Building a bridge between enzymatic and heterogeneous catalysis provides new cascade industrial processes for manufacturing. However, the reaction conditions of enzymatic and heterogeneous catalysis mutually cause deactivation of catalysts. Here, we overcame this challenge by developing a special protocol for the synthesis of hybrid catalysts. We utilized protein–polymer nanoconjugates as confined nanoreactors for the in situ synthesis of lipase–palladium (Pd) nanohybrids. The 0.8 nm Pd nanoparticles exhibited increased activity in racemization of (S)-1-phenylethylamine. At 55 °C, which matches the optimum temperature of lipase, the activity is more than 50 times that of commercial Pd/C. It was found that the Pd–O coordination in Pd subnanoclusters contributed to the high activity. In the dynamic kinetic resolutions of pharmaceutical intermediates (±)-1-phenylethylamine, (±)-1-aminoindan and (±)-1,2,3,4-tetrahydro-1-naphthylamine, the lipase–Pd nanohybrids displayed 7.6, 3.1 and 5.0 times higher efficiencies than the combination of commercial immobilized lipase Novozym 435 and Pd/C. The lipase–Pd nanohybrids can be reused without agglomeration and activity loss.
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The data that support the plots within this paper and other findings of this study are available from the corresponding author upon request.
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This work was supported by the National Key Research and Development Plan of China (2016YFA0204300), the National Natural Science Foundation of China (21622603, 21878174 and 51573085) and the Beijing Natural Science Foundation (JQ18006). The authors thank beamline BL14W1 (Shanghai Synchrotron Radiation Facility) for providing the beam time.
The authors declare no competing interests.
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Supplementary Methods, Supplementary Tables 1–10, Supplementary Figs. 1–52 and Supplementary References
Cartesian coordinates Pd_111_phenylethylamine
Cartesian coordinates Pd_111_imine
Cartesian coordinates Pd/(1/1/1)_partial_oxidation_phenylethylamine
Cartesian coordinates Pd/(1/1/1)_partial_oxidation_imine
Cartesian coordinates CALB_Pluronic_initial
Cartesian coordinates CALB_Pluronic_final
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Li, X., Cao, Y., Luo, K. et al. Highly active enzyme–metal nanohybrids synthesized in protein–polymer conjugates. Nat Catal 2, 718–725 (2019). https://doi.org/10.1038/s41929-019-0305-8
Nature Communications (2020)