Chemically induced phosphorescence from manganese(II) during the oxidation of various compounds by manganese(III), (IV) break and (VII) in acidic aqueous solutions

Chemiluminescence was observed during the manganese(III), (IV) and (VII) oxidations of sodium tetrahydroborate, sodium dithionite, sodium sulfite and hydrazine sulfate in acidic aqueous solution. From the corrected chemiluminescence spectra, the wavelengths of maximum emission were 689±5 and 734±5 nm when the reactions were performed in sodium hexametaphosphate and sodium dihydrogenorthophosphate/ orthophosphoric acid environments, respectively. The corrected phosphorescence spectrum of manganese(II) sulfate in a solution of sodium hexametaphosphate at 77 K exhibited two peaks with maxima at 688 and 730 nm. The chemical and spectroscopic evidence presented strongly supported the postulation that the emission was an example of solution-phase chemically induced phosphorescence of manganese(II) thereby, confirming earlier predictions that the chemiluminescence from acidic potassium permanganate reactions originated from an excited manganese(II) species.

Chemistry, spectroscopy and analytical applications of certain chemiluminescent reactions

Chemiluminescence, the production of light from a chemical reaction, has found widespread use in analytical chemistry. Both tris (2, 2’-bipyridyl) ruthenium (II) and acidic potassium permanganate are chemiluminescence reagents that have been employed for the determination of a diverse range of analytes. This thesis encompasses some fundamental investigations into the chemistry and spectroscopy of these chemiluminescence reactions as well as extending the scope of their analytical applications. Specifically, a simple and robust capillary electrophoresis chemiluminescence detection system for the determination of codeine, O6-methylcodeine and thebaine is described, based upon the reaction of these analytes with chemically generated tris(2,2'-bipyridyl)ruthenium(III) prepared in sulfuric acid (0.05 M). The reagent solution was contained in a glass detection cell, which also held both the capillary and the cathode. The resultant chemiluminescence was monitored directly using a photomultiplier tube mounted flush against the base of the detection cell. The methodology, which incorporated a field amplification sample introduction procedure, realised detection limits (3a baseline noise) of 5 x 10~8 M for both codeine and O6-methylcodeine and 1 x 10~7 M for thebaine. The relative standard deviations of the migration times and the peak areas for the three analytes ranged from 2.2 % up to 2.5 % and 1.9 % up to 4.6 % respectively. Following minor instrumental modifications, morphine, oripavine and pseudomorphine were determined based upon their reaction with acidic potassium permanganate in the presence of sodium polyphosphate. To ensure no migration of the permanganate anion occurred, the anode was placed at the detector end whilst the electroosmotic flow was reversed by the addition of hexadimethrine bromide (0.001% m/v) to the electrolyte. The three analytes were separated counter to the electroosmotic flow via their interaction with a-cyclodextrin. The methodology realised detection limits (3 x S/N) of 2.5 x 10~7 M for both morphine and oripavine and 5 x 10~7 M for pseudomorphine. The relative standard deviations of the migration times and the peak heights for the three analytes ranged from 0.6 % up to 0.8 % and 1.5% up to 2.1 % respectively. Further improvements were made by incorporating a co-axial sheath flow detection cell. The methodology was validated by comparing the results realised using this technique with those obtained by high performance liquid chromatography (HPLC), for the determination of both morphine and oripavine in seven industrial process liquors. A complimentary capillary electrophoresis procedure with UV-absorption detection was also developed and applied to the determination of morphine, codeine, oripavine and thebaine in nine process liquors. The results were compared with those achieved using a standard HPLC method. Although over eighty papers have appeared in the literature on the analytical applications of acidic potassium permanganate chemiluminescence, little effort has been directed towards identifying the origin of the luminescence. It was found that chemiluminescence was generated during the manganese(III), manganese(IV) and manganese(VII) oxidations of sodium borohydride, sodium dithionite, sodium sulfite and hydrazine sulfate in acidic aqueous solution. From the corrected chemiluminescence spectra, the wavelengths of maximum emission were 689 ± 5 nm and 734 ± 5 nm when the reactions were performed in sodium hexametaphosphate and sodium dihydrogenorthophosphate or orthophosphoric acid environments respectively. The corrected phosphorescence spectrum of manganese(II) sulfate in a solution of sodium hexametaphosphate at 77 K, exhibited two peaks with maxima at 688 nm and 730 nm. The chemical and spectroscopic evidence presented strongly supported the postulation that the emission was an example of solution phase chemically induced phosphorescence of manganese(II). Thereby confirming earlier predictions that the chemiluminescence from acidic potassium permanganate reactions originated from an excited manganese(II) species. Additionally, these findings have had direct analytical application in that manganese(IV) was evaluated as a new reagent for chemiluminescence detection. The oxidations of twenty five organic and inorganic species, with solublised manganese(IV), were found to elicit analytically useful chemiluminescence with detection limits (3 x S/N) for Mn(II), Fe(II), morphine and codeine of 5 x 10-8 M, 2.5 x 10-7 M, 7.5 x 10-8 M and 5 x 10-8M, respectively. The corrected emission spectra from four different analytes gave wavelengths of maximum emission in the range from 733 nm up to 740 nm indicating that these chemiluminescence reactions also shared a common emitting species, excited manganese(II). Whilst several analytical problems were addressed in this thesis and answers to certain questions regarding the fundamentals of acidic potassium permanganate chemiluminescence were proposed, there are several areas that would benefit from further research. These are outlined in the final chapter of this thesis.

