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ROMP polymer supported manganese porphyrins: Influence of CC bonds along polymer chains on catalytic behavior in oxidation of low concentration Fe2+
Reactive & Functional Polymers ( IF 4.5 ) Pub Date : 2020-02-12 , DOI: 10.1016/j.reactfunctpolym.2020.104530
Fanfan Li , Xuan Wang , Huanhuan Zhao , Yanwu Zhang

One unsaturated polymer support was prepared through ring opening metathesis polymerization (ROMP) of norbornene-2,3-dip-toluene sulfonate initiated by Grubbs 2nd initiator and manganese porphyrins were immobilized on polymer through transesterification reaction. To investigate the effect of Cdouble bondC bonds along polymer chains on the catalytic behavior, the obtained polymer supported catalyst (P-PPIXMnCl) was applied in oxidation of low concentration Fe2+ to mimic catalytic behavior of Ceruloplasmin. In the presence of P-PPIXMnCl, the conversion of Fe2+ reaches to 91.92% and 96.46% at 10 °C and 37.5 °C (body temperature), respectively. Compared to manganese porphyrins, P-PPIXMnCl can dramatically increase oxidation rate of Fe2+ and the catalytic kinetic shows that the oxidation reaction changes from second-order to third-order. Upon hydrogenation of ROMP polymer, the oxidation reaction still conforms to the second-order kinetics. Density functional theory (DFT) calculation shows that the Cdouble bondC bonds along polymer chains play an important role in the coordination with Fe2+ in the catalytic microenvironment. The real time morphology of supported catalysts in aqueous environment characterized by Cryo-TEM indicates that hydrogenation can shrink the morphology of polymer-water skeleton. The catalyst could be recycled six times without any significant loss in activity. The liner heterogeneous catalyst is expected to be used as drugs for treating excessive iron accumulation in the human body.



中文翻译:

ROMP聚合物负载的锰卟啉:双键沿聚合物链的C C键对低浓度Fe 2+氧化催化行为的影响

通过由Grubbs 2nd引发剂引发的降冰片烯-2,3-二甲苯甲苯磺酸盐的开环易位聚合(ROMP)制备了一种不饱和聚合物载体,并且通过酯交换反应将锰卟啉固定在聚合物上。为了研究双键沿着聚合物链的C C键对催化行为的影响,将获得的聚合物负载的催化剂(P-PPIXMnCl)用于低浓度Fe 2+的氧化以模拟铜蓝蛋白的催化行为。在P-PPIXMnCl存在下,Fe 2+的转化率在10°C和37.5°C(体温)下分别达到91.92 %和96.46%。与锰卟啉相比,P-PPIXMnCl可以显着提高Fe 2+的氧化速率催化动力学表明,氧化反应由二阶转变为三阶。在ROMP聚合物加氢后,氧化反应仍符合二级动力学。密度泛函理论(DFT)计算表明,双键沿着聚合物链的C C键在催化微环境中与Fe 2+配位起重要作用。Cryo-TEM表征的负载型催化剂在水环境中的实时形貌表明加氢可收缩聚合物-水骨架的形貌。该催化剂可以循环使用六次而活性没有任何明显的损失。衬里非均相催化剂有望用作治疗人体中铁过多的药物。

更新日期:2020-02-12
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