Progress and perspectives of heteroatom-doped nanozymes: from synthesis strategies to biomedical applications (2023)


Natural enzymes are proteins or RNAs that have strong catalytic activity. Classical enzyme theory divides natural enzymes into six categories based on their catalytic properties: oxidoreductase, transferase, hydrolase, lyase, isomerase and synthetase [1], [2], [3]. Due to their superior reaction activity, natural enzymes play an increasingly important role in biosensors, disease therapy, and the food industry.

However, the intrinsic drawbacks of natural enzymes, including their high production cost, complicated preparation process, and low stability, have severely limited their catalytic potential under unfavorable conditions. In the last 20 years, several nanomaterials have been discovered that catalyze some reactions like natural enzymes [7], [8], [9], [10], [11], [12]. The concept of nanozyme was first used to denote nanoparticles (NPs) with enzyme-like properties in 2004 [13]. It is important to point out that the discovery of iron oxide (Fe3O4) can act as a peroxidase mimetic (POD) was a turning point in nanozyme research [14], causing a worldwide boom in nanozyme research [15], [16], [17].

Previously reported nanozymes can generally be divided into three categories: (1) metal NPs [18], [19], (2) metal oxide/metal sulfide [20], [21] and (3) metal-based nanomaterials. carbon [22], [23]. These nanoenzymes have mainly activities similar to redox and hydrolytic enzymes [24]. Despite their excellent stability in adverse environmental conditions and sustainable large-scale production, the selectivity and catalytic activity of nanoenzymes are still inferior to their natural analogues [15], [16], [17]. To address these issues, researchers have developed regulatory strategies to optimize their enzyme-like activity that focus on their size, morphology, facet dependence, ligand modification, heteroatom doping, composition, and external stimuli.

Nanozymes were prepared with different sizes, morphologies and dominant aspects to tailor the enzymatic activity of their pure materials. Its size, specific surface area and optimal exposure of crystal facets have been used to increase its catalytic activity [25], [26], [7]. Ligand modification is another regulatory strategy to improve catalytic activity, using synthetic approaches to form a suitable microenvironment similar to the active site of the natural enzyme [27], [28], [29], [30]. Representative ligands were β-cyclodextrin and histidine. A recent study usedN, N-dicarboxymethylperylene diimide as a modifying ligand to efficiently change the POD-like property of CeCoO3. His strategy used the synergistic effects of different materials to improve the innate catalytic efficiency, making 1+1>2 possible [31], [32], [33]. Modification of external stimuli is also an accessible approach to accelerate the catalytic reaction by modulating enzyme-related factors such as temperature, environmental pH, and photo- and magneto-thermal effects [34], [35], [36]. Furthermore, heteroatom doping is another activity optimization strategy that has attracted much attention due to its diversity, efficiency and simplicity [37], [38], [39], [40]. Heteroatom doping is similar to surface modification. It has proven to be an excellent strategy for improving the physicochemical properties of pure materials, including their water solubility, stability, and optical and electronic structural properties. Furthermore, different heteroatom doping strategies using different doping approaches have been used to synthesize superior nanomaterials with enhanced catalytic properties. These studies have highlighted its great potential for applications in several areas, including degradation of environmental pollutants [41], [42], electrocatalytic reactions such as oxygen [43] and hydrogen evolution [44], other reactions related to energy conversion or storage [45], [46] and biomedical applications based on nanozymes [47], [48].

Previous reviews have discussed nanozyme design strategies, activity regulation, and biomedical applications [15], [16], [17]. For example, Ding et al summarized activity regulation methods, including size and morphology, doping, vacancy, surface modification, and hybridization, followed by a discussion of recent biomedical applications [ 49 ]. Him and others. discussed the recent progress of carbon dot-based nanozymes for biomedical and chemosensitive applications [50]. However, few have focused on the progress with heteroatom-doped nanozymes, including their catalytic properties related to the types of heteroatom doping, synthesis methods, influencing factors, and biomedical applications (eg, biosensors, antibacterial, anticancer, and antioxidant agents).

