Physical and magnetic properties of iron oxides [22].
\r\n\tIn the book the theory and practice of microwave heating are discussed. The intended scope covers the results of recent research related to the generation, transmission and reception of microwave energy, its application in the field of organic and inorganic chemistry, physics of plasma processes, industrial microwave drying and sintering, as well as in medicine for therapeutic effects on internal organs and tissues of the human body and microbiology. Both theoretical and experimental studies are anticipated.
\r\n\r\n\tThe book aims to be of interest not only for specialists in the field of theory and practice of microwave heating but also for readers of non-specialists in the field of microwave technology and those who want to study in general terms the problem of interaction of the electromagnetic field with objects of living and nonliving nature.
",isbn:"978-1-83968-227-8",printIsbn:"978-1-83968-226-1",pdfIsbn:"978-1-83968-228-5",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"8f6a41e4f5ce0e9c48628516d7c92050",bookSignature:"Prof. Gennadiy Churyumov",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10089.jpg",keywords:"Electromagnetic Wave, Microwave Energy Application, Electromagnetic Energy Generation, Intelligent Microwave Heating, Microwave Organic Chemistry, Microwave Reactor, Microwave Discharge, Microwave Plasma, Microwave Drying System, Tissue Microwave Heating, Measurement Automation, Industrial Microwave Process",numberOfDownloads:224,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"July 3rd 2020",dateEndSecondStepPublish:"July 24th 2020",dateEndThirdStepPublish:"September 22nd 2020",dateEndFourthStepPublish:"December 11th 2020",dateEndFifthStepPublish:"February 9th 2021",remainingDaysToSecondStep:"7 months",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:"Prof. Gennadiy I. Churyumov is a professor at two universities: Kharkiv National University of Radio Electronics, and Harbin Institute of Technology and a senior IEEE member.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"216155",title:"Prof.",name:"Gennadiy",middleName:null,surname:"Churyumov",slug:"gennadiy-churyumov",fullName:"Gennadiy Churyumov",profilePictureURL:"https://mts.intechopen.com/storage/users/216155/images/system/216155.jfif",biography:"Gennadiy I. Churyumov (M’96–SM’00) received the Dipl.-Ing. degree in Electronics Engineering and his Ph.D. degree from the Kharkiv Institute of Radio Electronics, Kharkiv, Ukraine, in 1974 and 1981, respectively, as well as the D.Sc. degree from the Institute of Radio Physics and Electronics, National Academy of Sciences of Ukraine, Kharkiv, Ukraine, in 1997. \n\nHe is a professor at two universities: Kharkiv National University of Radio Electronics, and Harbin Institute of Technology. \n\nHe is currently the Head of a Microwave & Optoelectronics Lab at the Department of Electronics Engineering at the Kharkiv National University of Radio Electronics. \n\nHis general research interests lie in the area of 2-D and 3-D computer modeling of electron-wave processes in vacuum tubes (magnetrons and TWTs), simulation techniques of electromagnetic problems and nonlinear phenomena, as well as high-power microwaves, including electromagnetic compatibility and survivability. \n\nHis current activity concentrates on the practical aspects of the application of microwave technologies.",institutionString:"Kharkiv National University of Radio Electronics (NURE)",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"2",totalChapterViews:"0",totalEditedBooks:"0",institution:null}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"24",title:"Technology",slug:"technology"}],chapters:[{id:"74623",title:"Influence of the Microwaves on the Sol-Gel Syntheses and on the Properties of the Resulting Oxide Nanostructures",slug:"influence-of-the-microwaves-on-the-sol-gel-syntheses-and-on-the-properties-of-the-resulting-oxide-na",totalDownloads:94,totalCrossrefCites:0,authors:[null]},{id:"75284",title:"Microwave-Assisted Extraction of Bioactive Compounds (Review)",slug:"microwave-assisted-extraction-of-bioactive-compounds-review",totalDownloads:12,totalCrossrefCites:0,authors:[null]},{id:"75087",title:"Experimental Investigation on the Effect of Microwave Heating on Rock Cracking and Their Mechanical Properties",slug:"experimental-investigation-on-the-effect-of-microwave-heating-on-rock-cracking-and-their-mechanical-",totalDownloads:28,totalCrossrefCites:0,authors:[null]},{id:"74338",title:"Microwave Synthesized Functional Dyes",slug:"microwave-synthesized-functional-dyes",totalDownloads:21,totalCrossrefCites:0,authors:[null]},{id:"74744",title:"Doping of Semiconductors at Nanoscale with Microwave Heating (Overview)",slug:"doping-of-semiconductors-at-nanoscale-with-microwave-heating-overview",totalDownloads:45,totalCrossrefCites:0,authors:[null]},{id:"74664",title:"Microwave-Assisted Solid Extraction from Natural Matrices",slug:"microwave-assisted-solid-extraction-from-natural-matrices",totalDownloads:25,totalCrossrefCites:0,authors:[null]}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"252211",firstName:"Sara",lastName:"Debeuc",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/252211/images/7239_n.png",email:"sara.d@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. 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by",editors:[{id:"4782",title:"Prof.",name:"Bishnu",surname:"Pal",slug:"bishnu-pal",fullName:"Bishnu Pal"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"60330",title:"Preclinical Aspects on Magnetic Iron Oxide Nanoparticles and Their Interventions as Anticancer Agents: Enucleation, Apoptosis and Other Mechanism",doi:"10.5772/intechopen.74176",slug:"preclinical-aspects-on-magnetic-iron-oxide-nanoparticles-and-their-interventions-as-anticancer-agent",body:'Due to the wide potential of applications in various fields, such as biotechnology, biomedicine, magnetic fluids, catalysis, magnetic data recording and storage media, magnetic resonance imaging, magnetic fluid hyperthermia, magnetic drug delivery, cell separation, magnetic paper and more recently in environmental protection, magnetic iron oxide nanoparticles (M-IONPs) are the main components of the modern technology [1–15]. In nature, many forms of iron oxides are found, but the most technologically used are the magnetite (Fe3O4), maghemite (γ-Fe2O3) and hematite (α-Fe2O3) (Figure 1).
Crystal structure of: A—hematite, B—maghemite and C—magnetite (the blue sphere is Fe2+/Fe3+ and the red sphere is O2−). The structures were adapted after the structures found in the Crystallography Open Database (http://www.crystallography.net).
Magnetite (Fe3O4), a natural mineral known as the black iron oxide, is relatively stable at room temperature, very quickly transforms in maghemite and shows the strongest magnetism compared to other transition metal oxides [16]. Fe3O4 has an inverse spinel structure with all the Fe2+ ions and half of the Fe3+ ions distributed in the octahedral sites and the other half of the Fe3+ ions distributed in the tetrahedral sites being surrounded by four oxygen atoms [17].
Spin magnetic moments of Fe3+ ions distributed in octahedral positions are parallely aligned, as well as those of Fe3+ ions distributed in tetrahedral positions but in the opposite direction, leading to an antiparallel coupling. Therefore, the spin moments of all Fe3+ ions mutually cancel out and do not contribute to the net magnetization of magnetite (Figure 2). All Fe2+ ions have magnetic moments aligned in the same direction so that their total magnetic moment is responsible for the net magnetization of magnetite. Therefore, the saturation magnetization of magnetite corresponds to the product between the spin magnetic moment of each Fe2+ ion and the number of Fe2+ ions, which corresponds to the mutual alignment of all Fe2+ ions in magnetite.
Spin magnetic moment distribution of Fe2+ and Fe3+ ions in the elemental cell of magnetite.
Magnetite is oxidized in the presence of air to maghemite, which is also ferrimagnetic, but has a slightly lower magnetic response. This process is called maghemitization and occurs at the surface of the crystals. Crystal centers are also oxidized, and the process is being carried out by diffusion of Fe2+ ions from inside to the surface of the crystals, where they are converted to Fe3+. The rate of the oxidation process is determined by the diffusion rate of Fe2+ ions and the distance to the surface. Therefore, the particles remain unaffected by the phenomenon of maghemitization, while the small ones are susceptible to oxidation even at room temperature.
As magnetite, maghemite (γ-Fe2O3) has a spinel structure with the oxygen ions disposed in a closely packed cubic lattice and the iron ions located at interstices. In γ-Fe2O3 not all the sites are occupied, Fe3+ ions are regularly distributed in only two-thirds of the sites and the rest of the sites remain vacant. After two sites filled with Fe3+ ions follows one vacant site [18, 19]. Maghemite is a metastable oxide, product of magnetite oxidation or a product resulting from the heating of other iron oxides.
At temperatures over 300°C, magnetite is oxidized to hematite (α-Fe2O3)—an anti-ferromagnetic iron oxide. Hematite (α-Fe2O3) has a corundum crystal structure with Fe3+ ions distributed in octahedral sites and oxygen ions in hexagonal close-packed arrangement. α-Fe2O3, the final product of the transformation of other iron oxides, is a red powder when it is finely divided, very stable at room temperature and very widespread in rocks and soils (Table 1) [20, 21].
Property | Oxide | ||
---|---|---|---|
Magnetite | Maghemite | Hematite | |
Molecular formula | Fe3O4 | γ-Fe2O3 | α-Fe2O3 |
Color | Black | Reddish-brown | Red |
Density (g/cm3) | 5.18 | 4.87 | 5.26 |
Melting temperature (°C) | 1583–1597 | — | 1350 |
Hardness | 5.5 | 5 | 6.5 |
Type of magnetism | Ferrimagnetic | Ferrimagnetic | Weakly ferromagnetic/anti-ferromagnetic |
Curie temperature (K) | 858 | 820–986 | 956 |
Saturation magnetization (Ms) at 300 K [A·m2/kg] | 92–100 | 60–80 | 0.3 |
Standard Gibbs free energy of formation ( | −1012.6 | −711.1 | −742.7 |
Crystallographic system | Cubic | Cubic or tetrahedral | Rhombohedral, hexagonal |
Structure type | Inverse spinel | Defect spinel | Corundum |
Lattice parameter (nm) | α = 0.8396 | α = 0.83474 (cubic); α = 0.8347; c = 2.501 (tetragonal) | α = 0.5034; c = 1.375 (hexagonal); αRh = 0.5427; α = 55.3° (rhombohedral) |
Physical and magnetic properties of iron oxides [22].
