. A system-based mathematical model was chosen as it offers advantages in cost and time over full Computational Fluid Dynamics (CFD) simulations. The model is intended to provide a means of optimizing the maneuvering performance of this new vessel type. In this study the hydrodynamic forces and control forces are investigated as individual components, combined in a vectorial setting, and transferred to a body-fixed basis. SPAR vessels are known to be very sensitive to large amplitude motions during maneuvers due to the relatively small hydrostatic restoring forces. Previous model tests of SPAR vessels have shown significant roll and pitch amplitudes, especially during course change maneuvers. Thus, a full 6 DOF equation of motion was employed in the current numerical model. The mathematical model employed in this study was a combination of the model introduced by the Maneuvering Modeling Group (MMG) and the Abkowitz (1964) model. The new model represents the forces applied to the ship hull, the propeller forces and the rudder forces independently, as proposed by the MMG, but uses a 6DOF equation of motion introduced by Abkowitz to describe the motion of a maneuvering ship. The mathematical model was used to simulate the trajectory and motions of the propelled SPAR vessel in 10˚/10˚, 20˚/20˚ and 30˚/30˚ standard zig-zag maneuvers, as well as turning circle tests at rudder angles of 20˚ and 30˚. The simulation results were used to determine the maneuverability parameters (e.g. advance, transfer and tactical diameter) of the vessel. The final model provides the means of predicting and assessing the performance of the vessel type and can be easily adapted to specific vessel configurations based on the generic SPAR-type vessel used in this study.

(Table 2) Collection sites and number of specimens of Usnea subgenus Neuropogon species

Usnea species of the Neuropogon group are amongst the most widespread and abundant macrolichens in Antarctic regions. Four principal species, U. antarctica, U. aurantiaco-atra, U. sphacelata and U. subantarctica, have been described on morphological grounds. However, identification to species level is often difficult and atypical morphologies frequently arise. Over 400 specimens were collected on the Antarctic Peninsula and Falkland Islands. Both morphological and molecular characters (ITS and RPB1) were used to compare samples to clarify taxonomic relationships. Morphological characteristics used included presence of apothecia, apothecial rays, soredia, papillae, fibrils, pigmentation and the diameter of the central axis as a proportion of branch diameter. Results revealed a very close relationship between U. antarctica and U. aurantiaco-atra, suggesting that they might constitute a species pair or be conspecific. Usnea sphacelata was comprised of at least two genetically distinct groups with no clear differences in morphology. One group included the first reported fertile specimen of this species. Usnea subantarctica was phylogenetically distinct from the other main Antarctic Usnea species, but clustered with U. trachycarpa. Genetic variation was evident within all species although there was no clear correlation between geographic origin and genetic relatedness. Phylogenetic analyses indicated that species circumscription in the Neuropogon group needs revision, with the principal species being non-monophyletic. None of the morphological characters, or groups of characters, used in this study proved to be completely unambiguous markers for a single species. However, axis thickness was supported as being informative for the identification of monophyletic lineages within the group.

Towards thiol functionalization of vanadium pentoxide nanotubes using gold nanoparticles

Template-directed synthesis is a promising route to realize vanadate-based 1-D nanostructures, an example of which is the formation of vanadium pentoxide nanotubes and associated nanostructures. In this work, we report the interchange of long-chained alkyl amines with alkyl thiols. This reaction was followed using gold nanoparticles prepared by the Chemical Liquid Deposition (CLD) method with an average diameter of ∼0.9 nm and a stability of ∼85 days. V2 O5 nanotubes (VOx-NTs) with lengths of ∼2 μm and internal hollow diameters of 20-100 nm were synthesized and functionalized in a Au-acetone colloid with a nominal concentration of ∼ 4 × 1 0- 3 mol dm-3. The interchange reaction with dodecylamine is found only to occur in polar solvents and incorporation of the gold nanoparticles is not observed in the presence of n-decane.

Interactive effects of ocean acidification and neighboring corals on the growth of Pocillopora verrucosa

The physical and chemical environment around corals, as well as their physiology, can be affected by interactions with neighboring corals. This study employed small colonies (4 cm diameter) of Pocillopora verrucosa and Acropora hyacinthus configured in spatial arrays at 7 cm/s flow speed to test the hypothesis that ocean acidification (OA) alters interactions among them. Interaction effects were quantified for P. verrucosa using three measures of growth: calcification (i.e., weight), horizontal growth, and vertical growth. The study was carried out in May-June 2014 using corals from 10 m depth on the outer reef of Moorea, French Polynesia. Colonies of P. verrucosa were placed next to conspecifics or heterospecifics (A. hyacinthus) in arrangements of two or four colonies (pairs and aggregates) that were incubated at ambient and high pCO2 (1000 µatm) for 28 days. There was an effect of pCO2, and arrangement type on multivariate growth (utilizing the three measures of growth), but no interaction between the main effects. Conversely, arrangement and pCO2 had an interactive effect on calcification, with an overall 23 % depression at high pCO2 versus ambient pCO2 (i.e., pooled among arrangements). Within arrangements, there was a 34-45 % decrease in calcification for solitary and paired conspecifics, but no effect in conspecific aggregates, heterospecific pairs, or heterospecific aggregates. Horizontal growth was negatively affected by pCO2 and arrangement type, while vertical growth was positively affected by arrangement type. Together, our results show that conspecific aggregations can mitigate the negative effects of OA on calcification of colonies within an aggregation.

