Owing to their unique physicochemical properties and comparable size to biomacromolecules, functional nanostructures have served as powerful supports to construct enzyme-nanostructure biocatalysts (nanobiocatalysts). Of particular importance, recent years have witnessed the development of novel nanobiocatalysts with remarkably increased enzyme activities. This review provides a comprehensive description of recent advances in the field of nanobiocatalysts, with systematic elaboration of the underlying mechanisms of activity enhancement, including metal ion activation, electron transfer, morphology effects, mass transfer limitations, and conformation changes. The nanobiocatalysts highlighted here are expected to provide an insight into enzyme-nanostructure interaction, and provide a guideline for future design of high-efficiency nanobiocatalysts in both fundamental research and practical applications.Catalysts 2020, 10, 338 2 of 15 nanoscale supports, such as nanoparticles, nanowires, microspheres, metal-organic frameworks, and nanoflowers, has also drawn extensive attention in recent years [5,[16][17][18][19][20][21][22]. A great deal of effort has also been made to design nanostructured supports with a variety of components including noble metal (e.g., Au) [23,24], metal oxides (e.g., Cu 2 O, Fe 3 O 4 , SiO 2 , Ti 8 O 15 , alumina) [16,25-33], polymer (e.g., Cu 2+ /PAA/PPEGA matrix, aldehyde-derived Pluronic polymer, polycaprolactone) [34-36], metal-organic frameworks (e.g., zeolitic imidazolate framework) [37-39], carbon based (e.g., carbon dots, carbon nanotubes) [40-44], and complex compounds (e.g., Cu 3 (PO 4 ) 2 ·3H 2 O, Ca 3 (PO 4 ) 2 , Co 3 (PO 4 ) 2 ·8H 2 O, Mn 3 (PO 4 ) 2 , Ca 8 H 2 (PO 4 ) 6 , Cu 4 (OH) 6 )SO 4 , CaHPO 4 , Zn 3 (PO 4 ) 2 , Mg-Al layered double hydroxide, CdSe/ZnS quantum dots) [17,[45][46][47][48][49][50][51][52][53][54][55][56][57][58][59]. These representative supports, which possess unique chemical and physical properties, such as controllable release of ion activator and synergic catalysts and response to external stimuli, are able to regulate the enzyme-support interaction and eventually lead to an unprecedented enhancement in immobilized enzyme activity [7,60,61].Overall, recent years have witnessed great success in the interactions between artificial nanostructured supports and natural enzymes for enhanced activity. This review will focus on recent advances in this field in the past 10 years, with an emphasis on various mechanisms behind the boosted catalytic activities, including reduced mass transfer limitation, interfacial ion activation, local heating effect, synergistic effects, conformational changes, substrate channeling and so on. A better understanding of the relationship between the characteristics of the nanostructured supports and the enhanced activities of nanobiocatalysts, may provide new insights in designing efficient nanobiocatalysts for various applications.
Mechanisms behind Enhanced Activities of NanobiocatalystsAn overview of recently reported nanobiocatalyst...