In situ, continuous monitoring of the photoinduced superhydrophilic effect: Influence of UV-type and ambient atmospheric and droplet composition

A controlled-atmosphere chamber, combined with a CCTV system, is used to monitor continuously the change in shape of water droplets on the self-cleaning commercial glass, Activ, and a sol-gel TiO2 substrate during their irradiation with either UVA or UVC light. This system allows the photoinduced superhydrophilic effect (PSH) exhibited by these materials to be studied in real time under a variety of different conditions. UVA was less effective than UVC in terms of PSH for both titania-coated glasses, and plain glass was unaffected by either form of UV irradiation and so showed no PSH activity. With UVA, ozone increased significantly the rate of PSH for both substrates, but had no effect on the wettability of plain glass. For both titania substrates and plain glass, no PSH activity was observed under an O-2-free atmosphere. A more detailed study of the PSH effect exhibited by Activ revealed that doping the water droplet with either an electron acceptor (Na2S2O8), electron donor (Na2S2O4), or simple electrolyte (KCl) in the absence of oxygen did not promote PSH. However, when Activ was UV irradiated, while immersed in a deoxygenated KCl solution, prior to testing for PSH activity, only a small change in contact angle was observed, whereas under the same conditions, but using a deoxygenated persulfate-containing immersion solution, it was rendered superhydrophilic. The correlation between organic contaminant removal and surface wetting was also investigated by using thick sol-gel films coated with stearic acid; the destruction of SA was monitored by FTIR and sudden wetting of the surface was seen to coincide with the substantial removal of the organic layer. The results of this work are discussed in the context of the current debate on the underlying cause of PSH.

A viologen-based UV indicator and dosimeter

A UV indicator/dosimeter based on benzyl viologen (BV2+) encapsulated in polyvinyl alcohol (PVA) is described. Upon exposure to UV light, the BV2+/PVA film turns a striking purple colour due to the formation of the cation radical, BV center dot+. The usual oxygen sensitivity of BV center dot+ is significantly reduced due to the very low oxygen permeability of the encapsulating polymer, PVA. Exposure of a typical BV2+/PVA film, for a set amount of time, to UVB light with different UV indices produces different levels of BV center dot+, as measured by the absorbance of the film at 550 nm. A plot of the change in absorbance at this wavelength, Delta Abs(550), as a function of UV index, UVI, produces a linear calibration curve which allows the film to be used as a UVB indicator, and a similar procedure could be employed to allow it to be used as a solar UVI indicator. A typical BV2+/PVA film generates a significant, semi-permanent (stable for > 24 h) saturated purple colour (absorbance similar to 0.8-0.9) upon exposure to sunlight equivalent to a minimal erythemal dose associated with Caucasian skin, i.e. skin type II. The current drawbacks of the film and the possible future use of the BV2+/PVA film as a personal solar UV dosimeter for all skin types are briefly discussed.

Development of a novel UV indicator and dosimeter film

A novel UV indicator is described, comprising nanocrystalline particles of titania dispersed in a film of a polymer, hydroxyl ethyl cellulose (HEC), containing: a mild reducing agent, triethanolamine (TEOA) and a redox indicator, methylene blue (MB). The UV indicator film is blue-coloured in the absence of UV light and loses colour upon exposure to UV light, attaining within a few min a steady-state degree of bleaching that can provide a measure of the irradiance of the incident light. The original blue colour of the film returns once the source of UV light is removed. The spectral characteristics of a typical UV indicator film, and its components, are discussed and the UV-absorbing action of the titania particles highlighted. From the measured %bleaching undergone by a typical UV indicator as a function of light irradiance the indicator appears fully bleached, within 7 min, by a UV irradiance of 3 mW cm (-) or greater. The mechanism by which the UV indicator works is described. The reversible nature of the UV indicator is removed by covering a typical UV indicator with a thin, largely oxygen impermeable, polymer film, such as the regenerated cellulose found in Sellotape(TM). The product is a UV dosimeter, the response of which is related to the intensity and duration of the incident UV light, as well as the amount of titania in the film. A typical UV dosimeter film is fully bleached by 250 mJ cm(-2) of UV light. The possible use of these novel indicators to measure UV exposure levels, irradiance and dose, is discussed.