Magnetic iron oxide nanoparticles (M-IONPs), magnetite (Fe3O4) and maghemite (γ-Fe2O3) are materials with iron-magnetic properties under their Curie temperatures (858 K and 986 K) (Table 1). The ferro- and ferrimagnetic compounds in their raw state present a multidimensional magnetic structure, without a permanent magnetic moment. The magnetic properties of a material depend on following parameters: (i) temperature, (ii) pressure and (iii) applied magnetic field. The properties of iron oxide nanoparticles by their usual sizes are not similar to the properties of larger scale compounds, which explain their use and interest in nanomedicine [23]. In order to define the behavior of the magnetic field, the key lays in the size and distribution of nanoparticles morphology [24]. A spherical, small nanoparticle made of soft materials with a diameter below the domain size shows an expendable magnetic anisotropy, so that their magnetic moment is free to rotate relatively to the particle and is thus superparamagnetic, i.e., paramagnetic under the Curie temperature [25]. The direction of the magnetic moment of the nanoparticles is determined by thermal fluctuation and the magnetic anisotropy, which tend to fixate on the crystalline structure or particle morphology [26].
The interaction between an external magnetic field and the magnetic field of a nanoparticle determines: (i) the orientation of the magnetic moment of the particle as to become parallel with the magnetic field applied to minimize energy and bipolar interaction and (ii) the transition of the particle in the direction of the gradient, as in magnetophoresis [26]. Many applications of the magnetic nanoparticles are based on their ability to be manipulated using magnetic fields. This capability depends on the effectiveness of the magnetophoretic force, determined by the time of the particle and the magnetic field gradient, to fasten or to move the particle [25]. The magnetophoretic force exercised over superparamagnetic nanoparticles with a single core is less effective due to their small diameter and magnetic moment, but in the case of multicore particles, the magnetic momentum induced in the field is strong enough to allow magnetic targeting to moderate values of the magnetic field intensity and field gradient. Therefore, in order to assess the applicability of magnetic particles or magnetic fixing, the magnetic momentum of the particles is more relevant than mass magnetization [25, 27].
The size and the size distribution of superparamagnetic iron oxide nanoparticles are important parameters for their biological application. Also, their magnetic properties are in close touch with their size. It has been demonstrated that the magnetic dipole-dipole interactions are significantly reduced in superparamagnetic iron oxide nanoparticles due to their scale of r6, r being the radius of the particle [28]. The advantages of using magnetic nanoparticles with sizes smaller than 100 nm are due to their surface efficiency to easily attach ligands and small settling velocities which give a high stability in suspension and improve tissue diffusion. Particles should be small enough to bypass the endothelial reticule system. They are supposed to remain in circulation after injection and be able to pass through the capital systems, organs and tissues, avoiding the embolus. Particle size is also important for getting an effect of improved permeability and retention. For example, particles larger than 10 nm may not penetrate the endothelium in physiological conditions, but can enter in pathological conditions, such as inflammations or tumors [28].
When magnetic nanoparticles loaded with medicinal substances are injected into the systemic circulation, size, morphology and surface charge are the three important parameters for their behavior in the bloodstream. Kupffer cells in the liver are very sensitive to both microorganisms and nanoparticles. Plasma proteins can easily adsorb onto their surface nanoparticles, depending on their size, surface charging and their morphology. Particles with sizes larger than 200 nm or below 10 nm are not suitable due to their absorption by the endoplasmic reticulum system [28].
Loading surface and biodistribution of superparamagnetic iron oxide nanoparticles play an important role in the colloidal stability. Surface charging can be described qualitatively by the nature and behavior of surface groups in the solution at a given pH and in the presence of an electrolyte. In terms of quantity, it can be measured as an electric potential in the double layer of the interfacial surface of the nanoparticles found in a suspension state. A high value of zeta potential is an indication of stability in dispersion of superparamagnetic iron oxide nanoparticles due to electrostatic interaction. Composition and structure of nanoparticles are very important for their interaction with biological fluids. In a known environment, superparamagnetic nanoparticle characteristics, such as the chemical composition, both core and neural crest cells, its size and size distribution, shape and angles of curvature, its crystalline structure, smoothness or surface roughness and hydrophobic or hydrophilic levels, are important for their in vivo applications. These features can determine their stationary time in the circulatory system [28].
Osaka and his colleagues [29] have reported a correlation between surface charge of magnetite nanoparticles and their cellular absorption efficiency on different cell lines. For example, a superparamagnetic particle with positive charge showed a greater internalization in human breast cancer cells in comparison with those charged negatively, while there was no difference in the degree of internalization in endothelial cells of human umbilical bladder. Thus, the superparamagnetic nanoparticles absorption depends not only on their surface properties but also on cell type.
Both the surface chemistry of magnetite particles and its properties are particularly important in various applications. Iron atoms at the surface of the magnetite particle that are not bound to oxygen atoms act as Lewis acids and coordinate the molecules that can give a pair of electrons. In aqueous systems, these atoms coordinate water molecules that rapidly dissociate resulting magnetite with functionalized surface with Fe-OH hydroxyl groups. So, the chemistry of the surface of magnetite particles is strongly dependent on the pH value; at low pH values, the surface of the magnetite particles is protonated (positively charged), and at high pH values, it is negatively charged (Figure 3). The preformed hydroxyl groups on the surface of magnetite have amphoteric character; therefore, they can react either as acids or bases [30].
The behavior of Fe3O4 nanoparticles depending on pH.
Another problem that arises after obtaining the magnetic iron oxide nanoparticles (M-IONPs) is their agglomeration that is installed due to the van der Waals forces and the magnetic forces. Nanoparticles without coatings (naked nanoparticles) are not stable in aqueous environments, easily aggregating and precipitating. After application in vivo, nanoparticles often form aggregates in the bloodstream and are retained by the macrophages. Therefore, they must be covered with a variety of fragments which have the property to eliminate or minimize their aggregation in physiological conditions [31]. The magnetic nanoparticles are coated with an impervious wrapper so that oxygen does not reach at the surface of the magnetic nanoparticles in order to ensure an effective stabilization of iron oxide nanoparticles. Some stabilizers, such as a surfactant or a polymer, usually are added during preparation to prevent the aggregation of nanosized particles. Most of these polymers stick to the nanoparticles surface in a specific substrate manner. Nanoparticle surfaces can be composed of several organic and inorganic materials, including polymer. Also, polymer coating materials can be classified in turn into synthetic and natural. Polymers such as poly-ethylene-co-vinyl acetate, poly-vinylpyrrolidone, poly-acid-lactic-co-glycolic, polyethylene glycol, etc. are typical examples of synthetic polymeric systems. Natural polymer coatings include gelatin, dextran, chitosan, etc. The molecules used for stabilization of magnetic nanoparticles must be biocompatible and biodegradable. The most common surfactant molecules are oleic acid, lauric acid, acids, sulfonic acids, alkanes and alkane phosphonates. The surfactants are amphiphilic compounds and they manifest their role at the interface between nanoparticles and solvent. However, magnetic nanoparticles covered with organic compounds, in suspension cannot be used for biological purposes, especially in the delivery of medicines. Changing the surface of nanoparticles post-synthesis is known as core-shell nanoparticles, also used widely. The most commonly used materials are polymers, silica or metals (e.g. gold, cadmium, selenium, silver). Coating materials protect the core against oxidation and therefore keep the magnetic property of nanoparticles. It is known that the iron oxide nanoparticles are non-toxic, but some coating materials may be toxic. For example, silicon dioxide is biocompatible, but is not biodegradable [28].
Many researchers have prepared magnetic nanoparticles covered with various surfactants or biomolecules that have been introduced directly in the synthesis process. For example, Salavati-Niasari et al. [32] have synthesized Fe3O4 nanoparticles covered with octanoic acid using a facile chemical precipitation method. The surfactant was present in the reaction system to improve dispersity. The authors have obtained magnetic nanoparticles with a size range of 25 nm. Liu et al. prepared magnetic nanoparticles coated with chitosan, for the immobilized lipase, using the co-precipitation method. They replaced water with 2% chitosan in acetic acid solution during the reaction process [33].
Atomic transfer radical polymerization (ATRP) is another common way to cover magnetic nanoparticles, developed by Wang et al. [34]. Due to the magnetic interaction of the iron oxide nanoparticles with biological fluids, the process of formation of free radicals of oxygen reactive species may be increased. To protect the environment in vivo from these toxic by-products, some materials have been used for biocompatible and rigid coatings, such as gold [28].
In the past decade, numerous synthesis methods have been developed to obtain M-IONPs. On the basis that the method of preparation plays an essential role in obtaining nanoparticles with tailored properties, the research work regarding the development of new synthesis methods to control the size, shape, morphology and magnetic properties of these nanoparticles is a permanent challenge. In the same time, the synthesis method has to be environmentally friendly, simple, inexpensive and reproducible. Many scientific publications have described efficient synthesis methods, which allow the obtaining of monodisperse magnetic nanoparticles, stable for a long time with controlled shape.
The synthesis method has to ensure the obtaining of magnetic nanoparticles with specific properties to their application domain by changing the experimental reaction conditions. For biomedical applications, superparamagnetic iron oxide nanoparticles with a specific surface chemistry (for in vivo applications), high magnetization values and a narrow size distribution of the particles with size below 100 nm are needed. Magnetite (Fe3O4) and maghemite (γ-Fe2O3) have attracted particular attention because, under certain synthesis conditions, they are superparamagnetic, being also biocompatible, thus becoming the magnetic nanomaterials most commonly used in medical applications.