Preparation and characterization of Pr0.6Sr0.4FeO3-δ-Ce0.9Pr0.1O2-δ nanofiber structured composite cathode for IT-SOFCs

In this work, Pr_0.6Sr_0.4FeO_3-δ -Ce_0.9Pr_0.1O_2-δ (PSFO-CPO) nanofibers were synthesized by a one-step electrospin technique for use in intermediate-temperature solid oxide fuel cell (IT-SOFC) applications. PSFO-CPO nanofibers were produced with a diameter of about 100nm and lengths exceeding tens of microns. The thermal expansion coefficient (TEC) matches with standard GDC electrolytes and the resulting conductivity also satisfies the needs of IT-SOFCs cathodes. EIS analysis of the nanofiber structured electrode gives a polarization resistance of 0.072Ωcm² at 800°C, smaller than that from the powdered cathode with the same composition. The excellent electrochemical performance can be attributed to the well-constructed microstructure of the nanofiber structured cathode, which promotes surface oxygen diffusion and charge transfer processes. All the results imply that the one-step electrospin method is a facile and practical way of improving the cathode properties and that PSFO-CPO is a promising cathode material for IT-SOFCs.

Storage stability of bevacizumab in polycarbonate and polypropylene syringes

Purpose To compare and examine the storage stability of compounded bevacizumab in polycarbonate (PC) and polypropylene (PP) syringes over a 6-month period. PC syringes have been used in a recent clinical study and bevacizumab stability has not been reported for this type of syringe. Methods Repackaged bevacizumab was obtained from Moorfields Pharmaceuticals in polycarbonate (PC) and polypropylene (PP) syringes. Bevacizumab from the stored syringes was analysed at monthly time points for a 6-month period and compared with bevacizumab from a freshly opened vial at each time point. SDS-PAGE electrophoresis and size-exclusion chromatography (SEC) was used to observe aggregation and degradation. Dynamic light scattering (DLS) provided information about the hydrodynamic size and particle size distribution of bevacizumab in solution. VEGF binding and the active concentration of bevacizumab was determined by surface plasmon resonance (SPR) using Biacore. Results SDS-PAGE and SEC analysis did not show any changes in the presence of higher molecular species (HMWS) or degradation products in PC and PP syringes from T0 to T6 compared to bevacizumab sampled from a freshly opened vial. The hydrodynamic diameter of bevacizumab in the PC syringe after six months of storage was not significantly different to bevacizumab taken from a freshly opened vial. Using SPR, the VEGF binding activity of bevacizumab in the PC syringe was comparable with bevacizumab taken from a freshly opened vial. Conclusion No significant difference over a 6-month period was observed in the quality of bevacizumab repackaged into prefilled PC polycarbonate and PP polypropylene syringes when compared to bevacizumab that is supplied from the vial.

Preparation of bionanoparticles derived from Spirulina platensis and its application for Cr (VI) removal from aqueous solutions

Spirulina platensis nanoparticles were prepared by mechanical agitation and were applied to removal Cr (VI) from aqueous solutions. Nanoparticles preparation was function of stirring rate and contact time. In the optimal conditions, Cr (VI) removal by nanoparticles as a function of pH and initial ion concentration was carried out. The optimal conditions for preparation were 10,000 rpm and 20 min, and the nanoparticles presented mean diameter of 215.6 nm and polydispersity index of 0.151. The best conditions for Cr (VI) removal were at pH 4 and ion concentration of 250 mg L 1, and the Cr (VI) removal percentage was 99.1%.

Preliminary design of a prestressed concrete viaduct

O presente Trabalho Final de Mestrado consiste na elaboração de um Estudo Prévio de um viaduto rodoviário, em betão armado pré-esforçado. O viaduto, com tabuleiro em laje vigada, é constituído por 10 tramos, prevendo-se que seja construído tramo a tramo, com juntas de betonagem a quintos de vão. A plataforma do viaduto é constituída por duas vias de tráfego com 3.5m cada, duas bermas de 1.00 m e dois passeios laterais com 1.10 m cada, perfazendo uma largura total de 11.20. O viaduto localiza-se em Polónia e foi dimensionado de acordo com os Eurocódigos e os Anexos Nacionais desse país.

