Great Toe Tip Reconstruction after Severe COVID-19 Using Hemi-pulp V-Y Advancement Flap: A Case Report.

"COVID toe," one of the extrapulmonary disorders of coronavirus disease 2019 (COVID-19), may result in toe necrosis. In this case, we successfully reconstructed a severe COVID-19-induced defect in the great toe by using an innervated hemi-pulp V-Y advancement flap. A 48-year-old woman was diagnosed with fulminant myocarditis due to COVID-19 and received intensive care. Even after the acute phase, a skin defect measuring 10 mm × 7 mm was noted, exposing the underlying bone on her right great toe tip. Because of ulceration, she was unable to start walking training. To continue rehabilitation, we reconstructed it with the innerved hemi-pulp V-Y advancement flap. The pain improved quickly, and rehabilitation was resumed. During the 6-month follow-up period, no cosmetic or functional complications were observed. Plantar pressure measurements demonstrated favorable loading on the great toe, and it was a favorable outcome in walking function. This flap is a valuable option as one of the innervated flaps for toe-end necrosis with preserved blood flow, which helps in implementing prompt gait rehabilitation.

Enhanced antitumor effects of novel intracellular delivery of an active form of menaquinone-4, menahydroquinone-4, into hepatocellular carcinoma.

Reduced cellular uptake of menaquinone-4 (MK-4), a vitamin K2 homolog, in human hepatocellular carcinoma (HCC) limits its usefulness as a safe long-term antitumor agent for recurrent HCC and produces des-γ-carboxy prothrombin (DCP). We hypothesized that effective delivery of menahydroquinone-4 (MKH), the active form of MK-4 for γ-glutamyl carboxylation, into HCC cells is critical for regulating HCC growth, and may enable it to be applied as a safe antitumor agent. In this study, we verified this hypothesis using menahydroquinone-4 1,4-bis-N,N-dimethylglycinate hydrochloride (MKH-DMG), a prodrug of MKH, and demonstrated its effectiveness. Intracellular delivery of MKH and subsequent growth inhibition of PLC/PRF/5 and Hep3B (DCP-positive) and SK-Hep-1 (DCP-negative) cells after MKH-DMG administration were determined and compared with MK-4. The activity of MKH-DMG against tumor progression in the liver alongside DCP formation was determined in a spleen-liver metastasis mouse model. MKH-DMG exhibited greater intracellular delivery of MKH in vitro (AUC0-72 hour of MKH) and increased growth-inhibitory activity against both DCP-positive and DCP-negative HCC cell lines. The phenomena of MKH delivery into cells in parallel with simultaneous growth inhibition suggested that MKH is the active form for growth inhibition of HCC cells. Cell-cycle arrest was determined to be involved in the growth inhibition mechanisms of MKH-DMG. Furthermore, MKH-DMG showed significant inhibition of tumor progression in the liver, and a substantial decrease in plasma DCP levels in the spleen-liver metastasis mouse model. Our results suggest that MKH-DMG is a promising new candidate antitumor agent for safe long-term treatment of HCC.

Olefin metathesis of the aligned assemblies of conjugated polymers constructed through supramolecular bundling.

The ordered structures constructed from an aligner molecule 1o and conjugated polymers (CPs) were efficiently converted into the poly-pseudo-rotaxane structures by the template-assisted ring-closing olefin metathesis (RCM) of olefinic groups at the peripheral positions of 1o. Moreover, the poly-pseudo-rotaxane structures permitted the separation of the crystalline ordered assemblies of CP by size exclusion chromatography and the preservation of the sheet morphologies after the treatment with trifluoroacetic acid. The morphologies and the periodicities of assemblies were also maintained after the retrieving treatments.

Allosteric function facilitates template assisted olefin metathesis.

Template assisted olefin metathesis of an allosteric host to give the corresponding bicyclic compound was achieved and can allosterically bind the template guest diamines, and with different affinity and cooperativity.

Cooperative C(60) binding to a porphyrin tetramer arranged around a p-terphenyl axis in 1:2 host-guest stoichiometry.

[structure: see text] Porphyrin tetramer 1 was newly designed and synthesized to construct a novel cooperative [60]fullerene (C(60)) binding system. Compound 1 has a p-terphenyl axis, which is expected to act as a scaffold for a guest-binding information transducer. In toluene, 1 can bind 2 equiv of C(60) to produce a 1:2 1/C(60) complex with association constants of 5800 M(-1) (K(1)) and 2000 M(-1) (K(2)). These values are significantly greater than those for control porphyrin dimers such as 2 and 3.