Hereinafter, the most popular synthesis methods used for obtaining M-IONPs will be described. After the chemical surface modification of magnetic nanoparticles by binding drugs, proteins, enzymes, antibodies, etc., they can be directed to an organ, tissue or tumor with the help of an external magnetic field. The methods described below allow to obtain magnetic nanoparticles with narrow size dimensions, desired shape and morphology, by changing the conditions and/or parameters of the synthesis. The most used and popular method for the synthesis of magnetite, being in the same time simple and efficient, is the chemical precipitation of iron salts [35–39].
The first synthesis of superparamagnetic iron oxide nanoparticles was reported by Massart, and the method consists in mixing two salts of Fe3+ and Fe2+ in a molar ratio of 2:1 in aqueous medium followed by precipitation of these salts using a precipitating agent (a base – NH3) under inert atmosphere or at elevated temperature, resulting a black magnetic precipitate [40]. The equation of the chemical reaction which underlies the formation of magnetite may be written as Eq. (1):
Magnetite is not stable at room temperature, being sensitive to oxidation in contact with air, easily transforming into maghemite, according to Eq. (2):
The precipitation process is based on two steps regarding the formation of the solids [41, 42]: (i) nucleation—a very short period, occurs only when the concentration of the constituent species reaches suprasaturation and (ii) slow controlled growth of the preformed nuclei, by diffusion from the solutions to the surfaces of the crystal. To avoid the formation of polydispersed nanoparticles, it is necessary that the two stages to be separated, i.e., nucleation does not take place simultaneously with crystal growth. By controlling the two processes, monodispersed magnetic particles can be obtained. If the nuclei start to form in the same time, the growth of these nuclei leads to particles with very narrow size distribution. Therefore, the size of the obtained particles can be controlled but only in the nucleation step because the size of the particles does not change during the growth process.
It has been shown that by controlling both the pH of the reaction medium and the ionic strength, it is possible to control the mean size of the particles. Jiang et al. have demonstrated that the size of the particles has an inverse proportionality with the pH and the ionic strength of the precipitation medium [43]. These two parameters (pH and the ionic strength) also affect the chemical surface of the crystals and the electrostatic surface charge [44].
Other parameters that can influence the size, shape and composition of the magnetic iron oxide nanoparticles are the nature of iron salts (chlorides, perchlorates, nitrates, sulfates, etc.) and the molar ratio Fe3+/Fe2+. Roth and co-workers published a good analysis regarding the influence of the reaction conditions on the formation of superparamagnetic iron oxide nanoparticles. The authors demonstrated that for obtaining particles with a size between 3 and 17 nm with high saturation magnetization a higher reaction temperature, higher iron salt concentration, Fe3+/Fe2+ molar ratio below 2 and a molar ratio of hydroxide ions/iron ions of 1.4:1 are needed [45].
Wu et al. investigated the effect of the vacuum drying method on the change of the morphology and magnetic properties of magnetic iron oxide nanoparticles (M-IONPs). They revealed that the obtained nanoparticles tend to agglomerate more easily when their average diameter decreased, but the structure and morphology are maintained better by ambient air drying. They also obtained magnetic nanoparticles with high saturation magnetization after drying the obtained nanoparticles in a vacuum at 70°C [36].
The same group of researchers in another study has synthesized Fe3O4 nanoparticles by utilizing ultrasonic-assisted chemical co-precipitation. They used high purity iron separated from iron ore tailings by an acidic leaching method and obtained superparamagnetic iron oxide nanoparticles without a protecting gas [46]. Pereira and co-workers have synthesized superparamagnetic Fe3O4 nanoparticles with small particle size (4.9–6.3 nm) and improved magnetic properties by one-step aqueous precipitation route based on the use of a new type of alkaline agents [47]. The alkaline agents that they have used include alkanolamines, isopropanol amine and diisopropanolamine. The base that they have used, instead of the most used—NaOH, leads to smaller particle sizes (up to 6 times) and enhanced saturation magnetization (up to 1.3 times). Generally, the size of the particles is proportionally with the magnetization saturation, but the above results showed improved magnetic properties while keeping their small size.
Besides the many advantages of the precipitation method (high saturation magnetization, rapid synthesis with high yield, versatility, nanoparticles with the desired morphology and characteristics), it shows several disadvantages, like oxidation, magnetic nanoparticles with particle size distribution that cannot be controlled, polydispersion and weak crystallization which leads to nanoparticles with low saturation magnetization.
Thermal decomposition of organometallic compounds in high boiling organic solutions in the presence of stabilizers is also a popular method for the synthesis of the spinel structured Fe3O4 and a very promising technique for obtaining high-quality superparamagnetic iron oxide nanoparticles. The magnetic nanoparticles obtained by this method proved to be superior to those obtained by precipitation, because the nucleation process can be separated by the growth process and the hydrolysis reaction is avoided [48].
The method is based on the decomposition of an iron precursor at high temperature in the presence of solvents which contain stabilizing surfactants (such as oleic acid or oleylamine) [49–51]. By varying the reaction mixtures and modifying the synthesis condition, it can be obtained M-IONPs with controlled size, size distribution and composition. The most commonly used precursors employed to prepare monodispersed M-IONPs with diameter ranging from 3 to 50 nm are of the form: (I) metal acetylacetonate—[M(acac)n] (where M = Fe, Co, Ni, Mn, Cr; n = 2 or 3) [52]; (II) metal cupferronates—[Mx(cup)x] (where cup = N-nitrosophenylhydroxylamine); (III) metal oxalate—[M(C2O4)n•2H2O]; (IV) metal carbonyl—Fe3(CO)12 [53] or Fe(CO)5 [50]; (V) metal acetate—[M(CH3COO)n]; (VI) metal carboxylate, (VII) metal-urea complex—[Fe(CON2H4)6](NO3)3 [54]; (VIII) Prussian Blue—Fe4[Fe(CN)6•14H2O] [55, 56]; (IX) metal chloride and (X) ferrocene—Fe(C2H5)2 [57].
Using the thermal decomposition method, it can be easy to control the size and morphology of magnetic nanoparticles by controlling the ratio of the starting reagents, i.e. the ratio between the organometallic compounds, surfactant and solvent. Reaction time, temperature and aging period are equally important for the control of size and morphology. Hyeon obtained monodispersed iron oxide nanoparticles with size range from 4 to 20 nm by thermal decomposition of Fe(CO)5 in the presence of oleic acid at 100°C. Initially, he obtained an iron-oleic acid complex, which was leaved to aging at high temperature (300°C) [50].
Pérez-Mirabet et al. used oleylamine both as stabilization agent (for the stabilization of the particles in solution) and as capping ligand (for the control of particles size), respectively, by one-pot thermal decomposition of Fe(acac)3 and M(acac)2 (M = Co, Mn, Cu and Zn) in oleylamine. They obtained magnetic spinel ferrite nanoparticles with average size of 12 nm and a saturation magnetization Ms = 76 emu/g, very close to the bulk magnetite (92 emu/g) [58].
This method is also suitable for synthesis of nanocubes and nanospheres, which are magnetic nanoparticles as well. Amara et al. synthesized Fe3O4 nanocubes and nanospheres by a new simple and single-step process [59]. They used various mixtures of ferrocene and polyvinylpyrrolidone (PVP) by solventless thermal decomposition. Lynch et al. obtained magnetic colloidal iron oxide nanoparticles by thermal decomposition. They generated gas bubbles (Ar) by boiling solvents. Their results illustrated that the argon bubbles had a stronger effect on the nucleation process of magnetic iron oxide nanoparticles than on their growth process [60]. Due to the nucleation process that involves boiling solvents, most often the accurate shape of the magnetic iron oxide nanoparticles is not fully reproducible using the thermal decomposition method.
A microemulsion is formed when a colloidal substance is dispersed in a solvent, that is not compatible with the substance (e.g. water and oil), through a surfactant. Finally, a microemulsion must be clear and stable, as long as it is an isotropic mixture of oil, water and surfactant. The surfactant forms a monolayer film at the oil/water interface, in which the hydrophilic head groups of the surfactant are dissolved in oil phase (consisting of a mixture of hydrocarbons and olefins) and the hydrophobic tail of the surfactant in the aqueous phase (consisting of metal salts) and vice versa, depending on the used surfactant. There are known two types of microemulsion: direct microemulsion, when the oil is dispersed in water and reversed microemulsion, when the water is dispersed in oil. Both have been used to synthesize the magnetic iron oxide nanoparticles with tailored size and shape. The most common surfactants that are widely used in the fabrication of M-IONPs by microemulsion method are bis(2-ethylhexyl) sulfosuccinate (AOT), sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB) and poly-vinylpyrrolidone (PVP). Throughout time, the microemulsion method proved to be a simple and versatile method for fabrication of nanosized magnetic nanoparticles [61–65].
According to the literature, the size of the resulted nanoparticles can be controlled if the surfactant is proper chose and also by varying the ratio of water/oil/surfactant, the initial concentration of the reactants and the droplet size and by controlling the reaction temperature and time [66, 67]. The size of the synthesized nanoparticles can also be controlled in suitable narrow range by carrying out the reaction in nanoreactor [62, 64, 67].
Lu et al. demonstrated that the surfactant nature has an important role on the final properties of the nanoparticles [64]. The authors have investigated the effect of SDS (anionic surfactant), DTAB and CTAB (cationic surfactants) and non-ionic surfactant on the preformed crystal, on stoichiometric situations and on the magnetic properties of the resulted Fe3O4 nanoparticles. In all the cases, the authors have obtained Fe3O4 nanoparticles with size less than 16 nm, but in the case of using the cationic surfactants also obtained a good saturation magnetization, which is an essential parameter for biological applications.
