Amyloid fibrillation of proteins is associated with a great variety of pathologic conditions. Development of new molecules that can monitor amyloidosis kinetics and inhibit fibril formation is of great diagnostic and therapeutic value. In this work, we have developed a biocompatible molecule that functions as an ex situ monitor and an in situ inhibitor for protein fibrillation, using insulin as a model protein. 1,2-Bis[4-(3-sulfonatopropoxyl)phenyl]-1,2-diphenylethene salt (BSPOTPE) is nonemissive when it is dissolved with native insulin in an incubation buffer but starts to fluoresce when it is mixed with preformed insulin fibril, enabling ex situ monitoring of amyloidogenesis kinetics and high-contrast fluorescence imaging of protein fibrils. Premixing BSPOTPE with insulin, on the other hand, inhibits the nucleation process and impedes the protofibril formation. Increasing the dose of BSPOTPE boosts its inhibitory potency. Theoretical modeling using molecular dynamics simulations and docking reveals that BSPOTPE is prone to binding to partially unfolded insulin through hydrophobic interaction of the phenyl rings of BSPOTPE with the exposed hydrophobic residues of insulin. Such binding is assumed to have stabilized the partially unfolded insulin and obstructed the formation of the critical oligomeric species in the protein fibrillogenesis process.
In this contribution, we conceptually present a new avenue to construction of molecular functional materials with high performance of circularly polarised luminescence (CPL) in the condensed phase. A molecule (1) containing luminogenic silole and chiral sugar moieties was synthesized and thoroughly characterized. In a solution of 1, no circular dichroism (CD) and fluorescence emission are observed, but upon molecular aggregation, both the CD and fluorescence are simultaneously turned on, showing aggregation-induced CD (AICD) and emission (AIE) effects. The AICD effect is supported by the fact that the molecules readily assemble into right-handed helical nanoribbons and superhelical ropes when aggregated. The AIE effect boosts the fluorescence quantum efficiency (F F) by 136 fold (F F , $0.6% in the solution versus $81.3% in the solid state), which surmounts the serious limitations of aggregationcaused quenching effect encountered by conventional luminescent materials. Time-resolved fluorescence study and theoretical calculation from first principles conclude that restriction of the lowfrequency intramolecular motions is responsible for the AIE effect. The helical assemblies of 1 prefer to emit right-handed circularly polarised light and display large CPL dissymmetry factors (g em), whose absolute values are in the range of 0.08-0.32 and are two orders of magnitude higher than those of commonly reported organic materials. We demonstrate for the first time the use of a Teflon-based microfluidic technique for fabrication of the fluorescent pattern. This shows the highest g em of À0.32 possibly due to the enhanced assembling order in the confined microchannel environment. The CPL performance was preserved after more than half year storage under ambient conditions, revealing the excellent spectral stability. Computational simulation was performed to interpret how the molecules in the aggregates interact with each other at the molecular level. Our designed molecule represents the desired molecular functional material for generating efficient CPL in the solid state, and the current study shows the best results among the reported organic conjugated molecular systems in terms of emission efficiency, dissymmetry factor, and spectral stability.
Light emission of a hyperbranched poly(silylenephenylene) is quenched exponentially by picric acid, with quenching constant up to $1.5 Â 10 5 L mol À1. This superamplification effect makes the polymer a highly sensitive chemosensor for explosive detection.
Two is better than one: a luminogen comprised of two units of tetraphenylethene (BTPE) emits more efficiently than that with one tetraphenylethene unit in the solid state; self-assembly of the BTPE molecules affords crystalline microfibers that fluoresce in 100% efficiency, giving the largest effect of aggregation-induced emission (alpha(AIE)-->infinity); BTPE-based electroluminescence devices emit in current efficiency up to approximately 7.3 cd/A.
