Abstract
Magnetic nanoparticles are an important class of nanomaterials. Several types of magnetic nanoparticles have been discovered in the recent years. The major mechanism of action of magnetic nanoparticles in cancer therapy is the production of hyperthermia. Hyperthermia increases local tissue heat and kills cancer cells. The major drawback which limits clinical utility of magnetic nanoparticles is the inherent toxicity, since normal surrounding tissue is also killed by hyperthermia. This review describes the latest advances in the field of magnetic nanoparticles, describing the important types with examples and major applications.
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1 Introduction
In the 1900s, infectious diseases were responsible for the major share of disease deaths. By the next century, most of these diseases were brought under control. In the current generation, cancer and heart diseases account for the major share of disease burden. Cancer is probably the most dreaded disease of the present century. Several treatment methods have been tried, but we have not been successful in eliminating cancer. Chemotherapy is one of the well-known modes of cancer therapy. Traditional chemotherapeutic agents had limited success, and some of them were also highly toxic. Hence, there is a need for newer modalities of cancer chemotherapy.
Magnetic nanoparticles (NPs) have a magnetic core, biocompatible coating, and surface functionalizations. Such a structure allows integration of targeting agents, chemotherapeutic and biotherapeutic agents. They have theranostic properties [1].
2 Hyperthermia Therapy
It is well-known that cancer cells die when exposed to higher temperatures. This is the basis of hyperthermia therapy, which is receiving increasing attention. The body is exposed to higher temperatures. In the case of cancer, local hyperthermia is used.
Heat can be produced by different means, like microwave, radiofrequency, ultrasound or magnetic hyperthermia. For smaller tumors, radio-ablation is used by a technique known as superficial hyperthermia, where the tissue is exposed to radiation. If needles are inserted into the tissues, it is known as interstitial hyperthermia [2,3,4].
Hyperthermia kills cells directly, but the more significant effects are produced when it is combined with other modalities of cancer therapy [5]. It increases blood perfusion as well as produced hyperbaric conditions, proving to be toxic to cancer cells [6]. There is hypothesis that the size of cancer cells may decrease with heat. However, it should be remembered that hyperthermia is not specifically toxic to cancer cells; it can also damage normal cells. Hence, hyperthermia is not without side effects. Side effects of heat include surface burns, swelling, blood clots, and bleeding complications [6]. Systemic toxicities including cardiovascular toxicity and systemic shock syndrome may occur [7]. The most important aspect is to be able to control the temperature inside the cells/body.
Targeted radiotherapy refers to delivery of higher dose of radiation to cancer cells without causing damage to nearby tissues. It is used in many types of cancers, including head and neck, brain, lung, and prostate cancers. Hyperthermia assists this process significantly [8].
Magnetic hyperthermia may trigger differentiation of cancer cells, preventing progression of cancer [9]. Dendrimers can form effective hybrid platforms with magnetic nanoparticles to form the basis of cancer therapy [10].
3 Magnetic Nanoparticles
Magnetic nanoparticles (MNPs) are a group of nanoparticles whose properties can be modified by application of magnetic fields. MNPs are particular in that they produce controlled increase in temperature. Temperature distribution can be controlled by the velocity, size, and distribution of MNPs within the body [11, 12].
Upon application of external magnetic field, MNPs are able to convert electromagnetic energy to thermal energy and thereby increase the temperature [13]. The increase in temperature enhances tumor oxygenation and chemo- and radio-sensitivity. The net effect is shrinkage in tumor size [14]. Heat may be dissipated as well, especially when alternating magnetic current is applied. Nanoparticles, including magnetic NPs, bring about thermal ablation of tumors. They have advantages over conventional heating methods [15].
Utilizing intra-tumoral Fenton reaction for cancer therapy is a new field known as chemodynamic therapy. The acidic pH of tumor environment is not exactly suited for normal Fenton reaction and hence requires enhancement [16].