Okoli et al. have prepared M-IONPs by the two types of microemulsion (water/oil and oil/water), to be used in binding and separation of proteins. The authors demonstrated that by using a water/oil microemulsion, it can obtain magnetic iron oxide nanoparticles with a surface area of 147 m2/g compared to 304 m2/g for the magnetic nanoparticles obtained by oil/water microemulsion [68, 69]. The M-IONPs specific surface area is inversely proportional with the size of nanoparticles, the higher is the specific surface area the smaller nanoparticles size is obtained.
The advantage of this method is the fact that it can be obtain magnetic nanoparticles with uniform morphology and controllable size; but the major drawbacks are the requirements of a large amount of solvent and the excess of surfactant that has to be eliminated.
In case of these methods, the reaction takes place in aqueous medium (the hydrothermal method) or in organic medium (solvothermal method), in reactors or autoclaves, at temperatures between 130 and 250°C under high vapor pressure, in the range 0.3–4 MPa [70–72]. Using this method, it can be obtained magnetic iron oxide nanoparticles with tailored properties (size and shape) by tuning the reaction conditions. The hydrothermal method is known as an environment-friendly process for the obtaining of M-IONPs, due to the raw materials used such as sulfates and chlorides—as cation source, dissolved in water [73].
Lin et al. [74] has used hydrothermal and solvothermal methods to obtain hollow M-IONPs. Briefly, they used FeCl3 (as source of iron), ethylene glycol (as reducing agent), ammonium acetate and urea were used to guide the formation of hollow magnetite spheres. After homogeneous dispersion, the mixture is transferred to a Teflon-lined stainless steel autoclave and sealed to heat at about 200°C for 8–24 h. The authors demonstrated that the Fe3+ ions on the surface of the hollow spheres exist in the form of Fe3O4, and the results are confirmed by the Mössbauer measurements. Tian et al. synthesized ultra-small monodisperse Fe3O4 nanoparticles, with precise size control of 1 nm, by solvothermal method [75]. They used Fe(acac)3 as iron source, n-octanol as a solvent and n-octylamine as a reductant. The authors obtained Fe3O4 nanoparticles with a size range from 4 to 6 nm, by varying the volume ratios of n-octylamine and n-octanol, without the need of a gas (N2) bubbling or reflux conditions. By comparing this method with the thermal decomposition methods for obtaining Fe3O4 nanoparticles, this solvothermal process was more convenient.
Stoia et al. [14] synthesized FexOy and FexOy/C nanocomposite by solvothermal method, with the purpose of using these nanocomposites as adsorbents for methylene blue removal from aqueous solutions. The authors used FeCl3 as iron source, 1,2-propanediol as solvent and diethylamine as precipitating agent. The activated carbon was introduced into system in order to obtain homogenous FexOy/C composites with high specific surface area and magnetic properties. Some researchers have attempted to modify the hydrothermal process. Ahmadi et al. obtained Fe3O4 nanoparticles at low temperature (140°C) without having to autoclave. They have studied kinetics of the reaction, but the magnetic properties of the resulted nanoparticles are inadequate in short reaction time (below 2 hours) [76].
As advantages, the hydrothermal and solvothermal methods are suitable for obtaining shape-controlled M-IONPs. As a disadvantage, in the case of hydrothermal technique, the reaction takes place for a long time and the amounts of resulting products are low [76].
The combustion method is an alternative to the currently used methods, being barely mentioned in the literature for the synthesis of M-IONPs. The combustion method have a lot of advantages due to the simplicity of the working technique, short reaction time and low energy consumption, being in the same time environmentally friendly.
The combustion method involves the strong exothermic redox reaction between an oxidizing agent (iron nitrate) and various reducing agents (fuels) of organic nature. The initiation of the combustion process takes place by rapidly heating the mixture of raw materials at relatively low temperatures below 500°C (Figure 4). The reaction stoichiometry has a decisive role in the characteristics of the reaction product, especially in the granule size, since a combustion reaction does not occur for any molar fuel/oxidizing agent ratio.
The general scheme for obtaining iron oxide magnetic powders using the combustion method.
The use of metallic nitrates in a mixture with a suitable fuel has the great advantage that, following the combustion reaction, the gases are released without a high risk of toxicity: CO2, N2 and H2O [77]. By using a proper fuel, proper auxiliary additives, as well as an appropriate oxidizing agent/fuel ratio, it can be tailored the size of the particles, the specific surface area and the crystallinity degree of the obtained material [78, 79].
Ianoş et al. reported a new combustion synthesis technique for the preparation of nanosized Fe3O4 nanoparticles [80]. The authors developed a new, facile and cheap scheme of installation for combustion synthesis of Fe3O4 nanoparticles in the absence of air. They also investigated the effect of both the reaction atmosphere (in the presence or in the absence of air) and the fuels nature on the properties of the resulted nanoparticles. Using sucrose, citric acid and glucose as fuels, the authors demonstrated that the reaction atmosphere is very important for obtaining Fe3O4 nanoparticles as a single crystalline phase. There were obtained Fe3O4 nanoparticles in the size range of 10 (when glucose was used as fuel) to 18 nm (when citric acid was used as fuel).
Mihoc et al. also investigated the effect of both the fuels nature and the reaction atmosphere for obtaining magnetic nanoparticles used as adsorbent for the removal of phenol and p-chlorophenol from wastewater [81]. The authors revealed that the working atmosphere influences the phase composition of the combustion reaction product. Using urea with ammonium chloride as fuels, the final product of reaction was α-Fe2O3 (when the reaction took place in air). Working in the absence of air, using oxalic, tartaric and citric acid as fuel, the single phase resulted in combustion reaction was Fe3O4, irrespective of the nature of the fuel.
Using the combustion method, the magnetic oxide nanoparticles are covered with some organic residues resulting from fuel combustion. Mihoc et al. demonstrated that these materials exhibit better adsorption capacity as compared with the naked magnetic oxides [82].
However, if it is desired to remove the residual carbon resulting from the combustion process, Ianos et al. found a method in which the residual carbon was eliminated by washing the magnetic nanoparticles several times with H2O2. They revealed that by combustion reaction between Fe(NO3)3•9H2O and C6H12O6 a black magnetic nanoparticle containing γ-Fe2O3 and residual carbon was obtained. The authors demonstrated that by H2O2 treatment of the resulted magnetic nanoparticles the carbon was removed by chemical oxidation, from 32.7 to 0.4%, and the color of the sample changed from black to reddish brown [83].
M-IONPs proved to be versatile due to the large range board of applications in medicine. Nanomedicine is an emerging field that offers new approaches but especially new solutions for many medical problems. For example, the discovery of antibiotics has been of historic importance, but over time, antibiotic resistance has become an issue and new approaches are therefore needed. Many groups of researchers have already demonstrated that the synergic effects of the antimicrobials agents (not only the antibiotics) with nanoparticles can be promoted as a new method for the severe infection treatments, even with low antimicrobial doses.
For the biomedical uses, only the M-IONPs which fulfill the following requirements are proper: superparamagnetic properties at room temperature, large saturation of magnetizations, biocompatibility and sizes around 20 nm for in vivo administration. To convert the pure magnetic nanoparticles in biocompatible colloidal suspensions, many researchers have proposed the use of different polymers like covering agents or surfactants like starch, heparin, chitosan, dextran, oleic acid, polyethylene glycol (PEG), etc.
Polymer coating can be accomplished during or after the synthesis of magnetic nanoparticles. Polyethylene glycol (PEG) is a water-soluble, biocompatible hydrophilic polymer that can be used successfully in the synthesis of biocompatible nanoparticles with increased resistance to blood circulation [84]. Another alternative to covered magnetic nanoparticles is the use of copolymers that produce core-shell nanoparticles with possible applications in drug transport (drug vector) [85].
The use of inorganic compounds such as gold, silver, silica gel and carbon as surfactants not only provides good stability to the nanoparticles but also allows functionalizing their surface by grafting certain biological ligands. Covering of magnetic nanoparticles with gold seems to be ideal because of its low reactivity; however, coating the magnetic nanoparticles directly with gold is very difficult due to the different nature of the two surfaces [86–89]. The silica gel is the most widely used compound in the preparation of functionalized iron oxide nanoparticles surface, because it has several advantages: excellent biocompatibility, hydrophilicity, the feasibility of integrating other functional groups on the surface due to terminal silanol groups that can react with different coupling agents, provides good stabilization of the magnetic iron oxide nanoparticles in the solution, prevents the interaction between the nanoparticles thus preventing the agglomeration of the particles over time and ensures better encapsulation [90]. A very good coating of carbon layers provides an effective barrier against oxidation and acidic erosion of magnetic nanoparticles. It is therefore possible to synthesize carbon-coated magnetic nanoparticles that are thermally stable, biocompatible and also have high oxidation stability, which is crucial for certain applications [89].
Iron ions play major biological roles in different physiological processes, including DNA synthesis, oxygen transport, mitochondrial respiration, heme synthesis, and in metabolic functions at central nervous system level (nitric oxide metabolism, oxidative phosphorylation and myelin and neurotransmitter synthesis). Moreover, iron proved to be an essential factor for an appropriate function of neurons by acting as cofactor for tyrosine hydroxylase, an enzyme with a critical role in dopamine synthesis and the viability of neural cells. A dysregulation of the iron homeostasis or transport leads to unbalanced physiological functions and cytotoxic reactions. The free intracellular Fe2+ ions react with hydrogen peroxide (H2O2) and determine the generation of reactive oxygen species (ROS), process known as Fenton reaction. An increased ROS concentration activates a cascade of events (release of iron ions into the cytosol by inducing an augmented permeability of the outer mitochondrial membrane and detrimental effects on lysosomal membrane; lipid peroxidation, damaged proteins, break of DNA chains and degradation of bases, mutations, deletions or translocations at nuclear level) that has as endpoint cell death. The pathologies that are associated with this type of cellular damage are aging, cancer and neurodegenerative diseases [91]. Another mechanism of inducing cell death by the iron ions is the apoptotic pathway via mitochondria, as follows: a high amount of iron ions into the mitochondria determine the opening of the mitochondrial transition pore, release of Ca2+ and cytochrome c and activation of apoptotic cascade [91, 92].
