The bicyclic cryptand 1,4,7, 10,13,16,21, 24-octaaza-bigcyclo [8, 8,8] hexacosan-3, 8, 12, 17, 20, 25-hex-one (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of...The bicyclic cryptand 1,4,7, 10,13,16,21, 24-octaaza-bigcyclo [8, 8,8] hexacosan-3, 8, 12, 17, 20, 25-hex-one (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of discrete neutral macrobicyclic units; the two cycles share the two tertiary amine nitrogen atoms, which exhibit an endo-cndo conformation. Three identical branches formed by 1, 2-diaminoethane link the two tertiary amine groups. The protonation reactions of cryptand (COBH) and its complex formation with copper (II) were investigated by potentiometry in water and in a DMSO/water (80:20 in mass ratio) mixture as solvents. The cryptand acts as a his-base through its two N-bridgehead and exhibits a strong cooperativity that favors the first protonation and makes the second one difficult (△pK= 5.0). An inward rotation of the amide groups to form hydrogen bonds accounts for this cooperativity. The interaction of COBH with copper (II) leads to several binuclear complex proton contents.展开更多
The characters of proton exchange membranes from sulfonated poly( aryl ether sulfone) s( SPAESs) containing fluorophenyl pendant groups are studied in this paper.Both the water uptake and the water content parameter( ...The characters of proton exchange membranes from sulfonated poly( aryl ether sulfone) s( SPAESs) containing fluorophenyl pendant groups are studied in this paper.Both the water uptake and the water content parameter( λ) of all SPAES membranes increase almost linearly with sulfonation degree( SD)and temperature.After being equilibrated in deionized water,the dimensional change in plane is much less affected by temperature than that in vertical direction.Under all the humidity condition the proton conductivities of these SPAES membranes increase with SD and temperature.A maximus proton conductivity of 0.38 S/cm is attained at 90 ℃ for SPAES-5 with a SD of 99.3% when the membrane is fully hydrated,higher than that of Nafion 115.But the proton conductivities of SPAES membranes decrease dramatically with the relative humidity and all of them are lower and more affected by relative humidity than that of Nafion 115 at relative humidity lower than 100%,which may be due to the cumulative effects of narrower channels with spherical clusters for proton migration,more rigid chains and larger tortuosity of SPAESs.展开更多
基金the National Natural Science Foundation of China (No.29875018) and the Natural Science Foundation of Gansu Province (ZS991-A25-
文摘The bicyclic cryptand 1,4,7, 10,13,16,21, 24-octaaza-bigcyclo [8, 8,8] hexacosan-3, 8, 12, 17, 20, 25-hex-one (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of discrete neutral macrobicyclic units; the two cycles share the two tertiary amine nitrogen atoms, which exhibit an endo-cndo conformation. Three identical branches formed by 1, 2-diaminoethane link the two tertiary amine groups. The protonation reactions of cryptand (COBH) and its complex formation with copper (II) were investigated by potentiometry in water and in a DMSO/water (80:20 in mass ratio) mixture as solvents. The cryptand acts as a his-base through its two N-bridgehead and exhibits a strong cooperativity that favors the first protonation and makes the second one difficult (△pK= 5.0). An inward rotation of the amide groups to form hydrogen bonds accounts for this cooperativity. The interaction of COBH with copper (II) leads to several binuclear complex proton contents.
基金National Natural Science Foundation of China(No.51608056)Open Foundation of National Engineering Laboratory of Highway Maintenance Technology of China(No.kfj140105)+1 种基金General Project Supported by Hunan Province Education Office,China(No.16C0025)Natural Science Foundation of Hunan Province,China(No.2018JJ3537)
文摘The characters of proton exchange membranes from sulfonated poly( aryl ether sulfone) s( SPAESs) containing fluorophenyl pendant groups are studied in this paper.Both the water uptake and the water content parameter( λ) of all SPAES membranes increase almost linearly with sulfonation degree( SD)and temperature.After being equilibrated in deionized water,the dimensional change in plane is much less affected by temperature than that in vertical direction.Under all the humidity condition the proton conductivities of these SPAES membranes increase with SD and temperature.A maximus proton conductivity of 0.38 S/cm is attained at 90 ℃ for SPAES-5 with a SD of 99.3% when the membrane is fully hydrated,higher than that of Nafion 115.But the proton conductivities of SPAES membranes decrease dramatically with the relative humidity and all of them are lower and more affected by relative humidity than that of Nafion 115 at relative humidity lower than 100%,which may be due to the cumulative effects of narrower channels with spherical clusters for proton migration,more rigid chains and larger tortuosity of SPAESs.
