Self-assembly of polypeptide/pi-conjugated polymer/polypeptide triblock copolymers in rod-rod-rod and coll-rod-coil conformations

Self-assembly in the bulk of a series of hybrid triblock copolymers formed by a poly(9,9-dihexylfluorene-2,7-diyl) (PHF) middle block and two poly(gamma-benzyl-L-glutamate) (PBLG) end blocks has been studied. Since the alpha-helical secondary structure of the PBLG block may be either maintained or suppressed depending on the solvent casting history, the PBLG-PHF-PBLG copolymers exhibit two different conformations: a rod-rod-rod or coil-rod-coil configuration, respectively. In order to provide insight into the influence of conformation on self-aggregation of these systems, three copolymers with different block ratio were investigated in both conformations using small- and wide-angle scattering techniques and transmission electron microscopy. Time-resolved photoluminescence measurements were performed on the same samples to explore the effect of morphology on photophysical properties. The observed photoluminescence spectra and dominant excited lifetimes of the poly(9,9-dihexylfluorene-2,7-diyl) block were found to differ markedly in rod-rod-rod and coil-rodcoil configurations and were correlated to the morphology of the self-assembled triblock copolymers

Hydration of a side-chain-free n-type semiconducting ladder polymer driven by electrochemical doping

We study the organic electrochemical transistors (OECTs) performance of the ladder polymer, poly(benzimidazobenzophenanthroline) (BBL) in an attempt to better understand how an apparently hydrophobic side-chain-free polymer is able to operate as an OECT with favorable redox kinetics in an aqueous environment. We examine two BBLs of different molecular masses from different sources. Both BBLs show significant film swelling during the initial reduction step. By combining electrochemical quartz crystal microbalance (eQCM) gravimetry, in-operando atomic force microscopy (AFM), and both ex-situ and in-operando grazing incidence wide-angle x-ray scattering (GIWAXS), we provide a detailed structural picture of the electrochemical charge injection process in BBL in the absence of any hydrophilic side-chains. Compared with ex-situ measurements, in-operando GIWAXS shows both more swelling upon electrochemical doping than has previously been recognized, and less contraction upon dedoping. The data show that BBL films undergo an irreversible hydration driven by the initial electrochemical doping cycle with significant water retention and lamellar expansion that persists across subsequent oxidation/reduction cycles. This swelling creates a hydrophilic environment that facilitates the subsequent fast hydrated ion transport in the absence of the hydrophilic side-chains used in many other polymer systems. Due to its rigid ladder backbone and absence of hydrophilic side-chains, the primary BBL water uptake does not significantly degrade the crystalline order, and the original dehydrated, unswelled state can be recovered after drying. The combination of doping induced hydrophilicity and robust crystalline order leads to efficient ionic transport and good stability.Comment: 24 pages, 5 figure

Wave-Guiding In Substrate Supported And Freestanding Films Of Insoluble Conjugated Polymers

We demonstrate that waveguiding is possible in substrate supported and freestanding films of insoluble conjugated polymers. Photoresist gratings were used to couple 1.06-1.53 mum radiation into the waveguides allowing the refractive indices, the birefringence, and the linear losses to be measured