Single mode and multimodes lasing emission from MEH-PPV doped polystyrene thin films with surface ripples formed by vapour-induced phase separation

We report single mode and multimodes lasing emission from conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) doped polystyrene ( PS) thin films with surface ripples. Surface ripples were formed by water vapour-induced phase separation. A single mode lasing emission at 606 nm with a line-width of less than 0.4 nm was obtained. The laser threshold was as low as 3.5 mu J pulse(-1). The side mode suppression ratio was 5.76 dB. The periodic changes of the refraction index in the MEH-PPV : PS blending film due to the phase separation should be attributed to the lasing actions.

Assembly of 'discrete' (H2O)(16) water clusters within a supramolecular compound of calixarene

A 'discrete' (H2O)(16) cluster, featuring four basic cyclic nine-membered rings and a twelve-membered ring, illustrates a new mode of supramolecular association of water molecules.

The structural transition of DNA-Tris(1,10-phenanthroline) cobalt(III) complexes in ethanol-water solution

The interaction of DNA with Tris(1,10-phenanthroline) cobalt(III) was studied by means of atomic force microscopy. Changes in the morphologies of DNA complex in the presence of ethanol may well indicate the crucial role of electrostatic force in causing DNA condensation. With the increase of the concentration of ethanol, electrostatic interaction is enhanced corresponding to a lower dielectric constant. Counterions condense along the sugar phosphate backbone of DNA when e is lowered and the phosphate charge density can thus be neutralized to the level of DNA condensation. Electroanalytical measurement of DNA condensed with Co(phen)(3)(3+) in ethanol solution indicated that intercalating reaction remains existing. According to both the microscopic and spectroscopic results, it can be found that no secondary structure transition occurs upon DNA condensing. B-A conformation transition takes place at more than 60% ethanol solution.

Study of methanol adsorption on mica, graphite and ITO glass by using tapping mode atomic force microscopy

Tapping mode atomic force microscopy (AFM) was applied to study the adsorption behavior of methanol on mica, highly oriented pyrolytic graphite (HOPG) and indium-tin oxide (ITO) coated glass substrates. On mica and HOPG substrates surfaces, the thin films of methanol with bilayer and multilayer were observed, respectively. The formation of irregular islands of methanol was also found on HOPG surface. On ITO surface only aggregates and clusters of methanol molecules were formed. The influence of sample preparation on the adsorption was discussed.

Intra-habitat heterogeneity of microbial food web structure under the regime of eutrophication and sediment resuspension in the large subtropical shallow Lake Taihu, China

Planktonic microbial community structure and classical food web were investigated in the large shallow eutrophic Lake Taihu (2338 km(2), mean depth 1.9 m) located in subtropical Southeast China. The water column of the lake was sampled biweekly at two sites located 22 km apart over a period of twelve month. Site 1 is under the regime of heavy eutrophication while Site 2 is governed by wind-driven sediment resuspension. Within-lake comparison indicates that phosphorus enrichment resulted in increased abundance of microbial components. However, the coupling between total phosphorus and abundance of microbial components was different between the two sites. Much stronger coupling was observed at Site 1 than at Site 2. The weak coupling at Site 2 was mainly caused by strong sediment resuspension, which limited growth of phytoplankton and, consequently, growth of bacterioplankton and other microbial components. High percentages of attached bacteria, which were strongly correlated with the biomass of phytoplankton, especially Microcystis spp., were found at Site 1 during summer and early autumn, but no such correlation was observed at Site 2. This potentially leads to differences in carbon flow through microbial food web at different locations. Overall, significant heterogeneity of microbial food web structure between the two sites was observed. Site-specific differences in nutrient enrichment (i.e. nitrogen and phosphorus) and sediment resuspension were identified as driving forces of the observed intra-habitat differences in food web structure.

Indium tin oxide refractometer in the visible and near infrared via lossy mode and surface plasmon resonances with Kretschmann configuration

The following article appeared in Torres, V., Beruete, M., Del Villar, I., & Sánchez, P. (2016). Indium tin oxide refractometer in the visible and near infrared via lossy mode and surface plasmon resonances with Kretschmann configuration. Applied Physics Letters, 108(4), doi:10.1063/1.4941077, and may be found at http://dx.doi.org/10.1063/1.4941077.