A graph-based hyper heuristic for timetabling problems

This paper presents an investigation of a simple generic hyper-heuristic approach upon a set of widely used constructive heuristics (graph coloring heuristics) in timetabling. Within the hyperheuristic framework, a Tabu Search approach is employed to search for permutations of graph heuristics which are used for constructing timetables in exam and course timetabling problems. This underpins a multi-stage hyper-heuristic where the Tabu Search employs permutations upon a different number of graph heuristics in two stages. We study this graph-based hyper-heuristic approach within the context of exploring fundamental issues concerning the search space of the hyper-heuristic (the heuristic space) and the solution space. Such issues have not been addressed in other hyper-heuristic research. These approaches are tested on both exam and course benchmark timetabling problems and are compared with the fine-tuned bespoke state-of-the-art approaches. The results are within the range of the best results reported in the literature. The approach described here represents a significantly more generally applicable approach than the current state of the art in the literature. Future work will extend this hyper-heuristic framework by employing methodologies which are applicable on a wider range of timetabling and scheduling problems.

Hybrid Graph Heuristics within a Hyper-heuristic Approach to Exam Timetabling Problems

This paper is concerned with the hybridization of two graph coloring heuristics (Saturation Degree and Largest Degree), and their application within a hyperheuristic for exam timetabling problems. Hyper-heuristics can be seen as algorithms which intelligently select appropriate algorithms/heuristics for solving a problem. We developed a Tabu Search based hyper-heuristic to search for heuristic lists (of graph heuristics) for solving problems and investigated the heuristic lists found by employing knowledge discovery techniques. Two hybrid approaches (involving Saturation Degree and Largest Degree) including one which employs Case Based Reasoning are presented and discussed. Both the Tabu Search based hyper-heuristic and the hybrid approaches are tested on random and real-world exam timetabling problems. Experimental results are comparable with the best state-of-the-art approaches (as measured against established benchmark problems). The results also demonstrate an increased level of generality in our approach.

A graph-based hyper heuristic for timetabling problems

This paper presents an investigation of a simple generic hyper-heuristic approach upon a set of widely used constructive heuristics (graph coloring heuristics) in timetabling. Within the hyperheuristic framework, a Tabu Search approach is employed to search for permutations of graph heuristics which are used for constructing timetables in exam and course timetabling problems. This underpins a multi-stage hyper-heuristic where the Tabu Search employs permutations upon a different number of graph heuristics in two stages. We study this graph-based hyper-heuristic approach within the context of exploring fundamental issues concerning the search space of the hyper-heuristic (the heuristic space) and the solution space. Such issues have not been addressed in other hyper-heuristic research. These approaches are tested on both exam and course benchmark timetabling problems and are compared with the fine-tuned bespoke state-of-the-art approaches. The results are within the range of the best results reported in the literature. The approach described here represents a significantly more generally applicable approach than the current state of the art in the literature. Future work will extend this hyper-heuristic framework by employing methodologies which are applicable on a wider range of timetabling and scheduling problems.

Cyto- and Genotoxicity assessment of manufactured nano cerium dioxide in the A549 cell line

In the past decades the growing application of nanomaterials (NMs) in diverse consumer products has raised various concerns in the field of toxicology. They have been extensively used in a broad range of applications and cover most of the industrial sectors as well as the medicine and the environmental areas. The most common scenarios for human exposure to NMs are occupational, environmental and as consumers and inhalation is the most frequent route of exposure, especially in occupational settings. Cerium dioxide NMs (nano-CeO2) are widely used in a number of applications such as in cosmetics, outdoor paints, wood care products as well as fuel catalysts. For such reason, nano-CeO2 is one of the selected NMs for priority testing within the sponsorship program of the Working Party of Manufactured Nanomaterials of the OECD. In this context, the aim of this study is to assess the safety of nano-CeO2 (NM-212, Joint Research Center Repository) through the characterization of its cytotoxicity and genotoxicity in a human alveolar epithelial cell line. A dispersion of the NM in water plus 0.05% BSA was prepared and sonicated during 16 minutes, according to a standardized protocol. DLS analysis was used to characterize the quality of the NM dispersion in the culture medium. To evaluate the cytotoxicity of nano-CeO2 in the A549 cell line, the colorimetric MTT assay was performed; the capacity of cells to proliferate when exposed to CeO2 was also assessed with the Clonogenic assay. The genotoxicity of this NM was evaluated by the Comet Assay (3 and 24h of exposure) to quantify DNA breaks and the FPG-modified comet assay to assess oxidative DNA damage. The Cytokinesis-Block Micronucleus (CBMN) assay was used to further detect chromosome breaks or loss. The nano-CeO2 particles are spherical, displaying a diameter of 33 nm and 28 m2/g of surface area. The results of the MTT assay did not show any decreased in cells viability following treatment with a dose-range of nano-CeO2 during 24h. Nevertheless, the highest concentrations of this NM were able to significantly reduce the colony forming ability of A549 cells, suggesting that a prolonged exposure may be cytotoxic to these cells. Data from both genotoxicity assays revealed that nano-CeO2 was neither able to induce DNA breaks nor oxidative DNA damage. Likewise, no significant micronucleus induction was observed. Taken together, the present results indicate that this nano-CeO2 is not genotoxic in this alveolar cell line under the tested conditions, although further studies should be performed, e.g., gene mutation in somatic cells and in vivo chromosome damage (rodent micronucleus assay) to ensure its safety to human health.