Novel UV-activated colorimetric oxygen indicator

The results of a detailed characterization study of a novel UV-activated colorimetric oxygen indicator are described. The indicator uses nanoparticles of titania to photosensitize the reduction of methylene blue by triethanolamine in a polymer encapsulation medium, using UVA light. Upon UV irradiation, the indicator bleaches and remains in this colorless state in the dark, unless and until it is exposed to oxygen, whereupon its original color is restored. The indicator is reusable and irreversible. The rate of color recovery is proportional to the level of oxygen present. A layer of PET (poly(ethylene terephthalate)), of thickness b, placed on top of the indicator film slows down its response, and the 90% recovery time is proportional to b.

Determination of diclofenac from paediatric urine samples by stir bar sorptive extraction (SBSE)-HPLC-UV technique

A novel stir bar sorptive extraction (SBSE) method coupled with high performance liquid chromatography (HPLC) and UV detection for the extraction of diclofenac (DIC) from paediatric urine samples has been developed and validated. Selectivity and sensitivity being the prime objectives of the bioanalytical method for clinical samples, an optimised SBSE protocol was developed that selectively extracted DIC from various concurrently administered drugs. The validated assay was found to be linear (r=0.9999) over a concentration range of 100-2000 ng mL(-1). SBSE showed consistent recoveries (similar to 70%) of DIC across the validated linearity range. Overall, the method exhibited excellent accuracy and precision across all QC concentrations, tested over three days. Calculated LOD and LOQ were found to be 12.03 ng mL(-1) and 36.37 ng mL(-1), respectively, however, for the experimental purposes, 100 ngmL(-1) was considered as the validated LOQ(accuracy and precision at this LQC was

Massive stars exploding in a He-rich circumstellar medium - I. Type Ibn (SN 2006jc-like) events

We present new spectroscopic and photometric data of the Type Ibn supernovae 2006jc, 2000er and 2002ao. We discuss the general properties of this recently proposed supernova family, which also includes SN 1999cq. The early-time monitoring of SN 2000er traces the evolution of this class of objects during the first few days after the shock breakout. An overall similarity in the photometric and spectroscopic evolution is found among the members of this group, which would be unexpected if the energy in these core-collapse events was dominated by the interaction between supernova ejecta and circumstellar medium. Type Ibn supernovae appear to be rather normal Type Ib/c supernova explosions which occur within a He-rich circumstellar environment. SNe Ibn are therefore likely produced by the explosion of Wolf-Rayet progenitors still embedded in the He-rich material lost by the star in recent mass-loss episodes, which resemble known luminous blue variable eruptions. The evolved Wolf-Rayet star could either result from the evolution of a very massive star or be the more evolved member of a massive binary system. We also suggest that there are a number of arguments in favour of a Type Ibn classification for the historical SN 1885A (S-Andromedae), previously considered as an anomalous Type la event with some resemblance to SN 1991bg.

Massive stars exploding in a He-rich circumstellar medium - II. The transitional case of SN 2005la

We present photometric and spectroscopic data of the peculiar SN 2005la, an object which shows an optical light curve with some luminosity fluctuations and spectra with comparably strong narrow hydrogen and helium lines, probably of circumstellar nature. The increasing full width at half-maximum velocity of these lines is indicative of an acceleration of the circumstellar material. SN 2005la exhibits hybrid properties, sharing some similarities with both Type IIn supernovae and 2006jc-like (Type Ibn) events. We propose that the progenitor of SN 2005la was a very young Wolf-Rayet (WN-type) star which experienced mass ejection episodes shortly before core collapse.

The VLT-FLAMES survey of massive stars: wind properties and evolution of hot massive stars in the Large Magellanic Cloud

