Anionic Oligothiophenes Compete for Binding of X‐34 but not PIB to Recombinant Aβ Amyloid Fibrils and Alzheimer's Disease Brain‐Derived Aβ

Deposits comprised of amyloid‐β (Aβ) are one of the pathological hallmarks of Alzheimer's disease (AD) and small hydrophobic ligands targeting these aggregated species are used clinically for the diagnosis of AD. Herein, we observed that anionic oligothiophenes efficiently displaced X‐34, a Congo Red analogue, but not Pittsburgh compound B (PIB) from recombinant Aβ amyloid fibrils and Alzheimer's disease brain‐derived Aβ. Overall, we foresee that the oligothiophene scaffold offers the possibility to develop novel high‐affinity ligands for Aβ pathology only found in human AD brain, targeting a different site than PIB.     

Effect of Oligothienyl Chain Length on Tuning the Solar Cell Performance in Fluorene‐Based Polyplatinynes

A series of solution‐processable and strongly visible‐light absorbing polyplatinynes containing oligothienyl–fluorene ring hybrids were synthesized and characterized. These rigid‐rod organometallic materials are soluble in polar organic solvents and show intense absorptions in the visible spectral region, rendering them excellent candidates for bulk heterojunction polymer solar cells. The photovoltaic behavior depends significantly on the number of thienyl rings along the polymer chain, and some of these polymer solar cells show high power conversion efficiencies (PCEs) of up to 2.9% and a peak external quantum efficiency to 83% under AM1.5 simulated solar illumination. The effect of oligothienyl chain length on improving the polymer solar cell efficiency and on their optical and charge transport properties is elucidated in detail. At the same blend ratio of 1:5, the light‐harvesting capability and PCE increase markedly with increasing number of thienyl rings. The power dependencies of the solar cell parameters (including the short‐circuit current density, open‐circuit voltage, fill‐factor, and PCE) were also examined. The present work opens up an attractive avenue to developing conjugated metallopolymers with broad and strong solar energy absorptions and tunable solar cell efficiency and supports the potential of metalated conjugated polymers for efficient power generation.     

Deciphering the Electronic Transitions of Thiophene-Based Donor-Acceptor-Donor Pentameric Ligands Utilized for Multimodal Fluorescence Microscopy of Protein Aggregates

Anionic pentameric thiophene acetates can be used for fluorescence detection and diagnosis of protein amyloid aggregates. Replacing the central thiophene unit by benzothiadiazole (BTD) or quinoxaline (QX) leads to large emission shifts and basic spectral features have been reported [Chem. Eur. J. 2015 , 21, 15133-13137]. Here we present new detailed experimental results of solvent effects, time-resolved fluorescence and examples employing multi-photon microscopy and lifetime imaging. Quantum chemical response calculations elucidate how the introduction of the BTD/QX groups changes the electronic states and emissions. The dramatic red-shift follows an increased conjugation and quinoid character of the π-electrons of the thiophene backbone. An efficient charge transfer in the excited states S₁ and S₂ compared to the all-thiophene analogue makes these more sensitive to the polarity and quenching by the solvent. Taken together, the results guide in the interpretation of images of stained Alzheimer disease brain sections employing advanced fluorescence microscopy and lifetime imaging, and can aid in optimizing future fluorescent ligand development.     

Inherently Chiral Spider‐Like Oligothiophenes

The racemate of an inherently chiral “spider‐like” octathiophene monomer T8₃ , in which chirality is generated by torsion in its backbone, was synthesized. The racemate was resolved into configurationally stable antipodes by HPLC on a chiral stationary phase. Electrooxidation of the enantiomers resulted in materials displaying high enantiorecognition ability towards the antipodes of some chiral probes. Moreover, the T8₃ racemate demonstrated great aptitude to stimulate formation of 3D rigid architectures if used as a cross‐linking monomer for molecular imprinting. This feature was exploited to devise a molecularly imprinted polymer‐based chemosensor selective for a thymine–adenine oligonucleotide.     

Synthesis,Electronic, and Morphological Properties of Tetrahedral Oligothiophenes with n‐Hexyl Terminal Groups

A series of tetrahedral oligothiophenes bearing n‐hexyl groups at the α‐positions of the terminal thiophene rings, (n‐C₆H₁₃(C₄H₂S)_n)₄C (Hex‐TnTM; n=1–4), has been synthesized by Kosugi–Migita–Stille coupling as a key reaction. Thanks to the improved solubility afforded by the terminal n‐hexyl groups, the largest homologue (n=4) was successfully obtained. Whereas the smaller derivatives (n=1, 2) were obtained as liquid substances, the larger derivatives (n=3, 4) were obtained as solids. Hex‐T3 TM partially adopts syn conformations between the adjacent thiophene rings in the crystal, probably owing to the packing force. Hex‐T3 TM not only appeared in the crystalline state but also the amorphous state, which was stable to up to 80 °C. Regardless of the terminal groups, the derivatives of n=2 exhibited a broad fluorescence with large Stokes shifts compared to the corresponding linear analogues, thereby suggesting the presence of intramolecular interactions between the bithiophene moieties. Interactions between terthiophene branches was also suggested in the radical cations of Hex‐T3 TM by cyclic voltammetry measurements.     

A Conjugated Thiophene‐Based Rotaxane: Synthesis,Spectroscopy, and Modeling

A dithiophene rotaxane 1 ?β‐CD and its shape‐persistent corresponding dumbbell 1 were synthesized and fully characterized. 2D NOESY experiments, supported by molecular dynamics calculations, revealed a very mobile macrocycle (β‐CD). Steady‐state and time‐resolved photoluminescence experiments in solution were employed to elucidate the excited‐state dynamics for both systems and to explore the effect of cyclodextrin encapsulation. The photoluminescence (PL) spectrum of 1 ?β‐CD was found to be blueshifted with respect to the dumbbell 1 (2.81 and 2.78 eV, respectively). Additionally, in contrast to previous observations, neither PL spectra nor the decay kinetics of both threaded and unthreaded systems showed changes upon increasing the concentration or changing the polarity of the solutions, thereby providing evidence for a lack of tendency toward aggregation of the unthreaded backbone.     

Crystallization and Organic Field-Effect Transistor Performance of a Hydrogen-Bonded Quaterthiophene

Crystalline thin films of π-conjugated molecules are relevant as the active layers in organic electronic devices. Therefore, materials with enhanced control over the supramolecular arrangement, crystallinity, and thin-film morphology are desirable. Herein, it is reported that hydrogen-bonded substituents serve as additional structure-directing elements that positively affect crystallization, thin-film morphology, and device performance of p-type organic semiconductors. It is observed that a quaterthiophene diacetamide exhibits a denser packing than that of other quaterthiophenes in the single-crystal structure and, as a result, displays enhanced intermolecular electronic interactions. This feature was preserved in crystalline thin films that exhibited a layer-by-layer morphology, with large domain sizes and high internal order. As a result, organic field-effect transistors of these polycrystalline thin films showed mobilities in the range of the best mobility values reported for single-crystalline quaterthiophenes. The use of hydrogen-bonded groups may, thus, provide an avenue for organic semiconducting materials with improved morphology and performance.