<p> Dinitrosyliron complexes have gained importance as a result of their biological and chemical relevance. Their biological significance stems from the roles exhibited by nitric oxide, including its ability to regulate blood pressure, to act as a biological messenger and because of its involvement in memory storage. Other functions that these dinitrosyliron-based complexes have displayed include their ability to transfer molecular oxygen to alkenes or phosphines, and its use in the polymerization of olefins. One area not yet extended to iron dinitrosyl complexes involves the synthesis of polymeric materials containing a conjugated backbone in the polymer. Thus, the next logical approach was to apply this idea, while investigating their potential to demonstrate unique properties such as optical, redox, and/or conducting behaviour exemplified by other inorganic and organometallic polymeric species. Hence, reactions involving Fe(NO)2(CO)2 and bidentate diphosphine ligands, bis(diphenylphosphino)methane (DPPM), trans-1,2-bis(diphenylphosphino)ethylene (t-DPPEN), 1,1 '-bis(diphenylphosphino) ferrocene (FcP2), bis(diphenylphosphino)acetylene (DPPA) and 1,4- bis(diphenylphosphino)benzene (DPPB) have been investigated. Three types of compounds arose from these reactions: the monometallic system Fe(DPPM)(N0)2(CO) 9, linear dimetallic molecules of the type Fe2(μ-L)(N0)4(CO)2 (L = PPh2CHzPPh2 10, PPh2C≡CPPh2 11, PPh2(p -6H4)PPh2 12, PPhzCH=CHPPhz 13, and PPh2((C5H4)2Fe) PPh2 14), and cyclic dimetallic species of the type Fe2(μ-L)(NO)4 (L = PPh2(p-C6H4)PPh2 15, PPh2CH2PPh2 16, and PPh2C≡CPPh2 17). These systems were isolated and characterized by the use of NMR and IR spectroscopy. The structures of compounds 10, 11, 16 and 17 were also determined by X-ray crystallography. The linear dimetallic compounds, 11, 13 and 14, were treated with tetracyanoethylene (TCNE) to afford compounds of the type Fe2(μ-L)(N0)4(TCNE)2 (L = PPhzC≡CPPh2 18 and PPh2((C5H4)2- Fe)PPh2 19) and [(TCNE)(NO)2Fe(μ-L)[Fe(NO)2(CO)] (L = PPh2CH=CHPPh2 20). These TCNE adducts were probed by means of cyclic voltammetry to investigate their potential redox properties; only compound 18 revealed communication between the two iron centres. </p> <p> Dinitrosyldicarbonyliron, Fe(NO)2(CO)2 and other four-coordinate dinitrosyliron systems have been extensively examined in terms of nucleophilic substitution, including the effects of both hard and soft bases. These findings prompted us to ask whether electrophiles attack dinitrosyliron complexes. Hence, Fe(NO)2(CO)2 1, and also the phosphine complexes Fe(NO)2(CO)(PPh3) 21, and Fe(NO)2(PPh3)2 22, have been treated with a variety of electrophiles (HCl, SiMe3Cl, Et30^+SbCl6-, trifluoroacetic acid (TFA) and trifluoromethanesulfonic acid (TFSA)) to probe the nucleophilic character of the iron centres. Moreover, another approach involved examining the nucleophilic nature of the iron nitrosyl salts, [PPN^+][Fe(CO)3(NO)], 24 and [N(Bu)4+][Fe(C0)3(NO)], 25. </p> / Thesis / Master of Science (MSc)

No description available.

No description available.

No description available.

No description available.

This thesis explores a rigorous approach to model the behaviour of an electrochemical cell. A simple planar electrochemical cell consisting of stainless steel electrodes separated by a sulfuric acid electrolyte layer is modeled from first principles. The model is a dynamic model and is valid under constant temperature conditions. The dynamic model is based on the Poisson-Nernst-Planck electrodiffusion theory and physical attributes such as the impact of nonlinear polarization, the stoichiometric reactions of the electrolyte and changes to the transport coefficients are investigated in stages. The system of partial differential equations has been solved using a finite element software package. The simulation results are compared with experimental results and discrepancies are discussed. The results suggest that the existing theory is not adequate in explaining the physics in the immediate vicinity of the electrode/electrolyte interface even though the general experimental and simulation results are in qualitative agreement with each other.

