Perylene-tethered pillar[5]arenes and C-boron-dipyrromethene (BODIPY) dyads were synthesized acting as emitters and organic triplet photosensitizers, respectively, for the purpose of improving the efficiency of triplet-triplet annihilation upconversion (TTA-UC). The photophysical properties of the sensitizers (guests) and the emitters (hosts) were not greatly influenced by the chemical modifications except for a notable decrease in the fluorescence quantum yields of the perlyene emitters due to the high local concentration. The perylene-tethered pillar[5]arenes form stable 1:1 complexes with a nitrile-bearing C-BODIPY dyad, showing association constants as high as 4.0 × 10 M. Through host-guest complexation, the efficiencies of both triplet-triplet energy transfer and TTA were significantly enhanced, which overcompensated for the loss of the fluorescence quantum yield of the emitters (hosts). Thus, an improved TTA-UC efficiency of 3.2% was observed even at a diluted concentration of 6 × 10 M, demonstrating for the first time the effectiveness of the supramolecular motif for enhancing TTA-UC without varying the inherent photophysical properties of sensitizers and emitters.
A series of Pt(II)–Schiff
base complexes were synthesized
as triplet sensitizers for the purpose of tuning the singlet and triplet
energy levels so as to minimize energy loss during triplet–triplet
annihilation (TTA) upconversion (UC). A deep-red to blue TTA-UC was
achieved with an unprecedentedly large anti-Stokes shift of 1.08 eV.
UC quantum yields of up to 21% (with a theoretical maximum efficiency
of 50%) were observed in solution. The complexes also showed efficient
UC emission in air-saturated hydrogels with a UC quantum yield up
to 14.8%, which is much higher than the highest previously reported
value. The low threshold excitation intensity provided by the present
system offers promising potential for application in terrestrial solar
energy conversion.
Visible-light-driven enantiodifferentiating photodimerization of 2-anthracenecarboxylic acid (AC) sensitized by Schiff base Pt(II) complex-grafted γ-cyclodextrins leads the first triplet-triplet annihilation-based catalytic photochirogenesis. The syn-head-to-tail (HT) photodimer 2 was achieved in up to 31.4% ee at 61.0% conversion in the presence of 0.5% equiv of the photocatalyst.
Alzheimer’s disease (AD) is an age-related irreversible neurodegenerative disorder characterized by extracellular β Amyloid(Aβ) deposition, intracellular neurofibrillary tangles and neuronal loss. The dysfunction of neurogenesis and increased degeneration of neurons contribute to the pathogenesis of AD. We now report that miR-211-5p, a small non-coding RNA, can impair neurite differentiation by directly targeting NUAK1, decrease neuronal viability and accelerate the progression of Aβ-induced pathologies. In this study, we observed that during embryonic development, the expression levels of miR-211-5p were down-regulated in the normal cerebral cortexes of mice. However, in APPswe/PS1ΔE9 double transgenic adult mice, it was up-regulated from 9 months of age compared to that of the age-matched wild type mice. Studies in primary cortical neuron cultures demonstrated that miR-211-5p can inhibit neurite growth and branching via NUAK1 repression and decrease mature neuron viability. The impairments were more obvious under the action of Aβ. Our data showed that miR-211-5p could inhibit cortical neuron differentiation and survival, which may contribute to the synaptic failure, neuronal loss and cognitive dysfunction in AD.
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