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.

Electrospinning of polymers for functional nanofibres

Nanofibres have wide applications in energy, environment and medical areas. This project examined new needleless electrospinning technologies for mass production of nanofibres. Functional nanofibres with side-by-side and core-sheath structures have been prepared and their properties have been elucidated.

Functional applications of electrospun nanofibers

With the rapid development of nanoscience and nanotechnology over the last two decades, great progress has been made not only in preparation and characterization of nanomaterials, but also in their functional applications. As an important one-dimensional nanomaterial, nanofibers have extremely high specific surface area because of their small diameters, and nanofiber membranes are highly porous with excellent pore interconnectivity. These unique characteristics plus the functionalities from the polymers themselves impart nanofibers with many desirable properties for advanced applications.

Applications of scanning electrochemical microscopy (SECM) for local characterization of AZ31 surface during corrosion in a buffered media

Different modes of scanning electrochemical mapping (SECM) such as surface generation/tip collection (SG/TC), amperometry, AC-SECM and potentiometry were employed to characterize the active/passive domains, hydrogen gas (H2) evolution and local pH on a corroding surface of AZ31 in simulated biological fluid (SBF). It was found that the main domains of H2 evolution are associated with lower insulating properties of the surface as well as higher local pH. The near surface pH was found to be highly alkaline indicating that, even in a buffered solution such as SBF, the local pH on a corroding AZ31 surface can be significantly different to the bulk pH. © 2014 Elsevier Ltd.

Biological response of myoblasts to three-dimensional electrically conductive fibrous scaffolds

 Inter-bonded three-dimensional fibrous scaffolds were fabricated using a template-aided melt bonding method. A high-throughput bioreactor was developed for dynamic cell culture of Myoblasts. The scaffolds after surface modification with a conducting polymer, polypyrrole, showed greatly enhanced cell viability, proliferation and differentiation especially under an electrical stimulation.

Tracking and tracing applications of 3G for SMEs

With dynamic growth and acceptance of mobile devices, many innovative business applications are beginning to emerge. Tracking and tracing seems to be one of the popular applications which many organisations have initiated, often facilitated by location based services provided by mobile network operators. However, there are many issues associated with the provisioning of this application with current technologies and business models. Small and Medium-size Enterprises (SMEs) that make up a significant segment of businesses worldwide do not yet seem able to benefit widely from these services. In this chapter, we initially review current technologies/ applications and the issues associated with them, drawing from research and the experiences of a long term ongoing action research project with SMEs in the trade sector. Subsequently, we explore the opportunities offered by 3G services/business applications to SMEs, and provide a broad critical outlook on future opportunities for SMEs to benefit from 3G services.

Analytical applications of acidic potassium permanganate as a chemiluminescence reagent

A critical review presented is of the literature concerning the use of acidic solutions of potassium permanganate to generate chemiluminescence during the oxidation of both organic compounds and inorganic species. A brief overview of the reagent’s historical origin is followed by a chronological survey of its analytical applications, from what we believe to be the first report in 1975 through to those published up until mid-2001. This review does not include those papers where potassium permanganate has been used either in alkaline conditions or in conjunction with other chemiluminescence reagents.

Some unusual applications of the `Error-bar` feature in Excel spreadsheets

This paper demonstrates how the "error-bar" feature can be used to extend the utility of "worldware" spreadsheet packages in producing high-quality graphs for university teaching and learning, and for research. To further utilize the advantages of spreadsheets in university education, this paper seeks to overcome some of the earlier reservations about the lack of scientific plotting capabilities of spreadsheet applications. Specific examples of educational material in the areas of enzyme kinetics, vibrational spectroscopy, vibronic spectroscopy, and mass spectrometry are discussed. It is argued that, where practical, university educators should use "worldware" packages to prepare teaching aids, since these would better prepare their students for future employment. The use of software features for purposes that were not envisioned by the programmers has additional educational benefits in fostering flexibility and innovation. Other graphing packages can also use the "error-bar" feature in a manner similar to that described here for Excel.

Applications of cognitive theories to children's fire safety education

Children under five have the highest rate of fire-related accidents (Australian Institute of Health and Welfare, 2001). It is therefore essential to develop effective fire safety education programs to prevent casualties due to a fire. At present, there are fire education programs conducted across Australia for primary school children. However, it is vital that these programs get their message across to the children in the most efficient manner to help children retain the information. The present study evaluated the effectiveness of the 'Fire Ed' program conducted in Victoria and assessed the retention of fire safety information in children in preparatory and Grade five levels. The findings suggest that the information is not retained over long periods of time. Suggestions are made to provide fire safety education in line with
theories of cognitive development to make it more effective.

Not just for romance: applications of speed dating in social work education

In this article we address how a contemporary adaptation of the 'speed dating' model was used for educational purposes with two cohorts of social work students. We outline the dimensions of 'speed dating' as a contemporary social phenomenon, then address how this model relates specifically to groupwork process, and can be used to facilitate social work student learning. The curriculum for two classroom group activities using the 'speed dating' model are outlined, the first to develop university level study skills, the second for debriefing field placement learning experiences. Finally we examine why the 'speed dating' metaphor was successful in provoking a playful yet constructively creative space for students to engage in groupwork process.

Development and applications of an experimental database for structural engineering education

A great number of research organisations in Japan have been conducting structural steel experiments for many years, particularly seismic tests of steel structures like cyclic-loading and pseudo-dynamic tests, in order to determine their seismic performances. However, the original test data gained by most research organisations are not well stored in an appropriate manner for distribution and possible usage by others. With the rapid development of information networks, structural engineers and researchers are able to exchange various types of test data through the Internet. In this paper, the authors present the development of a distributed collaborative database system for structural steel experiments. The database is made available on the Internet, and the use of Java language enables efficient interactive retrieval. The potential applications of the developed database system for structural engineering education are validated for the retrieval of experimental data and seismic numerical analysis.