Synthesis and metalation of polycatechol nanohoops derived from fluorocycloparaphenylenes.

Due to their unique topology and distinct physical properties, cycloparaphenylenes (CPPs) are attractive building blocks for new materials synthesis. While both noncovalent interactions and irreversible covalent bonds have been used to link CPP monomers into extended materials, a coordination chemistry approach remains less explored. Here we show that nucleophilic aromatic substitution reactions can be leveraged to rapidly introduce donor groups (-OR, -SR) onto polyfluorinated CPP rings. Demethylation of methoxide-substituted CPPs produces polycatechol nanohoop ligands that are readily metalated to produce well-defined, multimetallic CPP complexes. As catechols are recurring motifs throughout coordination chemistry and dynamic covalent chemistry, the polycatechol nanohoops reported here open the door to new strategies for the bottom-up synthesis of atomically precise CPP-based materials.

Lethal envenomation: medicolegal aspects of snakebites and religious snake handlers in Kentucky: a report of three cases with comment on medical, legal, and public policy ramifications.

Ritualistic serpent qua snake handling, which rests upon inveterate religious conviction arising out of literal interpretation of selected passages of the New Testament, is a rare ceremony practiced by a distinct minority of Christians predominantly in rural Appalachian regions of the United States commonly referred to as the Bible belt. The fervent, frenzied pursuit by anointed "sign-followers" of intimate contact with a variety of poisonous snakes, however, puts the handler together with sect members or bystanders at risk for lethal envenomation, particularly when prompt medical attention is held by the congregation of faith to contravene God's will. The authors report three separate cases of death due to envenomation by snakebite during a church service and the handler's faith-based refusal to seek treatment. Postmortem examination of each yielded similar physical findings attributable to various toxic sequelae of the complex venoms. A review of the injurious constituents of these chemical toxins also includes a discussion of complex pathophysiological mechanisms causing death. In addition, the authors review the history of representative legislative and judicial responses to the sensationally mortal phenomenon, all of which ineluctably grapple with fundamental Constitutional issues devolving from such controversial religious practices. We underscore the view that a thoroughly documented medicolegal investigation and autopsy are indispensable to both inform matters of public health and thereby contribute to the formulation of sound public policy.