Suitable methods need to be developed to produce localized hyperthermia and targeted release of chemotherapy drug. Many modifications of the basic technology have been investigated, and further, methods may need to be evaluated [17, 18].
Magnetic hyperthermia has been useful in the treatment of oral cancer [19, 20]. When exposed to alternating magnetic field, certain NPs can generate heat through hysteresis [21]. This phenomenon forms the basis of cancer therapy using MNPs [22]. Multifunctional magnetic gold nanomaterials have been used for the treatment of cancer [23,24,25].
4 Superparamagnetic Nanoparticles
5 Multifunctional Nanoparticles
Functionalized magnetoparticles sensitize tumors to X-rays and protons and act as radio-enhancers. These are thus used in cancer therapy [28]. Multifunctional nanoparticles (MFNPs) have wide theranostic potential; some examples of studies where they have been used are given below [29].
Mesoporous polydopamine nanosponges on a multifunctional platform have been used for the treatment of cancer [30]. Fe3O4-TMZ-ICG MNPs are produced by incorporating iron oxide NPs with temozolomide (TMZ) and indocyanine green (ICG). These agents enhance apoptosis-mediated death through various genes involved in the pathway. Such selective chemo-phototherapy using these agents has found applications in the treatment of brain cancer [31].
Core-shell-structured iron carbide (Fe5C2@Fe3O4) nanoparticles (NPs) produce reactive oxygen species (ROS), through the catalysis of the Fenton reaction. Normally, ROS-mediated therapy is an inefficient process, but these agents have showed great promise because of high efficiency and high specificity [32]. Biocompatible core-shell magnetic nanocomposite based on cross-linked chitosan hydrogels (using synthetic terephthaloyldiisothiocyanate as a cross-linker) is used for cancer therapy based on in vitro hyperthermia [33].
MFNPs have also been formed by genetically manipulating NK cells by genetic engineering and conjugating them with magnetic and fluorescent NPs. They have enhanced cancer cytotoxicity [34]. Silica-coated iron oxide NPs (SIO-MNPs) have enhanced radio-sensitivity in breast cancer cells [35]. Graphene oxide NPs kill cancer cells better when they are multifunctional, incorporated with iron oxide NPs and hyaluronic acid. This enables the use of magnetic hyperthermia and kills cancer cells better [36]. An oral drug delivery system [polyacrylic acid (PAA) and chitosan (CS) on Gd3+ -doped mesoporous hydroxyapatite nanoparticles (Gd-MHAp NPs)] has been developed which might be useful for orthotopic colon cancer therapy [37].
MFNPs have been used in the treatment of brain cancer [38]. Multifunctional iron oxide nanocomposites have been used for imaging-guided photothermal therapy of cancers [39]. Certain functionalized NPs are used for fluorescence imaging-guided photothermal therapy [40].
Magnetic NPs have also been used for imaging-guided immunotherapy [41]. MFNPs have also been used for metastatic cancers [42]. Cisplatin-functionalized NPs have been used for the treatment of breast cancer [43]. Some MFNPs [Fe3O4@KCTS, a core-shell type of magnetic nanoparticles, prepared by activating Fe3O4 with carbodiimide and cross-linking it with α-ketoglutarate chitosan (KCTS)] are also used for cancer detection [44]. Advantages include excellent loading efficiency, real-time monitoring, and improved cargo bioavailability and bioselectivity [45].
A triple-modal superparamagnetic iron oxide (Fe3O4), IR780, doxorubicin (DOX), and perfluoropentane (PFP) entrapped poly-lactide-co-glycolide (PLGA) nanoparticles (IR780/Fe3O4@PLGA/PFP/DOX NPs) have been used experimentally for breast cancer treatment [46].
Doxorubicin-loaded magnetic mesoporous silica nanoparticles (ND-MMSNs) have been used for targeting glioma cells. The platform has been used for imaging as well as therapeutic purposes [47].
PEGylated branched gold (Au)-iron oxide (Fe3O4) Janus nanoparticles (JNPs) are used for simultaneous trimodal imaging and photothermal therapy of cancer cells [48].
