Mario Kraft

Cationic polythiophene-surfactant self-assembly complexes: phase transitions, optical response, and sensing.

The absorption and photoluminescence spectra of the cationic conjugated polyelectrolyte poly[3-(6-trimethylammoniumhexyl)thiophene] (P3TMAHT) were observed to be dramatically altered in the presence of anionic surfactants due to self-assembly through ionic complex formation. Small-angle neutron scattering (SANS), UV/vis, and photoluminescence spectroscopy were used to probe the relationship between the supramolecular complex organization and the photophysical response of P3TMAHT in the presence of industrially important anionic surfactants. Subtle differences in the surfactant mole fraction and chemical structure (e.g., chain length, headgroup charge density, perfluorination) result in marked variations in the range and type of complexes formed, which can be directly correlated to a unique colorimetric and fluorimetric fingerprint. Our results show that P3TMAHT has potential as an optical sensor for anionic surfactants capable of selectively identifying distinct structural subgroups through dual mode detection.

A combination of Al-doped ZnO and a conjugated polyelectrolyte interlayer for small molecule solution-processed solar cells with an inverted structure

We successfully demonstrate a smart strategy to use aluminum doped ZnO (AZO) and the thiophene-based conjugated polyelectrolyte P3TMAHT as an interfacial layer in small molecule solution-processed inverted solar cells. Modification of AZO with a thin P3TMAHT layer increases the photovoltaic properties of the inverted cell as a result of reduction in the work function of the cathode with well aligned frontier orbital energy levels for efficient charge transport and reduced surface recombination. The inverted device achieved ∼16% performance improvement dominantly by recapturing part of the Voc losses when going from conventional to the inverted architecture. In addition, the inverted device using the AZO/P3TMAHT interlayer shows improved device stability in air compared to conventional devices.

Interactions of a zwitterionic thiophene-based conjugated polymer with surfactants

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 A) to thick cylindrical aggregates (∼20 A) 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.

Polyanionic, alkylthiosulfate-based thiol precursors for conjugated polymer self-assembly onto gold and silver.

Anionic, conjugated thiophene- and fluorene-based polyelectrolytes with alkylthiosulfate side chains undergo hydrolysis under formation of alkylthiol and dialkyldisulfide functions. The hydrolysis products can be deposited onto gold or silver surfaces by self-assembly from solutions of the anionic conjugated polyelectrolyte (CPE) precursors in polar solvents such as methanol. This procedure allows solution-based surface modifications of gold and silver electrodes using environmentally friendly solvents and enables the formation of conjugated polymer bilayers. The herein presented alkylthiosulfate-substituted CPEs are promising candidates for increasing the work function of gold and silver electrodes thus improving hole injection from such electrode assemblies into organic semiconductors.

Charge-Mediated Localization of Conjugated Polythiophenes in Zwitterionic Model Cell Membranes

The selective engineering of conjugated polyelectrolyte (CPE)-phospholipid interfaces is poised to play a key role in the design of advanced biomedical and biotechnological devices. Herein, we report a strategic study to investigate the relationship between the charge of the CPE side group and their association with zwitterionic phospholipid bilayers. The interaction of dipalmitoylphosphatidylcholine (DPPC) phospholipid vesicles with a series of poly(thiophene)s bearing zwitterionic, cationic, or anionic terminal groups (P3Zwit, P3TMAHT and P3Anionic, respectively) has been probed. Although all CPEs showed an affinity for the zwitterionic vesicles, the calculated partition coefficients determined using photoluminescence spectroscopy suggested preferential incorporation within the lipid bilayer in the order P3Zwit > P3Anionic ≫ P3TMAHT. The polarity probe Prodan was used to further qualify the position of the CPE inside the vesicle bilayers via Förster resonance energy transfer (FRET) studies. The varying proximity of the CPEs to Prodan was reflected in the Stern-Volmer quenching constants and decreased in the order P3Anionic > P3TMAHT ≫ P3Zwit. Dynamic light scattering measurements showed an increase in the hydrodynamic diameter of the DPPC vesicles upon addition of each poly(thiophene), but to the greatest extent for P3Anionic. Small-angle neutron scattering studies also revealed that P3Anionic specifically increased the thickness of the headgroup region of the phospholipid bilayer. Epifluorescence and atomic force microscopy imaging showed that P3TMAHT formed amorphous agglomerates on the vesicle surface, P3Zwit was buried throughout the bilayer, and P3Anionic formed a shell of protruding chains around the surface, which promoted vesicle fusion. The global data indicate three distinctive modes of interaction for the poly(thiophene)s within DPPC vesicles, whereby the nature of the association is ultimately controlled by the pendant charge group on each CPE chain. Our results suggest that charge-mediated self-assembly may provide a simple and effective route to design luminescent CPE probes capable of specific localization within phospholipid membranes.

