The combination of 1-benzenesulfinyl piperidine (BSP) and trifluoromethanesulfonic anhydride (Tf(2)O) forms a new, powerful, metal-free thiophile that can readily activate both armed and disarmed thioglycosides, via glycosyl triflates, in a matter of minutes at -60 degrees C in dichloromethane, in the presence of 2,4,6-tri-tert-butylpyrimidine (TTBP). The glycosyl triflates are rapidly and cleanly converted to glycosides, upon treatment with alcohols, in good yield and selectivity.
An effective solvothermal procedure has been developed to synthesize the new three-dimensional metal-organic framework, [ZnF(AmTAZ)].solvents, using either 3-amino-1,2,4-triazole (AmTAZ) or 3-amino-1,2,4-triazole-5-carboxylic acid (AmTAZAc) and a choice of several Zn(II) salts as starting materials. The three-dimensional structure displays open-ended, hollow nanotubular channels that are formed by hexanuclear metallamacrocyclic Zn(6)F(6)(AmTAZ)(6) rings. The framework integrity is maintained to 350 degrees C, at which point most of the guest solvent molecules have been removed, as evidenced by single-crystal X-ray analyses, (1)H solid-state NMR, and TGA measurements. At higher temperatures, the framework is converted either to zinc oxide (ZnO) when heated in air or to zinc cyanamide (ZnCN(2)) when heated in an inert atmosphere. In both cases, the as-grown, rodlike crystal shape is maintained during the solid-state transformation, suggesting a possible route for preparing one-dimensional crystalline nanomaterials.
Large vertebrates are strong interactors in food webs, yet they were lost from most ecosystems after the dispersal of modern humans from Africa and Eurasia. We call for restoration of missing ecological functions and evolutionary potential of lost North American megafauna using extant conspecifics and related taxa. We refer to this restoration as Pleistocene rewilding; it is conceived as carefully managed ecosystem manipulations whereby costs and benefits are objectively addressed on a case-by-case and locality-by-locality basis. Pleistocene rewilding would deliberately promote large, long-lived species over pest and weed assemblages, facilitate the persistence and ecological effectiveness of megafauna on a global scale, and broaden the underlying premise of conservation from managing extinction to encompass restoring ecological and evolutionary processes. Pleistocene rewilding can begin immediately with species such as Bolson tortoises and feral horses and continue through the coming decades with elephants and Holarctic lions. Our exemplar taxa would contribute biological, economic, and cultural benefits to North America. Owners of large tracts of private land in the central and western United States could be the first to implement this restoration. Risks of Pleistocene rewilding include the possibility of altered disease ecology and associated human health implications, as well as unexpected ecological and sociopolitical consequences of reintroductions. Establishment of programs to monitor suites of species interactions and their consequences for biodiversity and ecosystem health will be a significant challenge. Secure fencing would be a major economic cost, and social challenges will include acceptance of predation as an overriding natural process and the incorporation of pre-Columbian ecological frameworks into conservation strategies.
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