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Synthesis and Applications of Fe3O4/SiO2 Core-Shell Materials Maria Sonmez1*, Mihai Georgescu2, Laurentia Alexandrescu2, Dana Gurau2, Anton Ficai1, Denisa Ficai1, Ecaterina Andronescu1 1
POLITEHNICA University of Bucharest, Faculty of Applied Chemistry and Material Science; 1-7 Polizu St., Bucharest, Romania; 2National Research & Development Institute for Textiles and Leather- Division: Leather and Footwear Research Institute, 93 Ion Minulescu St., Bucharest, Romania Abstract: Multifunctional nanoparticles based on magnetite/silica core-shell, consisting of iron oxides coated with silica matrix doped with fluorescent components such as organic dyes (fluorescein isothiocyanate - FITC, Rhodamine 6G) or quantum dots, have drawn remarkable attention in the last years. Due to the bi-functionality of these types of nanoparticles (simultaneously having magnetic and fluorescent properties), they are successfully used in highly efficient human stem cell labeling, magnetic carrier for photodynamic therapy, drug delivery, hyperthermia and other biomedical applications. Another application of core-shell-based nanoparticles, in which the silica is Maria Sonmez functionalized with aminosilanes, is for immobilization and separation of various biological entities such as proteins, antibodies, enzymes etc. as well as in environmental applications, as adsorbents for heavy metal ions. In vitro tests on human cancerous cells, such as A549 (human lung carcinoma), breast, human cervical cancer, THP-1 (human acute monocytic leukaemia) etc. , were conducted to assess the potential cytotoxic effects that may occur upon contact of nanoparticles with cancerous tissue. Results show that core-shell nanoparticles doped with cytostatics (cisplatin, doxorubicin, etc.), are easily adsorbed by affected tissue and in some cases lead to an inhibition of cell proliferation and induce cell death by apoptosis. The goal of this review is to summarize the advances in the field of core-shell materials, particularly those based on magnetite/silica with applicability in medicine and environmental protection. This paper briefly describes synthesis methods of silica-coated magnetite nanoparticles (Stöber method and microemulsion), the method of encapsulating functional groups based on aminosilanes in silica shell, as well as applications in medicine of these types of simple or modified nanoparticles for cancer therapy, MRI, biomarker immobilization, drug delivery, biocatalysis etc., and in environmental applications (removal of heavy metal ions and catalysis).
Keywords: Core-shell nanoparticles, silica, magnetite, drug delivery, cytotoxicity, environment. 1. INTRODUCTION The combined functionalities of cores and shells have recently brought core/shell structured nanoparticles to the attention of researchers, particularly those consisting of an iron oxide core and silica shell, which exhibit unique magnetic responsivity, low cytotoxicity, and a chemically modifiable surface [1]. The formation of core-shell structures is followed conventionally by an encapsulation process, where the paramagnetic core is encapsulated by the silica shell layer with embedded organic dyes [2] or quantum dots [3]. Therefore, iron oxides (such as -Fe2O3 or Fe3O4) have been considered ideal candidates for core-shell structures owing to their strong paramagnetic properties [4]. The core is usually a magnetic and vulnerable material such as magnetite, which is susceptible to oxidation or dissolution in acid mediums [5]. Recently, Fe3O4 nanoparticles (MNPs) have attracted much research interest for applications in biomedical fields [6], such as carriers for targeted drug delivery [7, 8], hyperthermia [9-11], therapeutic agents, biomolecules separation [12, 13], magnetic separation in microbiology and detoxification of biological fluids [14], as well as contrast agents for magnetic resonance imaging (MRI) [15], and for enviromental application the removal of organic and inorganic pollutants [16]. Due to the use of these nanoparticles in medical applications, Fe3O4 must be chemically stable, biocompatible and must have a high degree of dispersion in various liquid mediums at different pH values [17]. For these requirements to be met, various types of materials have been discovered in recent years to be used as coating materials for Fe3O4 nanoparticles, including polymers [18], noble metals [19, 20] and *Address correspondence to this author at the POLITEHNICA University of Bucharest, Faculty of Applied Chemistry and Material Science; 1-7 Polizu St., Bucharest, Romania; E-mail:
