Sulfite oxidase is a mitochondria-located molybdenum-containing enzyme catalyzing the oxidation of sulfite to sulfate in the amino acid and lipid metabolism. Therefore, it plays a major role in detoxification processes, where defects in the enzyme cause a severe infant disease leading to early death with no efficient or cost-effective therapy in sight. Here we report that molybdenum trioxide (MoO3) nanoparticles display an intrinsic biomimetic sulfite oxidase activity under physiological conditions, and, functionalized with a customized bifunctional ligand containing dopamine as anchor group and triphenylphosphonium ion as targeting agent, they selectively target the mitochondria while being highly dispersible in aqueous solutions. Chemically induced sulfite oxidase knockdown cells treated with MoO3 nanoparticles recovered their sulfite oxidase activity in vitro, which makes MoO3 nanoparticles a potential therapeutic for sulfite oxidase deficiency and opens new avenues for cost-effective therapies for gene-induced deficiencies.
A longstanding goal of biomimetic chemistry is the design and synthesis of functional enzyme mimics. The past three decades have seen a wide variety of materials, including metal complexes, polymers and other biomolecules, that mimic the structures and functions of naturally occurring enzymes. Among these, inorganic nanoparticles offer huge potential, because they are more stable than their natural counterparts, while having large surface areas and sizes comparable to those [a] of natural enzymes. Therefore, a considerable number of "artificial enzymes" derived from inorganic nanomaterials have been reported. This microreview highlights the recent progress in the field of enzymatically active inorganic nanomaterials, including mimics of peroxidases, haloperoxidases, superoxide dismutases and sulfite oxidases, along with selected biotechnological applications and their future prospects.
Superoxide dismutases (SOD) are a group of enzymes that catalyze the dismutation of superoxide (O) radicals into molecular oxygen (O) and HO as a first line of defense against oxidative stress. Here, we show that glycine-functionalized copper(ii) hydroxide nanoparticles (Gly-Cu(OH) NPs) are functional SOD mimics, whereas bulk Cu(OH) is insoluble in water and catalytically inactive. In contrast, Gly-Cu(OH) NPs form water-dispersible mesocrystals with a SOD-like activity that is larger than that of their natural CuZn enzyme counterpart. Based on this finding, we devised an application where Gly-Cu(OH) NPs were incorporated into cigarette filters. Cigarette smoke contains high concentrations of toxic reactive oxygen species (ROS, >10 molecules per puff) including superoxide and reactive nitrogen species which lead to the development of chronic and degenerative diseases via oxidative damage and subsequent cell death. Embedded in cigarette filters Gly-Cu(OH) NPs efficiently removed ROS from smoke, thereby protecting lung cancer cell lines from cytotoxic effects. Their stability, ease of production and versatility make them a powerful tool for a wide range of applications in environmental chemistry, biotechnology and medicine.
Compared to conventional deposition techniques for the epitaxial growth of metal oxide structures on a bulk metal substrate, wet-chemical synthesis based on a dispersible template offers advantages such as low cost, high throughput, and the capability to prepare metal/metal oxide nanostructures with controllable size and morphology. However, the synthesis of such organized multicomponent architectures is difficult because the size and morphology of the components are dictated by the interplay of interfacial strain and facet-specific reactivity. Here we show that solution-processable two-dimensional Pd nanotetrahedra and nanoplates can be used to direct the epitaxial growth of γ-Fe 2 O 3 nanorods. The interfacial strain at the Pd−γ-Fe 2 O 3 interface is minimized by the formation of an Fe x Pd "buffer phase" facilitating the growth of the nanorods. The γ-Fe 2 O 3 nanorods show a (111) orientation on the Pd(111) surface. Importantly, the Pd@γ-Fe 2 O 3 hybrid nanomaterials exhibit enhanced peroxidase activity compared to that of isolated Fe 2 O 3 nanorods with comparable surface area because of a synergistic effect for the charge separation and electron transport. The metal-templated epitaxial growth of nanostructures via wet-chemical reactions appears to be a promising strategy for the facile and high-yield synthesis of novel functional materials.
Polypeptides are successfully incorporated into poly(l-lactide) (PLLA) chains in a ring-opening polymerization (ROP) of l-lactide by using them as initiators. The resulting ABA triblock copolymers possess molecular weights up to 11000 g·mol(-1) and polydispersities as low as 1.13, indicating the living character of the polymerization process. In a nonaqueous emulsion, peptide-initiated polymerization of l-lactide leads to well-defined nanoparticles, consisting of PLLA-block-peptide-block-PLLA copolymer. These nanoparticles are easily loaded by dye-encapsulation and transferred into aqueous media without aggregation (average diameter of 100 nm) or significant dye leakage. Finally, internalization of PLLA-block-peptide-block-PLLA nanoparticles by HeLa cells is demonstrated by a combination of coherent anti-Stokes Raman spectroscopy (CARS) and fluorescence microscopy. This demonstrates the promise of their utilization as cargo delivery vehicles.
The cover image shows inorganic nanoparticles that mimic the catalytic activity of naturally occurring enzymes. The nanoparticles are more stable and cost-efficient, and their high surface area endows them with a large number of active sites.
Surface functionalized ZrO2 nanoparticles show strong photoluminescence and are a versatile tool for cellular targeting due to their chemical functionality.
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