Whereas chain aggregation commonly quenches light emission of conjugated polymers, we here report a phenomenon of aggregation-induced emission enhancement (AIEE): luminescence of polyacetylenes is dramatically boosted by aggregate formation. Upon photoexcitation, poly(1-phenyl-1-alkyne)s and poly(diphenylacetylene)s emit blue and green lights, respectively, in dilute THF solutions. The polymers become more emissive when their chains are induced to aggregate by adding water into their THF solutions. The polymer emissions are also enhanced by increasing concentration and decreasing temperature. Lifetime measurements reveal that the excited species of the polymers become longer-lived in the aggregates. Conformational simulations suggest that the polymer chains contain n=3 repeat units that facilitate the formation of intramolecular excimers. The AIEE effects of the polymers are rationalized to be caused by the restrictions of their intramolecular rotations by the aggregate formation.
Hyperbranched poly(2,5-silole)s [hb-P1(m), m = 1, 6] are synthesized for the first time in this work. 1,1-Dialkyl-2,5-bis(4-ethynylphenyl)-3,4-diphenylsiloles [1(m)] were polymerized by TaBr5, affording hb-P1(m) with high molecular weights (M
w up to 2.5 × 105) in high yields (up to 98%). The structures of hb-P1(m) were characterized by spectroscopic methods and the degree of branching of hb-P1(6) was determined to be 0.55. The hyperbranched polymers are soluble and stable, with no changes in solubility observed after they have been stored under ambient conditions for more than two years. Absorption and emission spectra of hb-P1(m) are red-shifted from those of 1(m), indicating that the polymers are more conjugated than the monomers. Both 1(m) and hb-P1(m) are nonemissive or weekly fluorescent when dissolved in their good solvents but become highly emissive when aggregated in their poor solvents or fabricated into thin solid films, showing unusual phenomena of aggregation-induced (AIE) and -enhanced emissions (AEE). Restriction of intramolecular rotations in the aggregate state is rationalized to be the main cause for the AIE and AEE effects. Photoluminescence (PL) of 1(m) and hb-P1(m) is tunable by varying their concentrations and morphologies. The polymers are readily cured when heated to high temperatures or upon photoirradiation, furnishing cross-linked networks with novel excitation wavelength-dependent emissions in the red spectral region. Photolithography of hb-P1(m) generates fluorescent photopatterns, with the exposed and unexposed areas emitting lights with different colors. The polymers function as sensitive fluorescent chemosensors for the detection of explosives, with a superamplification effect observed in the emission quenching of the polymer nanoaggregates by picric acid.
Triphenylamine (TPA) is a well-known hole-transporting material but suffers aggregation-caused emission quenching in the solid state. Tetraphenylethene (TPE), on the other hand, is an archetypal luminogen that shows the phenomenon of aggregation-induced emission (AIE). In this work, TPA is attached to the TPE core as peripheral group to generate new AIE luminogens with enhanced hole-transporting property. The TPA-TPE adducts, named 1-[4′-(diphenylamino)biphenyl-4-yl]-1,2,2-triphenylethene (TPATPE) and 1,2-bis[4′-(diphenylamino)biphenyl-4-yl]-1,2-diphenylethene (2TPATPE) are synthesized in satisfactory yields by Suzuki coupling of 4-(diphenylamino)phenylboronic acid with 1-(4-bromophenyl)-1,2,2-triphenylethene and 1,2-bis(4-bromophenyl)-1,2-diphenylethene, respectively. Whereas the hybrid molecules are practically nonluminescent in the solution state, their aggregates in poor solvents and thin films emit intensely with fluorescence quantum yields up to 100%. Both TPATPE and 2TPATPE are thermally and morphologically stable, showing high thermal-degradation (T
d up to 430 °C) and glass transition (T
g = 119 °C) temperatures. Multilayer electroluminescence (EL) devices are constructed, which emit sky blue and green EL with maximum luminance of 32230 cd/m2 and current efficiency up to 13.0 cd/A. The devices without hole-transporting layers (HTL) show performances comparable to or better than those with HTL, presumably because of the high hole mobility of TPATPE and 2TPATPE coupled with the matching of their energy levels with the anode.
A polyferroplatinyne polymer can be patterned on the surface of Si wafer in ordered nanoline or nanodot shapes with PDMS molds through nanoimprint lithography (NIL), and subsequent thermal treatment gives rise to the nanopatterned arrays of L1(0) -FePt nanoparticles with the same periodicities. The method offers excellent potential to be utilized in the simple and rapid fabrication of bit patterned media for magnetic data recording.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.