What are inorganic nanozymes? Artificial or inorganic enzymes

Huang, Xiaolan

doi:10.1039/d2nj02088b

Cited by 7 publications

(21 citation statements)

References 287 publications

(553 reference statements)

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“…Coordination of phosphate groups to surface metal atoms may facilitate RNA hydrolysis by drawing electron density away from the phosphorous atom, thereby increasing its electrophilicity. Dissolved metal ions that act as Lewis acids (e.g., Pb 2+ , Zn 2+ ) are known to catalyze dissolved RNA via an analogous solution-phase mechanism (31,43), which has also been invoked to explain the hydrolysis of organic compounds containing phosphoester bonds on mineral surfaces (44)(45)(46)(47)(48). Like iron, aluminum atoms also form coordination bonds with phosphate groups (42); however, phosphate groups bound via coordination do not desorb readily from gibbsite and kaolinite (42), which may explain why RNA extracted from these minerals did not exhibit hydrolysis (Figure 3C,D).…”

Section: Proposed Mechanism Of Mineral-catalyzed Rna Hydrolysismentioning

confidence: 99%

“…While metal coordination is sufficient to catalyze hydrolysis of certain organic compounds containing phosphoester bonds (44)(45)(46)(47)(48), the specificity of goethite-catalyzed hydrolysis for RNA relative to DNA (Figure 1C) indicates the additional involvement of the 2′-hydroxyl group that is present in RNA but absent in DNA. Deprotonation of the 2′-hydroxyl group forms an oxyanion, which is a strong nucleophile that subsequently attacks the phosphorous atom (38), leading to cleavage of the phosphodiester bond (Figure 4).…”

Section: Proposed Mechanism Of Mineral-catalyzed Rna Hydrolysismentioning

confidence: 99%

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RNA hydrolysis at mineral-water interfaces

Zhang

Chatterjee

et al. 2022

Preprint

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The adsorption of DNA at mineral-water interfaces is well-established to increase its persistence in soils and sediments; however, adsorbed RNA in similar environments degrades rapidly, in some cases outpacing solution-phase degradation occurring over hours to days. Herein, we elucidate a novel abiotic mechanism by which RNA, but not DNA, degrades upon adsorption to surfaces of iron (oxyhydr)oxides such as goethite (α-FeOOH) that are abundant in soils and sediments. Upon adsorption to goethite, both single-stranded and double-stranded RNA hydrolyzed on the timescale of hours under environmentally relevant physicochemical conditions. The reaction products were consistent with iron present in goethite acting as a Lewis acid to accelerate non-selective hydrolysis of phosphodiester bonds comprising the RNA backbone. In contrast to well-established acid- or base-catalyzed RNA hydrolysis in solution, mineral-catalyzed hydrolysis was fastest at circumneutral pH, which allowed for both sufficient RNA adsorption and hydroxide concentration. We further confirmed that contact of the RNA with the mineral surface is necessary for hydrolysis to occur by demonstrating RNA degradation was inhibited by compact RNA conformation at elevated ionic strength and competitive adsorption with orthophosphate and organic matter. In addition to goethite, we observed RNA hydrolysis was also catalyzed by hematite (α-Fe2O3), but not by aluminum-containing minerals (e.g., montmorillonite). Given the extensive adsorption of nucleic acids to environmental surfaces, we anticipate previously overlooked mineral-catalyzed hydrolysis of RNA may be prevalent particularly in iron-rich soils and sediments, which must be considered across biogeochemical applications of nucleic acid analysis in environmental systems.

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Section: Proposed Mechanism Of Mineral-catalyzed Rna Hydrolysismentioning

confidence: 99%

Section: Proposed Mechanism Of Mineral-catalyzed Rna Hydrolysismentioning

confidence: 99%

RNA hydrolysis at mineral-water interfaces

Zhang

Chatterjee

et al. 2022

Preprint

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“…Numerous iron oxide colloids have been shown to exhibit similar intrinsic POD activity, including maghemite (Mah, γ-Fe 2 O 3 ) (Chen et al, 2012), hematite (Hem, α-Fe 2 O 3 ) (Chaudhari et al, 2012), two-dimensional lepidocrocite nanomaterials formed from graphene-templates (Peng et al, 2011), and Prussian blue-modified iron oxide magnetic compounds (Wang and Huang, 2011). These inorganic catalysts also display substrate selectivity, temperature responsiveness and pH dependence similar to natural enzymes (Gao et al, 2007;André et al, 2011;Huang and Zhang, 2012;Wei and Wang, 2013;Wu et al, 2019;Huang, 2018Huang, , 2019Huang, , 2022a. This observation has the potential to revolutionize various industries and applications, offering more efficient and customized catalytic processes.…”

Section: Introduction-inorganic Abiotic Nanocolloids As Efficient Cat...mentioning

confidence: 99%

Inorganic Fe-O and Fe-S oxidoreductases: paradigms for prebiotic chemistry and the evolution of enzymatic activity in biology

Huang,

Harmer,

Schenk

et al. 2024

Front. Chem.

