N-Methyl-D-aspartate (NMDA) is the prototypical agonist of the NMDA receptor subtype of ionotropic glutamate receptors. Stereogenic placement of a C-F bond at the 3-position of (S)-NMDA generates either the (2S,3S)- or (2S,3R)- diastereoisomers of 3F-NMDA. The individual diastereoisomers were prepared by synthesis in enantiomerically pure forms and it was found that (2S,3S)-3F-NMDA is an agonist with a comparable potency to NMDA itself, whereas the (2S,3R)-diastereoisomer has negligible potency. The difference in potency of these stereoisomers is attributed to a preference of the C-F bond (2S,3S)-3F-NMDA to adopt a gauche conformation to the C-N(+) bond in the binding conformation, whereas the (2S,3R)-3F-NMDA forces these bonds anti, losing electrostatic stabilisation, to achieve the required binding conformation. These observations illustrate the utility of stereoselective fluorination in influencing the molecular conformation of β-fluorinated amino acids and thus probing the active conformations of bioactive compounds at receptors.
Dwindling fossil fuels and improper waste management are major challenges in the context of increasing population and industrialization, calling for new waste-to-energy sources. For instance, refuse-derived fuels can be produced from transformation of municipal solid waste, which is forecasted to reach 2.6 billion metric tonnes in 2030. Gasification is a thermalinduced chemical reaction that produces gaseous fuel such as hydrogen and syngas. Here, we review refuse-derived fuel gasification with focus on practices in various countries, recent progress in gasification, gasification modelling and economic analysis. We found that some countries that replace coal by refuse-derived fuel reduce CO 2 emission by 40%, and decrease the amount municipal solid waste being sent to landfill by more than 50%. The production cost of energy via refuse-derived fuel gasification is estimated at 0.05 USD/kWh. Co-gasification by using two feedstocks appears more beneficial over conventional gasification in terms of minimum tar formation and improved process efficiency.
The reaction of acetylene ethers with difluorocarbene (CF(2)), generated from the Ruppert-Prakash reagent, unexpectedly gave rise to co-produced fluorinated bicyclic [2.1.1]-hex-2-ene and cyclohepta-1,4-diene ring products.
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