This review provides a comprehensive overview of recent developments in heteroatom-doped nanozymes for biomedical applications, such as antibacterial, anticancer, and antioxidant nanozymes and stimulatory biosensors ( Fig. 1A ). It first highlights the synthesis methods of heteroatom-doped nanozymes and the influencing factors. It then presents current progress in modifying its enzymatic activity and modulating factors (Figure 1B) to increase its catalytic efficiency in biomedical applications. Finally, the main existing obstacles and future challenges in the clinical translation of heteroatom-doped nanozymes for disease therapy are discussed. This review will facilitate the improvement of enzyme-like catalytic capabilities through heteroatom doping.

paragraphs of sections

Nanozymes doped with heteroatoms

Heteroatom-doped nanozymes are nanomaterials that contain heteroatoms doped compared to their parent nanozyme. Unlike composite materials, heteroatom doping does not create individual NPs or ions. Compared to undoped nanoenzymes, nanoenzymes doped with heteroatoms show higher catalytic activity due to improved electron transfer efficiency and other special properties (water solubility, vacancy, conductivity, light absorption, magnetic, fluorescent and magnetic resonance properties) [15], [16], [17],

Biomedical applications of nanozymes doped with heteroatoms

The superior enzymatic activity of heteroatom-doped nanozymes for the regulation of reactive O-species (ROS) highlights their increasing importance in practical energy storage, electrochemistry, environmental protection, and biomedical applications. This review primarily focuses on its use in biomedicine (Figure 5). The following chapter summarizes recent advances in biosensor, antibacterial, anticancer, and antioxidant applications over the past five years.

Conclusions and perspectives

This review summarizes recent progress in heteroatom-doped nanozymes and their applications as biosensors and anticancer therapeutics, antibacterial and antioxidant agents. Nanozymes have unique advantages over natural enzymes such as lower costs, higher stability, higher production yields, and tunable enzyme-like activities, making them a promising tool for widespread applications. Strategies have been developed to regulate heteroatom-doped nanozymes, such as size, morphology, and dependent side

Statement of competing interest

The authors declare that they have no known financial interests or personal relationships that could influence the work reported in this article.


This work was supported by the National Natural Science Foundation of China (21904064).

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What are the biomedical applications of Nanozymes? ›

Recently, many types of nanoparticles with inherent catalytic properties have been reported to achieve various biomedical applications, including oxygen-dependent tumor therapy, radiotherapy, chemodynamic therapy, bacterial infection diseases, and reactive oxygen species (ROS)-related diseases, etc.

What are the limitations of Nanozymes? ›

Unlike the natural enzymes that typically exhibit high catalytic activity and substrate selectivity, nanozymes usually have relatively low activity and poor specificity and mimic only limited types of enzymes, which severely limit their practical application.

Is a Nanozyme a new type of artificial enzyme? ›

Nanozymes are nanomaterial-based artificial enzymes. By effectively mimicking catalytic sites of natural enzymes or harboring multivalent elements for reactions, nanozyme systems have successfully served as direct surrogates of traditional enzymes for catalysis.

When was the Nanozyme discovered? ›

Nanozymes first appeared in the literature in 2004, when Scrimin and co-workers immobilized triazacyclononane/Zn2+ on gold nanoparticles (AuNPs) to cleave phosphodiester bonds (Figure 1A). The authors found that the activity of the immobilized catalyst was higher than the free metal complex.

What are five applications of nanoparticles in biomedical? ›

In recent years, there has been a steadily growing interest in using these nanosystems in different biomedical applications such as targeted drug delivery, hyperthermia, photoablation therapy, bioimaging and biosensors [3,4. McNamara and S.A.M.

Which nanoparticles are used for biomedical application? ›

Nanoscale materials integrate well into biomedical devices because most biological systems are also nanosized. The materials commonly used to develop these nanotechnology products are inorganic and metal nanoparticles, carbon nanotubes, liposomes, and metallic surfaces (Liu et al.

What are the benefits of Nanozymes? ›

Compared to natural enzymes, nanozymes exhibit the unique advantages including high catalytic activity, low cost, high stability, easy mass production, and tunable activity.

What are the disadvantages of synthesis of nanoparticles? ›

Using this method, it is difficult to control the size of the nanoparticles created, and many particles also show a strong tendency to aggregate. Due to aggregation of the nanoparticles within the bulk powder, surface functionalization can be challenging to impossible.

