Axially Chiral Spiro-Conjugated Carbon-Bridged p-Phenylenevinylene Congeners: Synthetic Design and Materials Properties.

Spiro-conjugated systems are attracting considerable interest for their chiroptical properties and because of their compact structure the small reorganization energy upon electronic excitation or ionization. We report here a modular and convergent synthesis of axially chiral spiro-conjugated carbon-bridged p-phenylenevinylenes (spiro-CPVs) in a racemic and optically active form where two carbon-bridged p-phenylenevinylene molecules are connected by a spiro carbon atom. Our synthetic design focuses on the C2 symmetry of the spiro-CPV molecules, relying on coupling of two 3-lithio-2-arylindene molecules on a carbon monooxide molecule that serves as the spiro carbon center in the target molecule. We prepared derivatives including those possessing phenol groups that facilitate optical resolution and also serve as a platform for the synthesis of a variety of optically active derivatives, which exhibit circularly polarized photoluminescence with high fluorescence quantum yields, large dissymmetry factors, and high photostability. For example, a bis(phenylethynyl) derivative exhibited a fluorescence quantum yield of 0.99 and a dissymmetry factor in luminescence of |glum| = 2.7 × 10-4, values highest among and comparable to those of reported CPL compounds, respectively. A tetrakis-diarylamine derivative shows hole mobility (µh = 3.84 × 10-5 cm2 V-1 s-1; space charge-limited current measurement of a spin-coated film) comparable to that of a popularly used hole-transporting material, spiro-OMeTAD (µh = 2.6 × 10-5 cm2 V-1 s-1), as well as high thermal and phase stability (T5d = 382 °C, Tg = 171 °C).

Citric Acid Modulated Growth of Oriented Lead Perovskite Crystals for Efficient Solar Cells.

Solar cells made of lead perovskite crystals have attracted much attention for their high performance, but far less attention as a subject of crystal engineering. Here, we report that citric acid (CA) and chloride anion, working together, modulate crystal growth of CH3NH3PbI3, producing sub-mm-sized cuboid crystals-a morphology more suitable for close packing in a thin film than the commonly observed elongated dodecahedral morphology. By using a 15 wt % CA-doped precursor solution, we formed a single layer of large, flat, and oriented cuboid crystals with minimum crystal domain boundaries and maximum contact with neighboring layers, and fabricated an archetypal inverted-structured device of 4 mm2 area, which showed, reproducibly and with little hysteresis, 16.75% power conversion efficiency (PCE), 26% higher than the PCE obtained for a polycrystalline film made without CA doping. Under weaker irradiation of a 1 cm2 device, the PCE improved from 14.52% (one sun) to 20.4% (0.087 suns). Under illumination with white light emitting diode, a 10 wt % CA-doped device showed PCE of 28.1%, suggesting an advantage of PVK-SCs for indoor applications. Further studies on crystal growth modulation will be beneficial for manufacturing efficient and stable lead perovskite solar cells.

Postoperative electron beam irradiation to prevent recurrence of refractory subungual exostosis: a case report.

Background: Subungual exostosis is a type of heterotopic ossification, which often has unclear margins. Therefore, marginal resection may cause recurrence and wide resection is sometimes required to achieve a complete cure. However, wide resection may cause postoperative nail deformity and revision of this deformity is generally difficult. The primary treatment of subungual exostosis is surgical treatment, and there have been no comprehensive reports on the efficacy of adjunctive treatments. Although postoperative electron beam irradiation has been successfully used after heterotopic ossification excision to prevent recurrence, there are no reports on the use of this procedure following subungual exostosis resection. Case Description: Herein, we report a case of refractory subungual exostosis that developed as a result of chronic irritation and inflammation caused by an ingrown nail and recurred after initial resection. We performed marginal resection of the lesion to preserve the nail matrix and nail bed as possible, a two-stage skin grafting procedure, and electron-beam irradiation to prevent recurrence. Conclusions: Excellent results were achieved both in terms of complete cure and cosmetic appearance, suggesting that electron-beam irradiation following refractory subungual exostosis excision may help prevent its recurrence. We expect a further study including many cases of subungual exostosis treated with postoperative electron-beam irradiation to be conducted.

Construction of a screening system for lipid-derived radical inhibitors and validation of hit compounds to target retinal and cerebrovascular diseases.

Recent studies have highlighted the indispensable role of oxidized lipids in inflammatory responses, cell death, and disease pathogenesis. Consequently, inhibitors targeting oxidized lipids, particularly lipid-derived radicals critical in lipid peroxidation, which are known as radical-trapping antioxidants (RTAs), have been actively pursued. We focused our investigation on nitroxide compounds that have rapid second-order reaction rate constants for reaction with lipid-derived radicals. A novel screening system was developed by employing competitive reactions between library compounds and a newly developed profluorescence nitroxide probe with lipid-derived radicals to identify RTA compounds. A PubMed search of the top hit compounds revealed their wide application as repositioned drugs. Notably, the inhibitory efficacy of methyldopa, selected from these compounds, against retinal damage and bilateral common carotid artery stenosis was confirmed in animal models. These findings underscore the efficacy of our screening system and suggest that it is an effective approach for the discovery of RTA compounds.

Chlorine-radical-mediated C-H oxygenation reaction under light irradiation.

The oxygenation of C(sp3)-H bonds is a key chemical reaction in the production of fine chemicals and pharmaceuticals. Hydrogen atom transfer has recently gained significant attention for its ability to functionalise C-H bonds. The C-H bond can be activated by transferring the H radical to a hydrogen acceptor such as the chlorine radical (Cl˙). Thus, the Cl˙ generated by light irradiation can be used to initiate C-H oxygenation reactions, in which molecular oxygen is used as the oxidant. In this review article, we have summarised the recent advances in the field of Cl˙-mediated C-H oxygenation reactions. Reactions with catalysts such as metal chlorides, organophotoredox catalysts (acridinium ions), and chlorine dioxide radicals under light irradiation have been discussed. We conclude the review by providing suggestions for future research studies in the field. We expect that this review article will provide valuable information for the development of Cl˙-mediated C-H oxygenation reactions, contribute to the understanding of the reactivity of Cl˙, and inspire other useful synthetic chemical applications for C-H oxygenation reactions.

One-step antibacterial modification of polypropylene non-woven fabrics via oxidation using photo-activated chlorine dioxide radicals.

In this study, we examined the modification of polypropylene non-woven fabrics (PP NWFs) via a one-step oxidation treatment using photo-activated chlorine dioxide radicals (ClO2˙). The oxidised PP NWFs exhibited excellent antibacterial activity against both Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). The mound structure and antibacterial activity in the modified PP NWFs disappeared upon washing with a polar organic solvent. After washing, nanoparticles of around 80 nm in diameter were observed in the solution. The results of several mechanistic studies suggest that nanoparticles can contribute to the antimicrobial activity of oxidised PP NWFs.