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Introductory Chapter: Incredible Spicy Iron Oxide Nanoparticles

Written By

Xiao-Lan Huang

Submitted: 10 December 2021 Published: 28 September 2022

DOI: 10.5772/intechopen.101982

From the Edited Volume

Iron Oxide Nanoparticles

Edited by Xiao-Lan Huang

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1. Introduction

1.1 The history of research

Iron oxide is one of the most abundant minerals on the earth, many of them can be presented as nanoparticle form, which includes several different phases, e.g., ferrihydrite (Fh), magnetite (Fe3O4), maghemite (γ-Fe2O3), and wüstite (Fe1 − xO). The structure, shape as well as size dependence make them have various functions. Moreover, all of these nanoparticles are also can be synthesized due to their innovative functions and applications. Recently the knowledge of iron oxide nanoparticles is expanding rapidly, especially after 2007. The paper numbers related to iron oxide nanoparticles were increased significantly, compared to the topic of iron oxide, and iron (Figure 1).

Figure 1.

The number of manuscripts related to iron, iron oxide, and iron oxide nanoparticles. Data are collected from Scopus by the end of Nov 2021.

In 1989, the first article concerning Iron Oxide Nanoparticles was published in Magnetic Resonance Imaging, based on Scopus (https://www.scopus.com). The published article was entitled “Superparamagnetic iron oxide nanoparticles as a liver MRI contrast agent: contribution of microencapsulation to improved biodistribution” [1].

Since then, the annual number of publications related to the topic of iron oxide nanoparticles still kept a single digit from 1990 to 2001, and jumped to 3 digits in 2007, and continued to increase up to 1722 (2021). Yet, the number of manuscripts of iron, and iron oxide, has also increased. Almost 10–18% of paper on the topic “iron oxide” has been related to iron oxide nanoparticles since 2009.

It is noted that the subjects related to the topic of iron oxide nanoparticles have also increased and shifted. In the early days (1989–2001), only 68 documents in 12 years were published in the following subjects: Materials science (23%), Medicine (17%), Physics and Astronomy (15%), Chemistry (12%), and Engineering (10%), and the corresponding 5 most frequent keywords in these manuscripts are Nuclear Magnetic Resonance Imaging, Iron, Contrast Medium, Nonhuman, and Animal Experiment. More than 1700 manuscripts a year in the recent 2 years were released in up to 28 subjects (Figure 2), including Materials Science (19%); Chemistry (15%), Chemical Engineering (11%); Engineering (11%); Biochemistry, Genetics, and Molecular Biology (10%); Physics and Astronomy (10%); Medicine (6%); Pharmacology, Toxicology, and Pharmaceutics (5%); Environmental Science (4%); Energy (2%); Agricultural and Biological Science (1%); Immunology and Microbiology (1%); and Computer Science (1%). The other involved subjects are Mathematics, Economics, Earth and Planetary Science, Neuroscience, Health Professions, Social Science, Business, Management and Accounting, Economics, Econometrics and Finance, Dentistry, Veterinary, Psychology, Nursing, even Arts and Humanities. The corresponding 10 most frequent keywords in these manuscripts are Iron Oxides, Iron Oxide Nanoparticles, Magnetic Nanoparticles, Superparamagnetic Iron Oxide Nanoparticle, Human, Nonhuman, Animal, Chemistry, Synthesis, and Particle Size.

Figure 2.

The number of subjects in the manuscripts related to iron oxide nanoparticles (2017–2021). Data are collected from Scopus by the end of Nov 2021.

These manuscripts were published in 160 journals annually in 11 different languages since 2017. The top 10 journals are Nanomaterials, International Journal of Nanomedicine, ACS Applied Materials and Interfaces, Scientific Reports, Journal of Magnetism and Magnetic Materials, Nanoscale, RSC Advances, International Journal of Biological Macromolecules, Materials Science and Engineering C, and Journal of Materials Chemistry B.

The support of the research related to iron oxide nanoparticles is also progressed extremely. The top 10 foundations were National Natural Science Foundation of China, National Institutes of Health, European Commission, Deutsche Forschungsgemeinschaft, Conselho Nacional de DesenvolvimentoCientífico e Tecnológico, National Research Foundation of Korea, U.S. Department of Health and Human Services, European Regional Development Fund, and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior during 2017 to 2021. The top 10 countries for this area are China, the United States, India, Iran, Germany, South Korea, Spain, France, Brazil, and the United Kingdom.

