Some examples of synthesis methods and applications of hydrogels.
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More than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\\n\\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\\n\\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\\n\\nAdditionally, each book published by IntechOpen contains original content and research findings.
\\n\\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\\n\\n\\n\\n
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Simba Information has released its Open Access Book Publishing 2020 - 2024 report and has again identified IntechOpen as the world’s largest Open Access book publisher by title count.
\n\nSimba Information is a leading provider for market intelligence and forecasts in the media and publishing industry. The report, published every year, provides an overview and financial outlook for the global professional e-book publishing market.
\n\nIntechOpen, De Gruyter, and Frontiers are the largest OA book publishers by title count, with IntechOpen coming in at first place with 5,101 OA books published, a good 1,782 titles ahead of the nearest competitor.
\n\nSince the first Open Access Book Publishing report published in 2016, IntechOpen has held the top stop each year.
\n\n\n\nMore than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\n\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\n\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\n\nAdditionally, each book published by IntechOpen contains original content and research findings.
\n\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\n\n\n\n
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A hydrogel is a three-dimensional (3D) network of hydrophilic polymers that can swell in water and hold a large amount of water while maintaining the structure due to chemical or physical cross-linking of individual polymer chains. Hydrogels were first reported by Wichterle and Lím (1960) [1]. By definition, water must constitute at least 10% of the total weight (or volume) for a material to be a hydrogel. Hydrogels also possess a degree of flexibility very similar to natural tissue due to their significant water content. The hydrophilicity of the network is due to the presence of hydrophilic groups such as -NH2, -COOH, -OH, -CONH2, - CONH -, and -SO3H.
\nHydrogels undergo a significant volume phase transition or gel-sol phase transition in response to certain physical and chemical stimuli. The physical stimuli include temperature, electric and magnetic fields, solvent composition, light intensity, and pressure, while the chemical or biochemical stimuli include pH, ions, and specific chemical compositions. However, in most cases such conformational transitions are reversible; therefore, the hydrogels are capable of returning to their initial state after a reaction as soon as the trigger is removed. The response of hydrogels to external stimuli is mainly determined by the nature of the monomer, charge density, pendant chains, and the degree of cross-linkage. The magnitude of response is also directly proportional to the applied external stimulus.
\nThere are numerous original papers, reviews, and monographs focused on the synthesis, properties, and applications of hydrogels. This chapter covers the fundamental aspects and application areas of hydrogels.
\nThe literature reports a number of classifications of hydrogels and presents several views. Hydrogels are mainly formed from biopolymers and/or polyelectrolytes. Concerning definitions of hydrogel types, according to the source, hydrogels can be divided into those formed from natural polymers and those formed from synthetic polymers [2]. Depending on the ionic charges on the bound groups, hydrogels may be cationic, anionic, or neutral. The types of cross-linking agents also can be the criteria for classification.
\nHydrogels can be physical, chemical, or biochemical. Physical gels can undergo a transition from liquid to a gel in response to a change in environmental conditions such as temperature, ionic concentration, pH, or other conditions such as mixing of two components. Chemical gels use covalent bonding that introduces mechanical integrity and degradation resistance compared to other weak materials. In biochemical hydrogels, biological agents like enzymes or amino acids participate in the gelation process.
\nClassification of hydrogels based on the different properties.
It is also possible to divide hydrogels into groups based on their structure: amorphous, semicrystalline, crystalline, and hydrocolloid aggregates [3]. Figure 1 clearly represents the classification of hydrogels based on their source and properties, along with detailed classifications based on their response, that is, physically, chemically, and biochemically responsive hydrogels (Figures 2 and 3).
\nIn situ hydrogel formation using chemical cross-linking and ionic interaction between alginate and calcium ions [
In situ hydrogel formation using an enzymatic cross-linking reaction with horseradish peroxidase (HRP) and H2O2 [
Based on the methods of preparation, hydrogels may be classified as homopolymer, copolymer, semi-interpenetrating network (semi-IPN) and interpenetrating network (IPN). Table 1 indicates some examples.
\nType of hydrogel | \nMonomer | \nCross-linker | \nSpecific reaction conditions | \nReferences | \nApplications | \n
---|---|---|---|---|---|
Poly(2-hydroxyethyl methacrylate) (PHEMA) | \nPolyethylene glycol dimethacrylate | \nPresence of benzoin isobutyl ether as the UV-sensitive initiator | \n[4, 5] | \nDrug delivery systems, contact lenses, scaffolds for protein recombination | \n|
2-Hydroxyethyl methacrylate (HEMA) | \n|||||
TEGDMA (triethylene glycol dimethacrylate) | \n|||||
Polyethylene glycol (PEG) | \nWound healing and functional tissues production | \n||||
Methacrylic acid (MAA) | \nTetra(ethylene glycol) dimethacrylate | \nFree-radical photopolymerization | \n[4–7] | \nDrug delivery, hydrogel dressing material | \n|
PEG-PEGMA | \n|||||
Carboxymethyl cellulose (CMC) | \n|||||
Polyvinylpyrrolidone (PVP) | \n|||||
Acrylamide/acrylic acid copolymer | \nTemplate copolymerization | \n[75] | \nDrug delivery | \n||
Linear cationic polyallylammonium chloride | \n|||||
Poly( acrylamide) (PNIPAM) | \n[76] | \nDrug delivery | \n|||
Chitosan | \n|||||
Acrylate-modified PEG and acrylate-modified hyaluronic acid | \nNo cross -linking agent | \nPresence of UV light and a photo-initiator | \n[63, 49] | \nTissue regeneration | \n|
Heparin | \nEDC/sulfo-NHS solution and low temperature | \n||||
Amine end-functionalized 4-arm star-PEG | \n
Some examples of synthesis methods and applications of hydrogels.
Homopolymers contain only one type of monomer in their structure, and based on the nature of the monomer and the technique used for polymerization, they may have a cross-linked structure (Figure 4).
\nStructures of (a) HEMA and (b) TEGDMA.
Copolymeric hydrogels are composed of two types of monomers, of which at least one is hydrophilic in nature (Figures 5–7).
\nSynthesis of the poly(e-caprolactone)-HEMA macromonomer.
Synthesis of the poly(2-hydroxyethyl methacrylate)-graft-poly(e-caprolactone) copolymer.
Dicyclohexylcarbodiimide (DCCI) method to synthesize PEG-containing macromonomers.
A semi-IPN forms when a linear polymer penetrates into another cross-linked network without any other chemical bonds between them. Semi-IPNs can more effectively preserve rapid kinetic response rates to pH or temperature due to the absence of a restricting interpenetrating elastic network while still providing the benefits like modified pore size, slow drug release, etc.
\nCombining of two polymers can lead to the formation of IPNs provided that one of them is already present in the solution and the other is synthesized or cross-linked in situ. This process is done by preparing a solution of monomers and initiators and then immersing a pre-polymerized hydrogel into this solution. The pore size and surface properties of an IPN can be modified to control the kinetics of drug release, environmental interactions of the hydrogel, and its mechanical features.
\nIt is worth to point here the self-assembling peptide systems that are synthetic amino acid-based molecules which undergo a sol-gel transition when brought to neutral pH and ionic concentration. These systems do not use cross-linking agents; hence, they can safely encapsulate cells and/or drugs without exposing them to toxic agents [49] (Figures 8 and 9).
\nIn situ hydrogel formation using photo-cross-linking.
Hydrogel formation by cross-linking of star-PEG and heparin.
The environment-sensitive hydrogels, also called “intelligent” or “smart” hydrogels, are currently the subject of considerable scientific research in various fields including biomedical, biotechnology, pharmaceutical, and separation science. In this section, we will introduce four classes of most used hydrogels.
\nAny pH-sensitive polymer structurally contains hanging acidic (e.g. carboxylic and sulfonic acids) or basic (e.g. ammonium salts) groups that respond to the pH changes in their environment by gain or loss of protons. Polyelectrolytes are polymers that have a large number of such ionizable groups. Anionic polyelectrolytes such as poly(acrylic acid) (PAA) are deprotonated in basic environmental conditions and then electrostatic repulsions between the chains strongly increase, which allow water molecules to penetrate causing drastic swelling of the hydrogel. However, in an acidic media, the acidic polymer protonates resulting in a decrease of charge density and polymer volume collapse (Figure 10). In contrast, cationic polyelectrolytes such as poly(
pH-dependent ionization of polyelectrolytes. (a) Poly(acrylic acid) and (b) poly(
Phase transition behavior of polyelectrolyte hydrogels. Acidic hydrogels (□) are ionized by deprotonation in basic solutions. Basic hydrogels (○) swell in acidic solutions due to the ionization of their basic groups by protonation. Amphiphilic hydrogels (Δ) contain both acidic and basic groups, therefore they show two-phase transitions.
Ionization of a polyelectrolyte takes place similar to acidic or basic groups of monoacids or monobases, but due to the electrostatic effects of neighboring groups, it will have a different dissociation constant (
The extent of swelling is influenced by any factor that alters this electrostatic repulsion including pH, ionic strength, and the type of counterions. Figure 12 shows this phenomenon. In this figure, hydrogel has two phases: one phase is separated, gel-like, and formed by polymer-polymer interactions. In this condition, the maximum hydrophobicity takes place and the shrinkage of hydrogel occurs. In the second phase, interactions between the solvent and the polymer create a mixed phase in which the polymer and the aqueous solution are mixed well. The maximal value of hydrophilicity and swelling occurs in this second phase [7].
\nPhase transition behavior of stimuli-responsive hydrogels.
Different pH-sensitive behaviors and degrees of swelling can be achieved by using different monomers. The most commonly studied ionic polymers for pH-responsive behavior include poly(acrylamide) (PAAm), PAA, poly(methacrylic acid) (PMAA), poly(diethylaminoethyl methacrylate) (PDEAEMA), and poly(dimethylaminoethyl methacrylate) (PDMAEMA). Polymers containing phosphoric acid derivatives have also been reported.
\nTemperature-sensitive hydrogels (thermogels) are aqueous monomer/polymer solutions, which have the ability to form a gel upon temperature change and have a slightly hydrophobic characteristic due to the presence of groups such as methyl, ethyl, and propyl, which preferably interact with water molecules by hydrogen bonds that cause the hydrogel to swell. These hydrogen bonds are correlated to the temperature. The structures of some of the temperature-sensitive hydrogels are shown in Figure 13.
\nStructures of some temperature-sensitive polymers.
As can be seen, the common characteristic of temperature-sensitive polymers is the presence of hydrophobic groups. Most polymers increase their water solubility as the temperature increases. However, in some cases water solubility decreases with an increase in temperature (inverse or negative temperature dependence) [9]. This unusual behavior produces a phenomenon of polymer phase transition as the temperature is raised to a critical value called the “lower critical solution temperature” or LCST, which is an entropy-driven process. In the case of hydrogels with negative thermosensitivity, right below the LCST, water is a good solvent for the polymer, and hydrogen bonding interactions between the polymer and water molecules lead to enhanced dissolution in water. However, when the temperature exceeds the LCST, these interactions are broken, and the polymer chains collapse and then precipitate in the media [10, 11]. These types of hydrogels comprise polymer chains that either possess moderately hydrophobic segments (if too hydrophobic, the polymer chains will not dissolve in water at all) or contain a mixture of hydrophilic and hydrophobic groups.
\nSome examples of poly(organophosphazene) thermogels.
As the temperature increases, positive thermosensitive hydrogels exhibit just the opposite behavior of negative thermosensitive hydrogels. The LCST of hydrogels can be modulated to increase by adding a hydrophilic component, or to decrease with a hydrophobic one. Due to this property, temperature-sensitive hydrogels swell below the LCST and collapse in an aqueous environment above this temperature, being thus suitable for controlled drug delivery. Among others, poly(
Other examples of thermosensitive hydrogels are collagen, agarose, hyaluronic acid, poly(organophosphazenes), and chitosan [58, 59] (Figure 14).