Based on these data, concerning the toxicity induced by iron ions, it is imperative to study the possible toxic effects induced by M-IONPs, mainly since these particles present a higher reactivity as compared with the normal sized ones. The magnetic character of iron oxide nanoparticles offers some advantages, including the capacity of this nanosized compounds to be driven to targeted sites by an external magnetic field, even to tissues and organs that are difficult to reach in normal conditions (blood brain barrier and central nervous system). M-IONPs penetrate into the cells via receptor-mediated endocytosis and settle into the lysosomes, organelles characterized by the presence of an acidic medium, where it takes place the metabolization of the nanoparticles and free iron ions are released into the cell [91].
In a previous study, it was demonstrated that M-IONPs penetrate differentially into the neural cells (glial cells, primary neurons of the cerebellum, microglia, astrocytes, oligodendrocytes and Schwann cells), based on their dimensions: large size nanoparticles were absorbed by endocytosis, whereas small sized ones via pinocytosis [91, 93]. It was also proved that exposure to M-IONPs has an impact on iron homeostasis by upregulating the proteins responsible for iron storage or export from the cell and by downregulating the proteins expression involved in iron uptake [94].
Besides these positive features, application of an external magnetic field leads to accumulation of M-IONPs in target cells and potential toxicity. The accumulation of iron into the cells after exposure to M-IONPs seems to be dependent on several factors, such as (i) concentration and dose of M-IONPs (high concentrations require a longer period for elimination—several months, whereas M-IONPs in low concentrations can be eliminated within 3 weeks), size (small size nanoparticles cumulate in increased concentrations as compared to large size nanoparticles), shape (spherical nanoparticles present a longer degradation process due to a small contact surface), coating (some coating agents may prolong the degradation process or may increase it), the functional groups (the positively charged functional groups present in M-IONPs structure increase their uptake by the cells) and cell type (microglia have a higher affinity for M-IONPs, whereas into the brain endothelial cells penetrate less nanoparticles) [91].
A significant number of studies sustained that M-IONPs exerted in vitro and in vivo toxicity. The main players responsible for toxic effects are considered to be the iron ions released from M-IONPs at lysosomal level, which react with hydrogen peroxide and lead to ROS generation [91]. Exposure of neural cells to M-IONPs was associated with a low concentration of ROS, but a reduced level of glutathione and mitochondrial membrane hyperpolarization [95]. Other studies conducted on healthy cell lines (both human and animal origin) pointed out that bare M-IONPs may induce cytotoxic effects via ROS generation, leading to cell death [96–98].
The oxidation state of iron (Fe2+ or Fe3+) plays a major role in determining the nanoparticles toxicity according to the studies that affirm that Fe3+ in Fe2O3 is more toxic than Fe2+ in Fe3O4 and causes more DNA oxidation [91, 99].
The concentration of M-IONPs is also important in the assessment of M-IONPs toxicity. In one of our previous studies developed on HaCat cells (human keratinocytes), it was shown that concentrations lower than 25 μg/mL did not induce toxicity in terms of viability and cytoskeleton changes (Figure 5) [100].
The impact of magnetite and maghemite obtained by combustion method on HaCat cell morphology after 24 h stimulation.
Shelat and coworkers indicated a dose-dependent cytotoxic effect of M-IONPs on mouse embryonic fibroblast (NIH 3 T3) [101]. It was also assessed the effect of negatively charged superparamagnetic iron oxide nanoparticles on heart cells and no changes in actin cytoskeleton were observed, whereas in the case of brain and kidney cells, a disruption of the actin cytoskeleton was detected, but some increased vascular permeability was seen after exposure [102].
Another sign of toxicity that was described after neural cells exposure to M-IONPs was represented by protein aggregation. In addition, it was shown that M-IONPs induce apoptosis of hepatocytes in a mitochondrial-dependent way consisting of upregulation of pro-apoptotic markers (Bax and Bad) and downregulation of bcl-2 (anti-apoptotic); decrease of mitochondrial membrane potential followed by the release of cytochrome c into the cytosol what leads to activation of caspases cascade and apoptosis induction (Figure 6) [91].
Mechanisms of toxicity induced by M-IONPs to normal cells (neural cells and hepatocytes): oxidative stress and apoptosis.
Based on the data that were presented in this section, it could be said that the mechanisms involved in M-IONPs toxicity are accumulation of iron ions, oxidative damage by generating reactive oxygen species, protein aggregation and apoptosis.
Mutagenic effects of M-IONPs on different murine and mammalian normal cell lines were clearly synthesized in an extensive review [103].
SPIONs (superparamagnetic iron oxide nanoparticles) are the most frequently used iron oxide nanoparticles in the biomedical applications due to their proper size (range between 50 and 200 nm) and the magnetic properties responsible for the lack of particle aggregates in vivo. Another type of iron oxide nanoparticles is represented by USPIONs (ultra-small superparamagnetic iron oxide nanoparticles), which have a diameter lower than 50 nm. The mandatory features of M-IONPs that must be analyzed in order to establish the bioavailability and the possible interactions with endogenous compounds (proteins, immune system cells, etc.) are: (i) size (the recommendable size for biomedical applications is between 10 and 200 nm; the ones that are too big will be assimilated by liver and spleen cells, the ones that are too small will be filtrated by the kidneys and their life in the bloodstream is reduced); (ii) superparamagnetism and (iii) presence of a coating agent [104].
The affinity of liver, spleen, bone marrow and lymph nodes for SPIONs after their removal from the blood by the mononuclear phagocytic system (MPS) after intravenous administration represents the reason for the study of this type of nanoparticles as contrast agents but also for their use as delivery tools for chemotherapeutic agents. USPIONs due to their small size possess the capacity to escape macrophages of MPS surveillance and their circulation time is higher, but they also encounter macrophages in deeper compartments.
The changes concerning the surface of the nanoparticles by using a coating agent proved to exert multiple roles: to improve colloids stability, to enhance the bioavailability and the bloodstream half-life and to reduce precipitation and formation of conglomerates [104, 105]. M-IONPs were used as drug delivery agents and as contrast agents based on their potential to activate at cellular and molecular levels [105].
Due to the multiple applications of M-IONPs in biomedical fields (drug delivery, as contrast agents, hyperthermia treatment), it was also verified the effects of the hollow nanoparticles (without payload) on different tumor cell lines.
As mentioned in the previous section, M-IONPs mediate DNA lesions in normal cells, and this property is also exerted in the case of tumor cells. The effect observed was dose-dependent and time-dependent and consisted of damage of tail length and DNA strand breaks. The results were similar in all the tumor cell lines tested: human breast cancer cell line (MCF-7), human fibrosarcoma cells, lung cancer and cervix carcinoma cells [103].
Another mechanism of M-IONPs by which are able to harm cancer cells is represented by the ability to induce magnetic hyperthermia in the form of heat generated by the release of energy after applying a high-frequency alternating magnetic field. The principle of action of this technique consists in raising the cell temperature abnormally to 41–45°C, which leads to significant detrimental effects that can be reversible in the case of normal cells whereas irreversible for cancer cells [105].
A novel proposed mechanism for M-IONPs-induced cell death is enucleation described by Paunescu and coworkers, process observed after exposure of breast cancer cells (MCF-7) and human melanoma (SK-BR-3) to magnetic iron oxide nanoparticles obtained by combustion synthesis [106]. The enucleation phenomena is well described for erythroid terminal differentiation process and there is also used a term in the literature “enucleation sign” that is specific for enhanced computed tomographic images of the ruptured hepatocellular carcinoma. The definition for this term is “the separation of tumor content with intraperitoneal rupture into the perihepatic space, which is seen as low attenuating lesion from peripheral enhancing rim on arterial phase imaging” [107]. The process observed by Paunescu et al. was described as a non-physiological process and it was unrelated with the process described for erythroblast enucleation [106].
The M-IONPs proved a cytotoxic effect against murine melanoma cells B16, cytotoxicity evaluated by the means of MTT viability assay [108].
Other mechanisms of action as anticancer agents may be attributed to M-IONPs, mechanisms that are related with the effects induced by the chemotherapeutical agents loaded in the engineered nanoparticles. The large surface-to-volume ratio characteristic for M-IONPs make them suitable to adsorb proteins or load drugs and attractive for in vivo applications, such as MRI, drug and gene delivery, cancer treatment, hard tissue repair and tissue engineering and biosensors [105].
Recent studies mention the use of M-IONPs as improved contrast agents in the diagnosis of cardiovascular pathologies, mainly in atherosclerosis for detection of unstable plaques by the means of MRI (magnetic resonance imaging) [104]. The commercial products based on M-IONPs applied as contrast agents in MRI are: Ferumoxytol (Feraheme—detection of primary tumors and cancer lymph node metastasis), Ferumoxides (Feridex—detection of liver lesions), Ferucarbotran (Resovist—detection of small focal liver lesions), Ferumoxtran—10 (Combidex or Sinerem—detection of metastatic disease in lymph nodes), etc. [104]. Some of these products are included in clinical trials for additional effects, such as Endorem—for tracking monocytes and inflammation cells, Feridex—to keep track of adult bone marrow-derived stromal cells for severe cases of Multiple Sclerosis therapy and Supravist (ferucarbotran—small size nanoparticles)—as enhancing blood pool agent [104, 109].