Exceedingly small magnetic iron oxide nanoparticles (ES-MIONs) (<5 nm) are used for magnetic resonance imaging (MRI) as well as for therapeutic purposes in cancer in experimental animals [49].
Dual surfaced dumbbell-like gold magnetic nanoparticles (Au–Fe3O4) are used for targeted aptamer delivery, and these are used as carriers for cancer hyperthermia therapy [50].
Superparamagnetic iron oxide particles have been successfully implemented for the treatment of gastric cancer [51].
Magnetically responsive microbubbles are used in the treatment of pancreatic cancer. Microbubbles are lipid or polymer stabilized gas filled particles [52].
Magnetically and thermally sensitive poly(N-isopropylacrylamide) (PNIPAAm)/Fe3O4–NH2 microgels encapsulated with curcumin (Cur) are used as controlled release cancer therapeutic drugs [53].
Colorectal cancer with liver metastasis has been treated by hybrid functionalized magnetic-gold NPs [54]. Magnetic MFNPs are used in the treatment of prostate cancer [55, 56] and bladder cancer [57].
Core-shell PB@MIL-100(Fe) dual metal-organic-frameworks (d-MOFs) nanoparticles are used for theranostic cancer therapy [58]. MFNPs enables Fenton reaction assisted photodynamic therapy [59].
Magnetotactic bacteria are aquatic organisms having strong biomedical applications. This is because of their hyperthermia effect, affecting cancer cell proliferation [60].
Stable hybrid nanobiocatalyst is formed when biomimetic silica (Si) nanoparticles are entrapped with Horseradish Peroxidase and magnetic nanoparticles. These NPs have wide applications in cancer therapy [61]. The degradable poly(AA-co-DMA) nanohydrogels with surface-tailorable functionalities are used with nanomaterials and drug molecules for cancer therapy [62].
Because of the superparamagnetic, biocompatible and biodegradable properties, iron oxide NPs are used in the treatment of breast cancer [63]. A multifunctional drug-loaded nanosystem (F/A-PLGA@DOX/SPIO) has been used in the treatment of lung cancer [64].
MFNPs are also used as radiosensitizers in the radiation therapy and imaging [65]. Up-conversion MFNPs are used for photodynamic therapy [66].
Copper sulfide NPs have wide applications in therapeutics [67].
SPIONs with gold NPs have been used for phototherapy [68].
Graphene oxide nanosheets are loaded by magnetic iron oxide nanoparticles (mGO), followed by the technique of layer-by-layer (LbL) self-assembly for the production of chitosan/sodium alginate functionalized mGOnaocomposites. They are used in targeted anticancer drug delivery and photothermal therapy [69].
A synergistic treatment platform was developed with plasmonic-magnetic hybrid nanoparticle (lipids, doxorubicin (DOX), gold nanorods, and iron oxide nanocluster (LDGI))-loaded mesenchymal stem cells (MSCs) for the imaging and treatment of triple negative breast cancer [70].
Cold atmospheric plasma (CAP) combined with magnetic NPs has been used in the treatment of lung cancer [71].
Magnetic nanogels made of thermosensitive and biocompatible polymers and core-shell nanoparticles with a magnetic core and molecularly imprinted polymer shell are both used for cancer therapy [72].
Dual-responsive multifunctional magnetic complex micelle (sPEG/HA/CSO-SS-Hex/Fe3O4/GA) consisting of reducible hexadecanol-modified chitosan oligosaccharide polymer micelle (CSO-SS-Hex) coated with hyaluronic acid (HA) and DCA grafted sheddable PEG-PLL (sPEG) copolymers and loaded with gambogic acid (GA) and Fe3O4 nanoparticles is used for the treatment of triple negative breast cancer [73].
Polymer-coated gold-ferric oxide superparamagnetic nanoparticles have theranostic applications [74].