\nElectro-sensitive hydrogels, as the name indicates, undergo shrinking or swelling in the presence of an applied electric field. Like pH-sensitive hydrogels, they are usually composed of polyelectrolytes. Under the influence of an electric field, a force on counterions and immobile charged groups is produced in the network, which attracts mobile ions to the electrodes. As a result, the hydrogel can swell and shrink regionally at the cathode and anode, respectively. This phenomenon leads to bending of the hydrogel, which is caused by ion concentration difference inside the hydrogel network and culture medium and can be explained by Flory’s theory of osmotic pressure [12–17]. The extent of bending depends on hydrogel structure and electrical field characteristics including strength, direction, and duration of the electrical stimulus. Electro-sensitive hydrogels can selectively be permeable for a specific molecular size and adjust the water permeability by expanding and contracting in micropore size under electrical stimulation [18]. Because electro-responsive hydrogels can transform electrical energy into mechanical energy and have promising applications in biomechanics, sensing, energy transduction, sound dampening, chemical separations, controlled drug delivery [33], and tissue engineering [20, 21], these polymers are an increasingly important class of smart materials. Hydrogels of acrylamide and carboxylic acid derivatives like PAA have been utilized as electro-sensitive and biocompatible smart muscle-based devices [22, 23].
\nPhoto-responsive hydrogels undergo a change in their properties when irradiated with light of the appropriate wavelength. Typically, these changes are the result of light-induced structural transformations of specific functional groups along the polymer backbone or side chains. Light-sensitive hydrogels can expand and contract upon exposure to ultraviolet (UV) or visible light. Visible light offers many advantages over UV light including wide availability, low cost, ease of manipulation, and clean operation. The mechanism of visible light-induced volume change of hydrogels is based on the induction of temperature changes by incorporating a photo-responsive functional group (chromophore) (e.g. trisodium salt of copper chlorophyllin) into the polymer network. Under exposure to a specific wavelength, the chromophore absorbs light which is then dissipated locally as heat, increasing the “local” temperature of the hydrogel [26]. The resulting temperature change alters the swelling behavior of the thermosensitive hydrogel [9]. Because of the thermal nature of the infrared radiation, it can also be used to elicit a hydrogel response in the absence of chromophores. If an additional functional group, such as an ionizable moiety of PAA, is incorporated into the hydrogel network, the light-responsive hydrogels become sensitive to pH changes also. This type of hydrogel can be induced to shrink by visible light and can be induced to swell by increasing the pH. The UV-sensitive hydrogels can be synthesized by introducing a leuco derivative molecule into the polymer network. Leuco derivatives are normally neutral but dissociate into ion pairs upon UV exposure. At a fixed temperature, the hydrogels discontinuously swelled in response to UV irradiation but shrank when the UV light was removed [24]. The potential applications of light-responsive hydrogels in the development of artificial muscles [25, 64], reversible valves in microfluidic devices [65], and temporal drug delivery were proposed.
\nHydrogels are used in many fields. This is due to their specific structures and compatibility with different conditions of use. Flexibility of hydrogels, which is because of their water content, makes it possible to use them in different conditions ranging from industrial to biological, and the biocompatibility of the materials used to produce them and also their chemical behavior in biological environments, which can be nontoxic, extends their applications to the medical sciences.
\nMajor applications and some examples of hydrogel usages are listed below. Note that it is not a complete listing but considers the most practical applications of hydrogels in medicine and industry.
\nControlled drug delivery systems (DDS), which are used to deliver drugs at certain rates for predefined periods of time, have been used to overcome the limitations of regular drug formulations. The marvelous properties of hydrogels make them a great choice in drug delivery applications. The hydrogel structures with high porosity can be obtained by controlling two factors: the degree of cross-linking in the matrix and the affinity of hydrogel to the aqueous environment in which swelling occurs. Due to the porous structures, hydrogels are highly permeable to different kinds of drugs and thus drugs can be loaded and, in proper conditions, released [27]. The possibility of releasing pharmaceuticals for long periods of time (sustained release) is the main advantage obtained from hydrogels in drug delivery investigations, which results in supplying a high concentration of an active pharmaceutical substance to a specific location over a long period of time.
\nBoth physical (electrostatic interactions) and chemical (covalent bonding) strategies can be employed to enhance the binding between a loaded drug and the hydrogel matrix to extend the duration of drug release. Hydrogels can store and protect various drugs from hostile environments, and release them at a desired kinetics of the release. Drug release can be activated on demand by local changes in pH, temperature, the presence of specific enzymes, or by remote physical stimuli.
\nSince the pH change occurs at many specific or pathological body sites, it is one of the important environmental parameters for DDS. The human body exhibits variations of pH along the gastrointestinal tract and also in some specific areas such as certain tissues (and tumoral areas) and subcellular compartments. Both acidic and basic polymers are employed in pH-sensitive DDS. PAA, PMAA, poly(L-glutamic acid), and polymers containing sulfonamide are the most commonly used acidic polymers for drug delivery. Typical examples of the basic polyelectrolytes include poly(2-(dimethylamino) ethyl methacrylate) and poly(2-(diethylamino) ethyl methacrylate), poly(2-vinylpyridine), and biodegradable poly(β-amino ester).
\npH-sensitive hydrogels were also used for extraction and determination purposes by different methodologies [28–31].
\nThermosensitive polymers, like pH-responsive systems, offer many possibilities in biomedicine.
\nAmong many temperature-sensitive polymers, poly(
Heavy metal pollution is commonly found in wastewater of many industrial processes and has been known to cause severe threats to the public health and ecological systems. The removal of heavy metal ions from various water resources is of great scientific and practical interest.
\nSynthetic cross-linked polyacrylate hydrogels have been used to remove heavy metal toxicity from aqueous media [27]. However, application of these synthetic materials on large scales may not be a practical solution because they are very costly.
\nThe pollution caused by heavy metal ions can be removed by well-known adsorption processes which, alongside flexibility in design and operation, offer the advantage of reusing the treated effluent. Also because of general reversibility of adsorption process, it is usually possible to regenerate the adsorbent to make the process most cost-effective.
\nThe use of hydrogels as adsorbents for the removal of heavy metals, recovery of dyes, and removal of toxic components from various effluents has been studied. Adsorbents with carboxyl, sulfonic, phosphonic, and nitrogen groups on their surface favor metal ion adsorption [77].
\nThe hydrogels were proven to be excellent dye adsorbent materials with extremely high amounts of methylene blue adsorption.
\nAmong hydrogel-forming materials, polyelectrolytes have a special significance in heavy metal ions’ removal. Many applications of polyelectrolytes in this area are due to their ability to bind oppositely charged metal ions to form complexes.
\nIn fact, having both cationic and anionic charges on the micro- or nano-gel provides additional advantages for the removal of two distinct species simultaneously. Hydrogels are versatile and viable materials that show potential for environmental applications.
\nChitosan, alginate, starch, and cellulose derivatives are biopolymer-based hydrogels, which were used to remove metal ions from aqueous media. It has been shown that the sorption mechanism and sorption capacity of heavy metal ions were influenced by the functional groups of the hydrogel. This is because of the participation of other processes like chelating and ion exchange rather than simple sorption in removal of metal ions [78, 79].
\nChitosan-based hydrogels are applicable in the removal of heavy metal ions due to the presence of multiple amino (NH2) and hydroxyl (OH) groups in their structure. This applicability originates from the tendency of metal ions to form chelates with the so-called amino groups. But after reaction of chitosan with cross-linkers, its alkalescence which is related to adsorption capacity is decreased. Chemical modification of these functional groups can improve not only the adsorption capacity but also the physicochemical properties of chitosan [79, 80]. Different approaches were employed by researchers to modify chitosan including the use of amino acid esters, oxo-2-glutaric acid, pyridyl, ethylenediamine, carbodiimide, aromatic polyimides, amine-functionalized magnetic nanoparticles, and glycine [81–83]. It is shown in these studies that both adsorption capacity and mechanical resistance of chitosan-based hydrogels will improve after modification of functional groups.
\nTissue engineering is defined as a combination of materials, engineering, and cells to improve or replace biological organs. This needs finding proper types of cells and culturing them in a suitable scaffold under appropriate conditions. Hydrogels are an appealing scaffold material because their structures are similar to the extracellular matrix of many tissues, they can often be processed under relatively mild conditions, and they may be delivered in a minimally invasive manner [32]. Adequate scaffold design and material selection for each specific application depends on several variables, including physical properties, mass transport properties, and biological properties and is specified by the intended scaffold application and environment into which the scaffold will be placed. For example, the type of scaffold used to produce artificial skin must be different from that used for artificial bone and thus different structures for materials are needed.
\nBoth synthetic and naturally derived materials can be used to form hydrogels for tissue engineering scaffolds.
\nSynthetic hydrogels are interesting because it is easy to control their chemistry and structure and thus alter their properties. Examples of polymeric synthetic materials which can be used to form hydrogels are poly(ethylene oxide) (PEO), poly(vinyl alcohol) (PVA) and poly(propylene fumarate) (PPF) [33] (Figure 15).
\nStructure of synthetic hydrogel-forming polymers: (a) PEO, (b) PVA (100% hydrolyzed), and (c) PPF.
Naturally derived hydrogel-forming polymers are other candidates for use in tissue engineering scaffolds because they either are natural extracellular matrix components or have properties similar to these matrices and they interact in a favorable manner in vivo. Examples are alginate and chitosan [32–34] (Figure 16).
\nStructure of naturally derived hydrogel-forming polymers: (a) alginate and (b) chitosan.
Hydrogels are used for three purposes in tissue engineering applications. They may be used as agents for filling vacant spaces, carriers for delivery of bioactive molecules, and 3D structures that act as a support for cells and help the formation of an ideal tissue.
\nAgents for filling vacant spaces (space-filling agents) include scaffolds that provide bulking, prevent adhesions, or act as bioadhesives [33]. To reach this aim, the most basic design requirements for a hydrogel are the abilities to keep a desired volume and structural integrity for the required time.
\nHydrogel scaffolds based on alginate, chitosan, and collagen show potential for use as general bulking agents. Synthetic hydrogels are often used as anti-adhesive materials because cells lack adhesion receptors to them and proteins often do not readily absorb to them if designed appropriately. Polyethylene glycol (PEG) has been used to prevent post-operative adhesions [32, 33].
\nHydrogels composed of chitosan and chitin derivatives are now used as biological adhesives in surgical procedures to seal small wounds out of which air and body fluids could leak, and to improve the effectiveness of wound dressings [37, 38].
\nAnother application of scaffold hydrogels that is quite different includes using them as vehicles to stabilize and deliver bioactive molecules to the target tissues and to encapsulate secretory cells. Currently, most drugs are delivered into patients systemically without the use of a scaffold, so large doses are usually required for a desired local effect because of enzymatic degradation of the drug and nonspecific uptake by other tissues. This is a costly process and can cause serious side effects. In addition, many factors, which are necessary or beneficial to the target tissue, may be toxic to other tissues. Thus, a vehicle or scaffold allowing for local and specific delivery to the desired tissue site is highly desirable in many situations. Ionically cross-linked alginate hydrogels and glutaraldehyde cross-linked collagen sponges are some of the examples to fulfill this requirement [39, 40].
\nAs hydrogels are highly hydrated 3D networks of polymers, they can provide chemical and mechanical signals and also an environment for cells to adhere, proliferate, and differentiate; thus, they are suitable for cell delivery and tissue development goals. Nowadays, hydrogel scaffolds are being used to produce a wide range of tissues, including cartilage, bone, muscle, fat, liver, and neurons. Based on the type of the desired tissue, different kinds of hydrogels can be utilized. For example, alginate has been used more widely than other hydrogels to assess the in vivo potential of hydrogel scaffolds for cartilage engineering and also as Schwann cell matrices in the area of nerve grafting, and collagen has been used for engineering large blood vessels [33].