We have studied the optical spectra of a sample of 28 O- and early B-type stars in the Large Magellanic Cloud, 22 of which are associated with the young star forming region N11. Our observations sample the central associations of LH9 and LH10, and the surrounding regions. Stellar parameters are determined using an automated fitting method ( Mokiem et al. 2005), which combines the stellar atmosphere code fastwind ( Puls et al. 2005) with the genetic algorithm based optimisation routine PIKAIA ( Charbonneau 1995). We derive an age of 7.0 +/- 1.0 and 3.0 +/- 1.0 Myr for LH9 and LH10, respectively. The age difference and relative distance of the associations are consistent with a sequential star formation scenario in which stellar activity in LH9 triggered the formation of LH10. Our sample contains four stars of spectral type O2. From helium and hydrogen line fitting we find the hottest three of these stars to be similar to 49- 54 kK ( compared to similar to 45- 46 kK for O3 stars). Detailed determination of the helium mass fraction reveals that the masses of helium enriched dwarfs and giants derived in our spectroscopic analysis are systematically lower than those implied by non-rotating evolutionary tracks. We interpret this as evidence for efficient rotationally enhanced mixing leading to the surfacing of primary helium and to an increase of the stellar luminosity. This result is consistent with findings for SMC stars by Mokiem et al. ( 2006). For bright giants and supergiants no such mass discrepancy is found; these stars therefore appear to follow tracks of modestly or non-rotating objects. The set of programme stars was sufficiently large to establish the mass loss rates of OB stars in this Z similar to 1/2 Z(circle dot) environment sufficiently accurate to allow for a quantitative comparison with similar objects in the Galaxy and the SMC. The mass loss properties are found to be intermediate to massive stars in the Galaxy and SMC. Comparing the derived modified wind momenta D-mom as a function of luminosity with predictions for LMC metallicities by Vink et al. ( 2001) yields good agreement in the entire luminosity range that was investigated, i.e. 5.0

The VLT-FLAMES survey of massive stars: observations centered on the Magellanic Cloud clusters NGC 330, NGC 346, NGC 2004, and the N11 region

We present new observations of 470 stars using the Fibre Large Array Multi-Element Spectrograph ( FLAMES) instrument in fields centered on the clusters NGC330 and NGC346 in the Small Magellanic Cloud (SMC), and NGC2004 and the N11 region in the Large Magellanic Cloud (LMC). A further 14 stars were observed in the N11 and NGC330 fields using the Ultraviolet and Visual Echelle Spectrograph (UVES) for a separate programme. Spectral classifications and stellar radial velocities are given for each target, with careful attention to checks for binarity. In particular, we have investigated previously unexplored regions around the central LH9/LH10 complex of N11, finding similar to 25 new O-type stars from our spectroscopy. We have observed a relatively large number of Be-type stars that display permitted Fe II emission lines. These are primarily not in the cluster cores and appear to be associated with classical Be-type stars, rather than pre main-sequence objects. The presence of the Fe II emission, as compared to the equivalent width of Ha, is not obviously dependent on metallicity. We have also explored the relative fraction of Be- to normal B-type stars in the field-regions near to NGC330 and NGC2004, finding no strong evidence of a trend with metallicity when compared to Galactic results. A consequence of service observations is that we have reasonable time-sampling in three of our FLAMES fields. We find lower limits to the binary fraction of O- and early B-type stars of 23 to 36%. One of our targets (NGC346-013) is especially interesting with a massive, apparently hotter, less luminous secondary component.

Blue luminous stars in nearby galaxies: Quantitative spectral analysis of M33 B-type supergiant stars

We present the detailed spectral analysis of a sample of M33 B-type supergiant stars, aimed at the determination of their fundamental parameters and chemical composition. The analysis is based on a grid of non-LTE metal line-blanketed model atmospheres including the effects of stellar winds and spherical extension computed with the code FASTWIND. Surface abundance ratios of C, N, and O are used to discuss the chemical evolutionary status of each individual star. The comparison of observed stellar properties with theoretical predictions of massive star evolutionary models shows good agreement within the uncertainties of the analysis. The spatial distribution of the sample allows us to investigate the existence of radial abundance gradients in the disk of M33. The comparison of stellar and H II region O abundances ( based on direct determinations of the electron temperature of the nebulae) shows good agreement. Using a simple linear radial representation, the stellar oxygen abundances result in a gradient of -0.0145 +/- 0.005 dex arcmin(-1) (or -0.06 +/- 0.02 dex kpc(-1)) up to a distance equal to similar to 1.1 times the isophotal radius of the galaxy. A more complex representation cannot be completely discarded by our stellar sample. The stellar Mg and Si abundances follow the trend displayed by O abundances, although with shallower gradients. These differences in gradient slope cannot be explained at this point. The derived abundances of the three alpha-elements yield solar metallicity in the central regions of the disk of M33. A comparison with recent planetary nebula data from Magrini and coworkers indicates that the disk of M33 has not suffered from a significant O enrichment in the last 3 Gyr.