Effect of alkali on methylene blue (CI Basic Blue 9) and other thiazine dyes

A detailed study of the action of alkali on methylene blue (Cl. Basic Blue 9) and other thiazine dyes was carried out through a combination of UV/visible spectroscopy, thin layer chromatography, mass and NMR spectrometry and computational methods. In 0.1 M aq alkali solution, methylene blue forms a highly coloured, lipophilic species that is mainly Bernthsen's methylene violet i.e. a hydrolysis decomposition product, this being contrary to the report of a red N-hydroxy methylene blue adduct. The nature of the heterocyclic nitrogen atom in C.I. Basic Blue 9 is discussed and it is concluded there is no basis for the proposal of nucleophile addition at this site of the dye. In contrast, other thiazine dyes are deprotonated by alkali to form their neutral, highly coloured, lipophilic conjugate base forms. (C) 2010 Elsevier Ltd. 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.

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.

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.

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.

VLT FORS spectra of blue supergiants in the Local Group galaxy NGC 6822

Half hour exposures using the ESO VLT/FORS1 combination at Paranal in Chile have allowed us to obtain spectra for three B supergiants in the dwarf irregular galaxy NGC 6822. The spectra have been analysed using non-LTE techniques and temperatures, gravities, helium content and abundances have been obtained. Overall the metallicity of NGC 6822 is found to lie between that of the LMC and of the SMC, in agreement with previous observations of H II regions and in contrast to the earlier findings of Massey et al. (1995). The analysis of H-alpha yields estimates of the mass-loss rates and wind momenta. These results demonstrate that significantly longer exposures with the same instruments will allow us to perform quantitative spectroscopy of blue supergiants in galaxies far beyond the Local Group.

A UKST survey of blue objects towards the galactic centre - a search for early-type stars

We have begun a search for early-type stars towards the galactic centre which are potentially young objects situated within the inner few kiloparsecs of the disk. U and V (or I) band photographic photometry from the UK Schmidt Telescope has been obtained to identify the bluest candidates in nineteen Schmidt fields (centred close to the galactic centre). We have spectroscopically observed these targets for three fields with the FLAIR multi-fibre system to determine their spectral types. In particular; ten early B-type stars have been identified and equivalent width measurements of their Balmer and HeI lines have been used to estimate atmospheric parameters. These early-type objects have magnitudes in the range 11.5 less than or equal to V less than or equal to 16.0, and our best estimates of their distance (given probable highly variable reddening in this direction together with errors in the plate photometry) suggest that some of them originated close to (i.e R-g

New identifications for blue objects towards the Galactic center: post-AGE stars, Be/disk stars and others

As part of a programme to investigate spatial variations in the Galactic chemical composition, we have been searching for normal B-type stars and A-type supergiants near the Galactic center. During this search we have found eleven peculiar stars, and in some cases performed detailed abundance analyses of them which suggest that they may be at a post-AGB evolutionary stage.