A spectrophotometric investigation of oxidation of chondroitin-4-sulfate(CS)as a sustainable and biodegradable sulfated macromolecule by oxyanion permanganate ion as multi-equivalent oxidant in acid perchlorate soluti...A spectrophotometric investigation of oxidation of chondroitin-4-sulfate(CS)as a sustainable and biodegradable sulfated macromolecule by oxyanion permanganate ion as multi-equivalent oxidant in acid perchlorate solutions at a constant ionic strength of 2.0 mol dm^(-3)has been studied.The experimental results on the influence of the concentration of the reactants the reaction rates revealed first-order dependence in MnO^(-)_(4),fractional second-order in[CS]and fractional first-order with respect to the hydrogen ion concentration.The hydrogen acid concentration dependence of the rate constants indicated that the oxidation rates were increased with increasing the acid concentration which means that the oxidation reaction is of acid-catalyzed nature.The oxidation of all other polysaccharides by this oxidant in acidic solutions indicated that the oxidation processes were proceeding throughout two distinct stages.The first stage was relatively slow,followed by a more fast reaction in the second stage.The addition of Mn^(2+)and F^(-)ions to the reaction mixtures indicated that the Mn^(3+)and/or Mn^(4+)as the reduced forms of permanganate were the reactive species in the second fast stage.Here,neither formation of Mn^(3+)and/or Mn^(4+)transient species nor presence of two stages in the oxidation reaction were detected in the oxidation process,and this result was found to be on contrary to that observed for oxidation of all other polysaccharides by this oxidant.Formation of 1:2 coordination biopolymer intermediate complexes prior to the rate-determining step was revealed,kinetically.Identification of the oxidation product revealed the formation of keto-acid as derivative precursor of CS oxidation.This product was identified by formation of 2,4-dinitrophenyhydrazone and dioxime as wells as by the bands at frequencies 3430(OH of COOH group);1760-1730 cm^(-1)(broad)for C=O of diketone;1639 cm^(-1)ofν_(as),OCO;1418 cm^(-1)ofν_(s)OCO and 1338 cm^(-1)of C-O-C,respectively,in the FTIR spectra.Two-electron transfer process of inner-sphere nature in the slowest step has been suggested.A tentative reaction mechanism in terms of the kinetic parameters have been suggested and discussed.展开更多
基金supported by the Department of Chemistry,Faculty of Science,Assiut University,Assiut,71516,Assiut,Egypt.
文摘A spectrophotometric investigation of oxidation of chondroitin-4-sulfate(CS)as a sustainable and biodegradable sulfated macromolecule by oxyanion permanganate ion as multi-equivalent oxidant in acid perchlorate solutions at a constant ionic strength of 2.0 mol dm^(-3)has been studied.The experimental results on the influence of the concentration of the reactants the reaction rates revealed first-order dependence in MnO^(-)_(4),fractional second-order in[CS]and fractional first-order with respect to the hydrogen ion concentration.The hydrogen acid concentration dependence of the rate constants indicated that the oxidation rates were increased with increasing the acid concentration which means that the oxidation reaction is of acid-catalyzed nature.The oxidation of all other polysaccharides by this oxidant in acidic solutions indicated that the oxidation processes were proceeding throughout two distinct stages.The first stage was relatively slow,followed by a more fast reaction in the second stage.The addition of Mn^(2+)and F^(-)ions to the reaction mixtures indicated that the Mn^(3+)and/or Mn^(4+)as the reduced forms of permanganate were the reactive species in the second fast stage.Here,neither formation of Mn^(3+)and/or Mn^(4+)transient species nor presence of two stages in the oxidation reaction were detected in the oxidation process,and this result was found to be on contrary to that observed for oxidation of all other polysaccharides by this oxidant.Formation of 1:2 coordination biopolymer intermediate complexes prior to the rate-determining step was revealed,kinetically.Identification of the oxidation product revealed the formation of keto-acid as derivative precursor of CS oxidation.This product was identified by formation of 2,4-dinitrophenyhydrazone and dioxime as wells as by the bands at frequencies 3430(OH of COOH group);1760-1730 cm^(-1)(broad)for C=O of diketone;1639 cm^(-1)ofν_(as),OCO;1418 cm^(-1)ofν_(s)OCO and 1338 cm^(-1)of C-O-C,respectively,in the FTIR spectra.Two-electron transfer process of inner-sphere nature in the slowest step has been suggested.A tentative reaction mechanism in terms of the kinetic parameters have been suggested and discussed.
