Ge Jun and Xiao Hai research group of Tsinghua University and Richard Gere of Fudan University jointly published a report on the new progress of enzyme and noble metal coupling catalytic system

Recently, Ge Jun, associate professor of Department of chemical engineering, Tsinghua University, Xiao Hai, associate professor of Department of chemistry, and Richard Zare, Professor of Fudan University, have made important achievements in the field of enzyme metal composite catalyst preparation, in which "highly active enzyme metal composite catalyst" is synthesized in protein polymer complex Nanohybrids synthesized in protein – polymer aggregates was recently published online in nature Catalysis (DOI: 10.1038 / s41929-019-0305-8) Catalysis is the basis of chemical industry, which provides a wealth of materials, energy and drugs for the development of human society Homogeneous catalysis, heterogeneous catalysis and enzyme catalysis are three basic forms of catalysis, which have their own extensive application fields and important values The coupling of the three is expected to develop a more efficient, environmental friendly and economic catalytic process, and to achieve the goal that a single form of catalysis is difficult to achieve, so as to provide new technologies for the sustainable development of the chemical industry However, the reaction conditions of homogeneous catalysis, heterogeneous catalysis and enzyme catalysis are often mismatched, which is easy to cause catalyst deactivation Among them, enzyme catalysts generally need to work at room temperature, atmospheric pressure, water solution isothermal and conditions Therefore, it is a key challenge to design the composite catalyst of enzyme, homogeneous catalyst and heterogeneous catalyst so that they have high catalytic activity under relatively mild conditions Fig 1 (a) preparation method of enzyme metal composite nano catalyst; (b) catalytic efficiency of lipase palladium composite catalyst in racemization and kinetic resolution; (c) catalytic performance of lipase palladium composite catalyst in dynamic kinetic resolution; (d) reusability; (E) free energy curve of racemization reaction calculated theoretically (source: nature Catalysis) in this work, the researchers used the limit structure of enzyme polymer conjugates to in-situ reduce and synthesize metal sub nano particles, so as to construct enzyme sub nano metal composite catalyst By means of extended X ray absorption fine structure, nanoscale electrospray ionization mass spectrometry and molecular dynamics simulation based on micro droplet reaction on-line rapid digestion of proteins, the process of reduction of metal sub nanoparticles in the domain structure of enzyme polymer conjugates was thoroughly analyzed Through the combination of various enzymes and metal particles, the researchers proved that the synthesis method has good universality Among them, the lipase / CALB Pluronic composite catalyst (0.8pd / CALB Pluronic) maintained the lipase activity well, and showed high activity in the palladium catalyzed racemization of (s) - 1-phenylethylamine, which was nearly 50 times higher than the commercial palladium carbon catalyst at relatively low temperature Based on the DFT calculation, it is found that the coordination between metal atoms and oxygen in the PD sub nanoclusters can improve the activity of the catalysts This composite catalyst can be applied to (±) - 1-phenylethylamine, (±) - 1-aminoindene, (±) - 1,2,3, 4-tetrahydro-1-naphthylamine and other amines were separated by chemical biological dynamic kinetic method to prepare important chiral drug intermediates Their catalytic efficiency was 7.6, 3.1 and 5 times higher than the combination of commercial immobilized lipase and Pd-C catalyst, respectively In this work, by controlling the synthetase metal sub nano cluster complex in the protein polymer binding nano confinement space, the interface regulation mechanism of protein and organic functional groups in the composite catalyst on metal sub nano particles was revealed, and the application of enzyme metal composite catalyst in the green synthesis of chiral drugs was explored This work provides a new idea for the coupling of enzyme catalysis and heterogeneous catalysis and their application in green biological manufacturing and environmental pollutant degradation The research work was supported by national key research and development plan, National Natural Science Foundation, Beijing Natural Science Foundation and other projects The first co authors of this paper are Li Xiaoyang, 2015 Ph.D student, Department of chemical engineering, Tsinghua University, Cao Yufei, 2018 Ph.D student, and Luo Kai, Department of chemistry, Fudan University Tsinghua University is the first unit of this paper The co authors of this paper are Ge Jun, associate professor of Department of chemical engineering, Tsinghua University, Xiao Hai, associate professor of Department of chemistry, and Richard Gere, Professor of Department of chemistry, Fudan University.