Water-based colourimetric optical indicators for the detection of carbon dioxide

Water-based colourimetric indicator films are shown to have increased operational lifetimes under ambient conditions compared to similar solvent-based counterparts. The response and sensitivity characteristics of a water-based, carbon dioxide-responsive ink are characterised and compared and contrasted to those of a similar solvent-based indicator. The changes in the response characteristics of the ink as a function of the amount of base (sodium hydrogen carbonate) and plasticizer (glycerol) contained in the ink are reported, as are the effects of varying ambient temperature and humidity. The ink is incorporated into a felt tip pen and applied to a number of different substrates, producing a distinct, reversible colour change on all tested surfaces, when a sufficient level of carbon dioxide is present. The possible application of the indicator is discussed briefly.

Intelligent pigments and plastics for CO2 detection

A novel CO2 intelligent pigment is incorporated into a thermoplastic polymer to create a long-lived CO2-sensitive plastic film which is characterised and then compared to a traditional solvent-based CO2 indicator film.

A comprehensive aerosol spray method for the rapid photocatalytic grid area analysis of semiconductor photocatalyst thin films

Indicator inks, previously shown to be capable of rapidly assessing photocatalytic activity via a novel photo-reductive mechanism, were simply applied via an aerosol spray onto commercially available pieces of Activ (TM) self-cleaning glass. Ink layers could be applied with high evenness of spread, with as little deviation as 5% upon UV-visible spectroscopic assessment of 25 equally distributed positions over a 10 cm x 10 cm glass cut. The inks were comprised of either a resazurin (Rz) or dichloroindophenol (DCIP) redox dye with a glycerol sacrificial electron donor in an aqueous hydroxyethyl cellulose (HEC) polymer media. The photo-reduction reaction under UVA light of a single spot was monitored by UV-vis spectroscopy and digital images attained from a flat-bed scanner in tandem for both inks. The photo-reduction of Rz ink underwent a two-step kinetic process, whereby the blue redox dye was initially reduced to a pink intermediate resorufin (Rf) and subsequently reduced to a bleached form of the dye. In contrast, a simple one-step kinetic process was observed for the reduction of the light blue redox dye DCIP to its bleached intermediates. Changes in red-green-blue colour extracted from digital images of the inks were inversely proportional to the changes seen at corresponding wavelengths via UV-visible absorption spectroscopy and wholly indicative of the reaction kinetics. The photocatalytic activity areas of cuts of Activ (TM) glass, 10 cm x 10 cm in size, were assessed using both Rz and DCIP indicator inks evenly sprayed over the films: firstly using UVA lamp light to activate the underlying Activ (TM) film (1.75 mW cm(-2)) and secondly under solar conditions (2.06 +/- 0.14 mW cm(-2)). The photo-reduction reactions were monitored solely by flat-bed digital scanning. Red-green-blue values of a generated 14 x 14 grid (196 positions) that covered the entire area of each film image were extracted using a Custom-built program entitled RGB Extractor(C). A homogenous degradation over the 196 positions analysed for both Rz (Red colour deviation = 19% UVA, 8% Solar: Green colour deviation = 17% UVA, 12% Solar) and DCIP (Red colour deviation = 22% UVA, 16% Solar) inks was seen in both UVA and solar experiments, demonstrating the consistency of the self-cleaning titania layer on Activ (TM). The method presented provides a good solution for the high-throughput photocatalytic screening of a number of homogenous photocatalytically active materials simultaneously or numerous positions on a single film; both useful in assessing the homogeneity of a film or determining the best combination of reaction components to produce the optimum performance photocatalytic film. (C) 2010 Elsevier B.V. All rights reserved.

A novel reversible relative-humidity indicator ink based on methylene blue and urea

A new relative-humidity sensitive ink based on methylene blue and urea is described which can utilise the deliquescent nature of urea.

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.

The Kinetics of Semiconductor Photocatalysis in Activity-Indicator Films

The kinetics of dye reduction, in photocatalyst indicator ink films on self cleaning glass, is studied with respect to dye concentration. The water-based, photocatalyst indicator inks comprised a redox dye, D-ox, a sacrificial electron donor (glycerol) and a polymer, hydroxyethyl cellulose. The dyes used were: Resazurin (Rz), dichloroindo-phenol (DCIP) and methylene blue (MB), although the latter required acidification of the ink (0.01M HCl) to make it work effectively under ambient conditions. Under anaerobic conditions, the photoreduction of each of the dyes, in an otherwise identical ink formulation, on Activ (TM) self-cleaning glass is zero-order with respect to [D-ox]. Seven commercial samples of Rz, each in a typical ink formulation, were tested on the same piece of self-cleaning glass under aerobic conditions and produced a striking range (over 280%) of different apparent activities for the glass, when there should have been none. The underlying cause of this variation in assessed activity is shown to be due to the combination of a variation in the purity of the commercial samples and the zero-order nature of the kinetics of indicator dye reduction. The relevance of this work and the latter observation, in particular to future use of these films for the rapid assessment of the activities of new and established photocatalytic films, is briefly discussed.

A Novel, Fast-Responding, Indicator Ink for Thin Film Photocatalytic Surfaces

A new photocatalyst indicator ink based on methylene blue (MB) is described that allows the presence and activity of a thin (15 nm) photocatalytic film to be assessed in seconds. The ink is very stable (shelf life > 6 months) and the color change (blue to colorless) striking. The ink utilizes a sacrificial electron donor, glycerol, to trap the photogenerated holes, leaving the photogenerated electrons to react with MB to produce its. reduced, leuco, form (LMB). The efficacy of the MB ink is due to the presence of acid in its formulation, which curtails significantly. the otherwise usual, rapid reoxidation of LMB by ambient O-2.

