• Incorporation of a Cationic Conjugated Polyelectrolyte CPE within an Aqueous Poly(vinyl alcohol) Sol

      Knaapila, M.; Stewart, Beverly; Costa, T.; Rogers, S.E.; Pragana, J.; Fonseca, S.M.; Valente, A.J.M.; Ramos, M.L.; Murtinho, D.; Costa Pereira, J.; et al. (2016-11-16)
      We report on a multiscale polymer-within-polymer structure of the cationic conjugated polyelectrolyte poly{[9,9-bis(6′-N,N,N-trimethylammonium)hexyl]fluorene–phenylene} (HTMA-PFP) in aqueous poly(vinyl alcohol) (PVA) sol. Molecular dynamics simulations and small-angle neutron scattering (SANS) data show that HTMA-PFP forms aggregates in water but becomes entangled by PVA (with a 1:1 molar ratio of HTMA-PFP to PVA) and eventually immersed in PVA clusters (with the ratio 1:4). This is attributed to the hydrophobic–hydrophilic balance. Contrast variation data with regular and deuterated PVA support a rigid body model, where HTMA-PFP is confined as locally isolated, but closely located, chains within PVA clusters, which alter correlation distances within the system. These results are supported by enhanced photoluminescence (PL) and ionic conductivity which, together with a red-shift in UV/vis absorption spectra, indicate the breakup of HTMA-PFP aggregates upon PVA addition.
    • Interactions of a zwitterionic thiophene-based conjugated polymer with surfactants

      Costa, T.; de Azevedo, D.; Stewart, Beverly; Knaapila, M.; Valente, A.J.M.; Kraft, M.; Scherf, U.; Burrows, H.D. (2015-12-15)
      In this paper we investigate the optical and structural properties of a zwitterionic poly[3-(N-(4-sulfonato-1-butyl)-N,N-diethylammonium)hexyl-2,5-thiophene] (P3SBDEAHT) conjugated polyelectrolyte (CPE) and its interaction in water with surfactants, using absorption, photoluminescence (PL), electrical conductivity, molecular dynamics simulations (MDS) and small-angle X-ray scattering (SAXS). Different surfactants were studied to evaluate the effect of the head group and chain length on the self-assembly. PL data emphasize the importance of polymer–surfactant electrostatic interactions in the formation of complexes. Nevertheless, conductivity and MDS data have shown that nonspecific interactions also play an important role. These seem to be responsible for the spatial position of the surfactant tail in the complex and, eventually, for breaking-up P3SBDEAHT aggregates. SAXS measurements on P3SBDEAHT-zwitterionic cocamidopropyl betaine (CAPB) surfactant complexes showed a specific structural organization of the system. The CAPB surfactant promotes a structural transition from pure P3SBDEAHT 3-dimensional aggregates (radius of gyration ∼85 Å) to thick cylindrical aggregates (∼20 Å) where all CAPB molecules are associated with the polymer. For molar ratios (in terms of the polymer repeat unit) >1 the SAXS interference maximum of the complexes resembles that of pure CAPB thus suggesting ongoing phase segregation in the formation of a “pure” CAPB phase.