Oligothiophene Nanoparticles: Photophysical and Electrogenerated Chemiluminescence Studies

Thiophene oligomer nanoparticles (NPs) were studied by fluorescence spectroscopy and electrogenerated chemiluminescence (ECL). Distinct spectroscopic differences between aggregates or NPs of thiophene hexamers having differing substitution patterns of solubilizing alkyl groups were observed. The α,ω-unsubstituted thiophene hexamer, <b>Hexamer-2</b>, exhibited fluorescence properties that were similar in solution and as colloidal NPs; there was only a small red shift compared with what was observed for the discrete system dissolved in tetrahydrofuran (THF). In contrast, the oligomer substituted in the α,ω-positions with branched alkyl substituents (<b>Hexamer-1</b>) displayed a gradual bathochromic shift of the fluorescence maximum in proportion to the amount of a poor solvent (water) added to the THF solution. Moreover, the fluorescence characteristics for the oligomer(s) dissolved in a mixture of THF and water were similar to those seen by annihilation ECL in a mixture of benzene/acetonitrile. On this basis, we conclude that annihilation ECL may be a useful technique for monitoring the formation of organic nanoparticles

Spectral Dependence of the Internal Quantum Efficiency of Organic Solar Cells: Effect of Charge Generation Pathways

The conventional picture of photocurrent generation in organic solar cells involves photoexcitation of the electron donor, followed by electron transfer to the acceptor via an interfacial charge-transfer state (Channel I). It has been shown that the mirror-image process of acceptor photoexcitation leading to hole transfer to the donor is also an efficient means to generate photocurrent (Channel II). The donor and acceptor components may have overlapping or distinct absorption characteristics. Hence, different excitation wavelengths may preferentially activate one channel or the other, or indeed both. As such, the internal quantum efficiency (IQE) of the solar cell may likewise depend on the excitation wavelength. We show that several model high-efficiency organic solar cell blends, notably PCDTBT:​PC70BM and PCPDTBT:​PC60/70BM, exhibit flat IQEs across the visible spectrum, suggesting that charge generation is occurring either via a dominant single channel or via both channels but with comparable efficiencies. In contrast, blends of the narrow optical gap copolymer DPP-DTT with PC70BM show two distinct spectrally flat regions in their IQEs, consistent with the two channels operating at different efficiencies. The observed energy dependence of the IQE can be successfully modeled as two parallel photodiodes, each with its own energetics and exciton dynamics but both having the same extraction efficiency. Hence, an excitation-energy dependence of the IQE in this case can be explained as the interplay between two photocurrent-generating channels, without recourse to hot excitons or other exotic processes

Ion-Regulated Allosteric Binding of Fullerenes (C₆₀ and C₇₀) by Tetrathiafulvalene-Calix[4]pyrroles

The effect of ionic species on the binding of fullerenes (C₆₀ and C₇₀) by tetrathiafulvalene-calix[4]­pyrrole (TTF-C4P) receptors and the nature of the resulting supramolecular complexes (TTF-C4P + fullerene + halide anion + tetraalkylammonium cation) was studied in the solid state through single crystal X-ray diffraction methods and in dichloromethane solution by means of continuous variation plots and UV–vis spectroscopic titrations. These analyses revealed a 1:1 stoichiometry between the anion-bound TTF-C4Ps and the complexed fullerenes. The latter guests are bound within the bowl-like cup of the C4P in a ball-and-socket binding mode. The interactions between the TTF-C4P receptors and the fullerene guests are highly influenced by both the nature of halide anions and their counter tetraalkylammonium cations. Three halides (F^–, Cl^–, and Br^–) were studied. All three potentiate the binding of the two test fullerenes by inducing a conformational change from the 1,3-alternate to the cone conformer of the TTF-C4Ps, thus acting as positive heterotropic allosteric effectors. For a particular halide anion, the choice of tetraalkylammonium salts serves to modulate the strength of the TTF-C4P-fullerene host–guest binding interactions and, in conjunction with variations in the halide anion, can be exploited to alter the inherent selectivity of the host for a given fullerene. Differences in binding are reflected in the excited state optical properties. Overall, the present four-component system provides an illustration of how host–guest binding events involving appropriately designed artificial receptors can be fine-tuned via the addition of simple ionic species as allosteric modulators

Exploration of a Series of 5‑Arylidene-2-thioxoimidazolidin-4-ones as Inhibitors of the Cytolytic Protein Perforin

A series of novel 5-arylidene-2-thioxoimidazolidin-4-ones were investigated as inhibitors of the lymphocyte-expressed pore-forming protein perforin. Structure–activity relationships were explored through variation of an isoindolinone or 3,4-dihydroisoquinolinone subunit on a fixed 2-thioxoimidazolidin-4-one/thiophene core. The ability of the resulting compounds to inhibit the lytic activity of both isolated perforin protein and perforin delivered in situ by natural killer cells was determined. A number of compounds showed excellent activity at concentrations that were nontoxic to the killer cells, and several were a significant improvement on previous classes of inhibitors, being substantially more potent and soluble. Representative examples showed rapid and reversible binding to immobilized mouse perforin at low concentrations (≤2.5 μM) by surface plasmon resonance and prevented formation of perforin pores in target cells despite effective target cell engagement, as determined by calcium influx studies. Mouse PK studies of two analogues showed <i>T</i>_1/2 values of 1.1–1.2 h (dose of 5 mg/kg iv) and MTDs of 60–80 mg/kg (ip)