Evanescent field sensing: optical nanofibres, whispering-gallery-mode microspherical and microbubble resonators

In this thesis, the evanescent field sensing techniques of tapered optical nanofibres and microspherical resonators are investigated. This includes evanescent field spectroscopy of a silica nanofibre in a rubidium vapour; thermo-optical tuning of Er:Yb co-doped phosphate glass microspheres; optomechanical properties of microspherical pendulums; and the fabrication and characterisation of borosilicate microbubble resonators. Doppler-broadened and sub-Doppler absorption spectroscopic techniques are performed around the D2 transition (780.24 nm) of rubidium using the evanescent field produced at the waist of a tapered nanofibre with input probe powers as low as 55 nW. Doppler-broadened Zeeman shifts and a preliminary dichroic atomic vapour laser lock (DAVLL) line shape are also observed via the nanofibre waist with an applied magnetic field of 60 G. This device has the potential for laser frequency stabilisation while also studying the effects of atom-surface interactions. A non-invasive thermo-optical tuning technique of Er:Yb co-doped microspheres to specific arbitrary wavelengths is demonstrated particularly to 1294 nm and the 5S1/2F=3 to 5P3/2Fʹ=4 laser cooling transition of 85Rb. Reversible tuning ranges of up to 474 GHz and on resonance cavity timescales on the order of 100 s are reported. This procedure has prospective applications for sensing a variety of atomic or molecular species in a cavity quantum electrodynamics (QED) experiments. The mechanical characteristics of a silica microsphere pendulum with a relatively low spring constant of 10-4 Nm-1 are explored. A novel method of frequency sweeping the motion of the pendulum to determine its natural resonance frequencies while overriding its sensitivity to environmental noise is proposed. An estimated force of 0.25 N is required to actuate the pendulum by a displacement of (1-2) μm. It is suggested that this is of sufficient magnitude to be experienced between two evanescently coupled microspheres (photonic molecule) and enable spatial trapping of the micropendulum. Finally, single-input borosilicate microbubble resonators with diameters <100 μm are fabricated using a CO2 laser. Optical whispering gallery mode spectra are observed via evanescent coupling with a tapered fibre. A red-shift of (4-22) GHz of the resonance modes is detected when the hollow cavity was filled with nano-filtered water. A polarisation conversion effect, with an efficiency of 10%, is observed when the diameter of the coupling tapered fibre waist is varied. This effect is also achieved by simply varying the polarisation of the input light in the tapered fibre where the efficiency is optimised to 92%. Thus, the microbubble device acts as a reversible band-pass to band-stop optical filter for cavity-QED, integrated solid-state and semiconductor circuit applications.

Position and structure of the subtropical/Azores front region from combined Lagrangian and remote sensing (IR/altimeter/SeaWIFS) measurements

The position and structure of the North Atlantic Subtropical Front is studied using Lagrangian flow tracks and remote sensing (AVHRR imagery: TOPEX/POSEIDON altimetry: SeaWiFS) in a broad region ( similar to 31 degree to similar to 36 degree N) of marked gradient of dynamic height (Azores Current) that extends from the Mid-Atlantic Ridge (MAR), near similar to 40 degree W, to the Eastern Boundary ( similar to 10 degree W). Drogued Argos buoy and ALACE tracks are superposed on infrared satellite images in the Subtropical Front region. Cold (cyclonic) structures, called storms, and warm (anticyclonic) structures of 100-300 km in size can be found on the south side of the Subtropical Front outcrop, which has a temperature contrast of about 1 degree C that can be followed for similar to 2500 km near 35 degree N. Warmer water adjacent to the outcrop is flowing eastward (Azores Current) but some warm water is returned westward about 300 km to the south (southern Counterflow). Estimates of horizontal diffusion in a Storm (D=2.2t10 super(2) m super(2) s super(-1)) and in the Subtropical Front region near 200 m depth (D sub(x)=1.3t10 super(4) m super(2) s super(-1), D sub(y)=2.6t10 super(3) m super(2) s super(-1)) are made from the Lagrangian tracks. Altimeter and in situ measurements show that Storms track westwards. Storms are separated by about 510 km and move westward at 2.7 km d super(-1). Remote sensing reveals that some initial structures start evolving as far east as 23 degree W but are more organized near 29 degree W and therefore Storms are about 1 year old when they reach the MAR (having travelled a distance of 1000 km). Structure and seasonality in SeaWiFS data in the region is examined.

