A 4-year 9-month-old Holstein-Friesian dairy cow presented with anorexia. On physical examination, swelling of superficial lymph nodes, pelvic masses, and prolonged urination posture after urinating a small amount were noted. Hematological examination revealed no lymphocytosis.
View Article and Find Full Text PDFWe synthesised thionium-ion embedded aromatic porphyrinoids: a free-base 5-thiaporphyrinium cation and its zinc complex. The sulphur atom effectively participates in the macrocyclic π-conjugation. Fluorescence quantum yields of thiaporphyrinium cations were lower than 1% unlike oxaporphyrinium cations.
View Article and Find Full Text PDFUsing artificial hemes for the reconstruction of natural heme proteins represents a fascinating approach to enhance the bioactivity of the latter. We report the synthesis of various metal 5-oxaporphyrinium cations as cofactors, and a cobalt 5-oxaporphyrinium cation was successfully incorporated into the heme-acquisition protein (HasA) secreted by Pseudomonas aeruginosa. We hypothesize that the oxaporphyrinium cation strongly binds to the HasA-specific outer membrane receptor (HasR) due to its cationic charge, which prevents the subsequent acquisition of heme.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2021
Replacement of the meso methine carbon atoms of porphyrins with heteroatoms is a powerful strategy for tuning their optical and electronic properties. In particular, 5-oxaporphyrin is an attractive target due to its importance as an intermediate in heme catabolism. In this work, we describe the synthesis and properties of a free-base 5-oxaporphyrinium cation, which was prepared by the ring-closure of a bilindione with trifluoromethanesulfonic anhydride.
View Article and Find Full Text PDFHydroxyisooxophlorin is an oxidatively degraded porphyrin that contains one carbonyl carbon, one hydroxymethylene group, and two sp-methine groups at its meso positions. Here we report that oxidation of a free-base meso-hydroxyporphyrin with [bis(trifluoroacetoxy)iodo]benzene in the presence of HO afforded two regioisomers of hydroxyisooxophlorins, 10-hydroxy-10-iso-5-oxophlorin and 15-hydroxy-15-iso-5-oxophlorin, as major and minor products, respectively. We also examined the reaction mechanism, acid-mediated isomerization, metal complexation behavior, and physical properties of these molecules.
View Article and Find Full Text PDFA nickel-mediated tandem double cyclization of ethynylene-linked dibromodiporphyrins afforded highly reactive etheno-fused diporphyrins, which undergo a thermal [2+2] cycloaddition at the fused C-C double bond to afford the cyclobutane moiety in X-shaped cyclobutane-linked tetraporphyrins. During the reaction of a Zn(II) complex precursor, the initial double cyclization product was converted into the diketodiporphyrin, which exhibits red chemiluminescence under ambient conditions.
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