Interdigitating organic bilayers direct the short interlayer spacing in hybrid organic–inorganic layered vanadium oxide nanostructures

Layered metal oxides provide a single-step route to sheathed superlattices of atomic layers of a variety of inorganic materials, where the interlayer spacing and overall layered structure forms the most critical feature in the nanomaterials’ growth and application in electronics, health, and energy storage. We use a combination of computer simulations and experiments to describe the atomic-scale structure, dynamics and energetics of alkanethiol-intercalated layered vanadium oxide-based nanostructures. Molecular dynamics (MD) simulations identify the unusual substrate-constrained packing of the alkanethiol surfactant chains along each V2O5 (010) face that combines with extensive interdigitation between chains on opposing faces to maximize three-dimensional packing in the interlayer regions. The findings are supported by high resolution electron microscopy analyses of synthesized alkanethiol-intercalated vanadium oxide nanostructures, and the preference for this new interdigitated model is clarified using a large set of MD simulations. This dependency stresses the importance of organic–inorganic interactions in layered material systems, the control of which is central to technological applications of flexible hybrid nanomaterials.

Impact of DWDM at 50GHz spacing in the 2µm waveban

In this paper, we show for the first time the impact of decreasing DWDM channel spacing to 50GHz in the 2mm waveband, using 6x12.5Gbit/s and 2x8Gbit/s OOK signals.

Small angle scattering characterisation of micellar systems and templated architectures

The work described in this thesis reports the structural changes induced on micelles under a variety of conditions. The micelles of a liquid crystal film and dilute solutions of micelles were subjected to high pressure CO2 and selected hydrocarbon environments. Using small angle neutron scattering (SANS) techniques the spacing between liquid crystal micelles was measured in-situ. The liquid crystals studied were templated from different surfactants with varying structural characteristics. Micelles of a dilute surfactant solution were also subjected to elevated pressures of varying gas atmospheres. Detailed modelling of the in-situ SANS experiments revealed information of the size and shape of the micelles at a number of different pressures. Also reported in this thesis is the characterisation of mesoporous materials in the confined channels of larger porous materials. Periodic mesoporous organosilicas (PMOs) were synthesised within the channels of anodic alumina membranes (AAM) under different conditions, including drying rates and precursor concentrations. In-situ small angle x-ray scattering (SAXS) and transmission electron microscopy (TEM) was used to determine the pore morphology of the PMO within the AAM channels. PMO materials were also used as templates in the deposition of gold nanoparticles and subsequently used in the synthesis of germanium nanostructures. Polymer thin films were also employed as templates for the directed deposition of gold nanoparticles which were again used as seeds for the production of germanium nanostructures. A supercritical CO2 (sc-CO2) technique was successfully used during the production of the germanium nanostructures.

Continuous non-destructive monitoring of cell health using impedance based interdigitated electrode structured sensors

This article examines some preliminary tests which were performed in order to evaluate the best electrode configuration (width and spacing) for cell culture analyses. Biochips packaged with indium tin oxide (ITO) interdigitated electrodes (IDEs) were used to perform impedance measurements on A549 cells cultured on the surface of the biochip. Several tests were carried out using a 10 mM solution of Sodium Chloride (NaCl), cell medium and the cell culture itself to characterize some of the configurations already fabricated in the facilities at Tyndall National Institute.

The formation of nanotubes and nanocoils of molybdenum disulphide

This work reports the successful realization of MoS2 nanotubes by a novel intercalation chemistry and hydrothermal treatment. An inorganic-organic precursor of hexadecylamine (HDA) and molybdenum disulphide (MoS2) were used in synthesizing the nanocomposite comprising laminar MoS2 with HDA intercalated in the interlaminar spacing. The formation of MoS2 nanotubes occurred during hydrothermal treatment (HT) by a self-organized rolling mechanism. The nanotubes were observed to have dimensions 2-12 µm in length and inner diameters typically in the range of 25-100 nm. We also report the formation of amorphous nanocoils of MoS2 obtained during similar procedures.

