Synthesis of mono-O-alkylated homooxacalix[3]arene and a protection–deprotection strategy for homooxacalix[3]arene

The regioselective synthesis of mono-O-alkylated homooxacalix[3]arene is accomplished for the first time. The synthetic route relies on two key steps: (i) a facile protection of two OH groups at the lower rim of the homooxacalix[3]arene and (ii) the deprotection of 9- anthrylmethyl groups via the Pd/C-catalyzed hydrogenation under atmospheric hydrogen. An efficient protection- deprotection strategy for the functionalization of homooxacalix[ 3]arene is presented

Synthesis and structures of O-anthrylmethyl-substituted hexahomotrioxacalix[3]arenes

O-Alkylation of 7,15,23-tri-tert-butyl-25,26,27-trihydroxy-2,3,10,11,18,19-hexahomo-3,11,19-trioxacalix[3]arene (1H₃) with 9-chloromethylanthracene 5 was carried out under different reaction conditions. Variation of the number of anthrylmethyl group introduced at the phenolic rim of hexahomotrioxacalix[3]arene 1H₃ was achieved through selective O-alkylation using stoichiometric amounts of 9-chloromethylanthracene 5 in acetone to afford the mono-O-alkylated product 2H₂An, the di-O-alkylated product 3HAn₂ and the tri-O-alkylated product partial-cone-4An₃, respectively. Interestingly, by using an acetone/benzene (1:1 v/v) mixed solvent system, the cone-4An₃ was successfully synthesized. These results suggest that the solvent can also control the conformation of the O-alkylation products. The possible reaction routes of the cone-4An₃ and partial-cone-4An₃ are also discussed

A pyrene-functionalized triazole-linked hexahomotrioxacalix[3]arene as a fluorescent chemosensor for Zn²⁺ ions

A new pyrenyl appended hexahomotrioxacalix[3]arene L featuring 1,2,3-triazole linkers was synthesized as a fluorescent chemosensor for Zn²⁺ in mixed aqueous media. It exhibited high affinity toward Zn²⁺, and the monomer and excimer emission of the pyrene moieties could be adjusted. The binding stoichiometry of the L·Zn²⁺ complex was determined to be 1:1, and the association constant (Ka) was found to be 7.05 × 10⁴ M⁻¹. The binding behavior with Zn²⁺ has been confirmed by ¹H NMR spectroscopic analysis

Synthesis and evaluation of a novel fluorescent sensor based on hexahomotrioxacalix[3]arene for Zn²+ and Cd²+

A novel type of selective and sensitive fluorescent sensor having triazole rings as the binding sites on the lower rim of a hexahomotrioxacalix[3]arene scaffold in a cone conformation is reported. This sensor has desirable properties for practical applications, including selectivity for detecting Zn²⁺ and Cd²⁺ in the presence of excess competing metal ions at low ion concentration or as a fluorescence enhancement type chemosensor due to the cavity of calixarene changing from a ‘flattened-cone’ to a more-upright form and inhibition of PET. In contrast, the results suggested that receptor 1 is highly sensitive and selective for Cu²⁺ and Fe³⁺ as a fluorescence quenching type chemosensor due to the photoinduced electron transfer (PET) or heavy atom effect

外側環軸関節の関節症性変化のリスク増加に関連する要因; 後ろ向き研究

Purpose Atlantodens osteoarthritis and atlantoaxial osteoarthritis cause neck pain and suboccipital headaches. Currently, knowledge on the risk factors for atlantoaxial osteoarthritis is lacking. This study aimed to investigate the factors related to the increased risk of atlantoaxial osteoarthritis. Methods We analyzed computed tomography (CT) images of the upper cervical spine of 1266 adult trauma patients for whom upper cervical spine CT was performed at our hospital between 2014 and 2019. The degree of atlantoaxial osteoarthritis was quantified as none-to-mild (not having osteoarthritis) or moderateto- severe (having osteoarthritis). Risk factors associated with atlantoaxial osteoarthritis were identified using univariate and multivariable logistic regression analyses. Results The study group included 69.4% men, and the overall average age of the study population was 54.9 ± 20.4 years. The following factors were independently and significantly associated with atlantoaxial osteoarthritis in the multivariable logistic regression analysis: age in the sixth decade or older (odds ratio [OR], 20.5; 95% confidence interval [CI], 6.2‒67.2, p < 0.001), having calcific synovitis (OR, 4.9; 95% CI, 2.4‒9.9, p < 0.001), women sex (OR, 3.3; 95% CI, 1.9‒5.7, p = 0.002), and not having atlantodens osteoarthritis (OR, 2.1; 95% CI, 1.2‒3.8, p = 0.014). Conclusion In the multivariable logistic regression analysis, age in the sixth decade or older, calcification of the transverse ligament, being women, and not having atlantodens osteoarthritis were found to be significantly associated with atlantoaxial osteoarthritis. Delayed diagnosis and treatment can be avoided by focusing on these risk factors.博士（医学）・甲第873号・令和5年3月15

