Simple method for the rapid simultaneous screening of photocatalytic activity over multiple positions of self-cleaning films

An intelligent ink, previously shown to be capable of rapidly assessing photocatalytic activity, was simply applied via a felt-pen onto a commercially available piece of Activ (TM) self-cleaning glass. The ink, comprising of redox dye resazurin and the sacrificial electron donor glycerol within an aqueous hydroxy ethyl cellulose (HEC) polymer media, was photocatalytically degraded in a two-step process. The key initial stage was the photo-reductive conversion of resazurin to resorufin, whereby a colour change from blue to pink occurred. The latter stage was the subsequent photo-reduction of the resorufin, where a slower change from pink to colourless was seen. Red and green components of red-green-blue colour extracted from flat-bed scanner digital images of resazurin ink coated photocatalytic films at intervals during the photocatalysis reaction were inversely proportional to the changes seen via UV-visible absorption spectroscopy and indicative of reaction kinetics. A 3 x 3 grid of intelligent ink was drawn onto a piece of Activ (TM) and a glass blank. The photocatalysis reaction was monitored solely by flat-bed digital scanning. Red-green-blue values of respective positions on the grid were extracted using a custom-built program entitled RGB Extractor (c). The program was capable of extracting a number of 5 x 5 pixel averages of red-green-blue components simultaneously. Allocation of merely three coordinates allowed for the automatic generation of a grid, with scroll-bars controlling the number of positions to be extracted on the grid formed. No significant change in red and green components for any position on the glass blank was observed; however, the Activ (TM) film displayed a homogenous photo-reduction of the dye, reaching maxima in red and minima in green components in 23 +/- 3 and 14 +/- 2 min, respectively. A compositionally graded N-doped titania film synthesised in house via a combinatorial APCVD reaction was also photocatalytically tested by this method where 247 positions on a 13 x 19 grid were simultaneously analysed. The dramatic variation in photocatalysis observed was rapidly quantified for all positions (2-3 hours) allowing for correlations to be made between thicknesses and N : Ti% compositions attained from Swanepoel and WDX analysis, respectively. N incorporation within this system was found to be detrimental to film activity for the photocatalysis reaction of intelligent ink under 365 nm light.

Method of rapid assessment of photocatalytic activities of self-cleaning films

An ink, comprising the redox dye resazurin (Rz) and the sacrificial electron donor glycerol, is shown to be capable of the rapid assessment of the photocatalytic activities of self-cleaning films. In the key initial stage of photocatalysis the ink changes from blue to pink. Prolonged irradiation bleaches the ink and eventually mineralizes it. The kinetics of the initial photoinduced color change is studied as a function of UV irradiance, [glycerol], [Rz], and temperature. The results reveal an apparent approximate quantum yield of 3.5 x 10(-3) and an initial rate, r(i), which increases with [glycerol] and decreases with [Rz]. It is proposed that the reduction of Rz, dispersed throughout the thick (ca. 590 nm) indicator film, may take place either via the diffusion of the dye molecules in the ink film to the surface of the underlying semiconductor layer and their subsequent reaction with photogenerated electrons and/or via the diffusion of alpha-hydroxyalkyl radicals, produced by the oxidation of the glycerol by photogenerated holes, or hydroxy radicals, away from the surface of the semiconductor into the ink film and their subsequent reaction with the dye molecules therein. The decrease in r(i) with [Rz] appears to be due to dimer formation, with the latter impeding the reduction process. The activation energy for the initial color-change process is low, ca. 9.1 +/- 0.1 kJ mol(-1) and not unlike many other photocatalytic processes. The initial rate of dye reduction appears to be directly related to the rate of destruction of stearic acid. The ink can be applied by spin-coating, stamping, or writing, using a felt-tip pen. The efficacy of such an ink for assessing the photocatalytic activity of any photocatalytic film, including those employed on commercial self-cleaning glasses, tiles, and paving stones, is discussed briefly.

Novel photochemistry of leuco-Methylene Blue

leuco-Methylene Blue has a previously unrecognized, very reactive, UV-driven triplet state photochemistry and, in particular, undergoes photo-oxidative quenching with dissolved oxygen.

Kinetics and mechanism of a fast leuco-Methylene Blue oxidation by copper(II)-halide species in acidic aqueous media

The kinetics of a fast leuco-Methylene Blue (LMB) re-oxidation to Methylene Blue (MB) by copper(II)-halide (Cl-, Br-) complexes in acidic aqueous media has been studied spectrophotometrically using a stopped-flow technique. The reaction follows a simple first order rate expression under an excess of the copper(II) species (and H+(aq)), and the pseudo-first order rate constant (k'(obs)) is largely independent of the atmosphere used (air, oxygen, argon). The rate law, at constant Cl- (Br-) anion concentration, is given by the expression: (d[MB+])/dt = ((k(a)K[H+] + k(b))/(1 + K[H+])).[Cu-II][LMB] = k'(obs)[LMB], where K is the protonation constant, and k(a) and k(b) are the pseudo-second order rate constants for protonated and deprotonated forms of LMB, respectively The rate law was determined based on the observed k'(obs) vs. [Cu-II] and [H+] dependences. The rate dramatically increases with [Cl-] over the range: 0.1-1.5 M, reflecting the following reactivity order: Cu2+(aq)

Photobleaching of methylene blue sensitised by TiO2: an ambiguous system?

