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The use of protonation to switch nonaromatic expanded porphyrins to their corresponding anti-aromatic forms has not been widely explored. Here, we show that free-base pyriamethyrin and dipyriamethyrin display nonaromatic character, as inferred from NMR spectroscopic analyses, their optical properties, and theoretical calculations. Addition of two protons extends the π - conjugation of these amethyrin analogues and yields formally anti-aromatic systems.
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http://dx.doi.org/10.1039/d0cc04400h | DOI Listing |
Org Lett
September 2025
Department of Chemistry, Indian Institute of Science Education and Research, Dr. Homi Bhabha Road, Pune 411008, Maharashtra, India.
Unlike aromatic porphyrins, conventional oxidative coupling reactions do not yield dimeric or oligomeric antiaromatic porphyrinoids. We describe here the first example of a β-β-linked antiaromatic expanded porphyrinoid through a novel synthetic strategy. It contains two 24π sapphyrin units, which undergo independent reversible two-electron oxidation to yield the aromatic tetracation.
View Article and Find Full Text PDFBiosens Bioelectron
December 2025
Key Lab for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China. Electronic address:
The sensitive and specific diagnosis of pheochromocytoma and paraganglioma (PPGL) remains challenging due to the low abundance of their detectable biomarker of catecholamines (CAs) in serum. Herein, we established an enzyme-assisted substrate recycling amplification model based on a hierarchically mesoporous UiO-66-NH (HMAUiO) to address these difficulties. Such porous platform was constructed by the Hofmeister ion-assisted nanoemulsion method with mesoporous size beyond 20 nm, in which Pt (II) meso-tetra(4-carboxyphenyl)porphyrin (TCPP-Pt) was incorporated within the microporous framework to form an HMAUiO-Pt sensing probe.
View Article and Find Full Text PDFJ Inorg Biochem
December 2025
Pharmaceutical Biochemistry and Bioanalytics, Pharmaceutical Institute, University of Bonn, Bonn, Germany. Electronic address:
Heme, a vital iron-containing molecule, serves fundamental roles in oxygen transport and electron transfer but also acts as an extracellular signaling entity, significantly influencing inflammatory responses. Elevated levels of labile heme resulting from hemolytic events or therapeutic treatments may activate inflammatory signaling pathways, particularly through the Toll-like receptor 4 (TLR4). In this study, we systematically expanded the previously developed Heme Knowledge Graph (HemeKG) to comprehensively incorporate recent findings regarding heme-TLR4 interactions.
View Article and Find Full Text PDFSignal Transduct Target Ther
August 2025
Department of Medical Ultrasound, National Clinical Research Center for Geriatrics, West China Hospital, Sichuan University, Chengdu, China.
A tumor cell membrane (CM)-based biomimetic membrane tumor vaccine is an emerging prevention and treatment strategy in tumor immunotherapy. However, a single CM mostly has a weak immune-boosting effect. Here, a heterogenic fusion membrane tumor vaccine, EV-CM, was successfully constructed by fusing extracellular vesicles (EVs) from S.
View Article and Find Full Text PDFSmall
August 2025
Department of Chemistry, School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi, 464-0802, Japan.
De novo protein design has been used to create functional protein assemblies, but its reliance on standard amino acids limits the integration of synthetic supramolecular strategies for precise control of molecular assemblies. Herein, an artificial protein assembly that integrates synthetic supramolecular design with de novo protein engineering is presented. Focusing on unit and connection rigidity, the Bi-Porphyrin Acquisition Designer protein (BiPAD), which captures two synthetic porphyrin molecules via state-of-the-art generative protein design to fuse α/β-folded porphyrin-binding motifs, is designed and created.
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