Applications of EIS in analysis and characterizations of different drug materials in variable matrices.
\r\n\tIt is a relatively simple process and a standard tool in any industry. Because of the versatility of the titration techniques, nearly all aspects of society depend on various forms of titration to analyze key chemical compounds.
\r\n\tThe aims of this book is to provide the reader with an up-to-date coverage of experimental and theoretical aspects related to titration techniques used in environmental, pharmaceutical, biomedical and food sciences.
In view of global energy crisis and environmental pollution, the search for renewable and clean energy resources and the development of eco-friendly systems for environmental remediation have received great attention. Solar energy is the prime renewable source of energy for every life on the earth. The amount of solar energy that strikes the Earth yearly in the form of sunlight is approximately ten thousand times the total energy that is consumed on this planet [1]. However, sunlight is diffuse and intermittent, which impedes its collecting and storage that play critical roles in the full exploitation of its potentials. As one of the most promising solutions for storing and converting solar energy, semiconductor photocatalysis has attracted much attention, since it provides an environmental benign strategy for splitting water into hydrogen and oxygen, reducing carbon dioxide into useful chemicals and fossil fuels, and completely eliminating all kinds of contaminants under the sunlight illumination under ambient conditions [2–4]. Generally, the fundamental principles of semiconductor photocatalysis have been extensively reported in previous works [5]. A photocatalytic reaction is initiated on the basis of the formation of photogenerated charges (such as electrons and holes) after capture of sunlight by a semiconductor. Consequently, electrons can transit from valence band (VB) to conduction band (CB) leaving behind holes in the VB. If the photogenerated electron–hole pairs’ separation is maintained, the photogenerated carriers can move to the semiconductor surfaces to react with the adsorbed small molecules (dioxygen and water), generating the redox foundations of active species which lead to water splitting and/or destruction of organic compounds [6]. It is also noted that the photogenerated electrons in the CB can also recombine with the photogenerated holes in the VB to dissipate the input energy in the form of heat or radiated light (see Figure 1). From the perspective of efficient utilization of solar energy, the recombination between the photogenerated electrons and holes is not desired, which limits the efficiency of a semiconductor photocatalyst. For better photocatalytic performance, the photogenerated electrons and holes must be separated effectively, and charges have to be transferred rapidly at the mean time across the photocatalysis to astrict the recombination.
Schematic illustration of the principle of photocatalysis.
To date, several semiconductors, including TiO2, ZnO, SnO2, BiVO4 and so forth, have been extensively investigated [7–10]. Among them, tantalate-based semiconductors with perovskite-type structure have certainly verified to be one of the brilliant photocatalysts for producing hydrogen from water and the oxidative disintegration of much organic containment [11]. For instance, NaTaO3 with a perovskite-type structure showed a quantum yield of 56% under ultraviolet light irradiation after lanthanum doping and NiO co-catalyst loading [12]. Nevertheless, because of their broad band gap, most tantalate-based semiconductors can only react under ultraviolet or near-ultraviolet radiation, which reduces the utilization of ~43% of the solar spectrum To efficiently utilize the sunlight in visible region, the design of visible-light response tantalate-based catalysts is current demanded. Up to now, numerous methodologies have been developed to prepare different visible-light-driven tantalate-based photocatalysts, including doping strategy, heterojunction, facet control and so on [13,14].
This chapter emphasizes certain topical works that concentrate on tantalate-based photocatalysts for solar energy application. The aim is to display that the rational design, fabrication and modifications of tantalate-based semiconductors have tremendous effects onto their final photocatalytic activity, simultaneously, providing some stimulating perspectives on the future applications.
Alkali tantalate-based perovskite semiconductors (likewise LiTaO3, NaTaO3 and KTaO3) have a general formula of ABO3 and have drawn a lot of attention due to the peculiar superconductivity, photocatalytic property, electrochemical reduction and electromagnetic features. There are two kinds of totally different cationic sites in a perovskite photocatalysis, in which A-site is coordinated by twelve O2–, and is usually occupied by relative bigger cations (Li, Na and K). The B-site is taken up by smaller cations (Ta) with a coordination of six, as illustrated in Figure 2. The bond angles of Ta–O–Ta are 143o for LiTaO3, 163o for NaTaO3 and 180o for KTaO3, respectively [15]. Wiegel and coworkers have reported the relationship between crystal structures and energy delocalization for alkali tantalates. When the Ta–O–Ta bond angle is close to 180o, the migration of excitation energy can be accelerated and the band gap decreases [16]. Thereby, the delocalization of excited energy of LiTaO3, NaTaO3 and KTaO3 increases in turn. This result suggests that KTaO3 may be predicted to be with the best photocatalytic activity.
Crystal structure of LiTaO3, NaTaO3 and KTaO3, respectively.