The photobleaching of methylene blue MB, sensitised by TiO2, in an aqueous solution is studied in the absence and presence of oxygen, in the absence of oxygen and in the presence of a sacrificial electron acceptor (SED), MB is photoreduced to its colourless leuco form, LMB, by the TiO2 photocatalyst. This same photoreduction process is observed even if an SED is not present, indicating that MB itself can act as an SED. The oxidation of LMB by oxygen to regenerate MB is significantly slower if the aqueous solution is acidified (0.01 mol dm(-3) HClO4) and, at low partial pressures, the rate of reaction depends directly upon the concentration of dissolved oxygen. The TiO2-sensitised photobleaching of MB is irreversible in an oxygen-saturated aqueous solution, as expected, since the bleaching was due to an oxidative process. However, in an acidified solution (0.01 mol dm(-3) HClO4), the photobleaching process, in an oxygen-saturated solution, generates LMB initially. The latter situation arises because, under acidic conditions, LMB reacts only very slowly with oxygen to form MB. The significance of these findings with respect to the popular use of photobleaching of MB as a demonstration of semiconductor photomineralisation is discussed. (C) 1999 Elsevier Science S.A. All rights reserved.

Pilgrimstad revisited - a multi-proxy reconstruction of Early/Middle Weichselian climate and environment at a key site in central Sweden

The site Pilgrimstad in central Sweden has often been cited as a key locality for discussions of ice-free/ice-covered intervals during the Early and Middle Weichselian. Multi-proxy investigations of a recently excavated section at Pilgrimstad now provide a revised picture of the climatic and environmental development between similar to 80 and 36 ka ago. The combination of sedimentology, geochemistry, OSL and 14C dating, and macrofossil, siliceous microfossil and chironomid analyses shows: (i) a lower succession of glaciofluvial/fluvial, lacustrine and glaciolacustrine sediments; (ii) an upper lacustrine sediment sequence; and (iii) Last Glacial Maximum till cover. Microfossils in the upper lacustrine sediments are initially characteristic for oligo- to mesotrophic lakes, and macrofossils indicate arctic/sub-arctic environments and mean July temperatures > 8 degrees C. These conditions were, however, followed by a return to a low-nutrient lake and a cold and dry climate. The sequence contains several hiatuses, as shown by the often sharp contacts between individual units, which suggests that ice-free intervals alternated with possible ice advances during certain parts of the Early and Middle Weichselian.

Design considerations for the autism spectrum disorder-friendly Key Stage 1 classroom

There is a growing consensus that an appropriate classroom environment will aid the performance of the pupil with autism spectrum disorder (ASD). There are, however, very few design guidelines available when considering ASD and the school environment. Such guidelines that do exist tend only to be in general terms. Therefore, this article seeks to highlight design considerations specifically for the ASD-friendly Key Stage 1 (age five to eight) classroom. It will first highlight some of the challenges for those with autism spectrum disorder in a school environment and the triad of challenges faced by architects and designers when considering ASD-friendly classroom design. It will then go on to describe the findings and results of a two-year study carried out in conjunction with the ASD teaching staff of Northern Ireland's Southern Education and Library Board. These consist of 16 specific design considerations for the Key Stage 1 ASD-friendly classroom applicable to all classrooms for pupils between five and eight years of age.

The blue supergiant Sher 25 and its intriguing hourglass nebula

The blue supergiant Sher 25 is surrounded by an asymmetric, hourglass-shaped circumsteller nebula. Its structure and dynamics have been studied previously through high-resolution imaging and spectroscopy, and it appears dynamically similar to the ring structure around SN 1987A. Here, we present long-slit spectroscopy of the circumstellar nebula around Sher 25, and of the background nebula of the host cluster NGC 3603. We perform a detailed nebular abundance analysis to measure the gas-phase abundances of oxygen, nitrogen, sulphur, neon and argon. The oxygen abundance in the circumstellar nebula (12 + log O/H = 8.61 +/- 0.13 dex) is similar to that in the background nebula (8.56 +/- 0.07), suggesting that the composition of the host cluster is around solar. However, we confirm that the circumsteller nebula is very rich in nitrogen, with an abundance of 8.91 +/- 0.15, compared to the background value of 7.47 +/- 0.18. A new analysis of the stellar spectrum With the FASTWIND model atmosphere code suggests that the photospheric nitrogen and oxygen abundances in Sher 25 are consistent with the nebular results. While the nitrogen abundances are high, when compared to stellar evolutionary models, they do not unambiguously confirm that the star has undergone convective dredge-up during a previous red supergiant phase. We suggest that the more likely scenario is that the nebula was ejected from the star while it was in the blue supergiant phase. The star's initial mass was around 50 M-circle dot which is rather too high for it to have had a convective envelope stage as a red supergiant. Rotating stellar models that lead to mixing of core-processed material to the stellar surface during core H-burning can quantitatively match the stellar results with the nebula abundances.

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.