Particulate and dissolved aluminum and titanium in the upper water column of the Atlantic Ocean

This study investigates the oceanic behavior of the lithogenic trace elements Al and Ti in the upper 200 m of the Atlantic Ocean. The distribution of both metals in the dissolved and particulate phases was assessed along an E-W transect in the eastern tropical North Atlantic (December 2009) and along a meridional Atlantic transect (April-May 2010). The surface water concentrations of particulate and dissolved Al and Ti reflected the previously observed pattern of atmospheric inputs into the Atlantic Ocean. Subsurface minima at stations with pronounced fluorescence maxima were observed, suggesting a link between biological productivity and the removal of both dissolved and particulate Al and Ti. This may include uptake mechanisms, adsorption and aggregation processes on biogenic particle surfaces and the formation of large, fast sinking biogenic particles, e.g., fecal pellets. Residence times in the upper water column (100 m) of the tropical and subtropical North Atlantic were estimated to range in the order of days to weeks in the particulate phases (Al: 3-22 days, Ti: 4-37 days) and were 0.9-3.8 years for Al and 10-31 years for Ti in the dissolved phases. Longer residence times in both phases in the South Atlantic are consistent with lower biological productivity and decreased removal rates. In the upper water column, Al was predominantly present in the dissolved form, whereas Ti mostly occurred in the particulate form. Largest deviations in the partition coefficients between the particulate and dissolved phases were found in the surface waters, together with excess dissolved Al over Ti compared to the crustal source. This likely reflects elevated dissolution of Al compared to Ti from atmospheric mineral particles.

Environmental variability and biodiversity of megabenthos on the Hebrides Terrace Seamount (Northeast Atlantic)

We present the first remotely operated vehicle investigation of megabenthic communities (1004-1695 m water depth) on the Hebrides Terrace Seamount (Northeast Atlantic). Conductivity-temperature-depth casts showed rapid light attenuation below the summit and an oceanographic regime on the flanks consistent with an internal tide, and high short-term variability in water temperature, salinity, light attenuation, aragonite and oxygen down to 1500 m deep. Minor changes in species composition (3-14%) were explained by changes in depth, substratum and oceanographic stability, whereas environmental variability explained substantially more variation in species richness (40-56%). Two peaks in species richness occurred, the first at 1300-1400 m where cooler Wyville Thomson Overflow Water (WTOW) mixes with subtropical gyre waters and the second at 1500-1600 m where WTOW mixes with subpolar mode waters. Our results suggest that internal tides, substrate heterogeneity and oceanographic interfaces may enhance biological diversity on this and adjacent seamounts in the Rockall Trough.

Surface Salinity in the North Atlantic Subtropical Gyre During the STRASSE/SPURS Summer 2012 Cruise

We investigated a 100 × 100 km high-salinity region of the North Atlantic subtropical gyre during the Sub-Tropical Atlantic Surface Salinity Experiment/Salinity Processes in the Upper-ocean Regional Study (STRASSE/SPURS) cruise from August 21, 2012, to September 9, 2012. Results showed great variability in sea surface salinity (SSS; over 0.3 psu) in the mesoscale, over 7 cm of total evaporation, and little diapycnal mixing below 36 m depth, the deepest mixed layers encountered. Strong currents in the southwestern part of the domain, and the penetration of freshwater, suggest that advection contributed greatly to salinity evolution. However, it was further observed that a smaller cyclonic structure tucked between the high SSS band and the strongest currents contributed to the transport of high SSS water along a narrow front. Cross-frontal transport by mixing is also a possible cause of summertime reduction of SSS. The observed structure was also responsible for significant southward salt transport over more than 200 km.

Controls on the contemporary distribution of lake thecamoebians (testate amoebae) in the Greater Toronto Area and their potential as water quality indicators.

Thecamoebians were examined from 71 surface sediment samples collected from 21 lakes and ponds in the Greater Toronto Area to (1) elucidate the controls on faunal distribution in modern lake environments; and (2) to consider the utility of thecamoebians in quantitative studies of water quality change. This area was chosen because it includes a high density of kettle and other lakes which are threatened by urban development and where water quality has deteriorated locally as a result of contaminant inputs, particularly nutrients. Fifty-eight samples yielded statistically significant thecamoebian populations. The most diverse faunas (highest Shannon Diversity Index values) were recorded in lakes beyond the limits of urban development, although the faunas of all lakes showed signs of sub-optimal conditions. The assemblages were divided into five clusters using Q-mode cluster analysis, supported by Detrended Correspondence Analysis. Canonical Correspondence Analysis (CCA) was used to examine species-environment relationships and to explain the observed clusterings. Twenty-four measured environmental variables were considered, including water property attributes (e.g., pH, conductivity, dissolved oxygen), substrate characteristics, sediment-based phosphorus (Olsen P) and 11 environmentally available metals. The thecamoebian assemblages showed a strong association with phosphorus, reflecting the eutrophic status of many of the lakes, and locally to elevated conductivity measurements, which appear to reflect road salt inputs associated with winter de-icing operations. Substrate characteristics, total organic carbon and metal contaminants (particularly Cu and Mg) also influenced the faunas of some samples. A series of partial CCAs show that of the measured variables, sedimentary phosphorus has the largest influence on assemblage distribution, explaining 6.98% (P < 0.002) of the total variance. A transfer function was developed for sedimentary phosphorus (Olsen P) using 58 samples from 15 of the studied lakes. The best performing model was based on weighted averaging with inverse deshrinking (WA Inv, r jack 2= 0.33, RMSEP = 102.65 ppm). This model was applied to a small modern thecamoebian dataset from a eutrophic lake in northern Ontario to predict phosphorus and performed satisfactorily. This preliminary study confirms that thecamoebians have considerable potential as quantitative water quality indicators in urbanising regions, particularly in areas influenced by nutrient inputs and road salts.