Hydrophilic graphene-based yolk-shell magnetic nanoparticles functionalized with copolymer pluronic F-127 (GYSMNP@PF127) produces hyperthermia and is used for cancer therapy [75].
Multifunctional iron–gold alloy nanoparticles are used for combined hyperthermia and dual stimuli-responsive drug delivery [76]. Poly lactic-co-glycolic acid (PLGA)-modified magnetic nanoplatform was synthesized with iron oxide NPs for enhanced apoptosis and therapy in human brain cancer [77].
Functionalized boron nitride nanotubes (BNNTs) are efficient tools for magnetohyperthermia treatment [78].
Gold MFNPs have significant theranostic properties. They have autophagy-based chemotherapeutic applications [79].
Nearly monodispersed magnetic Fe3O4@MTX-LDH/Au nanoparticles (NPs) containing methotrexate (MTX) produce hyperthermia and are used in cancer therapy [80].
The chemotherapeutic drug, sorafenib with PVA/SPIONs showed better anticancer efficiency than free sorafenib in the treatment of hepatocellular carcinoma [81].
Amphipathic chitosan-based nanomicelle with doxorubicin and SPIONs are used in the treatment of metastatic breast cancer [82].
Hydroxyapatite-coated iron oxide NPs are used for producing magnetic hyperthermia for the treatment of cancer cells [83].
Curcumin-loaded magnetic alginate/chitosan nanoparticles were used for therapy in MDA-MB-231 breast cancer cells [84].
6 Hybrid Nanoparticles
Hybrid NPs are formed by integrating Gd doped silicon nanoparticles (Si–Gd NPs), chlorine e6 (Ce6), doxorubicin (DOX), zeoliticimidazolate framework-8 (ZIF-8), poly(2-(diethylamino)ethyl methacrylate) polymers (HOOC-PDMAEMA-SH), and folic acid-polyethylene glycol-maleimide (MaL-PEG-FA) into one single nanoplatform. Such hybrid NPs are good theranostic agents [85].
Her2 functionalized gold-nanoshelled magnetic hybrid NPs are used as theranostic agents for dual-modal imaging and photothermal therapy of breast cancer cells. The advantages are non-invasive diagnosis and used as adjuvant therapy in SKBR3 cells [86].
7 Synthesis of Magnetic NPs
Production of sub-10 nm SPIONs is a challenging task. Several methods are available for the same. One such involves poly(ethylene glycol) (PEG) reactor adsorbed onto reduced graphene oxide nanosheets (rGO) via the microwave hydrothermal route [87].
Microrobots are small, non-invasive and can be subjected to robotic control. They are important vehicles for targeted therapy. Degradable hyperthermia microrobot (DHM) containing poly(ethylene glycol) diacrylate (PEGDA) and pentaerythritoltriacrylate (PETA) and magnetic Fe3O4 nanoparticles (MNPs) and 5-fluorouracil (5-FU) are useful agents for targeted therapy and hyperthermia [88].
8 Other NPs Producing Hyperthermia
Magnetic NPs are the main agents producing hyperthermia. However, there are some other NPs which also produce hyperthermia and hence may be used for the treatment of cancer.
Hyaluronic acid-based NPs include micelles, polymersomes, hydrogels, and nanoparticles. They bind to receptors over-expressed in certain cancers. They are important platforms for hyperthermic cancer therapy [89].
Near-infrared (NIR)-based iron oxide nanomaterials (NIR-IO) are excellent vehicles for tumor ablation and were found to have good biocompatibility and low cytotoxicity. They have great potential as theranostic agents in cancer [90].
Reactive oxygen species (ROS)-producing NPs have the natural ability to produce hyperthermia. Indeed magnetic NPs can also produce ROS by Fenton reaction and otherwise. This has been discussed earlier in this chapter [91].