The intrinsic magnetic properties, the biocompatibility and biodegradability and the capacity to respond to an external magnetic field are unique features that recommend magnetic iron oxide nanoparticles as promising nanomaterials in biomedical applications. The recent advances in this field led to the synthesis of engineered and targeted M-IONPs that might be successfully applied for smart therapies, including controlled drug release, hyperthermia treatment, magnetofection and gene delivery, mapping of lymph nodes and tissue engineering. M-IONPs could be considered theranostics tools based on their capacity to combine their use in diagnostic, treatment and follow-up of a pathology. Despite all these beneficial effects, an important matter should be taken into consideration when M-IONPs are administered in vivo, this matter consisting in the thorough analysis of the factors that might induce toxic reactions like size, charge, coating agent, functional groups and shape. There are still some challenges to achieve M-IONPs optimum efficacy and safety, but the existent drawbacks can be corrected by the improvement of their properties by the means of appropriate methods, further studies and inclusion in clinical trials.
This work was supported by a grant of Minister of Research and Innovation, CNCS-UEFISCDI, project number PN-III-P4-ID-PCE-2016-0765, within PNCDI III.
Despite the renewed interest in safeguarding research output, the changing storage carriers due to the fragility of storage carriers, lifespan, and handling practices are a cause of concern for the university libraries [1]. University libraries cannot avoid working in the cloud as they have become adaptive to inevitable and unpredictable changes occurring within the digital environment [1]. The university community places much emphasis on research and publication not only because it is presumed that research enriches teaching and the learning process, contributing to the body of knowledge, but also because it is a major determinant of institutional prestige and that of the nation at large [2].
\nIrrespective of the technological changes, stored research output in universities must be secured for future availability and accessibility [3]. Cloud storage has become an alternative for the storage of research output. According to Yuvaraj [4], university libraries have continued not only as only new technology adopters but rather cutting-edge IT users. Clearly, cloud computing as a cutting-edge IT platform proves to be a lasting technological innovation that continues to rise in usage [5].
\nHowever, owing to the technological age, university libraries are faced with new opportunities for innovative educational practices, hence providing electronic library services. Almost all university libraries are primarily concerned with enhancing teaching, learning, and research through the provision of timely information resources. On that basis, researches by Gabridge [6], Gold [7] and Jones [8] revealed the need for libraries to provide research data services. In providing timely information resources, modern libraries’ digital collections must be stored for future use and as backups to ensure continuous accessibility by library users.
\nWitten and Bainbridge [9] explained that a digital library is a focused “collection of various forms of digital objects” such as text, audio, and video, as well as their methods for access, retrieval, selection, organization, and maintenance. Rosenberg [10] also reiterated that a digital library can refer to information resources which are accessed by and delivered to users electronically or via a network [11]. Primarily, in developing countries, microfilms, databases, CD-ROMS, hard disks, external drives have been the existing platforms for storing library digital information, though these come with major drawbacks. For instance, these storage devices are exposed to threats such as theft, inadequate storage space, virus attacks and unauthorized accessibility among others. These drawbacks have been a major concern for academic libraries’ thus an ongoing debate and discussion on the new technology “cloud storage” as an alternative storage media.
\nTo a large extent, studies confirm that modern university libraries have greatly shifted from traditional roles (paper-based services) to digital library services. This paradigm shift has paved the way for library services to be accessed and delivered via the web [12]. For university libraries, the issue of using cloud services to store digital collections is particularly important as technological changes have paved the way for library services to be accessed and delivered via the web [12]. As more data and information is generated and stored in the cloud, either by design or default, university libraries need to be confident of the security of the digital collections. There is a growing interest in the implementation of cloud storage services which exposes university libraries to a new set of threats and vulnerabilities. McLeod and Gormly [13] concluded that if cloud service providers are to be used, their security, viability, sustainability, and trustworthiness must be paramount.
\nStudies have demonstrated that that cloud computing in libraries has widely examined the rise of data-intensive services in academic libraries with less emphasis on cloud storage security [14, 15]. Most of these studies were based on individual or small-scale survey data concentrated in one country. Owing to the extant gap in wide-scale exploratory studies, the present paper explored the risks associated with cloud storage services and how university libraries can ensure safe research output. In this light, the paper contributes significantly to the body of literature by unraveling new evidence from universities located in Ghana and Uganda on how academic libraries can secure research output with cloud services.
\nThe following sections include research questions, related literature, theoretical framework, research methodology, results, a summary of key findings, conclusion and recommendation.
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What are the existing storage carriers/media for storing research output in university libraries?
What are the reasons for university libraries moving research output into a cloud infrastructure?
What risks are associated with cloud storage services for university libraries?
In university libraries, how can research output store on the cloud service be secured?
Libraries use several types of media in storing digitized content or information (audio, video, text, images etc.). Each of the media suffers disadvantages with regard to reliability, high lifespan, ease of access and validation plus various costs. Enakrire and Baro [16] argued that these media include;
Magnetic disk drives are disk drives which are mostly mounted on computers. They are inexpensive, of very high-density, fast to use, and multiple user connectivities to the server are possible.
Magnetic tape, which comes in various formats and can only be effective for duplicate or backup copies. However, they are not recommended for primary storage.
Optical disks, for example, CD-R and DVD-R cost less, use low energy but exert high labor costs, poor accessibility, a periodic verification is not cost-effective and low density by today’s standards. Others are CD-RW and DVD-RW these are recommended for individual and day-to-day use but are not recommended for data preservation [17].
Until recently, evidence from the pool of literature shows that the concept of cloud is of the growing research area. Indeed, a lot more storage capabilities exist in the cloud. According to Mavodza [18], cloud computing is the delivering of hosted electronic services over the internet. Scale [19], opines that it is: “the sharing and use of applications and resources of a network environment to get work done without concerns about ownership and management of the network’s resources and applications, data are no longer stored on one’s personal computer, but are hosted elsewhere to be made accessible in any location and at any time”. Gosavi et al. [20] iterated that cloud computing harnesses the capabilities of resources like storage, scalability, and availability, which are accessible to university libraries as clients. Hence, depending on the needs of the clients, the infrastructure can be scaled up or down.
\nIn developed or developing countries, cloud storage provides promising advantages to university libraries. According to Li [21], cloud storage reduces the cost of hardware and software, and it makes the storage and management of data on the internet possible. It also reduces the work of Information Technology (IT) professionals as most of the system’s work is performed by the hosting company. Payment for the cloud storage service is by pay-as-you-go, which is convenient for organizations such as academic libraries which have budget restraints. Han [22] enumerates cost-effectiveness, flexibility, and data safety as a rationale for cloud storage in academic libraries. Han [23] alludes the advantages that cloud storage has over traditional storage to “availability, scalability, off-site storage, on-demand, and multi-tenancy” which allows different applications or different users to access the same resources to fit their needs. Han further states that data stored in the cloud can be easily transferred and duplicated globally to minimize data loss due to natural disasters.
\nHaris [24] also gives an analysis of the benefits of cloud storage especially for libraries and these include high performance, an avenue for collaboration, less “need for in-house technical expertise, cost savings, and more timely access” to the latest IT functionality. Haris further states that the cloud also provides a better workflow, “automated software updates, redundancy”, and backups. Cloud storage provides collaboration, particularly for academic and research libraries. Through the use of cloud technology, a collaboration between libraries, researchers, and students is promoted. The cloud also enables remote access to a wide range of research materials.
\nIn this section, the role of cloud computing in university libraries, specific cloud storage platforms and the risks associated with cloud storage are reviewed.
\nKaushik and Kumar [25] contend that cloud computing can offer many interesting possibilities for institutions such as libraries. Cloud computing is quite significant as it reduces technology cost, increases capacity reliability, and storage performance for some type of automation activities like library services. In recent times, cloud computing has made strong inroads into other commercial sectors and is now beginning to find more of its applications in the library and information environment.
\nAfter the personal computer and the internet, cloud computing also known as the third revolution is completely new in terms of technology. Potentially, cloud computing is an unraveled technology in university libraries as digital content can be stored in the cloud. Mobile devices are enabled using cloud computing by taking out an item or scanning a barcode [26]. Gosavi et al. [20] argued that when using cloud computing, users can be able to browse a physical shelf of books located in the library, choose an item or scan a barcode into his mobile device. More so, heritage materials or documents can be digitized, searched and accessed by library patrons. The new concept of cloud libraries includes OCLC, Library of Congress (LC), Exlibris, Polaris, Scribd, Discovery Service, Google Docs/Google Scholar, WorldCat and Encore [27].
\nNowadays, studies appear to be emerging in cloud computing. For instance, a paper presented by Saleem et al. [27] indicated that university libraries have adopted cloud computing technology to enhance library services by adding more values, attracting users and cost-effectiveness. In the cloud computing environment, clouds have vast resource pools with on-demand resource allocation and a collection of networked features. The new concept of cloud and libraries has generated a new model called cloud libraries.
\nIn the work of Zainab et al. [28], it was reported that the first reason of shifting research report into cloud computing is to reduce the total cost of ownership and maintenance of the cloud infrastructure. Secondly, scalability of the cloud service system is another objective, so that it is able to handle increased traffic. Due to the rapid expansion of the user group, we need to redesign the back-end web server with scalability in mind, such that it is able to accommodate an increasing number of concurrent users.
\nBased on the web traffic statistic, the average visit per month for the year 2012 is approximately 87,000 users and we expect the numbers will grow in the coming years as resources in the repository also grew. The high volume of transaction is causing The server to behave extremely sluggish and crashes frequently [28]. On the hand, migration is necessary in order to meet the increasing demand for storage space for full-text digital resources. File sizes of some digital resources are extremely large especially audio, video and images. Besides, as more users’ access and upload articles to the magnetic hard drives, university libraries face problems in fulfilling the storage space demand. The cloud storage service which promises and contributes to about 13 terabytes of storage space, can store over 12 million digital files of research output. Thus, it is very obvious that without a long-term plan, university libraries would not able to sustain the present storage demand from users in the future until alternative storage is assessed.
