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Kinetic Studies and Mechanism of Hydrogen Peroxide Catalytic Decomposition by Cu(II) Complexes with Polyelectrolytes Derived from L-Alanine and Glycylglycine

机译:Cu(II)与L-丙氨酸和甘氨酰甘氨酸衍生的聚电解质配合物催化过氧化氢的动力学及机理

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摘要

The catalytic decomposition of hydrogen peroxide by Cu(II) complexes with polymers bearing L-alanine (PAla) and glycylglycine (PGlygly) in their side chain was studied in alkaline aqueous media. The reactions were of pseudo-first order with respect to [H2O2] and [L-Cu(II)] (L stands for PAla or PGlygly) and the reaction rate was increased with pH increase. The energies of activation for the reactions were determined at pH 8.8, in a temperature range of 293–308 K. A suitable mechanism is proposed to account for the kinetic data, which involves the Cu(II)/Cu(I) redox pair, as has been demonstrated by ESR spectroscopy. The trend in catalytic efficiency is in the order PGlygly>PAla, due to differences in modes of complexation and in the conformation of the macromolecular ligands.
机译:在碱性水性介质中,研究了Cu(II)与侧链带有L-丙氨酸(PAla)和甘氨酰甘氨酸(PGlygly)的聚合物催化的过氧化氢分解。对于[H 2 O 2]和[L-Cu(II)](L代表PAla或PGlygly),反应是伪一级反应,反应速率随pH增加而增加。在293-308 K的温度范围内,在pH 8.8下确定了反应的活化能,并提出了一种合适的机理来解释动力学数据,其中涉及Cu(II)/ Cu(I)氧化还原对,如ESR光谱所证明的。由于络合方式和大分子配体构象的差异,催化效率的趋势为PGlygly> PAla。

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