Others include glutathione producing particles including ultra-small gadolinium oxide NPs. These are used for CT/MR-guided photothermal and radio-combination cancer therapy [92]. Iron-doped copper sulfide NPs also can produce hyperthermia and are used for MRI [93]. Iron-containing multifunctional nanozymes kills tumor cells efficiently [94]. Carboxymethyl chitosan (CMCS) is used as a nanodelivery system carrier for sustained intracellular release of rose bengal (RB) and doxorubicin (DOX) to achieve combinational drug treatment [95].
Magnetoliposomes containing MgFe2O4 nanoparticles are used in cancer therapy, allowing combined magnetic hyperthermia and chemotherapy [96]. Co-delivery system of (DOX/MEL)-loaded citric acid-functionalized Fe3O4 magnetic nanoparticles (CA-MNPs) is highly capable to be used in magnetically targeted cancer therapy [97].
Silk-PEI nanoparticles (SPPs) and magnetic-silk/PEI core-shell nanoparticles (MSPPs) were used for targeted delivery of c-myc antisense oligodeoxynucleotides (ODNs) into MDA-MB-231 breast cancer cells [98]. Gold nanocages (AuNCs) modified with hyaluronic acid (HA) and conjugated with anti-Glypican-1 (anti-GPC1) antibody, oridonin (ORI), gadolinium (Gd), and Cy7 dye have been used for the treatment of pancreatic cancer [99].
Folic acid (FA)-conjugated poly (lactic-co-glycolicacid) (PLGA)-polyethylene glycol (PEG) nano-noisome has been used for the treatment of cervical cancer [100]. Indocyanine green (ICG)-conjugated NPs are used for photothermaltumor therapy [101].
9 Magnetic Liposomes
Magnetic liposomes are used in cancer therapy [102]. Bacterial magnetosomes have been developed recently co-loaded with siRNA and doxorubicin, using polyethylineamine as a cross-linking agent. These nanocarriers are used in cancer therapeutics [103]. Magnetic nanoclusters have been also used for delivery of cisplatin for chemotherapy [104].
Neoadjuvantnano-photothermal therapy (NNPT) has been used in breast cancer treatment. When it is done before surgery, NNPT is found to improve the benefits of surgery [105].
Multifunctional nanohybrids have various applications in improving drug delivery of magnetic NPs [106]. Gadolinium-based nanoplatforms have been used for cancer therapy [107].
Superparamagnetic nanoparticles (SPIONs) have been coated with the amphiphilic copolymer INU-LA-PEG-FA and loaded with doxorubicin (DOXO-SPIONs) to function as smart agents for colon cancer therapy [108].
10 Ferroptosis
Iron-dependent cell death mediated by lipid peroxidation is known as ferroptosis. Fenton reaction produces reactive oxygen species, which also contributes to lipid peroxidation. Iron-based NPs can produce ferroptosis [109]. Ferroptosis is also used in the treatment of brain tumors [110]. Ferroptosis contributes to the hyperthermia in producing the effects of magnetic NPs.
11 Challenges
12 Conclusion
Various magnetic NPs have been described in the recent years. A complete description of the complete armamentarium of these species is beyond the scope of any publication. However, we have tried to focus on the latest and most important of this important group of NPs. The most important mechanism by which magnetic NPs work is by producing hyperthermia. In addition, ROS production and Fenton reaction, as well as ferroptosis, contribute to the same. There are other NPs which produce hyperthermia, but magnetic NPs are the most important among them. Future years shall reveal newer magnetic NPs, including MFNPs, with better functionalities. Indeed, as is the case with any NP, the main issue shall remain as toxicity. Once, we solve the toxicity paradox, magnetic NPs shall become one of the most important tools available to the physician for the treatment of a variety of cancers.
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Gopalakrishnan, S., Vaidyanathan, K. (2021). Magnetic Nanoparticles for Hyperthermia a New Revolution in Cancer Treatment. In: Joshy, K.S., Sabu, T., Thakur, V.K. (eds) Magnetic Nanoparticles. Gels Horizons: From Science to Smart Materials. Springer, Singapore. https://doi.org/10.1007/978-981-16-1260-2_6
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