\nA key area in the use of synthetic hydrogels for bioapplications is ophthalmology, especially contact lenses. A contact lens is a small optical device placed directly on the cornea to alter the corneal power. The first concept of using contact lenses was described by Leonardo da Vinci in 1508; this consisted of immersing the eye in a bowl of water. At the end of 1960, poly(2-hydroxyethyl methacrylate) (PHEMA) lenses were developed by Professor Otto Wichterle; this invention represents the most important step in contact lens development and the start of soft lenses’ era [41].
\nDirect placing of contact lenses on the surface of cornea prevents the exchange of atmospheric oxygen and thus disturbs the natural physiological metabolism of the cornea known as hypoxic stress, so a good contact lens must have maximum oxygen permeability. Mechanical stress to the cornea produces the same problems as the hypoxic stress, such as mitosis of the epithelial cells, elevated activity in protease and glycosidase, corneal sensitivity, and changes in corneal hydration and transparency. To reduce these stresses, the proper choice of contact materials and their shape are necessary.
\nHydrogels used for production of contact lenses can cover most of the requirements needed when using in different physiological conditions. For a hydrogel material that is used as a contact lens, there are some necessities to make it comfortable during usage. These necessities include amount of water content, good mechanical properties, permeability toward oxygen, wettability of surface, good optical facilities, stability toward hydrolysis and sterilization, having nontoxic nature, and having enough biological tolerance for living cells.
\nIn order to increase the water content of hydrogel and achieve an enhanced swelling effect, different types of monomers can be used. These include dihydroxy methacrylates, methacrylic acid, acrylamides, and many other monomers.
\nSilicone hydrogels represent an independent group of contact lens materials. The evolution of basic hydrogels gave rise to the production of this class, and they have good swelling properties and high permeability toward oxygen, which make them suitable for use in lenses. These properties are owing to their structure in which hydrophobic silicones are connected with hydrophilic chains in such a way that makes the resulting composite suitable both mechanically and optically.
\nHigh oxygen permeability is achieved with the siloxymethacrylate monomer commonly referred to as “TRIS.“ The methylene groups in the structure of TRIS represent the sites for hydrophilic modification (Figure 17).
\nStructure of siloxymethacrylate monomer (TRIS).
It is possible to incorporate linear or branched hydrophilic polymer chains into the structure of the polymer to form an interpenetrated network to reduce the drying by the lenses when using them normally. This means that the “wetting chains” are fixed only by physical bonds without any covalent attachments to the patterned hydrogels’ network [43].
\nStimuli-responsive polymers or hydrogels can change their volume significantly in response to small alterations of certain environmental parameters. Cationic polyelectrolytes dissolve (swell) more at low pH and anionic polyelectrolytes vice versa and this is due to ionization [44].
\nTwo types of transducers are used in pH-sensitive hydrogel sensors: transducers based on mechanical work performed by hydrogel swelling and shrinking and those observing changes in properties of free swelling gels [45].
\nThe ability of hydrogels to deform or to strain mechanically a transduction element resulting in a change of a special property of that element or in a change of a detectable distance is the basis of operation of transducers based on mechanical work of the hydrogel. They are classified as optical transducers, including reflective diaphragms and fiber Bragg grating sensors, and mechanical transducers, including microcantilevers and bending plate transducers.
\nTransducers of free swelling gels have to directly observe changes in one or more hydrogel properties and include optical, conductometric, and oscillating transducers. Optical transducers can directly measure changes in optical properties of hydrogels. A different approach is based on the observation of special fillings or surface coatings, which are changed or moved due to hydrogel swelling. Oscillating transducers are devices that keep changing their resonance frequency. Changes in the properties of a load result in a shift of this resonance frequency. This can be accompanied by a change of the signal amplitude. Conductometric transducers are based on measuring the conductivity of hydrogel as the degree of swelling changes [44].
\nCombining physical and chemical sensors results in a biosensor. There are two definitions for what a biosensor can do: it can be thought as a device that can sense and report a biophysical property of the system under study or a device that can deliver useful analytical information from transforming biochemical data. A common aspect in all biosensors is the presence of a biological recognition part that makes it possible to analyze biological information. Biosensors are becoming increasingly important as practical tools to cover a wide variety of application areas including point-of-care testing, home diagnostics, and environmental monitoring. Biological recognition part known as bioelement consists of different structures like enzymes, antibodies, living cells, or tissues but the point is its specificity toward one analyte and zero response to other interferents. There are various methods for coupling biomolecules with sensors including entrapment into membranes, physical adsorption, entrapment into a matrix, or covalent bonding [42, 44].
\nThe high water content and hydrophilic nature of hydrogels are similar to the void-filling component of the extracellular matrix and render them intrinsically biocompatible. Hence, an apparent application of hydrogels in biosensors is the protection and coating function of sensor parts to prevent undesired interaction with biological molecules or cells. Hydrogels can be used as immobilization matrices for the biosensing elements and provide excellent environments for enzymes and other biomolecules to preserve their active and functional structure.
\nThe interaction between analyte and sensing element results in a volume change in response to target component and this volume change is the basis of recognition in hydrogel-based sensors (Figure 18).
\nVolume increase of a hydrogel biosensor in response to an analyte.
Several types of sensing elements are used based on the nature of analyte but these elements can be categorized in two distinct groups: molecular interactions and living sensors.
\nMolecular interactions used for sensing analytes encompass different mechanisms. One of them is enzyme-substrate interactions. As enzymes are highly specific and efficient in their reactions with substrates, they may be used for precise determination of desired analytes’ concentrations. There are many examples for different sensors based on enzyme-substrate interactions in hydrogel matrices including detection of organic-phase alcohols, amino acids, ammonia, urea, glucose, hydrogen peroxide, etc. Glucose-responsive hydrogels that are capable of acting as long-term insulin depots in response to increased blood glucose levels and automatically release doses of insulin at appropriate times are a promising development and could obviate the need for frequent injection and therefore provide a more convenient treatment option that would improve treatment efficacy and quality of life for hundreds of millions of people. The swelling of a hydrogel in the presence of glucose molecules makes it possible to release insulin in a controlled manner [46] (Figure 19).
\nConcanavalin A-based glucose-responsive hydrogel swelling mechanism.
Antibody-antigen-based sensors that are affinity-based devices with a coupling of immunochemical reactions are another class of molecular interactions group. The general working principle of these sensors is based on the specific immunochemical recognition of antibodies (or antigens) immobilized on a transducer to antigen (or antibodies) that produce signals which depend on the concentration of the analyte. It is possible to use quartz crystal microgravimetry (QCM), surface plasmon resonance (SPR), or electrochemical methods for detection of the analyte.
\nThere are several other examples of molecular interaction-based sensing of analytes like nucleotide, oligonucleotide, DNA, etc.
\nAnother group of sensing elements is living sensors. They are combinations of hydrogels with living cells and microorganisms to form living cell-polymer composites for biosensing application. Microorganisms can detect a wide range of chemical substances, they are amenable to genetic modification and have a broad operating pH and temperature range, making them ideal as biological sensing materials. 3D structures, high water content, and biocompatibility are the main advantages of hydrogels that provide the ability to entrap cells or bacteria inside their networks enabling them to exchange gases in high rates and nourish the entrapped cells and in this way provide the possibility of usage of the cell-polymer composites in a biosensor. An instance is the use of
There are two different methods to use hydrogels in biosensors: they can be coated on the surface of a sensing device like an electrode or be used as a 3D matrix or support to maintain bioelements such as cells. Preservation of cells for certain time periods in a hydrogel matrix and pathogen sensing are other examples of applications in this group (Figure 20).
\nSchematic diagram of the A.
Spinal cord injury (SCI) is a complex regenerative problem because of the multiple facets of growth inhibition that occur following trauma to the cord tissue. Many of these injuries do not hurt the dura mater and some of the axons are yet alive in the injury site and can be recovered. In such conditions, inserting a preformed frame or DDS into the damaged spinal cord by surgical operations may cause subsequent lesion. One alternative for this method is the use of in situ-forming scaffolds. What happens after injection into the injured cord area is the fast conversion of viscoelastic hydrogel from liquid form to gel and adaptation to the tissue of injury site [49].
\nThe small spaces between spinal cord tissue and even transected parts formed after SCI will be filled by in vivo conversion of liquid hydrogel to the gel form. The gel, which now serves as a scaffold, will eliminate vacant spaces and forms a template for regeneration of the injured cord tissue by helping cellular penetration and matrix. In this way, it is not necessary to create preformed scaffolds for each patient individually and disconnecting viable tissue at the injury site to implant the preformed scaffold, which can cause further damage and loss of functionality, will be avoided [50, 51] (Figure 21).
\nInjection of liquid hydrogel into the site of injury.
Injectable materials, in their liquid state, can be uniformly mixed with cells and other therapeutics prior to delivery into the injury site. The mechanical properties of gel scaffolds can more closely match the properties of the spinal cord tissue, compared to most preformed biomaterial matrices [49, 51].
\nThere are some requirements for the design and use of injectable systems based on their functions and design parameters.
\nTheir functions include [49, 52–54]:
\nCreate a scaffold for cellular infiltration and axonal ingrowth. The gel material itself will serve to bridge the lesion site.
Encapsulation of drugs and maintenance of bioactivity throughout gelation and release. Injectable systems can provide a sustained and tunable delivery of these agents locally to the lesion site.
Support of suspended cell populations prior to injection, throughout the solidification process, and within the lesion site. Cellular therapies are more effective when delivered and maintained locally in the injured area as opposed to being delivered systemically (Figure 22).
Functions of injectable hydrogels.
The importance of design parameters is originating from the difficulty in isolating the effects of cross-linking and macromer concentration-dependent material properties such as mechanical stiffness, mesh or pore size, degradation rate, and bioactive ligand density.
\nDesign parameters include biocompatibility of used materials with the tissue of injured site, mild solidification conditions, suitable porosity and mesh size of the designed scaffold, mechanical properties of the gel material, degradation rate, and bioactivity [55–57].
\nInjectable hydrogels can be natural or synthetic with their own benefits and disadvantages. They can also be classified as physical and chemical gels [49, 62].
\nGenerally, physical hydrogels have the limitation of weak mechanical properties; thus, a combination of chemical and physical cross-linking has been used to overcome this weakness. For example, PNIPAAm-co-glycidyl methacrylate (GMA) and polyamidoamine (PAMAM) macromers undergo a dual-hardening physical and chemical gelation precess and form PNIPAAm-co-glycidyl methacrylate (GMA)/polyamidoamine (PAMAM) injectable hydrogel [58].
\nInjectable hydrogel systems are minimally invasive and patient friendly. Cells or bioactive molecules are easy to mix with polymer solutions and these mixtures are in situ and easily form the 3D microenvironments into any desired defect shapes.
\nThe fast developments in portable electronic equipments industry such as wearable devices, arbitrarily curved displays and even transparent mobile phones, require the fabrication of flexible, transparent, lightweight and efficient storage options [73]. To this end, the key issue is the simultaneous incorporation of mechanical robustness, optical transmittance, and electronic conductivity [74]. Because of the importance of high-performance flexible supercapacitors, the technique of the supercapacitors is still making rapid progresses. Recently, several strategies for flexible supercapacitors have been demonstrated, including coating active materials, such as RuO2 [66], MnO2 [67], V2O5 [68], NiOH [69], and graphene nanosheets [70] onto conductive fibers by electrochemical deposition or casting and fabrication of hydrogel or aerogel films based on graphene [73]. However, these methods suffer from several disadvantages that hinder their large-scale commercialization, such as high cost of noble metals or expensive carbon support materials, limited ionic/electronic conductivity, poor mechanical flexibility, and scalable electrochemical synthesis conditions.
\nElectrically conducting polymer hydrogels show great potential for the expected integration due to their excellent solid-liquid interface, good electric characteristics, and mechanical flexibility, and represent a promising material platform for emerging flexible energy storage devices [71, 72]. Conducting polymers such as polyaniline, polypyrrole, and their derivatives provide the unique electrical properties of metals or semiconductors, as well as attractive properties associated with conventional polymers, such as ease of synthesis and flexibility in processing; therefore, supercapacitor hydrogels are attracting much attention as new power sources [73]. Flexible solid-state supercapacitors provide high power density, long cycle life, and the potential to achieve relatively high energy density.
