The feasibility of laser cooling AlH and AlF is investigated using ab initio quantum chemistry. All the electronic states corresponding to the ground and lowest two excited states of the Al atom are calculated using multi-reference configuration interaction (MRCI) and the large AV6Z basis set for AlH. The smaller AVQZ basis set is used to calculate the valence electronic states of AlF. Theoretical Franck-Condon factors are determined for the A(1)Π→ X(1)Σ(+) transitions in both radicals and found to agree with the highly diagonal factors found experimentally, suggesting computational chemistry is an effective method for screening suitable laser cooling candidates. AlH does not appear to have a transition quite as diagonal as that in SrF (which has been laser cooled) but the A(1)Π→ X(1)Σ(+) transition transition of AlF is a strong candidate for cooling with just a single laser, though the cooling frequency is deep in the UV. Furthermore, the a(3)Π→ X(1)Σ(+) transitions are also strongly diagonal and in AlF is a practical method for obtaining very low final temperatures around 3 μK.
Three photocatalyst inks based on the redox dyes, Resazurin (Rz), Basic Blue 66 (BB66) and Acid Violet 7 (AV7, are used to assess the photocatalytic activities of a variety of different materials, such as commercial paint, tiles and glass and laboratory made samples of sol-gel coated glass and paint, which collectively exhibit a wide range of activities that cannot currently be probed by any one of the existing ISO tests. Unlike the ISO tests, the ink tests are fast (typically < 10 min), simple to employ and inexpensive. Previous work indicates that the Rz ink test at least correlates linearly with other photocatalytic tests such as the photomineralisation of stearic acid. The average time to bleach 90% of the key RGB colour component of the ink (red for Rz and BB66 inks) and green for AV7 ink) is determined, ca. 11% and ca 21%, respectively, which compare well with those reported for the current ISO tests. Additional work on commercial self-cleaning glass using an Rz ink showed that the change in the red component of the RGB image of the ink correlated linearly with that of the change of absorbance (at 608 nm) (as measured using UV/Vis spectroscopy) and the change in the a* component of the Lab colour analysis of the ink, as measured using diffuse reflectance spectroscopy. As a consequence, all three methods generate the same ttb(90).The advantages of the RGB digital image analysis method are discussed briefly.
Semiconductor-sensitised photocatalysis is a well-established and growing area of research, innovation and commercialisation; the latter being mostly limited to the use of TiO2 as the semiconductor. Most of the work on semiconductor photocatalytic systems uses oxygen as the electron acceptor and explores a wide range of electron donors; such systems can be considered to be examples of oxidative photocatalysis, OP. OP underpins most current examples of commercial self-cleaning materials, such as: glass, tiles, concrete, paint and fabrics. OP, and its myriad of applications, have been reviewed extensively over the years both in this journal and elsewhere. However, the ability of TiO2, and other semiconductor sensitisers, to promote reductive photocatalysis, RP, especially of dyes, is significant and, although less well-known, is of growing importance. In such systems, the source of the electrons is some easily oxidised species, such as glycerol. One recent, significant example of a RP process is with respect to photocatalyst activity indicator inks. paiis, which provide a measure of the activity of a photocatalytic film under test via the rate of change of colour of the dye in the ink coating due to irreversible RP. In contrast, by incorporating the semiconductor sensitiser in the ink, rather than outside it, it is possible to create an effective UV dosimeter, based on RP, which can be used as a sun-burn warning indicator. In the above examples the dye is reduced irreversibly, but when the photocatalyst in an ink is used to reversibly photoreduce a dye, a novel, colourimetric oxygen-sensitive indicator ink can be created, which has commercial potential in the food packaging industry. Finally, if no dye is present in the ink, and the semiconductor photocatalyst-loaded ink film coats an easily reduced substrate, such as a metal oxide film, then it can be used to reduce the latter and so, for example, clean up tarnished steel. The above are examples of smart inks, i.e. inks that are active and provide either dynamic information (such as UV dose or O2 level) or a useful function (such as tarnish removal), and all work via a RP process and are reviewed here.
The first example of an extruded polymer film containing the pH sensitive dye bromophenol blue (BPB) is described in which the polymer encapsulated dye changes colour from yellow to blue upon exposure to basic volatile nitrogen compounds, such as those given off by fish as it spoils. The latter include: trimethylamine (TMA), dimethylamine (DMA) and ammonia (NH 3), and are collectively known as total volatile basic nitrogen (TVB-N). The films' colourimetric response to specific levels of TMA, as measured using absorbance spectroscopy and digital photography coupled with RGB colour analysis, is reported. The indicator is then used as a fish spoilage indicator at 22 and 4 o C, whilst at the same time a microbiological study is carried out, and in both cases the results reveal a strong correlation between the change in colour of the indicator with the concentration of bacterial colony forming units on the fish; the latter is often used as a measure of fish freshness. The correlation arises because the increase in TVB-N in head space of the package is due to the gradual bacteria-induced decomposition of the fish. The colourimetric TVB-N plastic film indicator's potential as a spoilage indicator for packaged fresh fish is discussed briefly.
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