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2. Examples and importance of iron architecture

Many research, included several chapters in this book, specified that the importance of the crystal structure of iron oxide. The following excellent manuscripts [2, 3, 4, 5, 6, 7, 8, 9, 10, 11] serve as a refresher course and basic introduction to this field, particularly the book titled “The Iron Oxides: Structure, Properties, Reactions, Occurrences, and Use” [2], the paper “Iron oxides: From molecular clusters to solid. A nice example of chemical versatility” [3], “Size-driven structural and thermodynamic complexity in iron oxide’ [4], “Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism” [5], ‘Formation, stability, and solubility of metal oxide nanoparticles: Surface entropy, enthalpy, and free energy of ferrihydrite’ [6], “Crystal growth. Aqueous formation and manipulation of the iron-oxo Kegginion” [7], “Size-driven structural and thermodynamic complexity in iron oxide” [8], “Iron oxide surfaces”[9], “Unravelling the growth mechanism of the co-precipitation of iron oxide nanoparticles with the aid of synchrotron X-Ray diffraction in solution” [10] and “Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite”[11].

Here I list the top 5 citations of the original article related to iron oxide nanoparticles. They are “Intrinsic peroxidase-like activity ferromagnetic nanoparticles” [12], “Monodisperse MFe2O4 (M = Fe, Co, Mn) Nanoparticles” [13], “3D Nitrogen-Doped Graphene Aerogel-Supported Fe3O4 Nanoparticles as Efficient Electrocatalysts for the Oxygen Reduction Reaction” [14], “Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process” [15] and “Noninvasive detection of clinically occult lymph-node metastases in prostate cancer” [16]. The first [12] and the third [14] ones were related to the new characteristics of iron oxide nanoparticles, the second [13] and the fourth [15] were related to the synthesis of iron oxide nanoparticles. The fifth [16] was related to its application. The citation number of these top 5 papers indicated that the research related to the enzyme-like activity of iron oxide nanoparticles is still hot (Figure 3). From these extreme samples, readers can understand why the studies and application of iron oxide nanoparticles in recent decades have become incredibly spicy.

Figure 3.

The annual citation number of the top 5 papers related to iron oxide nanoparticles, data are collected from Scopus by the end of Nov 2021.

It is interesting to note that the catalytic phenomena on phosphate ester hydrolysis, e.g., adenosine triphosphate (ATP), glucose-6-phosphate (G6P), and inorganic condensed phosphate (e.g., pyrophosphate, PPi, and polyphosphate, poly-P) in artificial seawater was also initially observed in 2007 [17] in another independent research in the same period of Gao’s work [12]. The catalysis was further inhibited by the tetrahedral oxyanions with an order of PO4 < MoO4 < WO4, which is similar to the natural purple acid phosphatase (PAP) [18, 19]. A binuclear metal center (di-iron Fe-Fe or Fe-M (M as Mn and Zn) that produces orthophosphate due to the net transfer of the phosphoryl group to water, is essential for PAPs catalysis (Figure 4a) [20, 21, 22, 23, 24]. The author at that time claimed that the formation of diiron or polyiron with the μ-(hydr)oxo bridge through hydrolysis of iron during the aging process may contribute to the observed catalytic activity of inorganic iron oxide nanoparticles [17]. These inorganic iron oxide nanoparticles, void of protein, RNA, or any organic component might serve as an inorganic phosphoesterase. The corresponding results of phosphate ester hydrolysis, promoted by inorganic iron oxide nanoparticles with the Michaelis–Menten kinetics behavior, and hypothesis related to inorganic enzyme were published at RSC Advance [25] and Astrobiology [26] (Figure 4).

Figure 4.

Iron architecture in purple acid phosphatase and iron oxide nanoparticles, a: The μ-(hydr)oxo-bridges in purple acid phosphatase (PAP), and b: Fe-oxo-Fe structure in different iron oxides phases.