\nShi et al. have recently synthesized a 3D nanostructured conductive polypyrrole hydrogel via an interfacial polymerization method [73]. The high-performance flexible solid-state supercapacitor demonstrated promising capacitive properties and good electrochemical stability during long-term cycling. So far, many aspects such as conductivity and morphology of conductive polymer hydrogels have been extensively studied. However, the combination of stretchability and transparency is unique, and particularly long cycle stability has not been achieved before. In this regard, Hao et al. demonstrated a facile and smart strategy for the preparation of structurally stretchable, electrically conductive, and optically semitransparent α-cyclodextrin polyacrylamide-polyaniline hybrid hydrogel networks as electrodes, which show a high performance in supercapacitor application [74].
\nThis chapter aims to introduce briefly the hydrogels: a class of natural or synthetic polymeric materials that have the ability to hold huge amounts of water because of their specific structures and subsequent swelling properties. Based on this ability, they found a wide variety of applications, and because of the possibility to modify the polymeric structure to obtain desired functionality, the areas of applications are rapidly expanding. They can be designed in such a way that they can respond to a specific stimulus including pH, temperature, light, etc. at a predefined level and thus be stimuli responsive. Among their amazing characteristics, the biocompatibility and biodegradability make them a powerful candidate to use in biological and environmental applications as implants or materials for removal of toxic pollutants. In addition, conducting hydrogels are often a good choice in designing and fabrication of supercapacitors, which promise the most rapid developments in electronics.
\nSerious environmental and climate problems have been arisen due to the continuous consumption and depletion of fossil fuels [1, 2, 3, 4]. This problem would be worst in the coming days as the demand of energy is going increased day by day. Consequently, there is a need of clean and sustainable energy resources such as solar cells and batteries. The solar cell always needs sun light to generate continuous electricity supply. This problem can be sort out by integrating an energy storage device to the solar cell. Batteries can be used for the above work however their replacement and maintenance are major issues [1, 3, 5, 6, 7]. Supercapacitors have drawn much attention in recent years to be used in several applications such as industrial power and energy management. Moreover, they are very efficient (fast charging/discharging and long life), low-cost and environmentally friendly [8, 9, 10, 11]. They have larger power density than batteries and capability to deliver the charge quickly [12, 13, 14, 15]. A supercapacitor is fabricated with two electrodes separated by a separator, and electrolyte (Figure 1). The electrode materials have decisive role in the charge storage capacity; therefore, different materials and their combinations have been used in supercapacitor [2, 16, 17, 18, 19]. Supercapacitor can store the energy via two process (1) formation of electric double layer (EDL) at the electrode/electrolyte interface [4, 19, 20] and (2) redox reactions (pseudocapacitor) [16, 21, 22] (Figure 2). Carbon and silicon based materials are generally used for EDL capacitor whereas pseudocapacitor consists of metal oxides and conducting polymers. A hybrid supercapacitor technology has also been developed by combining the properties of EDLC and pseudocapacitor [24, 25, 26, 27].
Structure of (a) dielectric capacitor and (b) supercapacitor.
(a) Ragone plot for different devices. (b) Schematic representation of charge storage at high surface area electrode. (c) Different models for EDL: Helmholtz model, Gouy–Chapman model and Gouy–Chapman–Stern model. Charge storage process via redox process (pseudocapacitor); (d) bulk redox and (e) surface redox. (Reprinted with permission from Ref. [
Carbon based electrodes can offer high power and long cycle stability. However, low energy density is major concern with carbon electrodes [28, 29]. In the past decade, major efforts have been made developing a hybrid supercapacitor in order to meet the demands of high energy and high power density [30, 31]. Nano-sized structure of metal oxides can offer higher surface area to the electrode for good electrode/electrolyte ions interaction and short ion-diffusion length. Among metals oxides, iron oxides (FeO
A supercapacitor or ultracapacitor is an advanced technology which has much larger capacitance than a normal capacitor. Supercapacitors can store the energy about 10 times more than dielectric capacitors and return the energy back faster than batteries. They occupy the place between dielectric capacitors and rechargeable batteries in Ragone plot (Figure 2a). The charge storage process in supercapacitor is completely different than that of conventional capacitor. In electrostatic capacitor, two conducting electrodes are separated by a dielectric material. The charge is stored by the polarization process in the dielectric material. In case of supercapacitor, an electrolyte is filled between two electrodes of high surface area. During charging, opposite charge starts accumulating on the surface of electrodes. As the charge is stored physically with no chemical change, it is highly reversible and it shows stable behavior for a large number of cycles. Capacitance (C) is defined as the ratio of stored charge (Q) to the applied voltage (V)
C is directly proportional to the surface area (A) of each electrode and inversely proportional to the distance (d) between the electrodes
Where ε is the permittivity of the insulating material, A is the area of the electrode and d is the distance between the electrodes. The energy (E) of a capacitor is calculated by the following equation;
Power (P) is the energy delivered by a device per unit time. The maximum power is limited by equivalent series resistance (ESR) with the following relation
An EDLC has two electrodes which are immersed in an electrolyte and separated by a separator. Its charge storage is non faradaic in nature, there is no transfer of charge between electrode and electrolyte. Electric charge is accumulated electrostatically on electrode/electrolyte interface which is responsible for the formation of EDL (Figure 2b). The charging and discharging processes are highly reversible and there is no chemically change in the electrodes. This leads to the increased in cycle life, compared to batteries but less than conventional capacitor.
Pseudo means false so, as the name indicates this type of materials do not store charge like a conventional capacitor that is by forming EDL but work like a capacitor. The charge storage mechanism of such type of capacitor is faradaic in nature or the electrode reacts with the electrolyte to store charge (Figure 2d and e). Transition metal oxide and polymer show such kind of behavior. A reversible redox processes take place in which the valence electrons of electro active materials are transferred across the electrode/electrolyte interface, resulting in a potential-dependent capacitance (Figure 2e). The term pseudo-capacitance is used to distinguish this mechanism of charge storage from double layer. So we can say that that pseudo capacitance possess battery-like behavior with faradic reactions between electrodes and electrolyte. Table 1 shows the difference between EDLC and pseudocapacitor.
EDL capacitor | Pseudocapacitor |
---|---|
It stores charge by non-faradaic mechanism. | It stores charge by faradaic mechanism. |
Capacitance is low as compared to pseudo capacitance. | Capacitance is 10 times higher than EDLC. |
Large cycle stability | Poor cycle stability |
The charging/discharging curve is highly reversible | Reversible but not as compared to EDLC |
Comparison between EDLC and pseudocapacitor.
Fe2O3 electrode stores the charge via reversible oxidation/reduction reactions at the electrode and electrolyte interface. Low conductivity and poor cycling stability hamper its application in supercapacitor. Shivakumara et al. [36] have used porous α-Fe2O3 as electrode in supercapacitor. Porous α-Fe2O3 synthesized by sol–gel route offered BET surface area of 386 m2 g−1. α-Fe2O3 demonstrated specific capacitance of 300 F g−1 in 0.5 M Na2SO3 at a discharge rate of 1 A g−1. However, the electrode could retain only 73% of the initial capacitance after 1000 cycles.
Flower-like α-Fe2O3 nanostructures prepared by ethylene glycol mediated self-assembly process exhibited capacitance value of 127 F g−1 in 0.5 M Na2SO3 determined at a current density of 1 A g−1 [37]. Flower-like α-Fe2O3 has retained 80% of the initial capacitance after 1000 cycles. Despite of good value of capacitance, Fe2O3 does not meet the requirement of long cycle life. Change in volume during multiple cycles causes large degradation in the capacitance. Therefore, maximum efforts have been made towards shorting the diffusion length of electrolyte ions and minimizing the volume change by combining Fe2O3 with conducting materials.
Large efforts have been made to add a conductive phase to Fe2O3 electrodes to enhance overall capacitive performance. Abad et al. [38] have synthesized rGO-Fe2O3 nanocomposites by hydrothermal process for supercapacitor application. In the composite electrode, Fe2O3 nanoparticles have average size of 25 nm and are anchored on graphene sheets making good physical contact. The Fe2O3 nanoparticles prevent the restacking of rGO sheets which results in good accessibility of electrolyte ions to the electrode. rGO-Fe2O3 exhibited a specific capacitance of 291 F g−1 at 1 A g−1 in 1 M KOH aqueous solution. The performance was observed stable in the negative potential window of −1 to 0 V with three-electrode system. Fe2O3 worked well as negative electrode in asymmetric supercapacitor. A hybrid structure of porous Fe2O3 nanosheets on carbon fabric (CF-Fe2O3) was developed in order to overcome poor electrical conductivity and poor cycling stability of Fe2O3 [39]. Fe2O3 was deposited on CF via electrodeposition process. An asymmetric supercapacitor with CF-Fe2O3 as negative electrode and CF-Co3O4 as positive electrode was fabricated, which exhibited a good value of areal capacitance to be 842 mF cm−2. The asymmetric supercapacitor demonstrated maximum volumetric energy density of 6.75 mWh cm−3 and power density of 104 mW cm−3. The device retained 93% capacitance after 4000 cycles.
Jiang et al. [40] have synthesized Fe2O3/porous carbon nanocomposites (Fe2O3/HAC) by hydrothermal method. The porous carbon prevents the agglomeration of Fe2O3 nanoparticles and minimizes the ion diffusion path on the electrode surface, providing more flow channels for the ions. Fe2O3/HAC demonstrated larger capacitance of 156 F g−1 than that of individual components of HAC (145 F g−1) and Fe2O3 (90 F g−1). Redox peaks were observed in CV of both Fe2O3 and Fe2O3/HAC. The obtained CV consisted of a pair of oxidation peaks at −0.652 and −0.641 V and reduction peaks at −0.996 and −1.038 V, respectively. Fe2O3/HAC stores the charge via following mechanism;
A specific capacitance of 970 F g−1 was achieved from Fe2O3/rGO composite which was prepared by in situ synthesis and mechanical agitation methods [41]. This high value of capacitance is mainly due to the synergistic effect between Fe2O3 and rGO. rGO provides high electrical conductivity to the composite electrode and makes fast channels for the movement of charges. A degradation of 25% of capacitance was observed after 2000 cycles. A carbon shell layer has been coated on porous Fe2O3 nanowire arrays by hydrothermal route to improve the electrochemical properties of the electrode [42]. Fe2O3/C was used as the anode in solid state asymmetric supercapacitor with MnO2 as the cathode. A wide voltage of 2 V was achieved with this configuration. The fabricated device could give a maximum energy density of 30.625 Wh kg−1 and a maximum power density of 5000 W kg−1. The device exhibited good stability about 82% retention of capacitance after 10,000 cycles. A α-Fe2O3/MnOx and α-Fe2O3/C core-shell nanostructures were developed to design an asymmetric supercapacitor [43]. In the hybrid electrode, fast reversible redox-reactions occur on MnOx and α-Fe2O3 NR core facilitates electron transfer between shell and the current collector. Similarly, α-Fe2O3/C core-shell works as negative electrode. The asymmetric device fabricated with α-Fe2O3/C//α-Fe2O3/MnOx core-shell exhibited specific capacitance of 1.28 F cm−3 at a scan rate of 10 mV s−1 with voltage window of 0–2 V. The supercapacitor was able to retain 78% capacitance at the scan rate of 400 mVs−1 with a maximum energy-density of ∼0.64 mWh cm−3 and a maximum power-density of 155 mW cm−3. Zhang et al. [44] have developed Fe2O3@NiO nanorods on flexible carbon cloth by hydrothermal method. A specific capacitance of 800 mF cm−2 at 10 mA cm−2 was obtained with Fe2O3@NiO/CC electrode. Remarkable long cycle stability (96.8% capacitance retention after 16,000 cycles) was demonstrated by the electrode. This outstanding performance from Fe2O3@NiO/CC is due to the good electrical contact of active material with flexible carbon.