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silica [21]. Thus, the most promising and favourable coating material proved to be silica, as it not only protects magnetic nanoparticles against oxidation and agglomeration at wide pH ranges, but also improves their chemical stability. Moreover, the surface of silica is often finished with a silanol group, which can react with various chemicals and silane coupling agents to conjugate with a variety of biomolecules and specific ligands. Thus, SiO2 layers have good compatibility and hydrophilicity, indispensable properties for the use of these materials in biomedical applications [22]. The most common magnetite nanoparticle synthesis methods are the following: thermal decomposition [23], microemulsion, coprecipitation [24, 25], laser pyrolysis [26], solvothermal and sonochemical synthesis [27]. Chemical co-precipitation is the preferred route due to its advantages such as simple and easy processing operation, high yield of products with superior crystallinity and magnetic behaviors, low temperature and time of reaction and utilization of inorganic reactant. Silica coated magnetite can be modified by functionalization [28, 29], using different organosilanes as functionalizing agents as silica source [30]. Silica gel formation usually requires hydrolysis and condensation; however, Lin et al. [28] reported that when using sodium silicate as the precursor and adding acid to the solution, silica gel forms without hydrolysis. There are studies reporting that sodium silicate produced by treating rice hull ash with sodium hydroxide can be used as precursor for preparation of ionic imprinting amino modified silica [31], and sulfone modified silica [32, 33]. To make a core-shell structure, there is a major deficiency in using Fe3O4 nanoparticles obtained by co-precipitation, due to the large surface to volume ratio, high surface energy and magnetic dipole-dipole attractions between the particles, magnetic nanostructures are highly prone to aggregation. In this regard, in order to synthesize well-dispersed silica-coated MNPs, it is necessary to © 2015 Bentham Science Publishers
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modify and stabilize magnetite nanoparticles, before making coreshell nanostructures [34]. In this regard, Chang et al. [35] have reported the formation of silica layers on the surface of stabilized magnetite nanoparticles using oleic acid as surfactant. However, magnetite nanoparticles stabilized with surfactant could be used to obtain silicon coated nanoparticles, using the sol-gel method (or the Stöber method); the obtained composites are usually stained by surfactants and the coating process is difficult to control because surfactant molecules are easy to desorb from MNP by alcohol dissolution. Thus, at present, the Stöber method [36] and microemulsion, [37] are the most common methods of coating the surface of Fe3O4 nanoparticles with silica. As for the former method, the silica shells are formed through the hydrolysis and condensation of silane precursor, such as tetraethyl orthosilicate (TEOS). Due to the high hydrolysation rate of TEOS, formation of large aggregates and polydisperse products is inevitable. The microemulsion method uses micelles, which limit and control the coating of Fe3O4 core with silica. Currently, many synthesis approaches have been successfully developed to fabricate mesoporous -coated core-shell structures, for example, partial etching of silica shell to create random mesopores and calcinations with mesostructure-directing agent, noctadecyltrimethoxy-silane (C18TMS), to form disordered pore channels [38]. One general strategy for ordered mesoporous silica shells is a surfactant-templating route. 2. METHODS OF COATING MAGNETITE NANOPARTICLES WITH SiO2 Regarding silica as coating material, the two major approaches include the reverse microemulsion [39] and the sol-gel methods [40, 41]. In general, silica coating will increase the size of particles and the magnetic properties of composite NPs also will change [42]. It is noteworthy that silica thickness from 5 to 200 nm can be tuned by varying the concentration of ammonia and the ratio of tetraethoxysilane (TEOS) to water, moreover, silica coating was easily preformed on the iron oxide NPs’ surface through hydroxyl groups in the aqueous environment, especially using the Stöber method and sol-gel process. This resulted in better dispersion and less aggregation of the magnetic particles. Although there are still challenges in obtaining the magnetic composites with tunable structure and good dimension stability, many skillful approaches have been successfully employed [43]. 2.1. Stöber Methods This method is based on the hydrolysis and polycondensation of tetraethoxysilane (TEOS) in ethanol solution in the presence of water with ammonia as a catalyst, to create monodisperse, spherical, electrostatically-stabilized particles. The method can be used to coat SiO2 [44] directly onto clay minerals, hematite, zirconia and titania [45] due to the significant chemical affinity of these materials. Yongkang Sun et al. [46] have prepared superparamagnetic magnetite-silica core-shell nanoparticles for possible biological application using the Stöber method. In the first stage, they have synthesized a stable ferrofluid by modifying the surface of magnetite with citric acid. The silica coating is conveniently controlled by a dilute silicate solution pretreatment and subsequent Stober process directly in ethanol. Sachnin A. Kulkarni et al. [47] synthesize Fe3O4 coated with SiO2 using the co-precipitation method. The magnetization measurements confirm that the samples are super paramagnetic in nature. SEM analysis clearly shows that with the increase of TEOS amount, particle size also increases. Results prove that in the case of using Fe3O4/SiO2 nanoparticles, their size is uniform and almost