What are the disadvantages of biological synthesis of nanoparticles? ›

Synthetic methods for nanoparticle synthesis are frequently linked to many challenges, including the production of hazardous byproducts, instability issues, high prices, and major environmental concerns (Ashique et al., 2022). ...

What are the benefits of artificial enzymes? ›

Artificial enzyme-catalytic reactions occur in mild, aqueous conditions. As a result, they are more cost-effective, environmentally friendly, and more sustainable when compared to inorganic catalysts and other solvents.

What are the limitations of artificial enzymes? ›

Abstract. Enzymes have been used in organic chemistry and biotechnology for 100 years, but their widespread application has been prevented by a number of limitations, including the often-observed limited thermostability, narrow substrate scope, and low or wrong stereo- and/or regioselectivity.

What is most modern model about enzyme action called? ›

The induced-fit model was suggested by Daniel Koshland in 1958. It is the more accepted model for enzyme-substrate complex than the lock-and-key model.

How do nanozymes work? ›

Nanozymes are nanomaterials that display enzyme-like characteristics. They are an important way of connecting nanomaterials to biological systems. Many nanozymes mimic natural enzymes such as catalase and peroxidase, but future developments will lead to the production of novel artificial enzymes at the nanoscale.

What are the characteristics of nanozymes? ›

The general properties of nanozymes that need to be characterized include: size, shape, morphology, specific surface area, structure, composition, and so on.

What are the classification of nanozymes? ›

(26−39) In this part, in order to get a clearer understanding, we divide nanozymes into 2 categories: (1) oxidoreductase family, for example, oxidase, peroxidase, catalase, superoxide dismutase, and nitrate reductase, and (2) hydrolase family, including nuclease, esterase, phosphatase, protease, and silicatein (Table 1 ...

What are the benefits of nanoparticles in medicine? ›

This can help treat cancer patients with a customized treatment plan. Not only can nanoparticles significantly improve drug delivery, but scientists are also working on using nanotechnology to analyze DNA in a couple of minutes, and mechanically reverse plaque buildup in arteries.

What are 2 applications of nanoparticles? ›

Nanoparticles are used increasingly in catalysis to boost chemical reactions. This reduces the quantity of catalytic materials necessary to produce desired results, saving money and reducing pollutants. Two big applications are in petroleum refining and in automotive catalytic converters.

What are 4 uses of nanoparticles? ›

Nanoparticles are now being used in the manufacture of scratchproof eyeglasses, crack- resistant paints, anti-graffiti coatings for walls, transparent sunscreens, stain-repellent fabrics, self-cleaning windows and ceramic coatings for solar cells.

What is the impact factor of nanotechnology for biomedical applications? ›

The 2022-2023 Journal's Impact IF of Journal of Biomedical Nanotechnology is 3.641, which is just updated in 2023.

What is synthesis of nanomaterials for biomedical applications? ›

Synthesis of Bionanomaterials for Biomedical Applications summarizes a range of procedures, including green synthesis of metal nanoparticles, metal oxide nanoparticles, and other types of nanoparticles while also exploring the appropriate use of these nanoparticles in various therapeutic applications such as anticancer ...

What is an example of a Nanozyme? ›

In addition to Fe-based nanozymes, many other metal-based nanozymes were also found. For example, cerium dioxide nanoparticles, manganese dioxide nanoparticles, copper oxide nanoparticles, and cobalt tetroxide nanoparticles, which are all have peroxidase catalytic activity.

What are the applications of enzyme nanoparticles? ›

Enzyme nanoparticles have attracted the scientific community as they can be used for environment protection, biochemical engineering, and biomedicine. It is necessary to understand the nature of enzyme nanoparticles interactions with their analyte.

What are Nanodiamonds for biological applications? ›

Fluorescent nanodiamonds (FNDs) are a new class of carbon nanomaterials that offer great promise for biological applications such as cell labeling, imaging, and sensing due to their exceptional optical properties and biocompatibility.

What are the advantages and disadvantages of nanoparticle? ›

Nanotechnology offers the potential for new and faster kinds of computers, more efficient power sources and life-saving medical treatments. Potential disadvantages include economic disruption and possible threats to security, privacy, health and the environment.

Why is nanoparticles synthesis important? ›

Nanoparticles are integral components in a wide variety of applications, including medicine, semiconductors, catalysis, and energy. They are defined as particles with a size between 1-1000 nm. At smaller size scales, particles can behave differently than their bulk counterparts.