α-Fe2O3 has shown good electrochemical performance with graphitic (g-C3N4) carbon nitride [45]. The as-prepared g-C3N4/α-Fe2O3 composites with large specific surface area exhibited specific capacitance of 580 F g−1 determined at 1.0 A g−1 in 1M KOH. The Fe2O3 nanoparticles accommodate the space between the layers of g-C3N4 avoiding restacking and increasing the probability of interaction between Fe2O3 and electrolyte. Zhong et al. [46] have fabricated a heterostructure of Fe2O3 nanospheres anchored on FeS2 nanosheets by one-step hydrothermal approach for supercapacitor. The FeS2@Fe2O3 hybrid electrode demonstrated a specific capacitance of 255 F g−1 as well as good cycle stability, 90% capacitance retention after 5000 cycles. The excellent long cycle life could be ascribed to hybrid structure which can facilitate fast transportation of the electrolyte ions. A hybrid electrode of PEDOT coated onto Ti-doped Fe2O3 showed a remarkable capacitive performance [47]. A high value of areal capacitance of 1.15 F cm−2 at 1 mA cm−2 has been achieved with this strategy. Ti-Fe2O3@PEDOT demonstrated extraordinary cyclic stability of 96% retention in capacitance after 30,000 cycles, which is better than that of Ti-Fe2O3 (80.7%) and Fe2O3 (81.8%) electrodes. Ti-doping in the electrode enhances electrical conductivity and better utilization of Fe2O3. PEDOT has two important roles here, working as protective layer for Fe2O3 and relaxing the transfer of electrons.
A high specific capacitance of 1124 F g−1 has been achieved form a ternary composite of polyaniline/Fe2O3 decorated graphene coated on carbon cloth (Figures 3 and 4) at a current of 0.25 A g−1 in 1 M H2SO4 [48]. This large value of specific capacitance is due to the synergistic effects of individual component in the electrode. Graphene contributes as EDL capacitance and Fe2O3 and polyaniline as pseudocapacitance to the overall capacitance of hybrid electrode. In-situ polymerization of polyaniline also leads to improve the surface area of electrodes. Le et al. [50] have fabricated a hybrid electrode of polypyrrole-coated Fe2O3 nanotubes (Fe2O3@PPy) for high-performance electrode for aqueous asymmetric supercapacitor. A thin layer of polypyrrole was coated on Fe2O3 nanotubes by an in situ chemical oxidative polymerization method. Fe2O3@PPy could deliver a capacitance of 530 mF cm−2 at 1 mA cm−2. There is synergistic effect between PPy and Fe2O3, the shell of conducting PPy makes an ease transportation for charge carriers and improves stability of Fe2O3 nanotubes while charging/discharging process. The fabricated asymmetric supercapacitor with Fe2O3@PPy and MnO2 nanotubes could deliver energy density of 51.2 Wh kg−1 at a power density of 285.4 W kg−1 operated at high voltage of 2.0 V. 83.5% capacitance retention was observed over 5000 cycles with the asymmetric supercapacitor.
Schematic illustration of synthesis process of (a) Fe2O3 decorated graphene and (b) ternary Polyaniline/Graphene/Fe2O3 (PGF) composite on carbon cloth. (Reprinted with permission from Ref. [
Electrochemical behavior of the GF-CNT@Fe2O3//GF-CoMoO4 supercapacitor. (a) Full-cell structure. (b) CV curves, (c) rate capability, (d) cycling life, (e) Ragone plot of the asymmetric supercapacitor. Digital photos of the single electrode and full cell are depicted in insets of (c). (Reprinted with permission from Ref. [
Guan et al. [49] have developed an ultrahigh-energy and long-life supercapacitor anode material by coating a thin layer of Fe2O3 on graphite foam-carbon nanotube framework GF-CNT@Fe2O3. GF-CNT@Fe2O3 as anode was also integrated into a full supercapacitor cell with GF-CoMoO4 as cathode. A high energy density of ∼74.7 Wh kg−1 with power density of∼1400 W kg−1 has been obtained from the full device. The device also exhibited exceptional cycle stability, retention of about 95.4% capacitance after 50,000 cycles. These values make it a promising candidate for high performance supercapacitor. Improvement in the electrochemical performance of Fe2O3 based electrode may also be possible by introducing nitrogen in the electrode. In this regard, Zhao et al. [51] have synthesized nitrogen-doped graphene and Fe2O3 composites (NGFeCs) by hydrothermal method. NGFeCs exhibited improved electrochemical performance than GFeCs. The specific capacitance of NGFeCs electrode was determined to be 260.1 F g−1 (150.4 Fg−1 for GFeCs electrode) with current density of 2 A g−1. In addition to above, 82.5% retention in capacitance was observed after 1000 cycles. The improvement in the performance is due to the good electronic conductivity and increased active sites.
Self-assembled α-Fe2O3 mesocrystals/graphene nanohybrids demonstrated a good value of specific capacitance of 306.9 F g−1 at 3 A g−1 in an aqueous electrolyte and in voltage window of 1 V [33]. Porous structure of α-Fe2O3 mesocrystals/graphene nanohybrids with high electrical conductivity can provide fast transportation for electrolyte ions even at high discharge current densities. 2D α-Fe2O3/rGO nanocomposites fabricated by one-pot solvothermal approach exhibited specific capacitance value to be 903 F g−1 calculated at a current density of 1 A g−1 [52]. This value of capacitance was observed superior than α-Fe2O3 nanoplates. In the hybrid composite, α-Fe2O3 nanoplates were encapsulated in rGO nanosheets to form a porous structure. The α-Fe2O3/rGO nanocomposites with high electrical conductivity and 2D nanostructure promote the charge transportation between electrode and electrolyte, hence enhancing the electrochemical performance of the electrode.
Transition metal oxides (RuO2, MnO2, NiO, Fe2O3, Co3O4, etc.) have been used as electrode materials for supercapacitor application because they use rapid reversible redox reactions at the surface of active materials to offer high power density [9, 31, 53, 54, 55, 56, 57, 58]. Amongst the metal oxides, Fe3O4 is a better alternative electrode material for supercapacitor because of its low cost, natural abundance, environmental friendliness, high theoretical specific capacitance (2299 F g−1), large potential window and different valence states [59, 60, 61]. It has been seen in literature that Fe3O4 with various dimensions and morphology shows high value of specific capacitance [62].
The charge storage mechanism of Fe3O4 was investigated in various aqueous electrolytes such as sodium chloride, potassium hydroxide, sodium sulphate, sodium sulphite and sodium phosphate. Fe3O4 in the Na2SO3 electrolyte demonstrated a higher capacitance of 510 F g−1 with an operating potential of 1.2 V and this value was greater than those of other electrolytes [63]. Two pseudocapacitive mechanisms were purposed for Fe3O4 in the Na2SO3 electrolyte, which are given below
Eq. (7) represents the surface redox reaction of sulphur in the form of sulphate and sulphite anions while Eq. (8) represents the oxidation/reduction reaction between Fe(II) and Fe(III). It was observed that due to the addition of both the EDLC and pseudocapacitor, the capacitance of Fe3O4 in the Na2SO3 electrolyte rises and involves the reduction/oxidation of specially adsorbed sulphite anions as given by the following equations [63].
Many methods have been used to fabricate the Fe3O4 materials for supercapacitor application such as hydrothermal method [64, 65, 66, 67], Electroplating [63], sol-gel method [68], Chemical precipitation method [69], Hydrolysis and annealing process [70], solvothermal method [71], Electrospinning [72], Aerosol method [73]. Reports on different synthesis processes of Fe3O4 based electrodes and their specific capacitance values are given in Table 2.
Electrode | Synthesis process | Electrolyte | Capacitance | Ref. |
---|---|---|---|---|
Fe2O3/porous carbon | Hydrothermal | 6 M KOH | 256 F g−1 at 1 A g−1 | [40] |
FeS2 nanosheet@Fe2O3 nanosphere | Hydrothermal | 1 M Li2SO4 | 255 F g−1 at 1 A g−1 | [46] |
α-Fe2O3 nanostructures | Sol–gel route | 0.5 M Na2SO3 | 300 F g−1 at 1 A g−1 | [36] |
Polyaniline/graphene/Fe2O3 composites hydrogel | Microwave irradiation and in-situ polymerization | 1 M H2SO4 | 1124 F g−1 at 0.25 A g−1 | [48] |
α-Fe2O3/rGO | One-pot solvothermal approach | 1 M KOH | 903 F g−1 at 1 A g−1 | [52] |
Polypyrrole-coated Fe2O3 nanotubes | In situ chemical oxidative polymerization method | 1 M Na2SO4 | 530 mF cm−2 at 1 mA cm−2 | [50] |
Porous-Fe2O3@C nanowire | Hydrothermal route | 1 M Na2SO4 | 280 F g−1 at 1 Ag−1 and 241.3 mF cm−2 at 1 mA cm−2 | [42] |
α-Fe2O3/rGO composites | In situ synthesis and mechanical agitation methods | 6 M KOH | 970 F g−1 at 1 A g−1 | [41] |
Porous flowerlikeα-Fe2O3 | Ethylene glycol mediated self-assembly process | 0.5 M Na2SO3 | 127 F g−1 at 1 A g−1 | [37] |
Core-branch Fe2O3@NiO nanorods | Hydrothermal method | 3 M KOH | 800 mF cm−2 at 10 mA cm−2 | [44] |
Electrochemical capacitance of some Fe2O3 based electrodes.
Fe3O4@carbon nanosheet composite synthesized using ammonium ferric citrate precursor and graphene oxide as the structure-directing agent under a hydrothermal process was used as electrode in supercapacitor [59]. Fe3O4@carbon nanosheet composite exhibited a specific capacitance of 586 F g−1 at 0.5 A g−1 in KOH/PVA gel electrolyte. This composite showed excellent energy density of 18.3 Wh kg−1 and power density of 351 W kg−1.
Wang et al. [60] developed a simple route to fabricate the hybrid electrode of Fe3O4-doped porous carbon nanorods (Fe3O4-DCN) supported by three dimensional (3D) kenaf stem-derived macroporous carbon (KSPC) for supercapacitor. The 3D-KSPC/Fe3O4-DCN showed excellent specific capacitance of 285.4 F g−1 at the current density of 1 A g−1 and excellent cyclic stability in 2.0 M KOH electrolyte (Figure 5). Kumar et al. [61] prepared a hybrid electrode of 3D rGO NSs containing Fe3O4 NPs using one-pot microwave approach. The experimental studies showed that the as-synthesized Fe3O4/rGO hybrids were made of faceted Fe3O4 NPs with interconnected network of rGO NSs. The schematic formation mechanism is shown in Figure 6. This material as electrode in supercapacitor exhibited a specific capacitance of 455 F g−1 at the scan rate of 8 mV s−1.
(a) Schematic illustration of the formation process of carbon nanosheet embedded Fe3O4. (Reprinted with permission from Ref. [
Schematic formation mechanism of 3D Fe3O4/rGO hybrids. (Reprinted with permission from Ref. [
Chen et al. [74] fabricated a Fe3O4 film with regularly edge-affected cubic morphology on stainless foil using hydrothermal method and this film was used as electrode for supercapacitor. This film exhibited a specific capacitance of 118.2 F g−1 at the current of 6 mA in Na2SO3 electrolyte and good cycle stability about 88.75% capacitance retention after 500 cycles. Wang et al. [63] prepared the Fe3O4 film by an electroplating method to be used in supercapacitor as electrode. Fe3O4 film demonstrated a specific capacitance of 170 F g−1 in 1 M Na2SO3 electrolyte. Fe3O4 nanoparticles synthesized by sol gel method exhibited a specific capacitance of 185 F g−1 at the current of 1 mA in 3 M KOH electrolyte [68]. Brousse et al. [69] prepared Fe3O4 by chemical precipitation, which demonstrated a specific capacitance of 75 F g−1 in aqueous electrolyte of 0.1 M K2SO4. Liu et al. [64] synthesized Fe3O4 nanorods and carbon coated Fe3O4 nanorods via hydrothermal reaction and subsequent sintering procedure. Fe3O4 nanorods showed a specific capacitance of 208.6 F g−1 while carbon coated Fe3O4 nanorods exhibited a specific capacitance of 275.9 F g−1 at a current density of 0.5 A g−1 in 1 M Na2SO3 aqueous solution.
