Nanoconfined (Bio)Catalysts as Efficient Glucose‐Responsive Nanoreactors

Abstract

Herein, the design, synthesis, and characterization of bifunctional hybrid nanoreactors used for concurrent one‐pot chemoenzymatic reactions are shown. In the design, the enzyme, glucose oxidase, is wrapped with a peroxidase‐mimetic catalytic polymer. Hemin, the organic catalyst, is linked to the flexible polymeric scaffold through coordination to the imidazole groups that hang out the network. This spatial arrangement, which works as a metabolic channel, is optimized for cooperative chemoenzymatic reactions in which the enzyme catalyzes first. A deep characterization of the integrated nanoreactors demonstrates that the confinement of two distinct catalytic sites in the nanospace is very effective in one‐pot reactions. Moreover, besides its role as scaffold material, the polymeric mantel protects both the biocatalyst and the chemical catalyst from degradation and inactivation in the presence of organic solvents. Furthermore, the polymeric environment of the nanoreactors can be tailored in order to trigger the assembly of those into highly active heterogeneous hybrid catalysts. Finally, the new nanoreactors are applied to the efficient degradation of organic aromatic compounds using glucose as the only fuel.

Multienzyme Cascades Based on Highly Efficient Metal–Nitrogen–Carbon Nanozymes for Construction of Versatile Bioassays

“…Enzymes are biocatalysts that can perform their tasks with high efficiency and specificity. Hence, they can constitute as promising signal elements in many kinds of biosensing platforms. − As one of the hot topics in the enzyme-based platform, enzymatic cascade reactions (i.e., enzyme cascades) have sparked impressive attention and opened brand new possibilities in biosensing. − Due to coupled biocatalysis, enzyme cascades are able to produce exceedingly amplified signals . This most arresting superiority will provide a reliable and highly sensitive performance for quantitative detection of trace amounts of targets.…”

Metal–Organic Enzyme Nanogels as Nanointegrated Self-Reporting Chemobiosensors

“…The fine tuning of these nanogels allows their combination with inorganic, i.e., metal cations, or metal−organic, i.e., iron porphyrins, compounds for their potential use as heterogeneous catalysts or chemoenzymatic nanoreactors. 20 Herein, we envisioned the decoration of the polymeric mesh with fluorescent lanthanides, in particular, with cerium cations, 21,22 throughout the interaction with the phosphate groups distributed along the shell of the hybrid (Scheme 1B).…”

Bioresponsive, Electroactive, and Inkjet‐Printable Graphene‐Based Inks

“…We hypothesized that, by keeping all the components of the active material confined on the graphene flakes, the efficiency of the biocatalytic cycle should be strongly improved, in turn inducing a more sensitive response from the printed ink. [ 47 ] In fact, if GOx and CoPC are in close proximity, more rapid and efficient diffusion of the intermediate (H 2 O 2 ) from one catalytic site to the other is expected. Preparation of such nanoconfined assemblies required chemical modification of pristine EEG with 4‐phenylacetic acid diazonium tetrafluoroborate ( Figure ).…”

“…We propose that this positive effect is due to the nanometric distance between GOx and CoPC, which favors the rapid and efficient diffusion of H 2 O 2 from one component to the other, thereby improving the sensitivity of the method (Figure S17C, Supporting Information). [ 47 ]…”