Angew Chem Int Ed Engl
October 2024
Herein, we report the synthesis of double-walled noncovalent carbon nanotubes (CNTs) through host-guest complexation of nanotube fragments and tube-forming crystal engineering. As the smallest fragment of double-walled CNTs, a host-guest complex of perfluorocycloparaphenylene (PFCPP) and carbon nanobelt (CNB) was synthesized by mixing them in solvents. The immediate complexation of the PF[12]CPP⸧(6,6)CNB complex with a remarkably high association constant (K) of 2×10 L/mol was observed.
View Article and Find Full Text PDFIn recent years, fluorinated cycloparaphenylenes (FCPPs) have attracted attention as electron-negative CPPs as well as cyclic fluoroarenes. Herein, we report the synthesis of heterogenously polyhalogenated CPPs, chlorinated FCPPs (Cl-F[]CPPs; = 6, 8, 10, 12, 14), through nickel- and gold-based methods. The size-dependent photophysical behaviors of Cl-F[]CPPs, which are different from those of pristine CPPs, have been uncovered in this study.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Fluorinated cycloparaphenylenes (FCPPs) have attracted attention as electron-accepting CPPs as well as strained fluoroarenes. Herein, we report the synthesis and properties of novel FCPPs; F[8]CPP and F[6]CPP. Furthermore, the derivatization of F[8]CPP afforded a new carbon nanoring where sixteen pyrrole rings are densely substituted on the CPP framework.
View Article and Find Full Text PDFThe active metal template (AMT) strategy is a powerful tool for the formation of mechanically interlocked molecules (MIMs) such as rotaxanes and catenanes, allowing the synthesis of a variety of MIMs, including π-conjugated and multicomponent macrocycles. Cycloparaphenylene (CPP) is an emerging molecule characterized by its cyclic π-conjugated structure and unique properties. Therefore, diverse modifications of CPPs are necessary for its wide application.
View Article and Find Full Text PDFPurpose: This study analyzed the relationship between patient age and the prevalence and fluoroquinolone susceptibility of gram-positive cocci from the ocular surface flora before ophthalmic surgery.
Methods: This surveillance study included scraped samples from the conjunctival sac of 8923 eyes of 5490 patients (70.0 ± 13.
Peripheral structural modifications of arenes are widely used to control or improve the optoelectronic properties, molecular assembly, and stability of aromatic π-materials as well as to explore new functions. However, known modifications are often tedious and complex; therefore, a simple yet powerful modification strategy is needed. We discovered that annulation with a simple adamantane scaffold exerts a significant impact on the properties, alignment, and stability of aromatic π-systems.
View Article and Find Full Text PDFCycloparaphenylenes (CPPs) and carbon nanobelts (CNBs) represent some of the most iconic cyclic molecular nanocarbons in recent chemistry owing to their unique properties derived from rigid, strained, and cyclic π-conjugated systems. In the last decade, the synthesis of various sizes of CPPs and CNBs has been achieved that allowed not only for investigating their size-dependent properties and strategically using such properties in various applications but also understanding the fundamental features of cyclic π-conjugated systems and molecular nanocarbons in general. Herein, we report on the synthesis, size-dependent properties, and paratropic belt currents of methylene-bridged []cycloparaphenylenes ([]MCPP, = 6, 8, 10).
View Article and Find Full Text PDFThe design and synthesis of nitrogen (N)-doped molecular nanocarbons are of importance since N-doped nanocarbons have received significant attention in materials science. Herein, we report the synthesis and X-ray crystal structure of a nitrogen-inserted nonalternant aromatic belt. The palladium-catalyzed six-fold annulative double N-arylation provided an aromatic belt bearing six nitrogen atoms in one step from cyclo[6]paraphenylene--ethenylene, the precursor of the (6,6)carbon nanobelt.
View Article and Find Full Text PDFAromatic polymers are the first-choice platform for current organic materials due to their distinct optical, electronic, and mechanical properties as well as their biocompatibility. However, bare aromatic polymer backbones tend to strongly aggregate, rendering them essentially insoluble in organic solvent. While the typical solution is to install many solubilizing substituents on the backbones, this often provokes undesired property changes.
View Article and Find Full Text PDFPerfluorinated aromatic compounds, the so-called perfluoroarenes, are widely used in materials science owing to their high electron affinity and characteristic intermolecular interactions. However, methods to synthesize highly strained perfluoroarenes are limited, which greatly limits their structural diversity. Herein, we report the synthesis and isolation of perfluorocycloparaphenylenes (PFCPPs) as a class of ring-shaped perfluoroarenes.
View Article and Find Full Text PDFGraefes Arch Clin Exp Ophthalmol
November 2021
Purpose: To determine the relationship between fluoroquinolone susceptibility of gram-positive cocci (GPC) isolated from patients with bacterial keratitis and the age of the patients or the date of onset.
Methods: Bacterial isolates were obtained from corneal lesions of patients with infectious keratitis treated between January 2008 and December 2016. The fluoroquinolone susceptibility of GPC was assessed, and a retrospective review of microbiological records was performed.