Guan et al. [65] synthesized carbon nanotube/Fe3O4 (CNT/Fe3O4) nanocomposite by an easy and efficient hydrothermal method. CNT/Fe3O4 nanocomposite showed enhanced specific capacitances of 117.2 F g−1 (which is three times than that of pure Fe3O4) at current density of 10 mA cm−2 in 6 M KOH electrolyte. It also exhibited superior cyclic stability and energy density of 16.2 Wh kg−1. Lin et al. [66] synthesized Fe3O4/GO by using hydrothermal method, which showed a specific capacitance of 661 F g−1 at current density of 1 A g−1 in 1 M KOH electrolyte. Qi et al. [70] prepared the Fe3O4/rGO composites using hydrolysis route and subsequent annealing process for supercapacitor application. The Fe3O4/rGO composite showed specific capacitance of 350.6 F g−1 at 1 mV s−1 in 6 M KOH electrolyte (Table 3).
Electrode | Method | Electrolyte | Specific capacitance | Reference |
---|---|---|---|---|
Fe3O4 thin film | Electroplating | 1 M Na2SO3 | 170 F g−1 | [63] |
Fe3O4 nanoparticles | Sol–gel | 3 M KOH | 185 F g−1 | [68] |
Fe3O4 | Chemical precipitation method | 0.1 M K2SO4 | 75 F g−1 | [69] |
Fe3O4 nanorods | Hydrothermal | 1 M Na2SO3 | 208.6 F g−1 | [64] |
Fe3O4/graphene | Hydrothermal | 1 M KOH | 661 F g−1 | [66] |
Fe3O4/reduced graphene oxide | Hydrolysis and annealing process | 6 M KOH | 350.6 F g−1 | [70] |
Fe3O4/reduced graphene oxide | Solvothermal process | 1 M KOH | 480 F g−1 | [75] |
Fe3O4–carbon nanosheets | Hydrothermal and heat treatment | 1 M Na2SO3 | 163.4 F g−1 | [67] |
Fe3O4 doped double-shelled hollow carbon spheres | Aerosol, spray and in-situ polymerization methods | 6 M KOH | 1153 F g−1 | [76] |
Capacitance of Fe3O4 based electrodes synthesized by different process.
It is seen that iron oxides have demonstrated excellent performance in supercapacitor and asymmetric supercapacitor as well [71, 72, 73, 77, 78, 79]. Shi et al. [75] prepared the nanocomposites of Fe3O4 NPs connected to rGO sheets by using a solvothermal process. Fe3O4/rGO nanocomposites were utilized to prepare thin film supercapacitor electrodes by using a spray deposition technique without the addition of insulating binders. It was observed that the Fe3O4/rGO nanocomposite exhibited higher specific capacitance, 480 F g−1 at a discharge current density of 5 A g−1, which is larger than that of pure rGO or pure Fe3O4 NPs. Fe3O4/rGO nanocomposite exhibited energy density of 67 W h kg−1 and power density of 5506 W kg−1. Ultrathin nanoporous Fe3O4–carbon nanosheets synthesized by hydrothermal method demonstrated a specific capacitance of 163.4 F g−1 in 1 M Na2SO3 electrolyte [67].
Mu et al. [80] synthesized Fe3O4 nanosheets on one-dimensional (1D) carbon nanofibers (CNFs) using the electrospinning technique and solvent-thermal process. The Fe3O4/CNFs nanocomposite exhibited a specific capacitance of 135 F g−1 in 1 M Na2SO3 electrolyte. The high capacitance may be due to the improved electrical conductivity of the composite by adding the CNFs in Fe3O4. Li et al. [76] prepared the double-shelled hollow carbon spheres with conductive graphite structure and Fe3O4 species (C-C-Fe3O4) using aerosol, spray, and in-situ polymerization methods. The C-C-Fe3O4 showed remarkable value of specific capacitance to be 1153 F g−1 at current density of 2 A g−1. C-C-Fe3O4 also demonstrated good rate capability, 514 F g−1 at 100 A g−1. The electrode exhibited only 3.3% degradation in the capacitance after 8000 cycles. Energy density of 17–45 W h kg−1 and powder density of 400–8000 W kg−1 were achieved from the C-C-Fe3O4 electrode.
Recent progress on supercapacitor is to increase its specific capacitance, rate capability, cycle life and operating voltage by developing low cost and eco-friendly electrode materials. In this regard, iron oxide may be a suitable candidate with higher value of capacitance as negative electrode for asymmetric supercapacitor to be operated at wide voltage window. Therefore, a lot of work has been carried out on iron oxide based electrode for supercapacitor application. The electrochemical performance of iron oxide based electrodes has been reviewed and discussed in this chapter. It is observed that the synthesis process and morphology of iron oxide play important role in supercapacitor performance. Efforts have been made towards preparing a composite of iron oxide with high conductive materials in order to overcome its poor electrical conductivity. Nanostructure of iron oxide such as nanoparticles could enhance the active sites for electrochemical reactions. Iron oxide nanostructure with carbon can further increase the specific capacitance and energy density of supercapacitor. Synthesis of iron oxide nanoparticles/graphene nanocomposite seems to be more effective approach for high performance supercapacitor.
The authors declare no conflict of interest.
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",metaTitle:"Team",metaDescription:"Advancing discovery in Open Access for the scientists by the scientist",metaKeywords:null,canonicalURL:"page/team",contentRaw:'[{"type":"htmlEditorComponent","content":"Our business values are based on those any scientist applies to their research. We have created a culture of respect and collaboration within a relaxed, friendly and progressive atmosphere, while maintaining academic rigour.
\\n\\nCo-founded by Alex Lazinica and Vedran Kordic: “We are passionate about the advancement of science. As Ph.D. researchers in Vienna, we found it difficult to access the scholarly research we needed. We created IntechOpen with the specific aim of putting the academic needs of the global research community before the business interests of publishers. Our Team is now a global one and includes highly-renowned scientists and publishers, as well as experts in disseminating your research.”
\\n\\nBut, one thing we have in common is -- we are all scientists at heart!
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\\n\\nSara Uhac was appointed Managing Director of IntechOpen at the beginning of 2014. She directs and controls the company’s operations. Sara joined IntechOpen in 2010 as Head of Journal Publishing, a new strategically underdeveloped department at that time. After obtaining a Master's degree in Media Management, she completed her Ph.D. at the University of Lugano, Switzerland. She holds a BA in Financial Market Management from the Bocconi University in Milan, Italy, where she started her career in the American publishing house Condé Nast and further collaborated with the UK-based publishing company Time Out. Sara was awarded a professional degree in Publishing from Yale University (2012). She is a member of the professional branch association of "Publishers, Designers and Graphic Artists" at the Croatian Chamber of Commerce.
\\n\\nAdrian Assad De Marco
\\n\\nAdrian Assad De Marco joined the company as a Director in 2017. With his extensive experience in management, acquired while working for regional and global leaders, he took over direction and control of all the company's publishing processes. Adrian holds a degree in Economy and Management from the University of Zagreb, School of Economics, Croatia. A former sportsman, he continually strives to develop his skills through professional courses and specializations such as NLP (Neuro-linguistic programming).
\\n\\nDr Alex Lazinica
\\n\\nAlex Lazinica is co-founder and Board member of IntechOpen. After obtaining a Master's degree in Mechanical Engineering, he continued his Ph.D. in Robotics at the Vienna University of Technology. There, he worked as a robotics researcher with the university's Intelligent Manufacturing Systems Group, as well as a guest researcher at various European universities, including the Swiss Federal Institute of Technology Lausanne (EPFL). During this time he published more than 20 scientific papers, gave presentations, served as a reviewer for major robotic journals and conferences and, most importantly, co-founded and built the International Journal of Advanced Robotic Systems, the world's first Open Access journal in the field of robotics. Starting this journal was a pivotal point in his career since it proved to be the pathway to the foundation of IntechOpen with its focus on addressing academic researchers’ needs. Alex personifies many of IntechOpen´s key values, including the commitment to developing mutual trust, openness, and a spirit of entrepreneurialism. Today, his focus is on defining the growth and development strategy for the company.
\\n"}]'},components:[{type:"htmlEditorComponent",content:"Our business values are based on those any scientist applies to their research. We have created a culture of respect and collaboration within a relaxed, friendly and progressive atmosphere, while maintaining academic rigour.
\n\nCo-founded by Alex Lazinica and Vedran Kordic: “We are passionate about the advancement of science. As Ph.D. researchers in Vienna, we found it difficult to access the scholarly research we needed. We created IntechOpen with the specific aim of putting the academic needs of the global research community before the business interests of publishers. Our Team is now a global one and includes highly-renowned scientists and publishers, as well as experts in disseminating your research.”
\n\nBut, one thing we have in common is -- we are all scientists at heart!
\n\nSara Uhac, COO
\n\nSara Uhac was appointed Managing Director of IntechOpen at the beginning of 2014. She directs and controls the company’s operations. Sara joined IntechOpen in 2010 as Head of Journal Publishing, a new strategically underdeveloped department at that time. After obtaining a Master's degree in Media Management, she completed her Ph.D. at the University of Lugano, Switzerland. She holds a BA in Financial Market Management from the Bocconi University in Milan, Italy, where she started her career in the American publishing house Condé Nast and further collaborated with the UK-based publishing company Time Out. Sara was awarded a professional degree in Publishing from Yale University (2012). She is a member of the professional branch association of "Publishers, Designers and Graphic Artists" at the Croatian Chamber of Commerce.
\n\nAdrian Assad De Marco
\n\nAdrian Assad De Marco joined the company as a Director in 2017. With his extensive experience in management, acquired while working for regional and global leaders, he took over direction and control of all the company's publishing processes. Adrian holds a degree in Economy and Management from the University of Zagreb, School of Economics, Croatia. A former sportsman, he continually strives to develop his skills through professional courses and specializations such as NLP (Neuro-linguistic programming).
\n\nDr Alex Lazinica
\n\nAlex Lazinica is co-founder and Board member of IntechOpen. After obtaining a Master's degree in Mechanical Engineering, he continued his Ph.D. in Robotics at the Vienna University of Technology. There, he worked as a robotics researcher with the university's Intelligent Manufacturing Systems Group, as well as a guest researcher at various European universities, including the Swiss Federal Institute of Technology Lausanne (EPFL). During this time he published more than 20 scientific papers, gave presentations, served as a reviewer for major robotic journals and conferences and, most importantly, co-founded and built the International Journal of Advanced Robotic Systems, the world's first Open Access journal in the field of robotics. Starting this journal was a pivotal point in his career since it proved to be the pathway to the foundation of IntechOpen with its focus on addressing academic researchers’ needs. Alex personifies many of IntechOpen´s key values, including the commitment to developing mutual trust, openness, and a spirit of entrepreneurialism. Today, his focus is on defining the growth and development strategy for the company.