What are the advantages of biological synthesis of nanoparticles? ›

Biogenic nanoparticles are advantageous as their synthesis does not involve hazardous chemicals for reduction and stabilization unlike chemical and physical methods for nanoparticle synthesis (Bloch et al., 2021; Ghosh & Webster, 2021a, 2021b, 2021c.

What are bad things about nanoparticles? ›

Materials which by themselves are not very harmful could be toxic if they are inhaled in the form of nanoparticles. The effects of inhaled nanoparticles in the body may include lung inflammation and heart problems.

What are the limitations of nanoparticles? ›

Particle size

One of the biggest limitations in nanoparticle aided drug delivery is clearance by the reticuloendothelial system (RES) through opsonization and it is implicit here that the size influences clearance as well as distribution.

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Enzymes are used in industrial processes, such as baking, brewing, detergents, fermented products, pharmaceuticals, textiles, leather processing.

What is the use of enzymes in daily life? ›

Enzymes are used to make and improve nearly 400 everyday consumer and commercial products. They are used in foods and beverages processing, animal nutrition, textiles, household cleaning and fuel for cars and energy generation.

What are two medical uses of enzymes? ›

Enzymes are the preferred markers in various disease states such as myocardial infarction, jaundice, pancreatitis, cancer, neurodegenerative disorders, etc. They provide insight into the disease process by diagnosis, prognosis and assessment of response therapy.

What are three things that can negatively impact enzyme function? ›

Enzyme activity can be affected by a variety of factors, such as temperature, pH, and concentration.

What are two factors that negatively influence enzymes? ›

Enzymes are affected by pH and temperature

Various environmental factors are able to affect the rate of enzyme-catalysed reactions through reversible or irreversible changes in the protein structure. The effects of pH and temperature are generally well understood.

What are 4 things can affect the way enzymes work? ›

Several factors affect the rate at which enzymatic reactions proceed - temperature, pH, enzyme concentration, substrate concentration, and the presence of any inhibitors or activators.

Which enzyme model is more accurate? ›

A more accurate description of enzyme structure is the Induced Fit model of enzyme action. The Induced Fit model was proposed by Daniel Koshland in 1958. According to Koshland's hypothesis, the active site is shaped similarly enough and has specific chemical properties that attract a substrate to bind.

What would happen if there were no enzymes in the human body? ›

Enzymes are proteins

They act as catalysts, which means that they make biochemical reactions happen faster than they would otherwise. Without enzymes, those reactions simply would not occur or would run too slowly to sustain life. For example, without enzymes, digestion would be impossible.

Why are enzymes important? ›

Enzymes are proteins that help speed up chemical reactions in our bodies. Enzymes are essential for digestion, liver function and much more. Too much or too little of a certain enzyme can cause health problems. Enzymes in our blood can also help healthcare providers check for injuries and diseases.

What are nanozymes in COVID 19? ›

Gold nanozymes have been employed in rapid detection of SARS-CoV-19 (Pramanik et al. 2021). Indeed, samples taken in positive patients contain nucleocapsid phosphoprotein oligonucleotides that combine with thiol-functionalized gold nanozymes, which allow detection in 10 min by calorimetry (Kamaraj 2020).

What is the difference between traditional enzymes and nano enzymes? ›

Nanozymes are distinct from the natural biological enzymes in the following features: the enzymatic properties of nanozymes are modified by nanomaterial size, morphology, surface, composition; but may show only partial differences in terms of sensitivity to activators, inhibitors, pH, temperature, and light [6].

What are nanozymes in environment? ›

Nanozymes have been applied in the detection of heavy metal ions, molecules, and organic compounds, both quantitatively and qualitatively. Additionally, within the natural environment, nanozymes can be employed for the degradation of organic and persistent pollutants such as antibiotics, phenols, and textile dyes.

What are biomedical applications of nanozymes? ›

Recently, many types of nanoparticles with inherent catalytic properties have been reported to achieve various biomedical applications, including oxygen-dependent tumor therapy, radiotherapy, chemodynamic therapy, bacterial infection diseases, and reactive oxygen species (ROS)-related diseases, etc.