A hexahomotrioxacalix[3]arene-based ditopic receptor for alkylammonium ions controlled by Ag + ions 4

A receptor cone-1 based on a hexahomotrioxacalix[3]arene bearing three pyridyl groups 21 was successfully synthesized, which has a C3-symmetric conformation and is capable of binding 22 alkylammonium and metal ions simultaneously in a cooperative fashion. It can bind 23 alkylammonium ions through the -cavity formed by three aryl rings. This behaviour is consistent 24 with the cone-in/cone-out conformational rearrangement needed to reorganize the cavity for 25 endo-complexation. As a C3-symmetrical pyridyl-substituted calixarene, receptor cone-1 can also 26 bind a Ag + ion and the nitrogen atoms are turned towards the inside of the cavity and interact with 27 Ag +. After complexation of tris(2-pyridylamide) derivative receptor cone-1 with Ag + , the original 28 C3-symmetry was retained and higher complexation selectivity for n-BuNH3 + versus t-BuNH3 + was 29 observed. Thus, it is believed that this receptor will have a role to play in the sensing, detection, and 30 recognition of Ag + and n-BuNH3 + ions. 3

A Hexahomotrioxacalix[3]arene-Based Ditopic Receptor for Alkylammonium Ions Controlled by Ag+ Ions

A receptor cone-1 based on a hexahomotrioxacalix[3]arene bearing three pyridyl groups was successfully synthesized, which has a C3-symmetric conformation and is capable of binding alkylammonium and metal ions simultaneously in a cooperative fashion. It can bind alkylammonium ions through the -cavity formed by three aryl rings. This behaviour is consistent with the cone-in/cone-out conformational rearrangement needed to reorganize the cavity for endo-complexation. As a C3-symmetrical pyridyl-substituted calixarene, receptor cone-1 can also bind an Ag+ ion, and the nitrogen atoms are turned towards the inside of the cavity and interact with Ag+. After complexation of tris(2-pyridylamide) derivative receptor cone-1 with Ag+, the original C3-symmetry was retained and higher complexation selectivity for n-BuNH3+ versus t-BuNH3+ was observed. Thus, it is believed that this receptor will have a role to play in the sensing, detection, and recognition of Ag+ and n-BuNH3+ ions

Synthesis of Mono‑<i>O</i>‑alkylated Homo­oxa­calix­[3]­arene and a Protection–Deprotection Strategy for Homo­oxa­calix­[3]­arene

The regioselective synthesis of mono-<i>O</i>-alkylated homo­oxacalix­[3]­arene is accomplished for the first time. The synthetic route relies on two key steps: (i) a facile protection of two OH groups at the lower rim of the homo­oxacalix­[3]­arene and (ii) the deprotection of 9-anthrylmethyl groups via the Pd/C-catalyzed hydrogenation under atmospheric hydrogen. An efficient protection–deprotection strategy for the functionalization of homo­oxacalix­[3]­arene is presented

Synthesis of Mono‑<i>O</i>‑alkylated Homo­oxa­calix­[3]­arene and a Protection–Deprotection Strategy for Homo­oxa­calix­[3]­arene

The regioselective synthesis of mono-<i>O</i>-alkylated homo­oxacalix­[3]­arene is accomplished for the first time. The synthetic route relies on two key steps: (i) a facile protection of two OH groups at the lower rim of the homo­oxacalix­[3]­arene and (ii) the deprotection of 9-anthrylmethyl groups via the Pd/C-catalyzed hydrogenation under atmospheric hydrogen. An efficient protection–deprotection strategy for the functionalization of homo­oxacalix­[3]­arene is presented