Alkali tantalate with different sizes, morphologies and compositions can be prepared via traditional solid-state method, solvothermal, sol–gel, molten salt and other methods. Basically, the traditional solid-state method is quite often used to prepare alkali tantalates, which includes the high temperature processing of the combination of alkali salts and tantalum pentaoxide. Kudo and coworkers successfully prepared ATaO3 (A = Li, Na and K) materials with high crystallinity via solid-state method. It is found that all alkali tantalate showed superior photocatalytic activity toward stoichiometric water splitting under ultraviolet condition [17]. The high photocatalytic activity is chiefly depending on the high CB level consisting of Ta 5d orbitals [15]. Among them, KTaO3 is the most photocatalytic active, which may be ascribed to the fact that KTaO3 can absorb the most of photons and possesses the least distorted perovskite structure, being consistent with the above-mentioned discussion. The evolution rate of H2 and O2 was determined to be 29 and 13 μmolh–1, respectively. To improve more photocatalytic activity of ATaO3, a modified solid-state method was adopted by adding extra amount of alkali to compensate the loss [18]. When preparing the alkali tantalates with the existence of excess alkali, the photocatalytic activity of LiTaO3, NaTaO3 and KTaO3 materials were improved ten to hundred times. LiTaO3 is the naked alkali tantalate photocatalyst which showed the highest activity. This is because LiTaO3 possesses higher conduction band levels than that of NaTaO3 and KTaO3, which may predict higher transfer rate of excited energy and the subsequent higher phtocatalytic activity. This type of phenomena was likewise observed for CaTa2O6, SrTa2O6 and BaTa2O6 photocatalysts with similar crystal structures [19].
Ta–O–Ta bond angle in a 2 × 2 × 2 supercell of monoclinic phase NaTaO3. Red ball, green ball and grey ball represent O, Na and Ta atoms, respectively.
One should note that the synthetic strategy also has great influence on the structural features as well as photocatalytic activity. For instance, sol–gel method was also used to prepare NaTaO3 nanoparticles. By using CH3COONa 3H2O and TaCl5 as the raw materials and citric acid as the complexing agent, NaTaO3 nanoparticles with monoclinic phase that shows an indirect band gap, high densities of states near the band edges and a Ta–O–Ta bond angle close to 180o (Figure 3) are obtained. This result is quite different to NaTaO3 that was synthesized via solid-state method, which formed the orthorhombic phase that has a direct band gap and a Ta–O–Ta bond angle of 163°. It is found that monoclinic NaTaO3 has lots of effective states available for the photogenerated charge pairs. Meanwhile, the larger surface area and the advantageous features in the electronic and crystalline structures for the monoclinic NaTaO3 have resulted in a remarkably higher photocatalytic activity for the sol–gel synthesized NaTaO3 than that for the solid-state derived orthorhombic NaTaO3 [20]. Besides sol–gel method, the molten-salt approach is also adopted to prepare alkali tantalate materials [21,22]. By a convenient molten-salt process, a series of NaTaO3 and KTaO3 efficient photocatalysts is successfully synthesized, which are highly crystallized single crystal nanocubes (about 100 nm large). Doping tetravalent Zr4+ and Hf4+ in NaTaO3 and KTaO3 efficiently increases the activity and stability of catalyst at the same time, although the energy levels have no change. Moreover, Zr4+ and Hf4+ doping can also led to particle size reduction and nearly monodispersed feature of NaTaO3 and KTaO3 nanoparticles. In the absence of co-catalyst, the photocatalytic activity can reach 4.65 and 2.31 mmolh–1 toward H2 and O2 production, respectively [22]. A novel kind of strontium-doped NaTaO3 mesocrystals was also prepared by a common molten-salt way. The obtained three-dimensional architectures showed high crystallinity, preferred orientation growth and high surface area. The ability for hydrogen generation of photocatalyst achieves 27.5 and 4.89 mmolh–1 for methanol aqueous solution and pure water splitting under ultraviolet light irradiation [23]. However, either solid-state method or molten-salt approach often leads to ultra-low surface areas of alkali tantalates, which limits the photocatalytic activity. Hydrothermal synthesis is advantageous for regular nucleation of nanocrystals with well-defined particles, morphologies, crystallinity and surface areas [24]. For instance, nano-sized Ta2O5 and NaTaO3, KTaO3 and RbTaO3 cubes are prepared by a facile hydrothermal method [25]. It is observed that pH influences much in the process of tantalum compound nanoparticles preparation. The obtained morphologies ranging from agglomerated particles in acidic medium over sticks at neutral pH value to cubes in elementary media can be achieved, which are similar to titanates [26]. A microwave-assisted hydrothermal technique was reported using Ta2O5 and NaOH as starting materials under quite mild conditions with short reaction time. The BET surface area of NaTaO3 nanoparticles prepared by microwave-assisted hydrothermal method is about 1.5 times than that prepared by conventional hydrothermal method [27]. After loading NiO as co-catalyst, this photocatalyst showed photocatalytic activity for overall water splitting more than two times greater than those prepared by conventional hydrothermal process [28]. As an outstanding example, NaTaO3 nanoparticles through hydrothermal treatment highly improved the photocatalytic activity by a factor of 8 toward water splitting in comparison with the photocatalysts obtained by traditional solid-state method, which is attributed to their smaller particle size, larger surface area and higher crystallinity [29,30].