Different laboratory studies related to hydrolysis of phosphate ester further confirmed the orthophosphate releasing [27, 28, 29, 30, 31, 32, 33, 34]. It was noted that ferrous ion (Fe II) is presumed to be the dominant form of iron in the earliest ocean [35, 36], low levels of ferric ion (Fe III) would have been produced at the ocean surface as a result of photo-oxidation, even in the absence of oxygen in the atmosphere [37, 38]. Also, precipitated ferric ion, for example in green rust in the Archaean banded iron formations, was also likely to be present in the Hadean or the early Archean [39, 40, 41, 42, 43]. On the other hand, inorganic condensed phosphates (e.g., PPi), composed of orthophosphate (Pi) residue with the energy-rich phosphoanhydride bonds, are also critical to the emergence and evolution of life [44, 45, 46]. Phosphate esters, including ATP, G6P, and PPi, is a master group of compounds involved in signaling, free-energy transduction, protein synthesis, and maintaining the integrity of the genetic material [47, 48]. Hydrolysis of these phosphate esters is related to the formation and function of the most important two biopolymers of life: RNA/DNA that encodes genetic information [49] and protein which is related to the reversible phosphorylation [50].

Similar to purple acid phosphatase, the active metal centers of most oxidoreductases in nature also comprise the transition metals, for example, horseradish peroxidase (HRP) [51] with Fe, manganese peroxidase [52], oxalate oxidase [53, 54], manganese superoxide dismutase [55] and manganese catalases [56, 57] with Mn, and haloperoxidases [58, 59] with V, all exhibit the oxo ligand structure. This unique metal architecture or metal bond in the nanoparticles might also contribute to the “intrinsic peroxidase,” “intrinsic oxidase,” “intrinsic superoxide dismutase,” and “intrinsic catalase” feature from different inorganic metal oxides nanoparticles [12, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69]. It was noted that some PAPs also have activity of peroxidases [70]. Meanwhile, scientists have demonstrated that inorganic V2O5 nanomaterials have haloperoxidase-like activity in the presence of substrates such as Br- and H2O2 [68, 71]. The activity is due to the nanostructure of vanadium pentoxide, not the free vanadate in solution from leaching processes [68]. The nanowires of V2O5 are stacked in the [001] direction while their wires extend in the [100] direction, and a view of the (110) plane reveals extraordinary similarities with the haloperoxidase-active sites. Consequently, small amounts of hypobromous acid are continuously produced in the ocean to kill or inhibit the bacteria around the V2O5/paint [71]. The suggested mechanisms of the inorganic haloperoxidase, are also similar to those of natural vanadium haloperoxidase [58, 59]. Such V2O5/paint has been successfully applied to combat marine biofouling, i.e., the colonization of small marine microorganisms on the surfaces of ships that are directly exposed to seawater [71]. Like the nanoparticles of iron oxide and vanadium pentoxide, the intrinsic sulfite oxidase activity of molybdenum trioxide nanoparticles is also due to the oxo ligand of Mo [72], as revealed in the metal center of sulfite oxidase [73, 74]. The work using the in situ Raman spectroscopy on the changes of V-oxo (V=O) bond in the different V2O5 nanomaterials during H2O2 catalysis cycle further indicated that the catalytic characteristics in these metal oxide nanoparticles are due to the distinctive crystal structure or metal bond, i.e., not merely the simple surface area or particle size of the nanoparticles [75]. The different shapes and sizes of Fe3O4 nanocrystals and MnFe2O4 nanoparticles also demonstrated that the key role of metal oxides structure for their catalytic activity [76, 77], supported by the density functional theory calculation as well [78].