Temperature-regulated fluorescence and association of an oligo(ethyleneglycol)methacrylate-based copolymer with a conjugated polyelectrolyte--the effect of solution ionic strength.

Aqueous mixtures of a dye-labeled non-ionic thermoresponsive copolymer and a conjugated cationic polyelectrolyte are shown to exhibit characteristic changes in fluorescence properties in response to temperature and to the presence of salts, enabling a double-stimuli responsiveness. In such mixtures at room temperature, i.e., well below the lower critical solution temperature (LCST), the emission of the dye is strongly quenched due to energy transfer to the polycation, pointing to supramolecular interactions between the two macromolecules. Increasing the concentration of salts weakens the interpolymer interactions, the extent of which is simultaneously monitored from the change in the relative emission intensity of the components. When the mixture is heated above its LCST, the transfer efficiency is significantly reduced, signaling a structural reorganization process, however, surprisingly only if the mixture contains salt ions. To elucidate the reasons behind such thermo- and ion-sensitive fluorescence characteristics, we investigate the effect of salts of alkali chlorides, in particular of NaCl, on the association behavior of these macromolecules before and after the polymer phase transition by a combination of UV-vis, fluorescence, and (1)H NMR spectroscopy with light scattering and small-angle neutron scattering measurements.

Polyelectrolyte complexes of a cationic all conjugated fluorene-thiophene diblock copolymer with aqueous DNA.

We report on the structural and colorimetric effects of interaction of aqueous ∼0.06-1% poly[9,9-bis(2-ethylhexyl)fluorene]-b-poly[3-(6-trimethylammoniumhexyl)thiophene] bromide (PF2/6-P3TMAHT) with double-stranded DNA to form PF2/6-P3TMAHT(DNA)x where x is the molar ratio of DNA base pairs to P3TMAHT repeat units; x = 0.5 equals the nominal charge neutralization. PF2/6-P3TMAHT forms 20-40 nm sized particles with PF2/6 core and hydrated P3TMAHT exterior. The polymer particles form loose one-dimensional chains giving micrometer long branched chains (0.19 ≤ x ≤ 0.76) and subsequently randomly shaped aggregates (x = 1.89) upon DNA addition. Compaction of the P3TMAHT block and the 20-30 nm sized core is observed for x = 0.38-0.76 and attributed to the DNA merged within P3TMAHT domain with this structure disassembling with DNA excess. Structural transformations are followed by chromic changes seen as color changes from deep red (x < 0.076) to yellow (x = 0.19), nearly colorless (x = 0.38-0.76), and back to orange (x = 1.89). Both absorption and photoluminescence spectra display the distinct fluorene and thiophene bands and subsequent blue and red shifts when passing x = 0.5. Thiophene photoluminescence (PL) is significantly quenched by DNA with increasing x, and the changing P3TMAHT/PF2/6 band ratio allows quantitative DNA detection. Sixteen-fold dilution does not change aggregate structure, but PL is blue-shifted, indicating weakened intermolecular interactions.