\nIt is expected that migration of digital files would reduce downtime when scheduled backup and indexing, as well as site traffic, occur simultaneously. The previous system backup was very laborious and time-consuming. Often scheduled jobs would cause unnecessary downtime of the magnetic and optical systems. System downtime is unavoidable because the system was hosted without a redundant server.
\n\n
Amazon S3: Amazon Simple Storage Services (Amazon S3) provides a secure, durable, highly-scalable object storage (Amazon, 2015). It uses a web service interface to store and retrieve any amount of data. It is a pay as you use service. There are different storage classes designed for different uses; Amazon S3 standard, Glacier for long-term archive. The services include backup and archiving, disaster recovery, and big data analytics [29].
Google cloud storage: Allows storage and retrieval of any amount of data at any time. It facilitates the storage of data on Google’s infrastructure with high-reliability performance and availability (Google, 2015) [29]. The services include data storage, large unstructured data objects, uploading data, and managing data. The lowest storage class is $0.01 GB/month.
Microsoft Azure: Azure supports the selection of wide services including operating systems, frameworks, tools, and databases. It’s typically a platform-as-a-service and software-as-a-service. It provides secure private connections, storage solutions, and data residency and encryption features (Microsoft, 2015). It provides scale-as-you-need, pay-as-you-go service plan, and strong data protection security.
Other cloud storage platforms include Dropbox, SkyDrive, Box, Google Drive, Flickr, Google music, Apple iCloud, and Amazon cloud player.
Lili and Buer [30], highlighted that advancement in technology may not necessarily transform the cloud services into mainstream technology in academic libraries. A scan of literature [31, 32, 33], revealed that cloud security, interoperability, and regulatory perspectives are worrying. In addition, academic libraries may or may not completely lose control over IT and data. Sometimes, trust in the service provider, data portability, migration, copyright issues, and privacy is a big risk when it comes to adopting cloud computing technology.
\nPolicies guide institutions and operations on what to do and not to do. Cloud storage and applications are valuable resources that allow academic libraries to store large amounts of information and perform collaborative tasks more effectively. However, there are risks associated and that must be mitigated in order to properly secure the research assets placed into the cloud [32]. In this light, it is purposeful for the policy to provide the framework within which the libraries will be expected to operate for storage and process information in cloud environments. Basically, the policy should encompass the scope of work, software, research information, human resource, users, copyright and many more.
\nOnce a digital collection (scholarly works, publications/collections, and historical documents) is put on the cloud, it becomes available for all groups of users and this can be exposed to unauthorized access to data centers. “Cloud operators can dictate the manner in which users can access, use and reuse content or information via specific online services or applications. That is, the user interface ultimately dictates what can or cannot be done by end-users, regardless of what they are theoretically entitled to under the law” [34]. So, the question is whether academic libraries can allow such law to be overridden on as it has already fallen in the public domain. This indeed is likely to impact on copyright law in the context of online applications.
\nCloud storage service providers are not guided by standard regulations. As a result, some service providers are tempted to offer low-quality services to developing countries in Africa thus creating loopholes for cybercriminals to take advantage. As an emerging trend, this issue of no interoperability is of concern, if research assets can be secured on the cloud. Interoperability refers to the ability of a collection of communicating entities to share specific information and operate on it according to agreed-on operational semantics [35]. Even though the clients (academic libraries) desire standards for cloud interoperability, the reality currently is that standard efforts only focus on portability, which is the ability to migrate workloads and data from one provider to another.
\nLibrarians cannot sit unconcerned in this matter since the open access (OA) repositories are also part of collections of the library [36]. Though the OA repositories facilitate sharing of resources in educational research through portals that are modeled as gates to several repositories, it is a challenge because data synchronization is an issue when components in different clouds or internal resources work together, whether or not they are identical. Communication between clouds typically has a high latency, which makes synchronization difficult. Also, the two clouds may have different access control regimes, complicating the task of moving data between them [37].
\nThus, interoperability is required, not just between different components, but between identical components running in different clouds [38]. Such components often keep copies of the same data, and these copies must be maintained in a consistent state. The design approach must address management of “system of record” sources, management of data at rest and data in transit across domains that may be under control of a cloud service consumer or provider and data visibility and transparency.
\nNurnberg et al. [39] argued that full interoperability includes dynamic discovery and composition: the ability to discover instances of application components and combine them with other application component instances, at runtime. Application interoperability requires more than communications protocols. It requires that interoperating applications share common processes and data models. These are not appropriate subjects for generic standards, although there are specific standards for some particular applications and business areas.
\nObviously, the cost is a challenge for academic libraries. More especially, enterprise cloud storage platforms such as Amazon S3 and Microsoft Azure are paid for as you use the cloud services. Unfortunately, libraries that find it difficult to fund basic services will see that as an extra cost inhibiting them to withdraw from the cloud service. The cost comes with human resource and sometimes maintenance of servers.
\nThe paper adopts the development of a Cloud Storage Security Framework (CSSF) to support an integrative approach to understanding and evaluating security in cloud storage in university libraries. The framework enables understanding of the makeup of cloud storage security and its associated measures. Drawing upon CSSF, it indicates that security in cloud storage can be determined by seven factors: (1) security policies implementation in cloud storage, security measure that relates to (2) protecting the data accessed in cloud storage; (3) modifications of data stored; (4) accessibility of data stored in cloud storage; (5) non-repudiation to the data stored; (6) authenticity of the original data; (7) reliability of the cloud storage services.
\nThe framework is summarized in Figure 1.
\nCSSF. Source: Yahya [40].
In applying the framework to the current research, security of research output in the cloud infrastructure can be determined by ensuring that all the seven factors are met by the university library.
\nThis study aimed to explore security issues considered in migrating research output to the cloud service as input into the development of preservation or storage systems within the library environment. This section described an approach followed in the study. This included the research approach, purpose, instrumentation, and sources of data. Our paper adopted the qualitative approach to explore cloud computing in university libraries in the sub-Saharan Africa. Using a wide range of evidence and discovering new issues, the purpose of the paper was to explore the risks associated with cloud storage and security implications. The exploratory design was significant as the authors became more familiar with basic facts, settings, concerns, and generating new ideas. In this study, interviews were conducted with respective librarians in charge of research output within the (4) universities. Hence, the research sites were purposefully selected to ensure that they provided sufficient opportunities to test available infrastructure for storing research output. Again, since the paper was interested in only libraries with repositories, the institutions without OA repositories were excluded.
\nAn interview schedule on the research questions was presented to 4 librarians from the universities. Thus, participants for the investigation were made up of librarians in charge of institutional repositories. These four university libraries selected were; Balme Library, (University of Ghana—Legon), Kwame Nkrumah University of Science and Technology—KNUST library (Ghana), HamuMukasa Library, (Uganda Christian University), and The Iddi Basajjabalaba Memorial Library, (Kampala International University—Uganda). The thematic content analysis was used to analyze the qualitative data. The authors further reviewed scholarly research articles, explored in the context of research data storage in and outside Africa.
\nThis section draws reference from respective university libraries in the context of cloud storage security for research data.
\nThe University of Ghana (UG), the premier university and the largest university in Ghana was founded as the University College of the Gold Coast by Ordinance on August 11, 1948, for the purpose of providing and promoting university education, learning and research. The vision of the university is “to become a world-class research-intensive University over the next decade”. To achieve the vision, it “will create an enabling environment that makes the University of Ghana increasingly relevant to national and global development through cutting-edge research as well as high quality teaching and learning” (
Established in 1948, the Balme Library is the main library of the University of Ghana. In addition to the Balme Library, there are other libraries in the various Schools, Institutes, Departments, Halls of Residence and the Accra City Campus which form the University of Ghana Library System (
In UG, research assets (theses, journals, newspapers) in the form of PDFs, word files, conference papers, videos, and audio have been generated. In the context of this study, the existing storage media for storing research data include CDs, DVDs, external drives, servers, hard drives, microfiche, and microfilms. Others include networked drives, Google drive and Dropbox used by researchers and the library in storing research assets.
\nThe interviewee indicated that digital storage and backup is important because;
\n“Data may need to be accessed in the future to explain or augment subsequent research. Other researchers might wish to evaluate or use the results of previous research outputs as precedence to conduct other similar or extended studies”.
\nAgrawal and Nyamful [41] corroborated the findings in the present study. Accordingly, they reported that storage devices which stores and maintains large sets of data over time play an important role in mitigating big data challenges. Factors such as capacity, reliability, performance, throughput, cost, and scalability are involved in any ideal storage solution system. They argued that reliability is basically the retrieval of data in its original form without any loss. The issue of reliability takes into account both internal and external system failures and vulnerabilities. With the scale of data, the probability of losing some data during retrieval can be very high. In order to ensure continuous accessibility of data, storage is very necessary.
\nIt was revealed by the interviewee that
\n“there is no robust or enough backup plan when the primary server goes down. With an average of 3000 visits per day on the Institutional Repository (IR), we wish to keep The website availability as high as possible. To solve the problem, the IR team decided to move digital files to a cloud environment using virtualization technology”.
\nA study by Ji et al. [42], revealed a compelling need for storage and management of research output. Given the current development of data (text, audio, video, images, etc.), university libraries are employing techniques such as data compression, deduplication, object storage, and cloud storage.
\nThe Librarian in charge of research data opined that
\n“Unauthorized accessibility, physical damage, theft, and hacking are particular concerns with electronic data. Many research projects involve the collection and maintenance of human subject’s data and other confidential records that could become the target of hackers and thus integrity must be maintained. The costs of reproducing, restoring, or replacing stolen data and the length of recovery time in the event of a theft highlight the need for protecting the computer system and the integrity of the data”.
\nThe Librarian iterated that several issues are associated with storing research data on the cloud.