Inorganic nanomaterials with the enzyme-like activity were not generated by artificial synthesis processing, but their metal architecture in nanoparticles. Such catalytic kinetics also can be described by Michaelis–Menten equations, the same as the natural enzyme (protein and ribozymes) [79, 80, 81, 82] in modern biochemistry. Inorganic iron oxide nanoparticles from ferritin and magnetosomes are also already confirmed to have such enzyme-like activity [83, 84, 85, 86, 87]. This further validated that these inorganic iron oxide nanoparticles with enzyme-like activity are inorganic enzymes [25, 26, 88], not artificial enzymes [89, 90]. Transition metal sulfites, even selenide nanoparticles were anticipated to form due to a reducing atmosphere and ocean in the early earth environment [35, 91]. Greigite (Fe7S8), as an example, was detected in the laboratory under the simulated early Earth hydrothermal conditions [92]. Some of them were documented to have “intrinsic peroxidase” “intrinsic superoxide dismutase,” and/or “intrinsic catalase” activity, e.g., Fe3S4 [93], Fe7S8 [94], CuS [95], CuZnFeS [96], CdS [97], MoS2 [98], WS2 [99], FeS [100], FeSe [100], α-MnSe [101], MoSe2 [102], and CoSe2 [103]. It is not strange since many iron–sulfur proteins contain a cluster of multinuclear iron and inorganic sulfide, where the irons are coordinated by protein amino acid residues and sulfides with such function [104, 105, 106], e.g., alkyl hydroperoxide reductase with a disulfide bond structure [107]. Glutathione peroxidase with the selenocysteine as catalytic active center [108] was reported to scavenge hydrogen peroxide. These findings provide solid evidence that these biocatalysts can be presented before the protein and RNA world, and thereby offer a solution to the “chicken and egg” at life’s beginnings [109, 110]. All of these inorganic enzyme activities, due to their specialized crystal structure including but not limited to their surface area, do support the metabolism-first hypothesis, not the replicator-first scenario [111, 112], and are also to be considered highly important in the context of new theories about the emergence of life [113, 114, 115].

Actually, iron oxide nanoparticles are very common nanoparticles present in the soil, sediment, water, even air dust in our current earth environment [116, 117, 118, 119, 120]. It is very reasonable to expect that these iron oxide nanoparticles, as inorganic phosphatase, play a significant role for organic phosphorus in the water and soil nowadays too. This is an underestimated pathway for organic phosphorus transformation from the view of biogeochemistry [31, 121, 122, 123, 124, 125, 126], since different phosphate esters, especially monoesters, are the main components in the dissolved organic phosphorus in soils [127, 128, 129, 130] and waters [131, 132, 133, 134]. Furthermore, several recent investigations already confirmed that iron-rich nanoparticles (< 20 nm) are the main carriers of phosphorus in forest streams and soil solutions [135, 136, 137, 138, 139]. Keep in mind that many environmental factors also impact the activity of the catalysis of these inorganic enzymes, including the inorganic phosphatases [25, 26, 88]. The activity of inorganic phosphatases can be inhibited by some small organic molecules, e.g., citrate acid, due to the iron complex formation [26, 88]. The interaction of organic matter and iron oxide nanoparticles is very complex [140, 141, 142], the catalytic capacity, on the other hand, can also be enhanced when metal oxide nanoparticles surface modified with some especially organic ligand, e.g., glutathione, dendrimer, DNA, and protein, based on the progress of nanozyme and metal–organic frameworks from the view of bioengineering [143, 144, 145, 146, 147].

The fact of orthophosphate release from the hydrolysis of organic phosphorus, promoted by the iron oxide nanoparticles, transfigures the basic assumptions on the iron-sorbed phosphorus for the Redfield stoichiometry [148], which is a fundamental feature in the understanding of the biogeochemical cycles of the oceans [149, 150, 151, 152, 153]. Such new discovery related to the role of iron oxide nanoparticles significantly impacts the carbon and nutrient fluxes in global circulation models [154, 155, 156]. It also further challenges the notion of ocean iron fertilization as a potential method of removing atmosphere CO2 technologies to reduce the temperature increase for the coming climate changes [157, 158, 159, 160, 161, 162, 163]. The implications of its catalytic activity related to organic phosphorus transformation are not limited to the emergence of life, phytoavailability of phosphorus, but also go to global carbon and nutrient fluxes, and climate changes. The incredible spicy iron oxide nanoparticles!

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3. Additional references and perspectives

Iron oxide nanoparticles are also found in our everyday life, even if we don’t realize it. They are bioactive materials and may perform various biological functions in life activity, especially related to reactive oxygen species. They can be used as a valuable tool in cancer therapeutic application, which is presented in this book. The incredible spicy iron oxide nanoparticles!

I will argue that the applications of iron oxide nanoparticles do not stop at biomedicine. In addition to being extremely useful for green energy applications such as supercapacitors and hydroelectric cells, these inorganic iron oxide nanoparticles are also used extensively in the radio frequency and microwave applications discussed in this book. The incredible spicy iron oxide nanoparticles!