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After almost 32 years of teaching at the University of Trás-os-Montes and Alto Douro, she recently moved to the University of Évora, Department of Veterinary Medicine, where she teaches in the field of Animal Reproduction and Clinics. Her primary research areas include the molecular markers of the endometrial cycle and the embryo–maternal interaction, including oxidative stress and the reproductive physiology and disorders of sexual development, besides the molecular determinants of male and female fertility. She often supervises students preparing their master's or doctoral theses. She is also a frequent referee for various journals.",institutionString:null,institution:{name:"University of Évora",country:{name:"Portugal"}}},{id:"283019",title:"Dr.",name:"Oudessa",middleName:null,surname:"Kerro Dego",slug:"oudessa-kerro-dego",fullName:"Oudessa Kerro Dego",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/283019/images/system/283019.png",biography:"Dr. Kerro Dego is a veterinary microbiologist with training in veterinary medicine, microbiology, and anatomic pathology. Dr. Kerro Dego is an assistant professor of dairy health in the department of animal science, the University of Tennessee, Institute of Agriculture, Knoxville, Tennessee. He received his D.V.M. (1997), M.S. (2002), and Ph.D. (2008) degrees in Veterinary Medicine, Animal Pathology and Veterinary Microbiology from College of Veterinary Medicine, Addis Ababa University, Ethiopia; College of Veterinary Medicine, Utrecht University, the Netherlands and Western College of Veterinary Medicine, University of Saskatchewan, Canada respectively. He did his Postdoctoral training in microbial pathogenesis (2009 - 2015) in the Department of Animal Science, the University of Tennessee, Institute of Agriculture, Knoxville, Tennessee. Dr. Kerro Dego’s research focuses on the prevention and control of infectious diseases of farm animals, particularly mastitis, improving dairy food safety, and mitigation of antimicrobial resistance. Dr. Kerro Dego has extensive experience in studying the pathogenesis of bacterial infections, identification of virulence factors, and vaccine development and efficacy testing against major bacterial mastitis pathogens. Dr. Kerro Dego conducted numerous controlled experimental and field vaccine efficacy studies, vaccination, and evaluation of immunological responses in several species of animals, including rodents (mice) and large animals (bovine and ovine).",institutionString:"University of Tennessee at Knoxville",institution:{name:"University of Tennessee at Knoxville",country:{name:"United States of America"}}},{id:"251314",title:"Dr.",name:"Juan Carlos",middleName:null,surname:"Gardón Poggi",slug:"juan-carlos-gardon-poggi",fullName:"Juan Carlos Gardón Poggi",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/251314/images/system/251314.jpeg",biography:"Juan Carlos Gardón Poggi received University degree from the Faculty of Agrarian Science in Argentina, in 1983. Also he received Masters Degree and PhD from Córdoba University, Spain. He is currently a Professor at the Catholic University of Valencia San Vicente Mártir, at the Department of Medicine and Animal Surgery. He teaches diverse courses in the field of Animal Reproduction and he is the Director of the Veterinary Farm. He also participates in academic postgraduate activities at the Veterinary Faculty of Murcia University, Spain. His research areas include animal physiology, physiology and biotechnology of reproduction either in males or females, the study of gametes under in vitro conditions and the use of ultrasound as a complement to physiological studies and development of applied biotechnologies. Routinely, he supervises students preparing their doctoral, master thesis or final degree projects.",institutionString:null,institution:{name:"Valencia Catholic University Saint Vincent Martyr",country:{name:"Spain"}}},{id:"309529",title:"Dr.",name:"Albert",middleName:null,surname:"Rizvanov",slug:"albert-rizvanov",fullName:"Albert Rizvanov",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/309529/images/9189_n.jpg",biography:'Albert A. Rizvanov is a Professor and Director of the Center for Precision and Regenerative Medicine at the Institute of Fundamental Medicine and Biology, Kazan Federal University (KFU), Russia. He is the Head of the Center of Excellence “Regenerative Medicine” and Vice-Director of Strategic Academic Unit \\"Translational 7P Medicine\\". Albert completed his Ph.D. at the University of Nevada, Reno, USA and Dr.Sci. at KFU. He is a corresponding member of the Tatarstan Academy of Sciences, Russian Federation. Albert is an author of more than 300 peer-reviewed journal articles and 22 patents. He has supervised 11 Ph.D. and 2 Dr.Sci. dissertations. Albert is the Head of the Dissertation Committee on Biochemistry, Microbiology, and Genetics at KFU.\nORCID https://orcid.org/0000-0002-9427-5739\nWebsite https://kpfu.ru/Albert.Rizvanov?p_lang=2',institutionString:"Kazan Federal University",institution:{name:"Kazan Federal University",country:{name:"Russia"}}},{id:"210551",title:"Dr.",name:"Arbab",middleName:null,surname:"Sikandar",slug:"arbab-sikandar",fullName:"Arbab Sikandar",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/210551/images/system/210551.jpg",biography:"Dr. Arbab Sikandar, PhD, M. Phil, DVM was born on April 05, 1981. He is currently working at the College of Veterinary & Animal Sciences as an Assistant Professor. He previously worked as a lecturer at the same University. \nHe is a Member/Secretory of Ethics committee (No. CVAS-9377 dated 18-04-18), Member of the QEC committee CVAS, Jhang (Regr/Gen/69/873, dated 26-10-2017), Member, Board of studies of Department of Basic Sciences (No. CVAS. 2851 Dated. 12-04-13, and No. CVAS, 9024 dated 20/11/17), Member of Academic Committee, CVAS, Jhang (No. CVAS/2004, Dated, 25-08-12), Member of the technical committee (No. CVAS/ 4085, dated 20,03, 2010 till 2016).\n\nDr. Arbab Sikandar contributed in five days hands-on-training on Histopathology at the Department of Pathology, UVAS from 12-16 June 2017. He received a Certificate of appreciation for contributions for Popularization of Science and Technology in the Society on 17-11-15. He was the resource person in the lecture series- ‘scientific writing’ at the Department of Anatomy and Histology, UVAS, Lahore on 29th October 2015. He won a full fellowship as a principal candidate for the year 2015 in the field of Agriculture, EICA, Egypt with ref. to the Notification No. 12(11) ACS/Egypt/2014 from 10 July 2015 to 25th September 2015.; he received a grant of Rs. 55000/- as research incentives from Director, Advanced Studies and Research, UVAS, Lahore upon publications of research papers in IF Journals (DR/215, dated 19-5-2014.. He obtained his PhD by winning a HEC Pakistan indigenous Scholarship, ‘Ph.D. fellowship for 5000 scholars – Phase II’ (2av1-147), 17-6/HEC/HRD/IS-II/12, November 15, 2012. \n\nDr. Sikandar is a member of numerous societies: Registered Veterinary Medical Practitioner (life member) and Registered Veterinary Medical Faculty of Pakistan Veterinary Medical Council. The Registration code of PVMC is RVMP/4298 and RVMF/ 0102.; Life member of the University of Veterinary and Animal Sciences, Lahore, Alumni Association with S# 664, dated: 6-4-12. ; Member 'Vets Care Organization Pakistan” with Reference No. VCO-605-149, dated 05-04-06. :Member 'Vet Crescent” (Society of Animal Health and Production), UVAS, Lahore.",institutionString:"University of Veterinary & Animal Science",institution:{name:"University of Veterinary and Animal Sciences",country:{name:"Pakistan"}}},{id:"311663",title:"Dr.",name:"Prasanna",middleName:null,surname:"Pal",slug:"prasanna-pal",fullName:"Prasanna Pal",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/311663/images/13261_n.jpg",biography:null,institutionString:null,institution:{name:"National Dairy Research Institute",country:{name:"India"}}},{id:"202192",title:"Dr.",name:"Catrin",middleName:null,surname:"Rutland",slug:"catrin-rutland",fullName:"Catrin Rutland",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/202192/images/system/202192.png",biography:"Catrin Rutland is an Associate Professor of Anatomy and Developmental Genetics at the University of Nottingham, UK. She obtained a BSc from the University of Derby, England, a master’s degree from Technische Universität München, Germany, and a Ph.D. from the University of Nottingham. She undertook a post-doctoral research fellowship in the School of Medicine before accepting tenure in Veterinary Medicine and Science. Dr. Rutland also obtained an MMedSci (Medical Education) and a Postgraduate Certificate in Higher Education (PGCHE). She is the author of more than sixty peer-reviewed journal articles, twelve books/book chapters, and more than 100 research abstracts in cardiovascular biology and oncology. She is a board member of the European Association of Veterinary Anatomists, Fellow of the Anatomical Society, and Senior Fellow of the Higher Education Academy. Dr. Rutland has also written popular science books for the public. https://orcid.org/0000-0002-2009-4898. www.nottingham.ac.uk/vet/people/catrin.rutland",institutionString:null,institution:{name:"University of Nottingham",country:{name:"United Kingdom"}}},{id:"283315",title:"Prof.",name:"Samir",middleName:null,surname:"El-Gendy",slug:"samir-el-gendy",fullName:"Samir El-Gendy",position:null,profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRduYQAS/Profile_Picture_1606215849748",biography:"Samir El-Gendy is a Professor of anatomy and embryology at the faculty of veterinary medicine, Alexandria University, Egypt. Samir obtained his PhD in veterinary science in 2007 from the faculty of veterinary medicine, Alexandria University and has been a professor since 2017. Samir is an author on 24 articles at Scopus and 12 articles within local journals and 2 books/book chapters. His research focuses on applied anatomy, imaging techniques and computed tomography. Samir worked as a member of different local projects on E-learning and he is a board member of the African Association of Veterinary Anatomists and of anatomy societies and as an associated author at local and international journals. Orcid: https://orcid.org/0000-0002-6180-389X",institutionString:null,institution:{name:"Alexandria University",country:{name:"Egypt"}}},{id:"246149",title:"Dr.",name:"Valentina",middleName:null,surname:"Kubale",slug:"valentina-kubale",fullName:"Valentina Kubale",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/246149/images/system/246149.jpg",biography:"Valentina Kubale is Associate Professor of Veterinary Medicine at the Veterinary Faculty, University of Ljubljana, Slovenia. Since graduating from the Veterinary faculty she obtained her PhD in 2007, performed collaboration with the Department of Pharmacology, University of Copenhagen, Denmark. She continued as a post-doctoral fellow at the University of Copenhagen with a Lundbeck foundation fellowship. She is the editor of three books and author/coauthor of 23 articles in peer-reviewed scientific journals, 16 book chapters, and 68 communications at scientific congresses. Since 2008 she has been the Editor Assistant for the Slovenian Veterinary Research journal. She is a member of Slovenian Biochemical Society, The Endocrine Society, European Association of Veterinary Anatomists and Society for Laboratory Animals, where she is board member.",institutionString:"University of Ljubljana",institution:{name:"University of Ljubljana",country:{name:"Slovenia"}}},{id:"258334",title:"Dr.",name:"Carlos Eduardo",middleName:null,surname:"Fonseca-Alves",slug:"carlos-eduardo-fonseca-alves",fullName:"Carlos Eduardo Fonseca-Alves",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/258334/images/system/258334.jpg",biography:"Dr. Fonseca-Alves earned his DVM from Federal University of Goias – UFG in 2008. He completed an internship in small animal internal medicine at UPIS university in 2011, earned his MSc in 2013 and PhD in 2015 both in Veterinary Medicine at Sao Paulo State University – UNESP. Dr. Fonseca-Alves currently serves as an Assistant Professor at Paulista University – UNIP teaching small animal internal medicine.",institutionString:null,institution:{name:"Universidade Paulista",country:{name:"Brazil"}}},{id:"245306",title:"Dr.",name:"María Luz",middleName:null,surname:"Garcia Pardo",slug:"maria-luz-garcia-pardo",fullName:"María Luz Garcia Pardo",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/245306/images/system/245306.png",biography:"María de la Luz García Pardo is an agricultural engineer from Universitat Politècnica de València, Spain. She has a Ph.D. in Animal Genetics. Currently, she is a lecturer at the Agrofood Technology Department of Miguel Hernández University, Spain. Her research is focused on genetics and reproduction in rabbits. The major goal of her research is the genetics of litter size through novel methods such as selection by the environmental sensibility of litter size, with forays into the field of animal welfare by analysing the impact on the susceptibility to diseases and stress of the does. Details of her publications can be found at https://orcid.org/0000-0001-9504-8290.",institutionString:null,institution:{name:"Miguel Hernandez University",country:{name:"Spain"}}},{id:"350704",title:"M.Sc.",name:"Camila",middleName:"Silva Costa",surname:"Ferreira",slug:"camila-ferreira",fullName:"Camila