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monodisperse, compared to simple magnetite nanoparticles, which are agglomerated. The Stöber method is a promising method for producing surfactant free silica coatings, yet, the final particle size remains in the hundreds of nanometers to microns regime, which is too large for some of the biologic studies [48]. 2.2. Microemulsion Methods Uniformly sized MNPs can be synthesized using water-in-oil (W/O) microemulsion, an isotropic and thermodynamically stable single-phase system, with three components: water, oil and an amphiphilic molecule, called surfactant, which lowers the interfacial tension between water and oil, forming a transparent solution [49, 50]. MNPs are synthesized by mixing, precipitation reaction and aggregation processes resulting from the rapid coalescence of water nanodroplets containing reagents as nanoreactor [51]. The surfactant molecules surround the nanodroplet walls of the spherical water pool, which serve as cages for the growing particles, reducing the average size of the particles during the collision and aggregation process. The size of the water pool (W0 value, the water-tosurfactant molar ratio) is directly proportional to the size of the spherical nanoparticles, and therefore it can be changed in order to control and tune them. Mixing two identical water-in-oil microemulsions containing the desired reactants leads to microdroplets continuously colliding, coalescing and breaking, eventually forming a precipitate in the micelles [46, 52]. In reverse microemulsion, aqueous solution disperses in the organic phase, inside the self-assembly reverse micelles, forming several monodisperse nano-droplets. The advantage of the confined nanoreactor environment within the reverse micelle is that it yields highly monodisperse NPs and increases the incorporation of nonbonded non-polar molecules, which are often difficult to incorporate into the hydrophilic silica matrix [53]. To synthesize iron nanoparticles coated with uniformly thick layers of silica, the method of microemulsion is required (also known as water in oil). The microemulsion method has three main components: water, oil and surfactant. Using the reverse microemulsion, magnetite nanoparticles coated with uniformly thick silica layers were synthesized - approximately 1. 8-30 nm. In this method, micelles or reverse micelles are used as mini-reactor, to control the deposition of silica layers on magnetic nanoparticles. This method requires tedious steps to separate the magnetic nanoparticles from the surfactants in the microemulsion system. Jianping Yang et al. [54] develop dendritic mesoporous silica encapsulated magnetic nanospheres with radially oriented, large open, and controllable pore size (5. 7-10. 3 nm) and shell thickness (40-100 nm) are fabricated through an effective oil-water biphase stratification coating strategy. A methodology for the synthesis of both uncoated and silicacoated ultrasmall ( 500 nm [139]. Suh Cem Pang et al. [140] report a simple and efficient method for obtaining Fe3O4/SiO2/TiO2 core-shell nanoparticles using the sol-gel method coupled with ultrasound. Fe3O4 nanoparticles were encapsulated inside SiO2 nanospheres for 90 minutes. SiO2 nanospheres were then coated with a TiO2 layer using titanium (IV) isopropoxide (TIPP) as precursor and the sol-gel method. Transmission electron microscopy (TEM) proves that Fe3O4 nanoparticles were uniformly encapsulated in the SiO2 matrix and Fe3O4/SiO 2 core-shell nanoparticle size is approximately 120nm. The area of the specific surface of Fe3O4/SiO2/TiO2 nanoparticles measured by BET is approximately 138m2/g. Photocatalytic properties of Fe3O4/SiO2/TiO2 core-shell nanoparticles were established by degradation of methylene blue (MB) dye carried out in the presence and absence of UV light irradiation. It was noticed that, without irradiation, the concentration of MB dye remained almost constant in the first 24 hours in the case of using Fe3O4/SiO2 nanoparticles, and with irradiation, it was 20%. The degradation of MB dye was substantially enhanced by the addition of Fe3O4/SiO2/TiO2 coreshell nanoparticles with its concentration being degraded by up to 70% with UV irradiation. Greene David et al. [141] obtain CoFe2O4/SiO2/TiO2 core-shell magnetic nanostructures which have been prepared by coating of cobalt ferrite nanoparticles with the double SiO2/TiO2 layer using metallorganic precursors. New CoFe2O4/SiO2/TiO2 core-shell magnetic nanostructures are used as catalyst for methylene blue dye photo-oxidation. Titania/silica coated cobalt ferrite nanoparticles have been prepared by hydrolysis of titanium tetrabutoxide precursor in the presence of silica coated cobalt ferrite nanoparticles. The presence of thermally stable cobalt ferrite core enabled us to perform sintering of the CoFe2O4/SiO2/TiO2 core-shell nanostructures
