A brief introduction to the field of complex networks is carried out by means of some examples. Then, we focus on the topics of defining and applying centrality measures to characterise the nodes of complex networks. We combine this approach with methods for detecting communities as well as to identify good expansion properties on graphs. All these concepts are formally defined in the presentation. We introduce the subgraph centrality from a combinatorial point of view and then connect it with the theory of graph spectra. Continuing with this line we introduce some modifications to this measure by considering some known matrix functions, e.g., psi matrix functions, as well as new ones introduced here. Finally, we illustrate some examples of applications in particular the identification of essential proteins in proteomic maps.