Accommodating curvature in a highly ordered functionalized metal oxide nanofiber: synthesis, characterization and multi-scale modeling of layered nanosheets

A key element in the rational design of hybrid organic-inorganic nanostructures, is control of surfactant packing and adsorption onto the inorganic phase in crystal growth and assembly. In layered single crystal nanofibers and bilayered 2D nanosheets of vanadium oxide, we show how the chemisorption of preferred densities of surfactant molecules can direct formation of ordered, curved layers. The atom-scale features of the structures are described using molecular dynamics simulations that quantify surfactant packing effects and confirm the preference for a density of 5 dodecanethiol molecules per 8 vanadium attachment sites in the synthesised structures. This assembly maintains a remarkably well ordered interlayer spacing, even when curved. The assemblies of interdigitated organic bilayers on V2O5 are shown to be sufficiently flexible to tolerate curvature while maintaining a constant interlayer distance without rupture, delamination or cleavage. The accommodation of curvature and invariant structural integrity points to a beneficial role for oxide-directed organic film packing effects in layered architectures such as stacked nanofibers and hybrid 2D nanosheet systems.

Studies on Formica lugubris Zetterstedt in Ireland (Hymenoptera, Formicidae)

This thesis is based on studies of Formica lugubris from 1972-1975. While this species' range is diminishing in Ireland, the nests are quite common in the State plantations of South Tipperary. It is not certain that the species is indigenous. Above-ground activity occurs from late-February to the end of October; foraging begins in April. Two territorial "spring-battles" between neighbouring nests are described. Most active nests produced alatae of both sexes and flights were observed on successive June mornings above l7.5°C air temperature. Both polygyny and polycaly seem to be rare. Where the nests occur commonly, the recorded densities are similar to those reported from the continent. Most nests persisted at the same site since 1973. The nest-sites are described by recording an array of nest, soil, tree, vegetation and location variables at each site. Pinus sylvestris is the most important overhead tree. Nests seem to be the same age as their surrounding plantation and reach a maximum of c. 30 years. Nearest-neighbour analysis suggests the sites are overdispersed. Forager route-fidelity was studied and long-term absence from the route, anaesthetization and "removal" of an aphid tree had little effect on this fidelity. There were no identifiable groups of workers specifically honeydew or prey-carriers. Size-duty relationships of workers participating in adult transport are described. Foraging rhythms were studied on representative days: the numbers foraging were linearly related to temperature. Route-traffic passed randomly and an average foraging trip lasted c. four hours. Annual food intake to a nest with 25 000 foragers was estimated at approximately 75 kg honeydew and 2 million prey-items. Forager-numbers and colony-size were estimated using the capture-mark - recapture method: paint marking was used for the forager estimate and an interval radiophosphorus mark, detected by autoradiography, was used for the colony-size estimate. The aphids attended by lugubris and the nest myrmecophiles are recorded.

Invertebrate diversity in Irish and British forests

Ireland and Britain were once covered in natural forest, but extensive anthropogenic deforestation reduced forest cover to less than 1% and 5 %, respectively, by the beginning of the 20th century. Large-scale afforestation has since increased the level of forest cover to 11% in Ireland and 12% in Britain, with the majority of planted forests comprising small monoculture plantations, many of which are of non - native conifer tree species. At present the forest cover of Ireland and Britain generally consists of small areas of remnant semi-natural woodland and pockets of these plantation forests within a predominantly agricultural landscape. Invertebrates comprise a large proportion of the biodiversity found within forested habitats. In particular, spiders and carabid beetles play an important role in food webs as both predators and prey and respond to small-scale changes in habitat structure, meaning they are particularly sensitive to forest management. Hoverflies play an important role in control and pollination and have been successfully used as indicators of habitat disturbance and quality. This research addressed a number of topics pertinent to the forest types present in the contemporary Irish and British landscapes and aimed to investigate the invertebrate diversity of these forests. Spiders and carabid beetles were sampled using pitfall trapping and hoverflies were sampled using Malaise net trapping. Topics included the impacts of afforestation, the importance of open space, the choice of tree species, and the use of indicators for biodiversity assessment, as well as rare native woodlands and the effect of grazing on invertebrate diversity. The results are discussed and evidence-based recommendations are made for forest policy and management to protect and enhance invertebrate biodiversity in order to promote sustainable forest management in Ireland and Britain.