Ferreira",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/350704/images/17280_n.jpg",biography:"Graduated in Veterinary Medicine at the Fluminense Federal University, specialist in Equine Reproduction at the Brazilian Veterinary Institute (IBVET) and Master in Clinical Veterinary Medicine and Animal Reproduction at the Fluminense Federal University. She has experience in analyzing zootechnical indices in dairy cattle and organizing events related to Veterinary Medicine through extension grants. I have experience in the field of diagnostic imaging and animal reproduction in veterinary medicine through monitoring and scientific initiation scholarships. I worked at the Equus Central Reproduction Equine located in Santo Antônio de Jesus – BA in the 2016/2017 breeding season. I am currently a doctoral student with a scholarship from CAPES of the Postgraduate Program in Veterinary Medicine (Pathology and Clinical Sciences) at the Federal Rural University of Rio de Janeiro (UFRRJ) with a research project with an emphasis on equine endometritis.",institutionString:null,institution:null},{id:"41319",title:"Prof.",name:"Lung-Kwang",middleName:null,surname:"Pan",slug:"lung-kwang-pan",fullName:"Lung-Kwang Pan",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/41319/images/84_n.jpg",biography:null,institutionString:null,institution:null},{id:"125292",title:"Dr.",name:"Katy",middleName:null,surname:"Satué Ambrojo",slug:"katy-satue-ambrojo",fullName:"Katy Satué Ambrojo",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/125292/images/system/125292.jpeg",biography:"Katy Satué Ambrojo received her Veterinary Medicine degree, Master degree in Equine Technology and doctorate in Veterinary Medicine from the Faculty of Veterinary, CEU-Cardenal Herrera University in Valencia, Spain.Dr. Satué is accredited as a Private University Doctor Professor, Doctor Assistant, and Contracted Doctor by AVAP (Agència Valenciana d'Avaluació i Prospectiva) and currently, as a full professor by ANECA (since January 2022). To date, Katy has taught 22 years in the Department of Animal Medicine and Surgery at the CEU-Cardenal Herrera University in undergraduate courses in Veterinary Medicine (General Pathology, integrated into the Applied Basis of Veterinary Medicine module of the 2nd year, Clinical Equine I of 3rd year, and Equine Clinic II of 4th year). Dr. Satué research activity is in the field of Endocrinology, Hematology, Biochemistry, and Immunology in the Spanish Purebred mare. She has directed 5 Doctoral Theses and 5 Diplomas of Advanced Studies, and participated in 11 research projects as a collaborating researcher. She has written 2 books and 14 book chapters in international publishers related to the area, and 68 scientific publications in international journals. Dr. Satué has attended 63 congresses, participating with 132 communications in international congresses and 19 in national congresses related to the area. Dr. Satué is a scientific reviewer for various prestigious international journals such as Animals, American Journal of Obstetrics and Gynecology, Veterinary Clinical Pathology, Journal of Equine Veterinary Science, Reproduction in Domestic Animals, Research Veterinary Science, Brazilian Journal of Medical and Biological Research, Livestock Production Science and Theriogenology, among others. Since 2014 she has been responsible for the Clinical Analysis Laboratory of the CEU-Cardenal Herrera University Veterinary Clinical Hospital.",institutionString:null,institution:null},{id:"201721",title:"Dr.",name:"Beatrice",middleName:null,surname:"Funiciello",slug:"beatrice-funiciello",fullName:"Beatrice Funiciello",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/201721/images/11089_n.jpg",biography:"Graduated from the University of Milan in 2011, my post-graduate education included CertAVP modules mainly on equines (dermatology and internal medicine) and a few on small animal (dermatology and anaesthesia) at the University of Liverpool. After a general CertAVP (2015) I gained the designated Certificate in Veterinary Dermatology (2017) after taking the synoptic examination and then applied for the RCVS ADvanced Practitioner status. After that, I completed the Postgraduate Diploma in Veterinary Professional Studies at the University of Liverpool (2018). My main area of work is cross-species veterinary dermatology.",institutionString:null,institution:null},{id:"291226",title:"Dr.",name:"Monica",middleName:null,surname:"Cassel",slug:"monica-cassel",fullName:"Monica Cassel",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/291226/images/8232_n.jpg",biography:'Degree in Biological Sciences at the Federal University of Mato Grosso with scholarship for Scientific Initiation by FAPEMAT (2008/1) and CNPq (2008/2-2009/2): Project \\"Histological evidence of reproductive activity in lizards of the Manso region, Chapada dos Guimarães, Mato Grosso, Brazil\\". Master\\\'s degree in Ecology and Biodiversity Conservation at Federal University of Mato Grosso with a scholarship by CAPES/REUNI program: Project \\"Reproductive biology of Melanorivulus punctatus\\". PhD\\\'s degree in Science (Cell and Tissue Biology Area) \n at University of Sao Paulo with scholarship granted by FAPESP; Project \\"Development of morphofunctional changes in ovary of Astyanax altiparanae Garutti & Britski, 2000 (Teleostei, Characidae)\\". She has experience in Reproduction of vertebrates and Morphology, with emphasis in Cellular Biology and Histology. She is currently a teacher in the medium / technical level courses at IFMT-Alta Floresta, as well as in the Bachelor\\\'s degree in Animal Science and in the Bachelor\\\'s degree in Business.',institutionString:null,institution:null},{id:"442807",title:"Dr.",name:"Busani",middleName:null,surname:"Moyo",slug:"busani-moyo",fullName:"Busani Moyo",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Gwanda State University",country:{name:"Zimbabwe"}}},{id:"439435",title:"Dr.",name:"Feda S.",middleName:null,surname:"Aljaser",slug:"feda-s.-aljaser",fullName:"Feda S. Aljaser",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"King Saud University",country:{name:"Saudi Arabia"}}},{id:"423023",title:"Dr.",name:"Yosra",middleName:null,surname:"Soltan",slug:"yosra-soltan",fullName:"Yosra Soltan",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Alexandria University",country:{name:"Egypt"}}},{id:"349788",title:"Dr.",name:"Florencia Nery",middleName:null,surname:"Sompie",slug:"florencia-nery-sompie",fullName:"Florencia Nery Sompie",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Sam Ratulangi University",country:{name:"Indonesia"}}},{id:"428600",title:"MSc.",name:"Adriana",middleName:null,surname:"García-Alarcón",slug:"adriana-garcia-alarcon",fullName:"Adriana García-Alarcón",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"National Autonomous University of Mexico",country:{name:"Mexico"}}},{id:"428599",title:"MSc.",name:"Gabino",middleName:null,surname:"De La Rosa-Cruz",slug:"gabino-de-la-rosa-cruz",fullName:"Gabino De La Rosa-Cruz",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"National Autonomous University of Mexico",country:{name:"Mexico"}}},{id:"428601",title:"MSc.",name:"Juan Carlos",middleName:null,surname:"Campuzano-Caballero",slug:"juan-carlos-campuzano-caballero",fullName:"Juan Carlos Campuzano-Caballero",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"National Autonomous University of Mexico",country:{name:"Mexico"}}}]}},subseries:{item:{id:"18",type:"subseries",title:"Proteomics",keywords:"Mono- and Two-Dimensional Gel Electrophoresis (1-and 2-DE), Liquid Chromatography (LC), Mass Spectrometry/Tandem Mass Spectrometry (MS; MS/MS), Proteins",scope:"With the recognition that the human genome cannot provide answers to the etiology of a disorder, changes in the proteins expressed by a genome became a focus in research. Thus proteomics, an area of research that detects all protein forms expressed in an organism, including splice isoforms and post-translational modifications, is more suitable than genomics for a comprehensive understanding of the biochemical processes that govern life. The most common proteomics applications are currently in the clinical field for the identification, in a variety of biological matrices, of biomarkers for diagnosis and therapeutic intervention of disorders. From the comparison of proteomic profiles of control and disease or different physiological states, which may emerge, changes in protein expression can provide new insights into the roles played by some proteins in human pathologies. Understanding how proteins function and interact with each other is another goal of proteomics that makes this approach even more intriguing. Specialized technology and expertise are required to assess the proteome of any biological sample. Currently, proteomics relies mainly on mass spectrometry (MS) combined with electrophoretic (1 or 2-DE-MS) and/or chromatographic techniques (LC-MS/MS). MS is an excellent tool that has gained popularity in proteomics because of its ability to gather a complex body of information such as cataloging protein expression, identifying protein modification sites, and defining protein interactions. The Proteomics topic aims to attract contributions on all aspects of MS-based proteomics that, by pushing the boundaries of MS capabilities, may address biological problems that have not been resolved yet.",coverUrl:"https://cdn.intechopen.com/series_topics/covers/18.jpg",hasOnlineFirst:!0,hasPublishedBooks:!0,annualVolume:11414,editor:{id:"200689",title:"Prof.",name:"Paolo",middleName:null,surname:"Iadarola",slug:"paolo-iadarola",fullName:"Paolo Iadarola",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bSCl8QAG/Profile_Picture_1623568118342",biography:"Paolo Iadarola graduated with a degree in Chemistry from the University of Pavia (Italy) in July 1972. He then worked as an Assistant Professor at the Faculty of Science of the same University until 1984. In 1985, Prof. Iadarola became Associate Professor at the Department of Biology and Biotechnologies of the University of Pavia and retired in October 2017. Since then, he has been working as an Adjunct Professor in the same Department at the University of Pavia. His research activity during the first years was primarily focused on the purification and structural characterization of enzymes from animal and plant sources. During this period, Prof. Iadarola familiarized himself with the conventional techniques used in column chromatography, spectrophotometry, manual Edman degradation, and electrophoresis). Since 1995, he has been working on: i) the determination in biological fluids (serum, urine, bronchoalveolar lavage, sputum) of proteolytic activities involved in the degradation processes of connective tissue matrix, and ii) on the identification of biological markers of lung diseases. In this context, he has developed and validated new methodologies (e.g., Capillary Electrophoresis coupled to Laser-Induced Fluorescence, CE-LIF) whose application enabled him to determine both the amounts of biochemical markers (Desmosines) in urine/serum of patients affected by Chronic Obstructive Pulmonary Disease (COPD) and the activity of proteolytic enzymes (Human Neutrophil Elastase, Cathepsin G, Pseudomonas aeruginosa elastase) in sputa of these patients. More recently, Prof. Iadarola was involved in developing techniques such as two-dimensional electrophoresis coupled to liquid chromatography/mass spectrometry (2DE-LC/MS) for the proteomic analysis of biological fluids aimed at the identification of potential biomarkers of different lung diseases. He is the author of about 150 publications (According to Scopus: H-Index: 23; Total citations: 1568- According to WOS: H-Index: 20; Total Citations: 1296) of peer-reviewed international journals. He is a Consultant Reviewer for several journals, including the Journal of Chromatography A, Journal of Chromatography B, Plos ONE, Proteomes, International Journal of Molecular Science, Biotech, Electrophoresis, and others. He is also Associate Editor of Biotech.",institutionString:null,institution:{name:"University of Pavia",institutionURL:null,country:{name:"Italy"}}},editorTwo:{id:"201414",title:"Dr.",name:"Simona",middleName:null,surname:"Viglio",slug:"simona-viglio",fullName:"Simona Viglio",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRKDHQA4/Profile_Picture_1630402531487",biography:"Simona Viglio is an Associate Professor of Biochemistry at the Department of Molecular Medicine at the University of Pavia. She has been working since 1995 on the determination of proteolytic enzymes involved in the degradation process of connective tissue matrix and on the identification of biological markers of lung diseases. She gained considerable experience in developing and validating new methodologies whose applications allowed her to determine both the amount of biomarkers (Desmosine and Isodesmosine) in the urine of patients affected by COPD, and the activity of proteolytic enzymes (HNE, Cathepsin G, Pseudomonas aeruginosa elastase) in the sputa of these patients. Simona Viglio was also involved in research dealing with the supplementation of amino acids in patients with brain injury and chronic heart failure. She is presently engaged in the development of 2-DE and LC-MS techniques for the study of proteomics in biological fluids. The aim of this research is the identification of potential biomarkers of lung diseases. 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