Beyond Mimicking Enzymes: NewTAML/Peroxide Abstracts sp3 C–H Bonds to Initiate Biotranscendent Water-Purifying Mineralization of Fluoroquinolone Antibiotics
Xiaowei Ma, Longzhu Q. Shen, Minerva G. Schafer, Karl H. G. Schulz, Roberto R. Gil, Alexander D. Ryabov, Terrence J. Collins
TL;DR
A new catalyst surpasses enzyme-like activity to break down fluoroquinolone antibiotics in water, safely converting them into harmless minerals.
Contribution
The study introduces a novel TAML/peroxide catalyst that achieves biotranscendence by efficiently mineralizing fluoroquinolones.
Findings
The NewTAML catalyst activates hydrogen peroxide to rapidly oxidize fluoroquinolones like ofloxacin through unique desaturation and N-demethylation pathways.
Kinetic isotope effects of 8.6 and 3.8 were observed for desaturation and N-demethylation, respectively.
Final mineralization products include F–, CH3COO–, HCOO–, NO2–, and NO3–, indicating complete detoxification.
Abstract
In neutral aqueous media under ambient temperature, the bis-amido-bis-sulfonamido-ligated [FeIII{4-NO2C6H3-1,2-(NCOCMe2 NSO2)2CHMe}(OH2)]− NewTAML catalyst (2), activates hydrogen peroxide to mimic and greatly surpass enzymatic activity (biotranscendence) by sweeping fluoroquinolone antibiotics rapidly toward minerals. Stepwise identification of intermediates was paired with mechanistic examination of key steps. For ofloxacin, the 2/H2O2 activated catalyst (AC) first attacks ofloxacin’s piperazine unit in two enzyme-mimicking parallel pathways, cleaving secondary (desaturation) and primary (N-demethylation) sp3 C–H bonds via H atom abstraction to form dehydro- and desmethyl-ofloxacin, respectively; desaturation is a novel expression of TAML peroxidase-like reactivity. Kinetic data obtained with selectively deuterated ofloxacin compounds revealed for desaturation and N-demethylation,…
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Taxonomy
TopicsMetal-Catalyzed Oxygenation Mechanisms · Advanced Nanomaterials in Catalysis · Metal complexes synthesis and properties