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Oxidoreductases play crucial roles in electron transfer during biological redox reactions. These reactions are not exclusive to protein-based biocatalysts; nano-size (<100 nm), fine-grained inorganic colloids, such as iron oxides and sulfides, also participate. These nanocolloids exhibit intrinsic redox activity and possess direct electron transfer capacities comparable to their biological counterparts. The unique metal ion architecture of these nanocolloids, including electron configurations, coordination environment, electron conductivity, and the ability to promote spontaneous electron hopping, contributes to their transfer capabilities. Nano-size inorganic colloids are believed to be among the earliest ‘oxidoreductases’ to have ‘evolved’ on early Earth, playing critical roles in biological systems. Representing a distinct type of biocatalysts alongside metalloproteins, these nanoparticles offer an early alternative to protein-based oxidoreductase activity. While the roles of inorganic nano-sized catalysts in current Earth ecosystems are intuitively significant, they remain poorly understood and underestimated. Their contribution to chemical reactions and biogeochemical cycles likely helped shape and maintain the balance of our planet’s ecosystems. However, their potential applications in biomedical, agricultural, and environmental protection sectors have not been fully explored or exploited. This review examines the structure, properties, and mechanisms of such catalysts from a material’s evolutionary standpoint, aiming to raise awareness of their potential to provide innovative solutions to some of Earth’s sustainability challenges.

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“…This nanostructured material can detect a wide range of metabolites by mimicking enzyme functions such as oxidase, peroxidase, catalase, and superoxide dismutase without having any structural resemblance to natural enzymes [14–21] . Peroxidase‐like biomimics are the most well‐studied inorganic nanozymes for bioanalytes detection and immunoassay applications [22] . However, using a strong oxidizing agent, H 2 O 2, in a peroxidase‐like catalytic reaction is mandatory.…”

Section: Introductionmentioning

confidence: 99%

“…[14][15][16][17][18][19][20][21] Peroxidase-like biomimics are the most well-studied inorganic nanozymes for bioanalytes detection and immunoassay applications. [22] However, using a strong oxidizing agent, H 2 O 2, in a peroxidase-like catalytic reaction is mandatory. As a result, oxidase mimics catalytic reactions have attracted much attention and evolved as a suitable alternative for peroxidase mimics.…”

Section: Introductionmentioning

confidence: 99%

Vanadium‐Incorporated Mesoporous Silica as Oxidase Mimic for Colorimetric Dopamine Detection and Anticancer Activity

et al. 2023

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The intriguing features of artificial enzymes made nanozymes attractive in the field of biosensing and biomedical. Here, vanadium‐incorporated dendritic mesoporous silica (VMSN) as an oxidase mimicking nanozyme was utilized as a sensitive and selective colorimetric biosensor to detect dopamine (DA) and treat cancer cells. The nanozyme was successfully fabricated through the in‐situ incorporation of vanadium ions in the silica framework via a simple sol‐gel method using CTAB and mesitylene. The excellent oxidase‐like activity of VMSN was monitored by the oxidation of TMB. The kinetics, mechanism of the catalytic reaction and the effect of temperature, pH, and concentration on oxidase‐like activity were investigated thoroughly and further, based on the oxidase‐like activity, a fast and sensitive colorimetric sensing of dopamine developed with a LOD of 0.0021 μM and a linear range of 0–50 μM. The proposed colorimetric method was successfully used to determine DA concentration in commercially available dopamine hydrochloride injection.VMSN was further modified with folic acid and utilized against cancer cells in vitro. Neuroblastoma cells (SHSY‐5Y) show ROS generated by VMSN in the presence of oxygen, leading to enhanced cytotoxicity detrimental for SHSY‐5Y cells.

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What are inorganic nanozymes? Artificial or inorganic enzymes

Abstract: The research on inorganic nanozymes remains very active since the first paper on the “intrinsic peroxidase-like properties of ferromagnetic nanoparticles” was published in Nature Nanotechnology in 2007. However, there is...

Cited by 7 publications

References 287 publications

RNA hydrolysis at mineral-water interfaces

RNA hydrolysis at mineral-water interfaces

Inorganic Fe-O and Fe-S oxidoreductases: paradigms for prebiotic chemistry and the evolution of enzymatic activity in biology

Vanadium‐Incorporated Mesoporous Silica as Oxidase Mimic for Colorimetric Dopamine Detection and Anticancer Activity

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