UV dosimeter based on dichloroindophenol and tin(IV) oxide

A UVB specific dosimeter is described comprising: a redox dye (2,6-dichloroindophenol, DCIP), a semiconductor ( tin(IV) oxide, SnO2) and a sacrificial electron donor ( glycerol) dispersed in a polymer ( hydroxy ethyl cellulose, HEC) film. The dosimeter is blue in the absence of UVB light but rapidly loses colour on exposure to UVB light. The spectral characteristics of a typical UVB dosimeter film and the mechanism by which the colour change occurs are detailed. DCIP UVB dosimeter films exhibit a response that is related to the irradiance level and duration of UVB exposure, the level of SnO2 present and to a lesser extent the level of glycerol present. The response of the dosimeter appears to be independent of dye concentration and film thickness. Furthermore, DCIP UVB dosimeter films respond to solar simulated light, exhibiting a colour loss that can be simply related to the Minimal Erythemal Dose (MED) exposure for skin type II. As a consequence, such indicators have potential for measuring solar radiation exposure and providing an early warning of erythema for most Caucasian skin (i.e. skin type II).

Nanocrystalline SnO2-based, UVB-activated, colourimetric oxygen indicator

Nanocrystalline SnO2, ncSnO(2), is used as a photosensitiser in a colourimetric O-2 indicator that comprises a sacrificial electron donor, glycerol, a redox dye, methylene blue (MB), and an encapsulating polymer, hydroxyethyl cellulose (HEC). Upon exposure to a burst of UVB light the indicator is activated (photo-bleached) as the MB is photoreduced by the ncSnO(2) particles. In the absence of oxygen, the film stays bleached, but recovers its original colour upon exposure to oxygen. Unlike its TiO2-based predecessor, the HEC/glycerol/MB/ncSnO(2) O-2 indicator is not activated by UVA light from white fluorescent lamps, but is by UVB light. This feature provides much greater control in the activation of the indicator. Other work shows the rate of activation depends upon I-0.75, where I is the UVB irradiance, indicating a partial dependence upon the electron-hole recombination process. The half-life of the recovery of the original colour of a UV-activated film, t(50), is directly proportional to the ambient level of oxygen. The advantages of using this indicator in modified atmosphere packaging as a possible quality assurance indicator are discussed briefly. (c) 2008 Elsevier B.V. All rights reserved.

Hydrogen peroxide vapour indicator

A hydrogen peroxide vapour indicator is described comprising a triarylmethane dye, lissamine green (LG), dissolved in a polymer, polyvinyl alcohol (PVA). The indicator is green/blue in the absence of hydrogen peroxide vapour but is rapidly bleached in the presence of hydrogen peroxide vapour. The kinetics of LG bleaching appear approximately first order with respect [LG] and the concentration of H2O2, which, in turn, is proportional to the partial pressure of H2O2. However, the kinetics also appear to depend directly upon the reciprocal of the film thickness, implying some dependence upon the diffusion of the H2O2 vapour through the indicator film. Like most other H2O2 indicator films (such as starch-iodide paper), the LG/PVA indicator is not particularly selective and responds to most other volatile strong oxidising agents, such as ozone and chlorine. However, it is rapid in response (

Blue bottle light: lecture demonstrations of homogeneous and heterogeneous photo-induced electron transfer reactions

The classic, non-photochemical blue bottle experiment involves the reaction of methylene blue (MB) with deprotonated glucose, to form a bleached form of the dye, leuco-methylene blue (LMB), and subsequent colour recovery by shaking with air. This reaction is a popular demonstrator of key principles in kinetics and reaction mechanisms. Here it is modified so as to highlight features of homogenous and heterogeneous photoinduced electron transfer (PET) (Pure Appl. Chem., 2007, 79, 293-465) reactions, i.e. blue bottle light experiments. The homogeneous blue bottle light experiment uses methylene blue, MB, as the photo-sensitizer and triethanolamine as the sacrificial electron donor. Visible light irradiation of this system leads to its rapid bleaching, followed by the ready restoration of its original colour upon shaking away from the light source. The heterogeneous blue bottle light experiment uses titania as the photo-sensitizer, MB as a redox indicator and glucose as the sacrificial electron donor. UVA light irradiation of this system leads to the rapid bleaching of the MB and the gradual restoration of its original colour with shaking and standing. The latter 'dark' step can be made facile and more demonstrator-friendly by using platinised titania particles. These two photochemical versions of the blue bottle experiment are used to explore the factors which underpin homogeneous and heterogeneous PET reactions and provide useful demonstrations of homogeneous and heterogeneous photochemistry.

UV dosimeters based on neotetrazolium chloride

A novel UV dosimeter is described comprising a tetrazolium dye, neotetrazolium chloride (NTC), dissolved in a film of polymer, polyvinyl alcohol (PVA). The dosimeter is pale yellow/colourless in the absence of UV light, and turns red upon exposure to UV light. The spectral characteristics of a typical UV dosimeter film and the mechanism through which the colour change occurs are detailed. The NTC UV dosimeter films exhibit a response to UV light that is related to the intensity and duration of UV exposure, the level of dye present in the films and the thickness of the films themselves. The response of the dosimeter is temperature independent over the range 20-40 degrees C and, like most UV dosimeters, exhibits a cosine-like response dependence upon irradiance angle. The introduction of a layer of a UV-screening compound which slows the rate at which the dosimeter responds to UVR enables the dosimeter response to be tailored to different UV doses. The possible use of these novel dosimeters to measure solar UV exposure dose is discussed. (c) 2008 Elsevier B.V. All rights reserved.