\nOne interviewee pointed out that;
\n“Risks associated with cloud storage are crucial for the Balme Library. Storing research assets online via the Dropbox, mozy.com, Box.net, Adrive.com, Carbonite.com have proven the best alternative. However, a few associated risks include issues regarding property rights, copyright, data protection licenses or privacy. Other issues to consider is the fact that in the event of restoring data, it may be a bit slow and the service provider (Google Reader) could go out of service”.
\nKNUST Library has realized the need to digitize and store documents and research data generated by staff and students of the University, hence the decision to create the online Institutional Repository. The online repository showcases the intellectual output from the KNUST. In the earlier 2010, a server and scanners were acquired to support digitization processes. Since then, postgraduate thesis, reports, and few research articles have been uploaded unto the repository. Increasingly, the project has continued to receive acclamation internationally due to robust IT infrastructure in the library.
\nThe librarian for KNUST responded in this manner,
\n“Currently, the KNUST uses non-web based storage media to store data. There are two servers; one for the Library’s catalogue and another for the Institutional Repository. The library also uses an external hard drive as a backup, but both media are located in-house”.
\nReed et al. [43] asserted that “data backup plays an indispensable role in the computing system. Backup is one way to ensure data protection. By keeping copies of production data, backup protects data from a potential loss such as hardware and software loss, human errors, and natural disasters. The huge amount of data needing backup and archiving has reached several petabytes and may soon reach tens, or even hundreds of petabytes. The massive amount of data in today’s library environment may consume much storage.”
\nFurthermore, it was reported by the interviewee that
\n“The challenge faced with this kind of storage media is frequent memory crash, lack of expertise to manage the storage media, lack of space – the servers have low memory space, an interrupted power supply which uninterruptible power supply (UPS) is not even able to solve. Then finally, remote access to the information is denied because data is not online”. Thus, the need to seek cloud storage.
\nIt was evident from the interviewees that cloud computing environments are easily scalable and backup recovery is very easy in Infrastructure as a Service (IaaS) Providers, hence there is efficient incident response whenever data needs to be recovered.
\nThe authors sought to find what risks were associated with cloud storage. Cost and data security were concerns raised by the managers of the repositories. Agrawal and Nyamful [41] argued that the state of preventing a system from vulnerable attacks is considered as the system’s security. Security risks involved with the use of cloud computing have various risk factors for the library environment. Seven important identity factors for risk in a cloud computing model are access, availability, network load, integrity, data security, data location, and data segregation.
\nUganda Christian University has been in existence for 11 years having only one library which uses traditional devices. In the year 2015, the library launched its institutional repository. The storage media for storing research data in Uganda Christian University library is examined as follows:
\nUganda Christian University has both traditional and modern storage devices. Traditional storage includes CDs, flash disks, card catalog and later introduced modern storage like creating an institutional repository where dissertations and research papers are kept safely for future use.
\nThe Librarian in charge of the research data output of the Uganda Christian University observed that;
\n“For modern storage devices, Google drive is currently used to store documents such as student Theses works, proposals, and the day to day statistics. This started early last year when the learning commons was opened. This is used because it is cheap and can be accessed easily by staff and students while doing their work”.
\nIn this twenty-first century, information is not just in print but digitally created and reused by researchers and patrons within academic institutions. There is a need for digital information storage at Uganda Christian University because of the advantages. Prior to cloud storage, institutions invested heavily in data centers and servers even though they may not have used its storage space. The cloud storage allows institutions’ (academic libraries) only pay for computing resources they use. By using cloud storage one can achieve a lower variable cost than can be gotten on the traditional storage devices.
\nHowever, using cloud storage by Uganda Christian University academic library has some risks. Lack of internet access or less bandwidth is a major issue. Specifically, when the internet is down its difficult for data to be retrieved thus inconveniencing the patrons. Secondly, sensitive information for the institution can be disclosed accidentally or deliberately in cloud services if not handled well especially when demand grows. Thus, the inappropriate accessibility of the institution data can be compromised.
\nFor an institution like Uganda Christian University Library to ensure the safety of its research information in the cloud, the following must be considered.
avoid unauthorized accessibility of research data using strong passwords.
Privacy policy services settings must always be checked by appropriate management.
The Iddi Basajjabalaba Memorial Library (The IBML) is an integral part of Kampala International University (KIU). It is the intellectual hub of the university that supports the study, teaching, research and social information needs of the university. The IBML has grown over the years from one small room in 2001 manned by one member of staff and serving 700 users to an eight ultra-modern building serving over 20,000 users. The IBML system has evolved over time from the manual system providing print information resources to automated circulation services and digital information resources. In 2014, The IBML set up a digital repository to capture, store, and disseminate the intellectual content of the university. The digital content includes research articles, papers written by university staff, PhD theses, and other university publications. DSpace software was used for this project and it is hosted locally on a networked server. The repository data is backed up on an external hard drive with several terabytes of storage capacity.
\nThe IBML has not ventured much into cloud storage because data is still stored locally. Researchers, academic staff, and students typically use external hard drives, flash disks, CDs, DVDs, emails and Google Drive to store their data. Not many use Dropbox, OneDrive, and other Cloud storage media. However, this trend is risky because the library faces several challenges especially power outages that lead to a computer crash, theft of computer hard drives, and other storage media. There is also a danger of data breaches by unauthorized persons since the repository server is not within the confines of the library. Therefore, cloud storage is an important choice for the library to use in order to mitigate the danger of data loss.
\nFigure 2 depicts how university libraries provide library services via cloud services. Due to the unreliability of non-web based storage media, university libraries have refocused attention to an alternative; cloud service which is web-based. In providing library services to university faculty, students and researchers; research assets in the form of electronic theses/dissertation, articles, research datasets, research reports are stored in the cloud. It is important to note that cloud services provide advantages like large storage space, data back-up among others which non-web based media does not have. However, alternative storage media (cloud computing) appears to accommodate the concerns of university libraries. Putting in place, security of content, defining accessibility levels, adherence to copyright and legal issues, cloud storage policy, among others, safety of research assets on the cloud service is safer.
\nCloud computing in university libraries.
The paper discovered pertinent and important findings which were very vital for drawing a conclusion and informing policy makers.
\nFrom the study, it can be concluded that all the sampled academic libraries used magnetic disk drives (hard disk drives) for storing research outputs and assets and optical disks (CD-R and DVD-R).
\nFrom the empirical evidence, it is concluded that information enhances knowledge, which affects behavior, and leads to development warranting its preservation. University libraries have the digital format as text, audio, video, and image which facilitates easy sharing of information. Storage is needed for current and future generation of researchers and academia as a whole. In addition, digital storage makes information easily accessible to users as compared to “analog items”. This is due to the ability to easily copy the information on storage devices and carry around. Furthermore, digital storage facilitates the easy sharing of information.
\nSpecifically, copyright law infringement, unauthorized data accessibility, policy issues, the security of content, no interoperable cloud standards were identified as the risks associated with cloud storage in academic libraries.
\nCloud computing offers university libraries improved storage solutions. In the era of IT, the library and information environment face numerous challenges including constant change of storage platforms. Notably, the storage of research output is primary to the functions of university libraries. Thus, there is a need for storage security; as it is a reality in the current technological environment.
\nIn the developed world, some university libraries have already built and managed their own research data centers comparable to the developing world. Indeed, to avoid loss of data integrity, large digital storage in the cloud must be backed up, maintained and re-produced to avoid stress on the local server infrastructure. In conclusion, the opportunities offered by cloud computing via its storage services could ensure that university libraries gain more control over research output.
\nUniversity libraries must consider investing in cloud infrastructure as it assures large savings or cost effectiveness in operational cost and tech-start-ups [44], paying for what you use and risk transfer and availability [45], scalability, accessibility [4], on-demand service, access to a large network, rapid elasticity and resource sharing [46]. Above all, Gosavi et al. [20] pointed out that libraries are likely to benefit from cloud storage in the area of self-healing, multi-tenancy, linearly scalable, service-oriented, SLA driven, virtualized and flexibility of services.
\nThe paper contributes to knowledge by protecting research data in cloud storage systems. Furthermore, the implication of the findings gives significant input to policymakers, information professionals and future researchers. Finally, with qualitative data, the adopted framework indicates how the security of cloud storage can be implemented successfully.
\nThe authors recommends the following; security/confidentiality of content, the resilience of librarians, determining access levels and enterprise cloud storage platforms if research output can be secured on the cloud;
\nContent concerns raised by Cave et al. [47] and Genoni [48] require consultation with legislation or the legal office of the academic institution. This is to say that the type of records and length of time for keeping research output must be determined, and policy put in place. In a fast-changing library environment, the technology for storage of research output suffers from obsolescence hence the need for regular back-ups to avoid data loss. Whichever way one considers the issue, storage and access concerns are central, leading to the consideration to make the cloud a viable option.
\nThere is a need for university librarians to maintain the character of resilience and also be adaptive to inevitable and unpredictable changes that occur at an accelerated pace. It is therefore required of librarians to provide a wide variety of information from an equally varied selection of sources and formats through teams (working together) and particularly with the prevalence of cloud use. Since cloud computing enables almost a new streamlined workflow, cooperation through team building or network can be very laudable.
\nTo overcome the enumerated challenge of unauthorized access to data centers, academic libraries must be concerned with the levels of accessibility; ranging from completely open access to highly private. In securing the content of the research assets on the cloud, different levels of accessibility or privileges must be assigned to the different users within the network. For instance, students, researchers, librarians, users outside the university community must be assigned roles as such.
\nThe authors highly recommends the enterprise cloud storage platforms such as Amazon Simple Storage Services (Amazon S3), Google cloud storage and Microsoft Azure. This is because they provide secure, durable, highly-scalable object storage, allows retrieval of any amount of data at any time and high-reliability performance and wide services including operating systems, frameworks, tools, and databases.
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