Electrochemical noise refers to the spontaneous fluctuations in potential and current that can be observed on a corroding metal. The use of electrochemical noise for obtaining information on the corrosion process generates much interest in research fields. One important application is the measurement of corrosion rate. This can be achieved using the electrochemical noise of a pair of electrically coupled corroding metals to obtain an estimate of electrochemical impedance - an abstract quantity that reflects various aspects of the corrosion process.There are a number of problems associated with estimation of impedance information from the electrochemical noise data, particularly regarding data pre-treatment, accuracy and precision. In addition, the present methods are incomplete: current literature does not offer information regarding the phase of the impedance; and assumptions regarding symmetry of an electrode pair cannot be tested without additional measurements.The thesis addresses the above mentioned problems. Specifically,analysis of the impedance estimation process is given to determine how precision can be affected by various factors;a novel signal processing technique is described that is shown to yield a local optimum precision;the application of the proposed signal processing to time varying systems is demonstrated by use of a time varying, frequency dependent impedance estimate;a technique for recovering phase information, given certain conditions, is suggested so that Nyquist impedance diagrams can be constructed; anda technique for testing the symmetry of a coupled pair of corroding metals is described.An integral part of electrochemical noise analysis is the software used for numerical computation. The Matlab package from MathWorks inc. provides an extensible platform for electrochemical noise analysis. Matlab code is provided in Appendix A to implement ++ / much of the theory discussed in the thesis.Impedance analysis and many other electrochemical corrosion monitoring techniques are primarily used for uniform corrosion, where the corrosion patterns occur uniformly over the exposed surface. In order to map localised corrosion, where the corrosion is typically concentrated within a small area, a wire beam electrode can be used. A wire beam electrode is a surface that is divided into a matrix of mini-electrodes so that the corrosion rate at different points can be monitored. However, manual connection of each mini-electrode to the measurement device can prove cumbersome. The final chapter of this thesis describes the design and testing of specialised multiplexing hardware to automate the process.In general, the thesis shows that by careful conditioning of the electrochemical noise prior to analysis, many of the problems with the technique of impedance estimation from the electrochemical noise data can be overcome. It is shown that the electrochemical noise impedance estimation can be extended to encompass a time varying, frequency dependent quantity for studying dynamic systems; that phase information can be recovered from electrochemical noise for the purpose of constructing Nyquist impedance diagrams; and that asymmetric electrodes can be detected without requiring additional measurements.

This dissertation explores the use of nanocarbons both as conductive supports for redox enzyme electrochemistry and as electrocatalytic components for the nonmediated detection of biogenic analytes. More specifically, the influence of nitrogen doping of these nanocarbons (referred to herein as nitrogen-doped carbon nanotubes, or N-CNTs) on their bioelectrocatalytic performance is studied through direct enzyme adsorption and exploitation of the N-CNTs' inherent reactivity toward H₂O₂ to create H₂O₂-based sensing strategies. Both nondoped CNTs and N-CNTs may be effectively incorporated into biogenic sensing assemblies, as demonstrated herein using a variety of electrochemical techniques. Chapter 1 gives a general overview of the scope of this research and describes previous studies conducted within our laboratories that demonstrate our CNTs' promise as biogenic electrode materials. Chapter 2 describes the chemical vapor deposition (CVD) method used to prepare both CNTs and N-CNTs and establishes their suitability for use in the detection schemes outlined in later chapters through long-term stability studies. Additionally, the redox activity of Fe nanoparticles entrapped in the CNTs as a result of this CVD growth process is examined using a host of electrochemical experiments. Importantly, the data presented in this chapter show that these Fe particles do not explain the observed electrocatalytic response of the CNTs. Chapter 3 explores the direct adsorption of horseradish peroxidase (HRP) at both nondoped and N-CNTs. Spectroscopic and electrochemical assays are used to compare the extent of HRP enzymatic activity upon immobilization at both types of CNTs. Both types of HRP/CNT composites are then utilized in a quantitative H₂O₂ sensing strategy. Chapter 4 discusses the intrinsic reactivity of N-CNTs toward H₂O₂. Koutecky-Levich plots are used to demonstrate differences in H₂O₂ consumption mechanisms between NCNTs and traditional peroxidases. By replacing HRP with N-CNTs in an amperometric glucose detection scheme, the versatility of N-CNTs as a peroxidase substitute for biogenic analyte detection is demonstrated. Chapter 5 outlines future directions for this research, including possible strategies for improving electron transfer between HRP and both types of CNTs. This chapter also presents a newly developed, mediated oxidase-substrate electrochemical detection method that can easily be modified to incorporate CNTs.

This thesis explores a rigorous approach to model the behaviour of an electrochemical cell. A simple planar electrochemical cell consisting of stainless steel electrodes separated by a sulfuric acid electrolyte layer is modeled from first principles. The model is a dynamic model and is valid under constant temperature conditions. The dynamic model is based on the Poisson-Nernst-Planck electrodiffusion theory and physical attributes such as the impact of nonlinear polarization, the stoichiometric reactions of the electrolyte and changes to the transport coefficients are investigated in stages. The system of partial differential equations has been solved using a finite element software package. The simulation results are compared with experimental results and discrepancies are discussed. The results suggest that the existing theory is not adequate in explaining the physics in the immediate vicinity of the electrode/electrolyte interface even though the general experimental and simulation results are in qualitative agreement with each other.

The objective of this research was to design and evaluate an instrumental method for electroanalysis in highly resistive media. A coulostatic detector for high performance liquid chromatography was designed and constructed. Equations were developed to describe the detector's performance under regenerative and nonregenerative experimental conditions. With mobile phases of high resistance, the detector was found to respond to both electroactive and ionic electroinactive species with the magnitude of the observed signal depending on the recent history of the electrode. Thus, the elimination of iR drop by the coulostatic method does not provide a straightforward method for electroanalysis in highly resistive media. At low electrolyte concentrations, double-layer effects become prominent. A method was devised to quantitate the static double-layer effect at solid electrodes.