Chem Commun (Camb)
November 2020
Strigolactones (SLs) are plant hormones that suppress shoot branching through perception by their receptor protein DWARF 14 (D14). The artificial regulation of SL signaling has been considered a potent agricultural technique because plant architecture is strongly related to crop yield. In this communication, we describe the development of a small-molecule D14 inhibitor that functions at sub-micromolar levels.
View Article and Find Full Text PDFPurpose: We previously reported the presence of multidrug-resistant staphylococci on the ocular surface of glaucoma patients using prostaglandin analog drops for more than 1 year. Here, we investigated the effect of benzalkonium chloride (BAC) on these multidrug-resistant staphylococci.
Methods: was isolated from the conjunctival sacs of 32 eyes of 32 patients comprised of 13 eyes treated with 0.
The synthesis, structure, and properties of methylene-bridged [6]cycloparaphenylene ([6]CPP), a nonalternant aromatic belt, are described. This belt-shaped methylene-bridged [6]CPP, in which each phenylene unit is tethered to its neighbors by methylene bridges, was constructed through 6-fold intramolecular nickel-mediated aryl-aryl coupling of triflate-functionalized pillar[6]arene in 18% isolated yield. As compared to the analogous [6]CPP, the methylene bridges coplanarize neighboring paraphenylene units and enhance the degree of π-conjugation, which results in a significant decrease in energy gap.
View Article and Find Full Text PDFCubane (CH), a cubic alkane, has long attracted attention owing to its unique 3D structure. In order to utilize the cubane scaffold widely in science and technology, a powerful method for synthesizing diverse cubane derivatives is required. Herein, we report the synthesis of mono-, di-, tri-, and tetra-arylated cubanes.
View Article and Find Full Text PDFHexa--hexabenzocoronene (HBC) is known to be a poorly soluble polycyclic aromatic hydrocarbon for which direct functionalization methods have been very limited. Herein, the synthesis of hexaborylated HBC from unsubstituted HBC is described. Iridium-catalyzed six-fold C-H borylation of HBC was successfully achieved by screening solvents.
View Article and Find Full Text PDFThe synthesis, structures, and properties of highly twisted, nonplanar aromatic macrocycles are described. These macrocycles with an approximately 90° twist angle were synthesized by an effective synthetic approach through a quadruple Suzuki-Miyaura coupling of 4,5-bisarylphenanthrene, a novel axially chiral nonplanar building block. By varying the cross-coupling partner as the spacer, a family of twisted macrocycles was synthesized, allowing for a systematic study of the effect of the spacer on macrocycle shape and photophysical properties.
View Article and Find Full Text PDFThe ability of α-borylated naphthalene-based aromatic compounds is important because it provides ready access to interesting novel extended π-systems. In this report, we disclose the Ni-catalyzed α-selective C-H borylations of naphthalene-based aromatic compounds. The reaction proceeds with -xanthenoxanthene and other aromatic compounds to regioselectively afford the α-borylated products without directing groups.
View Article and Find Full Text PDFThe synthesis of sterically hindered phenanthrenes acid-catalyzed bisannulation reaction is described. Treatment of 1,4-benzenediacetaldehyde with terminal aryl alkynes in the presence of B(CF) provides 4,5-diarylphenanthrenes in good yields with excellent regioselectivity. The use of internal alkyne substrates enabled the synthesis of sterically hindered 3,4,5,6-tetrasubstituted phenanthrenes displaying augmented backbone helicity.
View Article and Find Full Text PDFPurpose: The present study aimed to investigate the effectiveness of adjunctive therapy involving the Rho-associated, coiled-coil-containing protein kinase (ROCK) inhibitor ripasudil in lowering intraocular pressure (IOP) in patients with different subtypes of glaucoma, on the basis of the time of IOP measurement STUDY DESIGN: Retrospective study METHODS: In total, 58 patients who underwent adjunctive therapy with ripasudil at a single institution were included. They were classified into a primary open-angle glaucoma (POAG) group, an exfoliation glaucoma (XFG) group, and a secondary glaucoma associated with uveitis, or steroid glaucoma (SG), group. The average IOPs within 6 months before (pre-IOP) and after (post-IOP) the addition of ripasudil were compared among the 3 groups.
View Article and Find Full Text PDFWe investigated the psychometric properties of the simplified Japanese version of the Athens Insomnia Scale (AIS-SJ) using baseline data from the Fukushima Health Management Survey. Data from 22 878 men and 27 669 women aged 16 years and older were analysed (M = 52.9 ± 18.
View Article and Find Full Text PDFPurpose: To explore interactions between pilocarpine and the ROCK inhibitor, ripasudil, on IOP and pupil diameter in human eyes, and morphological and functional changes in outflow tissues in vitro.
Methods: IOP and pupil diameter were measured after pilocarpine and/or ripasudil, which were topically applied in healthy subjects. Human trabecular meshwork (HTM) cells were used in a gel contraction assay, for the evaluation of phosphorylation of myosin light chain and cofilin, and immunostaining for cytoskeletal proteins.