Jean-Hong Chen

A Dual-Emission Förster Resonance Energy Transfer Nanoprobe for Sensing/Imaging pH Changes in the Biological Environment

A dual-emission nanoprobe that can sense changes in the environmental pH is designed based on the concept of pH-responsive Förster resonance energy transfer induced by the conformational transition of an associating polyelectrolyte, N-palmitoyl chitosan, bearing a donor (Cy3) or an acceptor (Cy5) moiety. We demonstrate that the developed pH-responsive nanoprobe can be used to ratiometrically image and thus discriminate the pH changes in the biological environment at different length scales.

Scattering study of the conformational structure and aggregation behavior of a conjugated polymer solution.

The conformational structure and the interchain aggregation behavior of a semirigid conjugated polymer bearing a decyl side chain, poly(2,3-diphenyl-5-decyl-1,4-phenylenevinylene) (DP10-PPV), in solutions with chloroform and toluene have been investigated by means of small-angle neutron scattering (SANS), static light scattering (SLS) and dynamic light scattering (DLS). The radius of gyration, persistence length, and the second virial coefficient of the polymer in dilute solution as determined by SLS were higher in chloroform than in toluene; consequently, the polymer assumed a more extended wormlike chain conformation in the former. The difference in the strength of interaction in the two solvents gave rise to contrasting aggregation behavior of the polymer in the semidilute regime. While only a minor fraction of the polymer underwent segmental association in chloroform, a considerable fraction of it formed clusters (microgels) with several micrometers in size in toluene. These clusters were further found to consist of sheetlike nanodomains. Compared with the DP-PPV bearing a shorter hexyl side chain, DP6-PPV, the aggregates of DP10-PPV in toluene were weaker as they could be easily disrupted by moderate heating. This was attributed to a lack of strong pi-pi interaction between the DP10-PPV segments due to the greater steric hindrance imposed by the longer decyl side chains.

Aggregation of conjugated polymers in aromatic solvent.

Segments of conjugated polymers display the propensity to aggregate in solutions with common organic solvents. Here we revealed that the segmental aggregation of a conjugated polymer, poly(9,9-bis(2-ethylhexyl)fluorene-2,7-diyl), (PF2/6), in toluene was stabilized by the polymer-solvent complex formation through pi-pi stacking induction of solvent molecules and polymer segments. In this case, a portion of the solvent was trapped inside the aggregate domains upon bringing the system to the subambient temperatures. The residence time of these associated solvent molecules became long enough to yield a separate upfield-shifted NMR resonance. The line-shape of this resonance revealed alignment of the polymer segments in the aggregates. A portion of the solvent was frozen in the compact structure due to the formation of strong polymer-solvent complex.

Gelation Behavior of Poly(9,9-dioctylfluorene)/Poly[9,9-di(2-ethylhexyl)-fluorenyl-2,7-diyl] Blend in Methylcyclohexane Solutions

We investigated the gelation behavior of the blend of two light-emitting polyfluorenes, i.e., poly(9,9-dioctylfluorene-2,7-diyl) (PF(8)) and poly[9,9-di(2-ethylhexyl)-fluorenyl-2,7-diyl] (PF(2/6)), in solutions with methylcyclohexane (MCH). Upon prolonged aging at room temperature, dynamic light scattering revealed that phase separation in the initially well-mixed solutions occurred via spinodal decomposition, yielding a PF(8)/PF(2/6)-enriched phase and an isotropic solvent-rich phase. Sheetlike aggregates in which a portion of the PF(8) chains adopted the β conformation were formed in the polymer-enriched phase, as revealed by small-angle X-ray scattering and optical spectroscopy. Macroscopically, the phase separation transformed the original viscous liquid solution into a gel. Measurements of the gelation temperature (T(gel)), gel-to-sol transition temperature (T(g-s)), and spinodal decomposition temperature (T(SD)) indicated that gelation (and hence phase separation) became more difficult with increasing content of PF(2/6). The presence of PF(2/6) also hindered formation of the β-phase of PF(8.) Therefore, the microstructure and photophysical properties of PF(8)/PF(2/6) in MCH solution can be tuned by the composition of the two polymers.

Regioregularity effect on the self-assembly behavior of poly(3-hexylthiophene): the significance of triad sequence

Poly(3-hexylthiophene) (P3HT) is one of the most widely studied conjugated polymers for applications in polymer-based photovoltaics and thin-film transistors. The regioregularity index (RR) represented by the mole percentage of the head-to-tail (HT) dyad in the polymer molecule has been considered as a key factor governing both the kinetics and thermodynamics of the self-assembly of P3HT. In this study, we reveal that the configurational sequence beyond dyad plays an equally important role by demonstrating that two P3HT samples bearing almost identical RR value and average molecular weight displayed very different self-assembly kinetics. Counterintuitively, the semidilute xylene solution of the P3HT with slightly smaller RR value exhibited a much faster gelation. In the bulk state, this sample also showed faster crystallization kinetics and higher melting point. Characterization of the configurational structure by nuclear magnetic resonance (NMR) spectroscopy showed that the P3HT with the smaller RR value contained a higher population of HT-HT triad sequence. Therefore, knowledge of this system parameter, which has been omitted prevalently, is essential for the delicate control of the morphological formation of P3HT for enhancing its photophysical properties.