During the course of the research underlying this thesis, Alina Sekretaryova was enrolled in Forum Scientium, a multidisciplinary doctoral programme at Linköping University, Sweden Alina Sekretaryova, 2016, unless otherwise noted. Cover design by Alina Sekretaryova Linköping studies in science and technology Dissertation No. 1738 Printed in Sweden by LiU-Tryck, Linköping, Sweden, 2016 iii ABSTRACT Bioelectrocatalytic systems are based on biological entities, such as enzymes, whole cells, parts of cells or tissues, which catalyse electrochemical processes that involve the interaction between chemical change and electrical energy. In all cases, enzymes, isolated or residing inside cells or part of cells, implement biocatalysis. Electron transfer phenomena, within the protein molecules and between biological redox systems and electronics, enable the development of various bioelectrocatalytic systems, which can be used both for fundamental investigations of enzymatic biological processes by electrochemical methods and for applied purposes, such as power generation, bioremediation, chemical synthesis and biosensing.Electrical communication between the biocatalysts redox centre and an electrode is essential for the functioning of the system. This can be established using two main mechanisms: indirect electron transfer and direct electron transfer. The efficiency of the electron transfer influences important parameters such as the turnover rate of the biocatalyst, the generated current density and partially the stability of the system. These in turn determine the response time, sensitivity, detection limit and operational stability of biosensors or the power densities and current output of biofuel cells, and hence they should be carefully considered when designing bioelectrocatalytic systems.This thesis focuses on approaches that facilitate electron transfer in bioelectrocatalytic systems based on mediated and direct electron transfer mechanisms. Both fundamental aspects of electron transfer in bioelectrocatalytic systems and applications of such systems for biosensing and power generation are considered. First, a new hydrophobic mediator for oxidases, unsubstituted phenothiazine, and its improved electron transfer properties in comparison with commonly used mediators are discussed. Application of the mediator in electrochemical biosensors is demonstrated by glucose, lactate and cholesterol sensing. Utilisation of mediated biocatalytic cholesterol oxidation as the anodic reaction for the construction of a biofuel cell, acting as a power supply and an analytical device at the same time, is investigated as a "self-powered" biosensor. In addition, the enhancement of mediated bioelectrocatalysis by the employment of microelectrodes as a transducer is examined. The effect of surface roughness on the current response of the microelectrodes under conditions of convergent diffusion is considered. The applicability of the laccase-based system for total phenol analysis of weakly supported water is demonstrated. Finally, a...