42 research outputs found

    Interaction between Poly(9,9-bis(6′-N,N,N-trimethylammonium)hexyl)fluorene phenylene) Bromide and DNA as Seen by Spectroscopy, Viscosity, and Conductivity: Effect of Molecular Weights and DNA Secondary Structure

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    The interaction between three poly(9,9-bis(6-N,N,N-trimethylammonium)hexyl)fluorene phenylene) bromide (HTMA-PFP) samples of different molecular weights (Mn = 14.5, 30.1 and 61.3 kg/mol) and both dsDNA and ssDNA secondary structures has been studied using UV−visible absorption and fluorescence spectroscopies (including steady-state, time-resolved, and anisotropy measurements for the latter), viscosity, and electrical conductivity in 4% (v/v) DMSO−water mixtures. At low nucleic acid concentrations, formation of a 1:1 complex in terms of HTMA-PFP repeat units and DNA bases occurs. This interaction results in quenching of polymer emission. For higher molar ratios of DNA to HTMA-PFP, corresponding to charge neutralization, a second process is observed that is attributed to aggregate formation. From the changes in the absorption spectra, the polymer aggregation constant and the aggregate absorption spectra were calculated by applying an iterative method. Polymer aggregation dramatically quenches HTMA-PFP fluorescence in the region of the electroneutrality point. Under these conditions, the ratio of the emission intensity at 412 nm (maximum) to that at 434 nm (I412/I434) reaches a minimum, the electrical conductivity decreases, and the viscosity of the solution remains constant, showing that the DNA concentration can be determined through various HTMA-PFP physicochemical properties. With respect to the photophysical parameters (emission quantum yield, shape and shift of emission spectra), no significant differences were observed between dsDNA and ssDNA or with conjugated polymer or DNA molecular weight. The two short-lived components in the fluorescence decays are attributed to the presence of aggregates. Aggregates are also suggested to be responsible for the decrease in the fluorescence anisotropy through interchain exciton migration

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

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    NoWe 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

    Solubilization of Poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)] fluorene-2,7-diyl} in Water by Nonionic Amphiphiles

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    In the presence of the nonionic alkyloxyethylene surfactant n-dodecylpentaoxyethylene glycol ether (C12E5), the anionic conjugated polyelectrolyte (CPE) poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl} (PBS-PFP) dissolves in water, leading to a blue shift in fluorescence and dramatic increases in fluorescence quantum yields above the surfactant critical micelle concentration (cmc). No significant changes were seen with a poly(ethylene oxide) of similar size to the surfactant headgroup, confirming that specific surfactant−polyelectrolyte interactions are important. From UV−visible and fluorescence spectroscopy, dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (cryo-TEM), and electrical conductivity, together with our published NMR and small-angle neutron scattering (SANS) results, we provide a coherent model for this behavior in terms of breakup of PBS-PFP clusters through polymer−surfactant association leading to cylindrical aggregates containing isolated polymer chains. This is supported by molecular dynamics simulations, which indicate stable polymer−surfactant structures and also provide indications of the tendency of C12E5 to break up polymer clusters to form these mixed polymer−surfactant aggregates. Radial electron density profiles of the cylindrical cross section obtained from SAXS results reveal the internal structure of such inhomogeneous species. DLS and cryo-TEM results show that at higher surfactant concentrations the micelles start to grow, possibly partially due to formation of long, threadlike species. Other alkyloxyethylene surfactants, together with poly(propylene glycol) and hydrophobically modified poly(ethylene glycol), also solubilize this polymer in water, and it is suggested that this results from a balance between electrostatic (or ion-dipole), hydrophilic, and hydrophobic interactions. There is a small, but significant, dependence of the emission maximum on the local environment
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