Ethanol-induced water stress and fungal growth

Fungal growth inhibition by ethanol was compared with that caused by five other agents of water stress (at 25, 40 and 42.5°C), using Aspergillus oryzae. Ethanol, KCl, glycerol, glucose, sorbitol, and polyethylene glycol 400 were incorporated into media at concentrations corresponding to water activity (a(w)) values in the range 1 to 0.75. Generally, as temperature increased there was a decrease in the a(w) value at which optimum growth occurred. The a(w) limit for growth on KCl, glycerol, glucose, sorbitol, or polyethylene glycol 400 media was about 0.85, regardless of temperature. However, the a(w) limit for growth on ethanol media varied between 0.97 and 0.99 a(w) and was temperature-dependent. Water stress accounted for up to 31, 18 and 6% of growth inhibition by ethanol at 25, 40, and 42.5°C, respectively. For media containing ethanol, the decrease in growth rate per unit of a(w) reduction was greater as temperature increased. However, ethanol-induced water stress remained constant regardless of temperature, suggesting that other inhibitory effects of ethanol are closely temperature- dependent. Water stress may account for considerably more than 30% of growth inhibition by ethanol in cells that remain metabolically active at higher ethanol concentrations.

Characterization of water-soluble organic matter from urban aerosols

Water-soluble organic matter (WSOM) from atmospheric particles comprises a complex array of molecular structures that play an important role on the physic-chemical properties of atmospheric particles and, therefore, are linked to several global-relevant atmospheric processes which impact the climate and public health. Due to the large variety of sources and formation processes, adequate knowledge on WSOM composition and its effects on the properties of atmospheric aerosol are still limited. Therefore, this thesis aims at providing new insights on the molecular composition of WSOM from fine atmospheric aerosols typical of an urban area (Aveiro, Portugal). In a first step, adsorption phenomena of semivolatile organic compounds on quartz fibre filters employed in the collection of atmospheric aerosols were assessed. Afterwards, atmospheric aerosol samples were collected during fifteen months, on a weekly basis. A mass balance of aerosol samples was performed in order to set the relative contribution of elemental carbon, WSOM and water-insoluble organic matter to the aerosol mass collected at the urban area of Aveiro, with a special focus on the assessment of the influence of different meteorological conditions. In order to assess the chemical complexity of the WSOM from urban aerosols, their structural characteristics were studied by means of Fourier transform infrared infrared - Attenuated Total Reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning 13C nuclear magnetic resonance (CPMAS 13C NMR) spectroscopies, as well as their elemental composition. The structural characterization of aerosol WSOM samples collected in the urban area highlighted a highly complex mixture of functional groups. It was concluded that aliphatic and aromatic structures, hydroxyl groups and carboxyl groups are characteristic to all samples. The semi-quantitative assessment of the CPMAS 13C NMR data showed different distributions of the various functional groups between the aerosol samples collected at different seasons. Moreover, the presence of signals typical of lignin-derived structures in both CPMAS 13C NMR and FTIR-ATR spectra of the WSOM samples from the colder seasons, highlights the major contribution of biomass burning processes in domestic fireplaces, during low temperature conditions, into the bulk chemical properties of WSOM from urban aerosols. A comprehensive two-dimensional liquid chromatography (LC x LC) method, on-line coupled to a diode array, fluorescence, and evaporative light scattering detectors, was employed for resolving the chemical heterogeneity of the aerosol WSOM samples and, simultaneously, to map the hydrophobicity versus the molecular weight distribution of the samples. The LC x LC method employed a mixed-mode hydrophilic interaction column operating under aqueous reversed phase mode in the first dimension, and a size-exclusion column in the second dimension, which was found to be useful for separating the aerosol WSOM samples into various fractions with distinct molecular weight and hydrophobic features. The estimative of the average molecular weight (Mw) distribution of the urban aerosol WSOM samples ranged from 48 to 942 Da and from 45 to 1241 Da in terms of UV absorption and fluorescence detection, respectively. Findings suggest that smaller Mw group fractions seem to be related to a more hydrophobic nature.