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3. Ultrafast Charge-Transfer Dynamics in the Iron–Sulfur Complex of Rhodobacter capsulatus Ferredoxin VI

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5. Detoxification of bisphenol A via sulfur-mediated carbon–carbon σ-bond scission

   https://doi.org/10.1039/D2SU00138A  

   Thiounn, Timmy; Karunarathna, Menisha S.; Lauer, Moira K.; Tennyson, Andrew G.; Smith, Rhett C. (May 2023, RSC Sustainability)

   Environmental contamination with bisphenol A (BPA), produced via degradation of plastic waste, constitutes a major hazard for human health due to the ability of BPA to bind to estrogen receptors and thereby induce hormonal imbalances. Unfortunately, BPA cannot be degraded to a “safe” material without breaking C–C σ-bonds, and existing methods required to break these bonds employ petroleum-derived chemicals and environmentally-harmful metal ions. Therefore, there is an urgent need to develop new “green” methods to break BPA into monoaryl compounds without the use of such reagents and, ideally, convert those monoaryls into valuable materials that can be productively utilized instead of being discarded as chemical waste. Herein we report a new mechanism by which O , O ′-dimethyl bisphenol A (DMBPA), obtained from BPA-containing plastic via low-temperature recycling, undergoes C–C σ-bond cleavage via thiocracking, a reaction with elemental sulfur at temperatures lower than those used in many thermal plastic recycling techniques ( e.g. , <325 °C). Mechanistic analyses and microstructural characterization of the DMBPA-derived materials produced by thiocracking elucidated multiple subunits comprising monoaryl species. Impressively, analyses of recoverable organics revealed that >95% of DMBPA had been broken down into monoaryl components. Furthermore, the DMBPA–sulfur composite produced by thiocracking (BC90) exhibited compressive strength (∼20 MPa) greater than those of typical Portland cements. Consequently, this new thiocracking method creates the ability to destroy the estrogen receptor-binding components of BPA wastes using greener techniques and, simultaneously, to produce a mechanically-robust composite material that represents a sustainable alternative to Portland cements. 

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