Part I: A study of factors affecting the performance of infrared and Raman spectrometers. Part II: Investigation of the redox chemistry of the Mytilus edulis foot protein using infrared spectroelectrochemistry

In Part I of this dissertation, methods of testing the performance of infrared and Raman spectrometers are described. Methods and standard reference materials were developed to investigate the wavenumber and photometric accuracy of Fourier transform infrared (FT-IR) spectrometers are discussed in Chapters 2 and 3. The method to determine the wavenumber accuracy, described in Chapter 2, used the single-beam spectra of a 6-layered isotactic polypropylene (iPP) polymer film sandwiched between two BaF2 infrared transparent windows. The shift with temperature of the center of gravity of the 840-cm-1 band of iPP was found to be sufficiently small that this band can be used to assess the wavenumber accuracy of FT-IR spectrometers. A method of determining the photometric accuracy and signal-averaging capability of FT-IR spectrometers using single-beam spectra of a sample of polyethylene terephthalate (MylarRTM) mounted between two BaF2 windows is described in Chapter 3. The Mylar spectra were then evaluated using a number of statistical programs written during this project. This method was then used to evaluate the performance of three commercial FT-IR instruments in our laboratory.; Raman spectrometry has recently experienced a surge of popularity with the development of Fourier transform (FT) Raman spectrometers and instruments based on the use of charge-coupled device (CCD) array detectors. Many of these instruments involve excitation of the Raman spectrum with near-infrared (NIR) lasers to minimize interferences caused by fluorescence. The problems associated with current bench-top NIR FT- and CCD-Raman spectrometers are examined in Chapters 4 and 5. A detailed investigation into the instrumental problems with these spectrometers is described in Chapter 4. It has been found that NIR excitation of Raman spectra can lead to a number of problems that have not been observed previously. Several of these problems are discussed in Chapter 5.; Although the popularity of Raman spectrometers has increased rapidly over the past decade, the development of standards to test these instruments has not kept pace. The need for standard reference material to determine the resolution of a grating Raman spectrometer is such a case. In Chapter 6, the development of standards for this purpose is described. It is well-known that the full width at half height of narrow bands is dependent on the resolution at which the spectrum is measured. Using this concept, a method was developed to construct a calibration curve to determine the resolution of a CCD-Raman spectrometer from spectra measured at higher resolution on a FT-Raman spectrometer.; The preliminary results of project designed to help elucidate the mechanism of adhesion of a mussel protein, Mytilus edulis, are described in Part II of this dissertation. This protein allows the mussel to adhere to various surfaces, including rocks, wooden piers, metal ships and concrete barriers. 3,4-Dihydroxyphenylalanine (commonly known as ℓ-dopa) is believed to play an active role in binding the protein to the various surfaces and cross-liking it to other proteins. External single-reflection mid-infrared spectroelectrochemistry was used to investigate the redox chemistry of ℓ-dopa and analogous molecules hydroquinone and epinephrine and the results are described in Chapter 8. It was found that the products of electrochemical oxidation of these three molecules under similar conditions of pH, ionic strength and electrode potential was quite different, with only hydroquinone oxidizing to the expected quinone.