Survey of contact lens prescribing to infants, children, and teenagers

Purpose. To determine the types of contact lenses prescribed for infants (aged 0 to 5 years), children (6 to 12 years), and teenagers (13 to 17 years) around the world.

Methods. Up to 1000 survey forms were sent to contact lens fitters in each of 38 countries between January and March every year for 5 consecutive years (2005 to 2009). Practitioners were asked to record data relating to the first 10 contact lens fits or refits performed after receiving the survey form.

Results. Data were received relating to 105,734 fits [137 infants, 1,672 children, 12,117 teenagers, and 91,808 adults (age ≥18 years)]. The proportion of minors (<18 year old) fitted varied considerably between nations, ranging from 25% in Iceland to 1% in China. Compared with other age groups, infants tend to be prescribed a higher proportion of rigid, soft toric, and extended wear lenses, predominantly as refits for full-time wear, and fewer daily disposable lenses. Children are fitted with the highest proportion of daily disposable lenses and have the highest rate of fits for part-time wear. Teenagers have a similar lens fitting profile to adults, with the main distinguishing characteristic being a higher proportion of new fits. Orthokeratology fits represented 28% of all contact lenses prescribed to minors.

Conclusions. Patterns of contact lens prescribing to infants and children are distinctly different to those of teenagers and adults in a number of respects. Clinicians can use the data presented here to compare their own patterns of contact lens prescribing to minors.

Can eLearning provide tools for capacity-building to improve performance in the nonprofit sector?

Can E-learning 2.0 provide a platform for improving performance in nonprofit organizations? It is argued that Web 2.0 technologies provide the tools that today’s students rely on in the learning environment. As such they may be the means to attract and retain learners in training and education programs designed to improve performance. E-learning delivered through a blended learning model has proven to be effective in corporate training and higher education. Can the interactive, collaborative model offered in E-learning 2 prove to be as effective? This paper reviews the literature on blended learning and capacity-building as background for a discussion of the potential that e-learning models enhanced by web 2.0 technologies have for expanding access to education and training and facilitating implementation of skills and knowledge gained in the workplace. We suggest that increasing training opportunities for staff and making nonprofit management education more accessible through online programs is not enough to meet the challenge. What is needed at this point is practicable education and training delivered in today’s user’s environment, that is online and “on the go.”

New empirical evidence on the bid-ask spread

In this article, we model the determinants of spread for 734 firms listed on the NYSE over the period 1 January 1998 to 31 December 2008. We propose a panel data model of the determinants of spread. There are four main messages emerging from our work. We find a statistically significant effect of volume on spread inconsistent with the work of Johnson (2008). On price, we find mixed results, consistent with the literature. On the effect of price volatility on spread, our results are completely the opposite of the cross-sectional literature but sides with the relatively recent work of Chordia et al. (2001). We allow for persistence of spread as a determinant of spread and find significant evidence of spread persistence across all 16 sectors. Finally, we examine size effects and find statistically strong evidence of size effects based on the relationship between price and spread, persistence and spread, and volatility and spread.