This paper describes a previously unreported class of sterically crowded tetracene derivatives that have both phenyl and ethynyl substituents. The steric crowding above and below the tetracene core prevents overlap between the extended p-systems of the acenes. Substituent effects cause these tetra-substituted tetracenes to have absorbance and fluorescence spectra red shifted from either disubstituted derivatives or rubrenes, such that they have spectra similar to diarylpentacenes, but with higher quantum yields of fluorescence and greater photostability. These new molecules also undergo cycloaddition reactions with 1 O 2 , giving regioisomeric mixtures of endoperoxides, and in contrast to longer acenes, the ethynyl substituents show only a modest stabilizing effect to photooxidation. Ethynylated tetracenes also exhibited photochromism, with their endoperoxides undergoing cycloreversion to yield the acene starting material at room temperature in the dark.
This communication describes new conjugated polymers that bear diarylanthracene or diaryltetracene pendants and respond to singlet oxygen by interrupting energy transfer resulting in blue-shifted fluorescence.
This paper describes thin films comprising acenes dispersed in a conjugated polymeric host that have a ratiometric photoluminescence response to singlet oxygen. These films also respond to irradiation of protein-bound sensitizers, which represents a solution to the problem of protein-conjugated polymer non-specific interactions.
Abnormal cerebrospinal fluid (CSF) levels of β-amyloid peptides (Aβ42) and Tau and cognitive decline are typical characteristics of Alzheimer’s disease (AD). Since dysregulation in lipid metabolism accompanies abnormal amyloid formation, we quantified glycerophospholipids (GP) and sphingolipids (SP) in CSF fractions from participants with late-onset AD (LOAD, n = 29) or with Other Dementia (OD, n = 10) to determine if alterations in lipid metabolism account for pathological differences. Aβ42 and total Tau levels were determined using a sandwich ELISA. Liposomal-based fluorescent assays were used to measure phospholipase A2 (PLA2) and acid or neutral sphingomyelinase (aSMase, nSMase) activities. Supernatant fluid (SF) and nanoparticle (NP) lipids were quantified using LC-MS/MS. Although CSF Aβ42 and Tau levels are similar, phosphatidylserine (PS) in SF and ceramide (CM) levels in NP are significantly higher in OD compared with LOAD. The aSMase but not the nSMase activity is higher in OD. PLA2 activity in CSF from OD subjects positively correlates with several GP classes in SF and NP fractions but not in LOAD fractions. Our data indicate differences in CSF lipid metabolism between dementia variants. Higher levels of inflammatory and apoptotic lipids may induce faster neuronal death, resulting in the earlier cognitive decline in patients with OD phenotypes.
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