What are the limitations of nanozymes? ›

Unlike the natural enzymes that typically exhibit high catalytic activity and substrate selectivity, nanozymes usually have relatively low activity and poor specificity and mimic only limited types of enzymes, which severely limit their practical application.

What are few unique characteristics of nanoparticles? ›

2.2 Which are the important physical and chemical properties of nanomaterials?
  • Size, shape, specific surface area, aspect ratio.
  • Agglomeration/aggregation state.
  • Size distribution.
  • Surface morphology/topography.
  • Structure, including crystallinity and defect structure.
  • Solubility.

What are Nanozymes made of? ›

Abstract. “Nanozyme” is used to describe various catalysts from immobilized inorganic metal complexes, immobilized enzymes to inorganic nanoparticles.

When were Nanozymes invented? ›

In 2004, Scrimin and co-workers coined the term “nanozyme” and applied triazacyclonane-functionalized gold nanoparticles as catalysts for transphosphorylation reaction.

What is the classification of nanoparticle? ›

Classification of NPs. Based on their composition, NPs are generally placed into three classes: organic, carbon-based, and inorganic [23].

What are the biomedical applications of nanocellulose? ›

Nanocellulose is a biomaterial highly applicable to biomedical industry, specifically in tissue engineering, drug delivery, cartilage replacements, tissue engineering, cardiovascular applications, wound dressings and medical implants.

What are the biomedical applications of nanofibers? ›

Nanofibrous materials are also used in other biomedical applications such as medical implants, wound dressings, antimicrobial agents, drug delivery vehicles, biomimetic actuators, dental materials, enzyme immobilization scaffolds, and protective textiles for chemical and biological threats.

What are the applications of nanomaterials in biological research? ›

They are widely used in biological research as fluorescence imaging tools for applications such as cell labeling and biomolecule tracking. The small size of quantum dots also enables them to be suitable for biomedical applications such as medical imaging and diagnostics.

Why are nanodiamonds important? ›

Nanodiamonds also possess many desirable mechanical properties. Compared to other nanomaterials, their properties include superior hardness, better chemical stability, and thermal conductivity. Nanodiamonds can also resist harsh environments and have a lower friction coefficient.

What can be used for biological synthesis of nanoparticles? ›

Green synthesis methods utilize biological agents such as viruses, bacteria, fungi, algae, and plants for the synthesis of nanoparticles.

What are the applications of nanotechnology in drug delivery and biomedical? ›

Through the manipulation of size, surface characteristics and material used, the nanoparticles can be developed into smart systems, encasing therapeutic and imaging agents as well as bearing stealth property. Further, these systems can deliver drug to specific tissues and provide controlled release therapy.

What are the advantages of nanocellulose? ›

The intrinsic properties of nanocellulose include high mechanical strength with high Young's modulus, low gas permeability, broad surface modification capacity, high specific surface area, elevated biocompatibility and biodegradability, lack of toxicity, thixotropic properties, high absorbability, and photonic ...

What are the applications of biomedical materials? ›

Doctors, researchers, and bioengineers use biomaterials for the following broad range of applications: Medical implants, including heart valves, stents, and grafts; artificial joints, ligaments, and tendons; hearing loss implants; dental implants; and devices that stimulate nerves.

What are the 6 main applications in nanomedicine? ›

  • Drug delivery.
  • Applications.
  • Imaging.
  • Sensing.
  • Sepsis treatment.
  • Tissue engineering.
  • Medical devices.
  • See also.

What effect do nanoparticles have on enzyme activity? ›

Nanoparticles are solid dispersion particulates of size range 10-1000 nm. They cause enhancement of particle mobility, diffusion, thermal stability, storage capacity, greater surface area and also modulate catalytic activity of the attached enzymes.

How are nanoparticles advantages in biomedical applications? ›

Nanoparticles can be easily synthesized and modified so that they have novel electronic, optical, magnetic, medical, catalytic, and mechanical properties. Such a powerful modification results in a high surface-to-volume ratio and quantum size effect, which depend greatly on their size, structure, and shape.

What is the use of nanoparticles in medical devices? ›

It is here that emerging nanomaterials can provide such desired properties over traditional materials. These properties include increased optical strength, surface conjugation, antibacterial and antimicrobial activities, bioavailability, and biocompatibility.


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