Bioinspired chemistry at MOF secondary building units

Abstract

This perspective describes recent developments and future directions in bioinorganic chemistry and biomimetic catalysis centered at metal–organic framework secondary building units.

Direct NO Reduction by a Biomimetic Iron(II) Pyrazolate MOF

“…Metal‐organic frameworks (MOFs) are promising platforms for the design of biomimetic materials [1–4] . They are often assembled using linkers with weak‐field donor groups such as carboxylates or azolates that are similar to those found in the active sites of metalloenzymes.…”

“…In contrast to small molecule complexes, the biomimetic reactivity of iron‐based MOFs toward NO has not been thoroughly explored [2, 4] . Coordinatively unsaturated iron sites in MIL‐88(Fe), MIL‐101(Fe), and Fe 2 (dobdc) have been shown to exhibit strong and reversible interactions with NO (Figure 1 a).…”

Metal–Organic Framework Disintegrants: Enzyme Preparation Platforms with Boosted Activity

“…[14][15][16] However,t hese heterogeneous biocatalytic systems often suffer from the decrease of catalytic efficiency or low enzyme availability due to the diffusion issue caused by the supports.I nt he past decade,metal-organic frameworks (MOFs) have emerged as anew class of enzyme supports (enzyme@MOFs,@= encapsulating) which can effectively incorporate and stabilize enzymes, [17][18][19][20] owing to their adaptable structures,h igh porosity,t unable pore size,a nd customizable functionality. [21][22][23][24] Interestingly,M OFs can be degradable under mild conditions. [25] Herein, we propose anew enzyme preparation strategy that the protective shell of enzyme (MOFs) can also serve as the disintegrating agent that is disintegrable to release enzymes and their activators when necessary.M ore interestingly,t he MOFs shell can be directly constructed by enzyme activators (such as metal ions) that provide ap roximity effect for enzymes and their activators.T he simultaneously released enzymes and their activators can sufficiently interact and greatly promote the catalytic performance.T his multi-functional enzyme formulation platform can combine the benefits of enzyme immobilization (for example,t he enhancement of enzyme stability for storage and operation) and homogeneous biocatalysis (fast diffusion, high activity) for enzyme stabilization and activation.…”

Recent Advances of Precise Cu Nanoclusters in Microporous Materials

“…zeozymes). [33][34][35][36] Historically, zeolites were one of the first inorganic scaffolds that can stabilise SAs and NCs due to the framework confinement and unique framework functionalities. [37] The most studied catalysis applications are the selective oxidation of methane and the selective catalytic reduction (SCR) of NOx (as illustrated in Figure 2).…”

“…Crystalline and porous zeolites and MOFs can also be used to host SAs and NCs with well‐defined structures to construct artificial metalloenzymatic systems ( cf . zeozymes) . Historically, zeolites were one of the first inorganic scaffolds that can stabilise SAs and NCs due to the framework confinement and unique framework functionalities .…”