Influence of Hofmeister I^– on Tuning Optoelectronic Properties of Ampholytic Polythiophene by Varying pH and Conjugating with RNA

A significant tuning of optoelectronic properties of polythiophene (PT) chains due to Hofmeister iodide (I^–) ion is demonstrated in ampholytic polythiophene [polythiophene-g-poly­{(N,N,N-trimethylamino iodide)­ethyl methacrylate-co-methacrylic acid}, APT] at different pHs. In acidic medium, the absorption and emission signals of PT chromophore exhibit appreciable blue shift in the presence of I^– as counteranion only. The cooperative effect of undissociated -COOH and quaternary ammonium groups immobilize I^– near the apolar PT chain causing threading of grafted chains and hence twisting of the backbone attributing to the blue shift. As medium pH is increased, dethreading of the PT backbone occurs due to ionization of -COOH group, releasing quencher iodide ions from the vicinity of the PT chains resulting in a red shift in absorption and a sharp hike in fluorescence intensity (390 times) for an increase of excitons lifetime. With an increase of pH, morphology changes from a multivesicular aggregate with vacuoles to smaller size vesicles and finally to nanofibrillar network structure. Dethreading is also found when APT interacts with RNA showing a significant hike of fluorescence (22 times) for displacing iodide ions forming a nanofibrillar network morphology. Threading and dethreading also affect the resistance, capacitance, and Warburg impedance values of APT. Molecular dynamics simulation of a model APT chain in a water box supports the threading at lower pH where the iodide ions pose nearer to the PT chain than that at higher pH causing dethreading. So the influence of Hofmeister I^– ion is established for tuning the optoelectronic properties of a novel PT based polyampholyte by changing pH or by conjugating with RNA.