From mechanochemistry to biocatalysis: first mechanosynthesis of a GOx - Iron(III) Trimesate metal organic framework Alessandra Scano a , Giada Mannias a , Edmond Magner b , Sarah Hudson b and Guido Ennas a a Department of Chemical and Geological Sciences, University of Cagliari and INSTM Unit, Italy, b Department of Chemical Sciences and Bernal Institute, University of Limerick, Ireland Cascade reactions and biomimetic strategies are being increasingly applied to the assembly of natural and de signed molecules. Such processes, in which ideally a single event triggers the conversion of a starting material to a product, which then becomes a substrate for the next reaction until termination leads to a stable final product, are highly desirable not only due to their elegance, but also because of their efficiency and economy in terms of reagent consumption and purification. Often, these multistep, one-pot procedures are accompanied by dramatic increases in molecular complexity and impressive selectivity. The demand for more efficient and environmentally benign chemical processes requires bi-/multifunctional catalysts containing different classes of active sites. The integration of biocatalysis with chemical catalysis in novel catalytic systems such as metal organic frameworks (MOFs) can allow chemo and regioselectivity of the catalysts and process simplification, avoiding costly time and energy consuming isolation as well as purification of intermediate products.The preparation of enzymes- MOF hybrid composites is of great interest, as it would greatly expand the applications of MOFs in bioanalysis, biocatalysis and in general in biomedicine, significantly increasing the stability and recyclability of the enzyme. Current strategy consists of animmobilization of enzymes by a post-synthetic attachment or incorporation in the MOF prefabricated structure. Successful adsorption of proteins into MOFs with extremely large pores has recently been reported. 1 However, due to the large size of the protein molecules compared to the much smaller aperture of most MOFs, a general method for preparing enzyme-MOFs is still a great challenge. Recent studies have paved the way for new one-pot synthesis methods of MOFs as a support for the immobilisation of enzymes/proteins. 2 Here, we present the first preparation of a hybrid glucose oxidaseenzyme (GOx) - Iron(III) Trimesate MOF by a rapid one-pot solid-state mechanochemical strategy. In a typical mechanosynthesis, Iron(III) nitrate, trimesic acid (1,3,5-benzenetricarboxylic acid), tetramethyl ammonium hydroxide and GOx were milled using a Spex 8000 Mixer/Mill. Influence of GOx concentration and different milling times on the final product were investigated. Our synthetic process avoids the use of organic solvents and strong acidic conditions, allowing the incorporation of GOx into the Iron(III) Trimesate MOF, while maintaining its enzymatic biological activity in combination with the well-known MOF intrinsic peroxidase-like activity.Both enzymatic and MOF catalytic activity was demonstrated by the colorimetric assay consisting of a first glucose oxidation catalysed by GOx to yield H 2 O 2 , and the subsequent 3,3',5,5'-tetramethylbenzidine oxidation reaction catalysed by the Iron(III) Trimesate. This study represents an important step toward the creation of a suite of hybrid enzyme-MOFs to be used as biocatalysts in one-pot multicomponent coupling and sequential (tandem) reactions. References 1. Deng, H. et al., Science 2012, 336,1018−1023 2. Raja D.S. et al., Comm. Inorg. Chem 2015, 35, 332-350
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