The transport properties of liquid mixtures confined within porous media can change significantly from those observed for bulk mixtures due to changes in the liquid structuring within the pore space.Here,pulsed field ...The transport properties of liquid mixtures confined within porous media can change significantly from those observed for bulk mixtures due to changes in the liquid structuring within the pore space.Here,pulsed field gradient NMR was used to measure the diffusion coefficient of ethanol in ethanol-water liquid mixtures confined within silicas with pore diameters of 6 nm and 3 nm as a function of composition.For liquids imbibed within the 6 nm pores,the composition dependence of the ethanol diffusion coefficient closely followed that of the bulk liquid mixture and the absolute diffusion coefficients were reduced by a tortuosity factor of 3,with a minor contribution due to liquid-surface interactions.For liquids imbibed within the 3 nm pores,the diffusion coefficient of ethanol decreased as the composition of ethanol within the pore space increased,and for single-component ethanol imbibition the effective tortuosity was 63.Fast field cycling NMR experiments showed that the diffusion behaviour was not controlled by an increase in ethanol adsorption strength.A geometric analysis of the pore space was consistent with a highly confined system in which most molecules interacted with the pore walls.Under such confinement,the liquid structuring within the bulk pore space did not reflect that of the bulk liquid mixtures,and the observed decrease in diffusion coefficient as ethanol composition increased was consistent with an increase in confinement due to the larger size of the ethanol molecule.展开更多
α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to syn...α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesizeα-chiral amides from benzyl ammonium salts and isocyanates.The key to success is using a chiral 2,2-bipyridine ligand(-)-Ph-SBpy,enabling high yield(up to 95%)and enantiomeric ratio(up to 98:2 er)under mild conditions.Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate,enhancing selectivity and efficiency.The synthetic utility is showcased through transformations of the enantioenriched amides,and the mechanism and enantioselectivity are supported by experimental and computational studies.展开更多
文摘The transport properties of liquid mixtures confined within porous media can change significantly from those observed for bulk mixtures due to changes in the liquid structuring within the pore space.Here,pulsed field gradient NMR was used to measure the diffusion coefficient of ethanol in ethanol-water liquid mixtures confined within silicas with pore diameters of 6 nm and 3 nm as a function of composition.For liquids imbibed within the 6 nm pores,the composition dependence of the ethanol diffusion coefficient closely followed that of the bulk liquid mixture and the absolute diffusion coefficients were reduced by a tortuosity factor of 3,with a minor contribution due to liquid-surface interactions.For liquids imbibed within the 3 nm pores,the diffusion coefficient of ethanol decreased as the composition of ethanol within the pore space increased,and for single-component ethanol imbibition the effective tortuosity was 63.Fast field cycling NMR experiments showed that the diffusion behaviour was not controlled by an increase in ethanol adsorption strength.A geometric analysis of the pore space was consistent with a highly confined system in which most molecules interacted with the pore walls.Under such confinement,the liquid structuring within the bulk pore space did not reflect that of the bulk liquid mixtures,and the observed decrease in diffusion coefficient as ethanol composition increased was consistent with an increase in confinement due to the larger size of the ethanol molecule.
基金the National Natural Science Foundation of China(Nos.22150410339,W2432012,22301233 and 22171218)the Ministry of Science and Technology China(No.wgxz2022188)。
文摘α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesizeα-chiral amides from benzyl ammonium salts and isocyanates.The key to success is using a chiral 2,2-bipyridine ligand(-)-Ph-SBpy,enabling high yield(up to 95%)and enantiomeric ratio(up to 98:2 er)under mild conditions.Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate,enhancing selectivity and efficiency.The synthetic utility is showcased through transformations of the enantioenriched amides,and the mechanism and enantioselectivity are supported by experimental and computational studies.
