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A leak-free, reagentless biosensor for glucose is demonstrated as one application of the bulk modified electrode with three-dimensional self-assembled monolayers reported here. The preparation of the electrode and the electrochemical investigations of its behavior are described. It is shown that model enzymes can be incorporated in these materials so that the biomolecules retain their activity and the SAMs their dense structure and charge-mediation properties. A range of electrochemical applications are foreseen for such electrodes.