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钴(III)、镍(II)和铜(II)与配体1,3-双[(2-氨基乙基)氨基]-2-丙醇的单核配合物的合成、表征及其类过氧化氢酶活性

Synthesis and Characterization of Cobalt(III), Nickel(II) and Copper(II) Mononuclear Complexes with the Ligand 1,3-bis[(2-aminoethyl)amino]-2-propanol and Their Catalase-Like Activity.

作者信息

Pires Bianca M, Silva Daniel M, Visentin Lorenzo C, Rodrigues Bernardo L, Carvalho Nakédia M F, Faria Roberto B

机构信息

Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, Rio de Janeiro, Brazil.

NanoBusiness Informação e Inovação Ltda., Rio de Janeiro, Rio de Janeiro, Brazil.

出版信息

PLoS One. 2015 Sep 17;10(9):e0137926. doi: 10.1371/journal.pone.0137926. eCollection 2015.

Abstract

In this work, we present the synthesis and characterization of two new mononuclear complexes with the ligand 1,3-bis[(2-aminoethyl)amino]-2-propanol (HL), Co(L)(H2O)2 (1), Ni(HL)2 (2), as well as the known complex Cu(HL)2 (3) for comparison. Their abilities to catalyze the dismutation of H2O2 and the oxidation of cyclohexane were investigated. The complexes were characterized by X-ray diffraction, elemental analysis, electronic and infrared spectroscopy, cyclic voltammetry, electrospray ionization mass spectrometry (ESI-MS) and conductivity measurements. The X-ray structures showed that the nickel (2) and copper (3) complexes are tetracoordinated, with the metal ion bound to the nitrogen atoms of the ligand. On the other hand, the cobalt complex (1) is hexacoordinated, possessing additional bonds to the alkoxo group of the ligand and to a water molecule. Neither of the complexes was able to catalyze the oxidation of cyclohexane, but all of them exhibited catalase-like activity, following Michaelis-Menten kinetics, which suggest resemblance with the catalase natural enzymes. The catalytic activity followed the order: Ni(HL)2 (2) > Cu(HL)2 (3) > Co(L)(H2O)2 (1). As far as we know, this is the first description of a nickel complex presenting a significant catalase-like activity.

摘要

在本工作中,我们报道了两种含配体1,3-双[(2-氨基乙基)氨基]-2-丙醇(HL)的新型单核配合物Co(L)(H₂O)₂ (1)、Ni(HL)₂ (2)的合成与表征,以及用于对比的已知配合物Cu(HL)₂ (3)。研究了它们催化H₂O₂歧化反应和环己烷氧化反应的能力。通过X射线衍射、元素分析、电子和红外光谱、循环伏安法、电喷雾电离质谱(ESI-MS)以及电导率测量对这些配合物进行了表征。X射线结构表明,镍(2)和铜(3)配合物为四配位,金属离子与配体的氮原子结合。另一方面,钴配合物(1)为六配位,与配体的烷氧基和一个水分子存在额外的键合。这些配合物均不能催化环己烷的氧化反应,但它们都表现出类似过氧化氢酶的活性,遵循米氏动力学,这表明它们与天然过氧化氢酶相似。催化活性顺序为:Ni(HL)₂ (2) > Cu(HL)₂ (3) > Co(L)(H₂O)₂ (1)。据我们所知,这是首次对具有显著类似过氧化氢酶活性的镍配合物进行描述。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f430/4574563/0a296fb4d579/pone.0137926.g001.jpg

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