当前位置: X-MOL 学术J. Porphyr. Phthalocyanines › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Investigating axial ligand impact on pinch-porphyrin peroxidase activity with [bis(o-methylpyridino) (dimethylesterprotoporphyrinato)Fe(III)] chloride
Journal of Porphyrins and Phthalocyanines ( IF 1.5 ) Pub Date : 2023-07-10 , DOI: 10.1142/s1088424623501055
Alejandra Romero-Morán 1 , Samuel Hernández-Anzaldo 1 , Hugo Vazquez-Lima 2 , Yasmi Reyes-Ortega 1
Affiliation  

The synthesis and characterization of a novel hexacoordinated compound as a product of the reaction between chlorodimethylesterprotoprphyrin–Fe(III) 1 and 2–methylpiridine (2–CH3Py) was performed. The [bis(o–methylpyridino)(dimethylesterprotoporphyrinato)Fe(III)] chloride 2 is a compound of the family of the pinch–porphyrins, a model of peroxidase enzymes. We analyzed 2 using UV-Vis, 1H NMR, and EPR spectroscopies, as well as kinetic quantifications of its peroxidase activity and computational analysis, to evaluate the presence of the pinch-ligand coordinated to 1 in a series of pinch-ironprotoporphyrin complexes, as previously reported. Our investigation revealed that the oxidant activity of Compound I derived from peroxidase activity determination of 1 and 2, respectively, is better controlled when a heterohydrocarbonated chain is attached to the pyridyl groups that coordinate axially to 1; an effect evidenced by a decrease of the activation energy value associated with Compound 0 formation during the reaction performed by pinch–porphyrin, with the picdien axial ligand and hydrogen peroxide. When correlating the contribution of s=3/2 in the quantum mixed-spin state (qms), s=3/2, s=5/2, of iron(III)-based complexes with their peroxidase activity, we found that when the qms s=3/2, s=5/2, of iron(III) had 80% character s=3/2, the peroxide activity increased significantly. This could be a fundamental trait that could affect the peroxidase activity owing to the distortion of the iron geometry associated with its coordination number when omethylpyridine is used as an axial ligand.



中文翻译:

研究[双(邻甲基吡啶)(二甲酯原卟啉)Fe(III)]氯化物的轴向配体对捏卟啉过氧化物酶活性的影响

进行了一种新型六配位化合物的合成和表征,该化合物是氯二甲酯原卟啉-Fe(III) 1和2-甲基吡啶(2-CH 3 Py)之间反应的产物。[双(邻甲基吡啶基)(二甲基酯原卟啉)Fe(III)]氯化物2是捏卟啉家族的化合物,是过氧化物酶的模型。我们使用 UV-Vis、1 H NMR 和 EPR 光谱以及过氧化物酶活性的动力学定量和计算分析对 2 进行了分析,以评估与1配位的夹缩配体的存在。如先前报道的,在一系列夹断-铁原卟啉复合物中。我们的研究表明,当杂烃链连接到与1轴向配位的吡啶基上时,分别由12的过氧化物酶活性测定得出的化合物 I 的氧化活性得到更好的控制;在捏卟啉、picdien 轴向配体和过氧化氢进行反应期间,与化合物 0 形成相关的活化能值降低证明了这一效应。当关联贡献时s=3/2 处于量子混合自旋态 (qms),s=3/2,s=5/2,铁(III)基复合物及其过氧化物酶活性,我们发现当 qmss=3/2,s=5/2, 铁(III)有80%的特性s=3/2时,过氧化物活性显着增加。这可能是一个基本特征,由于与其配位数相关的铁几何形状的扭曲,可能会影响过氧化物酶活性。--甲基吡啶用作轴向配体。

更新日期:2023-07-10
down
wechat
bug