Reconstituting redox active centers of heme-containing proteins with biomineralized gold toward peroxidase mimics with strong intrinsic catalysis and electrocatalysis for H2O2 detection
| Autor: | Ru Li, Xiaoxia Lv, Minmin Dong, Shuai Li, Shuo Zhang, Yao Jiang, Liyan Zhang, Hua Wang, Lijun Chen |
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| Rok vydání: | 2017 |
| Předmět: |
biology
Kinetics Inorganic chemistry Biomedical Engineering Biophysics Substrate (chemistry) 02 engineering and technology General Medicine 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Combinatorial chemistry 0104 chemical sciences Catalysis chemistry.chemical_compound chemistry Electrochemistry biology.protein Enzyme reconstitution 0210 nano-technology Heme Biotechnology Peroxidase Biomineralization Hemin |
| Zdroj: | Biosensors and Bioelectronics. 87:1036-1043 |
| ISSN: | 0956-5663 |
| Popis: | A facile and efficient enzymatic reconstitution methodology has been proposed for high-catalysis peroxidase mimics by remolding the redox active centers of heme-containing proteins with the in-site biomineralized gold using hemoglobin (Hb) as a model. Catalytic hemin (Hem) was extracted from the active centers of Hb for the gold biomineralization and then reconstituted into apoHb to yield the Hem-Au@apoHb nanocomposites showing dramatically improved intrinsic catalysis and electrocatalysis over natural Hb and Hem. The biomineralized gold, on the one hand, would act as "nanowires" to promote the electron transferring of the nanocomposites. On the other hand, it would create a reactivity pathway to pre-organize and accumulate more substrates towards the active sites of the peroxidase mimics. Steady-state kinetics studies indicate that Hem-Au@apoHb could present much higher substrate affinity (lower Michaelis constants) and intrinsic catalysis even than some natural peroxidases. Moreover, the application feasibility of the prepared artificial enzymes was demonstrated by colorimetric assays and direct electrocatalysis for H2O2 sensing, showing a detection limitation low as 0.45μM. Importantly, such a catalysis active-center reconstitution protocol may circumvent the substantial improvement of the intrinsic catalysis and electrocatalysis of diverse heme-containing proteins or enyzmes toward the extensive applications in the chemical, enviromental, and biomedical catalysis fields. |
| Databáze: | OpenAIRE |
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