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at 600°C in order to produce photocatalytically active anatase and rutile forms of TiO2. The photocatalytic degradation of organic compounds of olive mill wastewater (OMWW) was investigated by Yana Ruzmanova et al. [142] using core-shell-shell Fe3O4/SiO2/TiO2 nanoparticles as catalyst. The photo degradation process was optimized by using 1. 5 g/L core-shell-shell nanoparticles. The obtained results showed a high activity of synthesized nanoparticles for photocatalytic degradation of the OMWW organic compounds. Moreover, the recovery of the magnetic core photo catalyst by using a magnetic trap was proven. CONCLUSION In the last years, integrating nanotechnology with molecular biology and medicine has led to the emergence of a new developing research field, that brings significant advantages to current diagnosis and treatment methods. The most common types of multifunctional nanoparticles in this field are core-shell structures. They are known as the new generation of nanoparticles, combining components with different functionalities into a single unique entity, thus taking advantage of their synergy in various applications in medicine and environmental protection. Thus, magnetite nanoparticles (MNPs) are among the most common structures used as core to obtain core-shell system due to their superparamagnetic properties, while also having high magnetic susceptibility. However, metal oxides tend to agglomerate and have a low chemical stability in various biological mediums and require stabilization. The most promising coating material for magnetite nanoparticles is silica, because it has the role of preventing aggregation of nanoparticles in a wide range of pH, provides chemical stability, good biocompatibility and hydrophilicity, and the silanol group at the silica surface can react with silane coupling agents, and, as a result, it can be conjugated with different biomolecules, ligands etc., for use in various biomedical applications and in removal of metal ions. The literature abounds in papers dealing with magnetite/silica core-shell NPs and particularly those with application in medicine (bioimaging, cell targeting, bioseparation, MRI, drug delivery etc.). The efficient use of core-shell nanoparticles for biomedical applications, such as targeted drug delivery depends on a series of factors concerning size, magnetism, physical-chemical properties of the loaded drug, field intensity and geometry, depth of the target tissue, blood rate flow etc. , all these playing a key role in the effectiveness of the drug delivery method. Thus, many research studies have focused on testing core-shell structures on various human cancer cells, such as A549 (human lung carcinoma), breast, human cervical cancer, THP-1 (human acute monocytic leukaemia), etc. Results prove that core-shell structures based on magnetite-silica doped with cytostatics are easily adsorbed by cancer cells and in some cases lead to the inhibition of cell proliferation and cell death by apoptosis. However, in the case of studying in vitro cytotoxicity of simple and SiO2-coated iron oxide nanoparticles on A549 (human lung carcinoma) and HeLa (human cervix carcinoma) cells, the results indicate that simple magnetite nanoparticles have high toxicity while silica-coated magnetite improves particle stability in biological mediums and reduces toxicity and genotoxic effects. This proves that surface chemistry plays a vital role and requires special attention in the case of using these nanoparticles in biological applications and reduction of toxicity. Current clinical investigations on cancer treatment by combined techniques such as chemo- and thermotherapy prove that the combination of these two types of therapies often has incongruous therapeutic effectiveness, because the thermotherapy and drugs do not take effect simultaneously in the same tumorgenic regions. To assess risks involved in testing these devices in vitro or in vivo, few authors have subjected core-shell materials to in-depth
Synthesis and Applications of Fe3O 4/SiO2 Core-Shell Materials
cytotoxicological studies and none to batch-to-batch reproducibility. The drug production process must be controlled and reproducible, to ensure that nanomaterials contained in the medical device are rigorously identical. It is the only way to ensure that subsequent biological risk assessment of the medical device containing nanomaterials is viable for all batches. However, the literature is full of different and inconsistent results from one laboratory to another and therefore, from batch to batch. Many research projects have tried to fill the voids regarding the potential toxicity of nanostructures, but the knowledge we have so far is incomplete. The surface chemistry of NP was proven of crucial importance for protein adsorption and its effect on cell toxicity. Methodologies of characterization and development of all aspects regarding the potential toxicity of precursors are not yet fully elucidated. Inter-laboratory data interpretation is still difficult, partly due to the lack of nanostructures and reference protocols, while the relevance of toxicological tests used for conventional materials have not yet been established and validated for nanomaterials. Therefore, adding these technical deficiencies to the incoherence and variations from batch to batch, assessment of biological risks in using these nanostructures as precursors remains an open issue. CONFLICT OF INTERESTS The authors declare that there is no conflict of interests regarding the publication of this paper. ACKNOWLEDGEMENTS The work has been funded by the Sectoral Operational Programme Human Resources Development 2007-2013 of the Ministry of European Funds through the Financial Agreement POSDRU/159/1. 5/S/134398. REFERENCES [1] [2] [3] [4]
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Accepted: September 16, 2015
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