Influx of solar photons and heavy charged particles from Saturn’s magnetosphere on Titan’s atmosphere -mainly comprised of methane and nitrogen - induce an intense organic photochemistry which leads to the formation of a large amount of aerosols in suspension in the atmosphere. In order to infer the role of nitrogen in aerosol formation processes we produced laboratory analogs of Titan’s aerosols. In this work, we compare the composition of different analogs by using high resolution mass spectrometry and propose an additional study using gas-chromatography coupled to mass-spectrometry for a new kind of analog produced by polymerization of cryogenically trapped gaseous neutral species. The comparison of these materials emphasizes the importance of ion chemistry processes for the inclusion of nitrogen in molecules constituting Titan's tholins. A statistical approach is also used for the treatment of high resolution mass spectra of these highly complex organic materials. This method allows distinguishing molecular families that can be reconstructed by an ideal co-polymer. We investigate several co-polymer reconstructions, and we suggest that a HCN (or CH3CN) /C2H4 based co-polymer agrees well with the polymeric structure of tholins produced with 5% of methane in nitrogen.