A novel calix[4]arene derivative 2 with amino functional groups at the lower rim was first prepared via introduction of nitro functional groups and amination of the dinitro derivative of calix[4]arene. The optically a...A novel calix[4]arene derivative 2 with amino functional groups at the lower rim was first prepared via introduction of nitro functional groups and amination of the dinitro derivative of calix[4]arene. The optically active monomers were synthesized by dehydration of L-leucine (and L-isoleucine) and 3,3',4,4'-benzophenonetetracarboxylic- 3,3',4,4'-dianhydride (3) followed by reaction with thionyl chloride to form 5a and 5b. Two methods, polymerization under microwave irradiation and solution polymerization in CH2Cl2/TEA, were then employed to carry out the condensation polymerization of 2 with the optically active monomers 5a and 5b, respectively. The polymerization conditions affected the kind of resulting polymers, poly(amide-imide)s (PAIs) 6a and 6b and poly(ester-imide)s (PEIs) 6a' and 6b' were obtained selectively in good yields and moderate inherent viscosities. Sorption-extraction experiments were carried out using cram picrate extraction method and verified good binding ability of the resulting calixarene-based polymers towards silver, alkali metal and toxic heavy metal cations. Also thermogravimetric analysis indicated that the resulting PAIs and PEIs were thermally stable.展开更多
The new ferrous-selective modified carbon paste electrodes (I and II) based on 5,5’-(propane-1,3-diylbis(sulfanediyl))bis(3-benzyl-4H-1,2,4-triazol-4-amine) (electrode I, A-ionophore) and 5,5’-(butane-1,4-diyl-bis(s...The new ferrous-selective modified carbon paste electrodes (I and II) based on 5,5’-(propane-1,3-diylbis(sulfanediyl))bis(3-benzyl-4H-1,2,4-triazol-4-amine) (electrode I, A-ionophore) and 5,5’-(butane-1,4-diyl-bis(sulfane- diyl))bis(3-benzyl-4H-1,2,4-triazol-4-amine) (electrode II, B-ionophore) as ionophores are described. These electrodes exhibit Nernstian slopes of 30.2 ± 0.5 and 29.1 ± 0.5 mV·decade-1, linear range of 1.0 × 10-7 - 1.0 × 10-2 mol·L-1 Fe(II) ion and detection limit of 1.0 × 10-7 mol·L-1 Fe(II) ion for electrode (I) and electrode (II), respectively. Both electrodes (I and II) have a fast response time of about 15 sand can be used for at least 3 months. The two electrodes revealed a good selectivity for Fe(II) over a wide variety of other metal ions and could be used in the pH range of 1.8 - 3.0 without any divergence in potential. The proposed sensors were successfully applied for the determination of Fe(II) ion in different real samples.展开更多
Ionophores selectively sensitive to primary amines have been synthesized which display low potentiometric selectivity coefficients for K^+, Na^+ and NH_4^+ ions, secondary and tertiary amines as well as quaternary amm...Ionophores selectively sensitive to primary amines have been synthesized which display low potentiometric selectivity coefficients for K^+, Na^+ and NH_4^+ ions, secondary and tertiary amines as well as quaternary ammonium ions. These ionophores include macrocyclic polyethers with dinaphthyl subunits and azocrown ether with nitrogen donor atoms. The feasibility of these ionophores for preparing primary amine drug selective electrodes was investigated in detail. Practically usable PVC membrane electrodes sensitive to primary amine drugs, such as mexiletine, dopamine, metaraminol and tryptamine, and aliphatic primary amines have been prepared with these ionophores as neutral carriers. Direct potentiometric methods for assaying these drugs have been proposed by using the prepared electrodes. The proposed primary amine drug selective electrodes are remarkably superior to those based on ion-associates. Compared with the electrodes based on common ethers, the interference by K^+, Na^+ and NH_4^+ ions is substantially reduced. A digital simulation of the electrochemical process concerning the membrane transport was performed and some interesting conclusions have been drawn.展开更多
基金supported by the Isfahan University of Technology(IUT),IR Iran(ARH) and grant GM 33138 (AER) from the national Institute of health,USA and center of Excellency in chemistry research(IUT).
文摘A novel calix[4]arene derivative 2 with amino functional groups at the lower rim was first prepared via introduction of nitro functional groups and amination of the dinitro derivative of calix[4]arene. The optically active monomers were synthesized by dehydration of L-leucine (and L-isoleucine) and 3,3',4,4'-benzophenonetetracarboxylic- 3,3',4,4'-dianhydride (3) followed by reaction with thionyl chloride to form 5a and 5b. Two methods, polymerization under microwave irradiation and solution polymerization in CH2Cl2/TEA, were then employed to carry out the condensation polymerization of 2 with the optically active monomers 5a and 5b, respectively. The polymerization conditions affected the kind of resulting polymers, poly(amide-imide)s (PAIs) 6a and 6b and poly(ester-imide)s (PEIs) 6a' and 6b' were obtained selectively in good yields and moderate inherent viscosities. Sorption-extraction experiments were carried out using cram picrate extraction method and verified good binding ability of the resulting calixarene-based polymers towards silver, alkali metal and toxic heavy metal cations. Also thermogravimetric analysis indicated that the resulting PAIs and PEIs were thermally stable.
文摘The new ferrous-selective modified carbon paste electrodes (I and II) based on 5,5’-(propane-1,3-diylbis(sulfanediyl))bis(3-benzyl-4H-1,2,4-triazol-4-amine) (electrode I, A-ionophore) and 5,5’-(butane-1,4-diyl-bis(sulfane- diyl))bis(3-benzyl-4H-1,2,4-triazol-4-amine) (electrode II, B-ionophore) as ionophores are described. These electrodes exhibit Nernstian slopes of 30.2 ± 0.5 and 29.1 ± 0.5 mV·decade-1, linear range of 1.0 × 10-7 - 1.0 × 10-2 mol·L-1 Fe(II) ion and detection limit of 1.0 × 10-7 mol·L-1 Fe(II) ion for electrode (I) and electrode (II), respectively. Both electrodes (I and II) have a fast response time of about 15 sand can be used for at least 3 months. The two electrodes revealed a good selectivity for Fe(II) over a wide variety of other metal ions and could be used in the pH range of 1.8 - 3.0 without any divergence in potential. The proposed sensors were successfully applied for the determination of Fe(II) ion in different real samples.
基金Project supported by the Science Foundation of the National Education Council, China. Part of work was done in Electroanalytical Chemistry Laboratory, Changchun Institute of Applied Chemistry, Academia Sinica.
文摘Ionophores selectively sensitive to primary amines have been synthesized which display low potentiometric selectivity coefficients for K^+, Na^+ and NH_4^+ ions, secondary and tertiary amines as well as quaternary ammonium ions. These ionophores include macrocyclic polyethers with dinaphthyl subunits and azocrown ether with nitrogen donor atoms. The feasibility of these ionophores for preparing primary amine drug selective electrodes was investigated in detail. Practically usable PVC membrane electrodes sensitive to primary amine drugs, such as mexiletine, dopamine, metaraminol and tryptamine, and aliphatic primary amines have been prepared with these ionophores as neutral carriers. Direct potentiometric methods for assaying these drugs have been proposed by using the prepared electrodes. The proposed primary amine drug selective electrodes are remarkably superior to those based on ion-associates. Compared with the electrodes based on common ethers, the interference by K^+, Na^+ and NH_4^+ ions is substantially reduced. A digital simulation of the electrochemical process concerning the membrane transport was performed and some interesting conclusions have been drawn.