I do appreciate the contributions of all authors of this book. Indeed, this book has covered much significant progress of iron oxide nanoparticles, especially its medical and green energy applications. However, some very important components related to iron oxide nanoparticles in nature are still missing. I encourage readers to look up the following reviews to have a BIG picture of iron oxide nanoparticles.

Guo and Barnard [117] focused their review, titled “Naturally occurring iron oxide nanoparticles: morphology, surface chemistry and environmental stability”, on the several phases (ferrihydrite, goethite, hematite, magnetite, maghemite, lepidocrocite, akaganéite, and schwertmannite) commonly found in water, soils, and sediments. Their functions in various aspects are closely related to their shapes, sizes, and thermodynamic surroundings. Phase transformations and the relative abundance are sensitive to changes in environmental conditions.

Braunschweig et al. [164], in their study “Iron oxide nanoparticles in geomicrobiology: From biogeochemistry to bioremediation”, examine a number of factors influencing the microbial reactivity of Fe oxides, including particle size, solubility, ferrous iron, crystal structure, and organic molecules. It highlights the differences between natural and synthetic Fe oxides.

By using the title “Iron solubility, colloids, and their impact on iron oxide formation from solution”, Baumgartner and Faivre [165] started their review from the iron solubility, and its speciation in water as well as phase transformation processes from solution to solid and vice versa. It included experimental findings and theoretical concepts of iron (oxyhydr)oxide dissolution and formation in aqueous solution: hydrolysis, nanoparticle size-dependent aspects of solubility and particle formation pathways, nucleation, growth, and oriented attachment.

A article by Claudio et al. [166] focused on the importance of iron oxide nanoparticles in the soil, especially related to soil fertility, plant nutrition, and the interaction of phosphorus, sulfate, molybdate, and pollutants (arsenic or chromium) from the traditional view of soil chemistry with the title “ Iron Oxide Nanoparticles in Soils: Environmental and Agronomic Importance”. While Vindedahl et al. [141], under the title “ Organic matter and iron oxide nanoparticles: Aggregation, interactions, and reactivity”, addressed the chemistry of iron oxide nanoparticles in aqueous environments, e.g., the effect of pH, organic matter sorption, and solid-state transformations. Both can help readers understand the fate, transport, and chemical behavior of nanoparticles in complex environments.

Nanozymes are defined by Wei and Wang as nanomaterials with enzyme-like properties [89, 167]. In comparison to a previous literature review on this topic [89] (2013, cited 302 documents), “Nanomaterials with enzyme-like characteristics (nanozymes): Next-generation artificial enzymes (II)” [167] cites 1212 documents. It provides a general overview of this research field, including the type of nanozymes and their representative nanomaterials, catalytic mechanisms as well as broad applications. The challenges and the directions for advancing nanozyme research were also suggested by the authors. However, the concept of “artificial enzymes” or “enzyme mimics” cannot be applied to these inorganic nanozymes. Specifically, inorganic nanomaterials possessing enzyme-like activity are attributed to their unique architecture, as previously noted. Such inorganic nanomaterials architecture is not created artificially but rather is intrinsic to the mineral crystal itself. Scientists only observed enzyme-like activities in nanomaterials but did not create these feathers. To distinguish inorganic nanozymes from the previously existing classification of enzymes (proteins) and ribozymes (RNAs) as biocatalysts, I proposed classifying them as inorganic enzymes.

Malhotra et al., with the title “Potential Toxicities of Iron Oxide Magnetic Nanoparticles: A Review” [168], addressed the safety of engineering iron oxide nanoparticles for different applications. Many factors, including their surface to volume ratio, chemical composition, size, and dosage, retention in the body, immunogenicity, organ-specific toxicity, breakdown, and elimination from the body can impact their toxicity. More research is needed to further assess its safety.

Our book, together with these additional manuscripts and reviews, aims to provide an active source in the field of nanoscience while creating a bridge between scientists and engineers working in the fields of mineralogy, biology, chemistry, geology, agronomy, medicine, environmental sciences, as well as the green energy industry.

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Written By

Xiao-Lan Huang

Submitted: 10 December 2021 Published: 28 September 2022