Research on solvent effects is an important and long-standing topic,but there still is some room,especially for the special solvent effect of fluoroalcohols.In this work,we investigated the stability of phenoxyl radic...Research on solvent effects is an important and long-standing topic,but there still is some room,especially for the special solvent effect of fluoroalcohols.In this work,we investigated the stability of phenoxyl radical in monohydric alcohol solvents through in-situ electron paramagnetic resonance detections.The decay behavior of phenoxyl radical showed a reasonable relationship with the mesoscopic structure of alcohols,characterized by smalland wide-angle X-ray scattering.Moreover,the distinct solvent effects of fluoroalcohols were emphasized,and the significant influence of van der Waals distance in the solvents was suggested.Overall,the stability of phenoxyl radical in alcohols was quantified and correlated with the solvent structures.We believe that the established method for stability study on radicals will encourage solvent effect studies on various organic reactions,and the proposed solvent effects in fluoroalcohols may inspire the development of green solvents in both industrial conversions and organic synthesis.展开更多
A highly sensitive stopped-flow spectrophotometry kinetic method was proposed for quantification phenoxyl radicals based on their accelerating effect on the oxidation of nicotinamide adenine dinucleotide （NADH）. Phe...A highly sensitive stopped-flow spectrophotometry kinetic method was proposed for quantification phenoxyl radicals based on their accelerating effect on the oxidation of nicotinamide adenine dinucleotide （NADH）. Phenoxyl radicals generated from as low as 1×10^-8 mol/L 2,4-DCP can be readily detected with the proposed method and the detecting limit was 2.5×10^-9 mol/L.展开更多
基金supported by the National Natural Science Foundation of China(grant numbers 22103068 and 22303079)Zhejiang Provincial Natural Science Foundation of China(grant number LGC22B050010)the National Key R&D Program of China(grant number 2022YFA1503200)
文摘Research on solvent effects is an important and long-standing topic,but there still is some room,especially for the special solvent effect of fluoroalcohols.In this work,we investigated the stability of phenoxyl radical in monohydric alcohol solvents through in-situ electron paramagnetic resonance detections.The decay behavior of phenoxyl radical showed a reasonable relationship with the mesoscopic structure of alcohols,characterized by smalland wide-angle X-ray scattering.Moreover,the distinct solvent effects of fluoroalcohols were emphasized,and the significant influence of van der Waals distance in the solvents was suggested.Overall,the stability of phenoxyl radical in alcohols was quantified and correlated with the solvent structures.We believe that the established method for stability study on radicals will encourage solvent effect studies on various organic reactions,and the proposed solvent effects in fluoroalcohols may inspire the development of green solvents in both industrial conversions and organic synthesis.
基金The authors gratefully acknowledge financial support from the National Natural Science Foundation of China （No. 20275027 and No. 20377032）.
文摘A highly sensitive stopped-flow spectrophotometry kinetic method was proposed for quantification phenoxyl radicals based on their accelerating effect on the oxidation of nicotinamide adenine dinucleotide （NADH）. Phenoxyl radicals generated from as low as 1×10^-8 mol/L 2,4-DCP can be readily detected with the proposed method and the detecting limit was 2.5×10^-9 mol/L.