Introducing foreign elements, including metal ions or non-metal ions, into semiconductor host matrix is one of the most effective methods to modulate the electronic structure of the host semiconductor and produce enhanced photocatalytic performance. Owing to a big difference in radius of A- and B-site ions in alkali tantalates, the dopants can selectively permeate into the A or B sites, which determine chemical composition, surface features, electronic structure and their photocatalytic properties. To date, studies on the alkali tantalates derived by doping strategy are thoroughly investigated. La-doped NaTaO3 is the most active photocatalyst in photocatalytically splitting water area [12]. In this case, the catalytic activity of NaTaO3 is extremely modulated by doping with La3+. For example, the crystallinity growths and a surface stair structure with nanometer-scale features are constructed, which improve the separation efficiency of the photogenerated electron–hole pairs and the photocatalytically splitting water activity. The surface step structure is also formed in alkaline earth metal ion doped NaTaO3, which showed improvement of photocatalytic water splitting properties [31]. Bi3+ doped NaTaO3 nanoparticles are prepared under different initial stoichiometric ratio by traditional solid-state reaction, which showed visible light absorption and tunable photocatalytic activity. Controlling the original molar ratio of the reactants, the intrusion of bismuth at sodium site and tantalum site in NaTaO3 can be well-modulated and the optimum performance can be easily changed. Occupancy of Bi atom at Na site of NaTaO3 is not contributing to increase visible light absorption while occupancy of Bi at Ta site or at both Na and Ta site induces visible light absorption and the subsequent methyl blue degradation under visible light [32,33]. La, Cr codoping NaTaO3 system is also developed by spray pyrolysis from aqueous and polymeric precursor solution. The hydrogen evolution rate of La, Cr codoped NaTaO3 was enhanced 5.6 times to 1467.5 μmol g–1h–1, and the induction period was shortened to 33%, compared to the identical values achieved by the Cr-doped NaTaO3 photocatalyst prepared from aqueous precursor solution [34]. Besides metal ion doping, several non-metal ions are also incorporated into the host matrix of alkali tantalates for improved visible light absorption and photocatalytic performance [35,36]. A plane-wave-based density functional theory calculation is conducted to predict the doping effects on the variations of the band structure of non-metal ions doped NaTaO3. There were studies about nitrogen, sulfur, carbon and phosphorus monodoping and nitrogen–nitrogen, carbon–sulfur, phosphorus–phosphorus and nitrogen–phosphorus codoping. Nitrogen and sulfur monodoping can improve the valence band edge to higher and keep the ability to split water into H2 and O2 remain unchanged, as is shown in Figure 4. Double hole-mediated codoping can decrease the band gap dramatically. Nitrogen–nitrogen, carbon–sulfur and nitrogen–phosphorus codoping could narrow band gap to 2.19, 1.70 and 1.34 eV, respectively, which could absorb visible light.
Band alignment of non-metal ions doped NaTaO3. The position of the valence band edge of pure NaTaO3 is adopted from experiment [37].
Defect chemistry plays an important role in modulating the electronic structure, charge carrier conductivity and photocatalytic performance [38]. Defect chemistry often shows different impacts on the photocatalytic efficiency for most of the semiconductors. Previous literature on NaTaO3 indicated that the accretion of the extra quantity of Na in the synthesis of NaTaO3 blocked construction of sodium ion defects in NaTaO3 crystals, leading to the extreme enhancement of photocatalytic activity [18]. Basically, the native defects, such as oxygen vacancies and sodium ion defects, are often observed in NaTaO3. Oba and coworkers investigated the formation energies and electronic structure of lattice vacancies, antisite defects and lanthanum impurities in NaTaO3 using first-principles calculations based on density-functional theory [39]. Under oxygen-poor environments, oxygen vacancy as a double donor is a main defect. In La-NaTaO3, the replacement of La at Ta site is similar to make up as a shallow acceptor under oxygen-rich environments whereas the replacement of La at Na site forms as a double donor under oxygen-poor environments. The location predilection of lanthanum leads to self-compensation in heavily doped cases, which have great impact on the change in carrier concentration and photocatalytic activity [12]. Defective center not only alters the carrier concentration but also induces visible light absorption. In Eu3+ doped NaTaO3, a nonstoichiometric Na/Ta molar ratio led to site-selective occupation of Eu3+ dopant ions, which resulted in a monotonous lattice expansion and local symmetry distortion [11]. The site-selective occupation of Eu3+ gave rise to certain types of defective centers due to the charge difference between Eu3+ ions and Na+ and/or Ta5+ ions, which is crucial to the modification of absorption in visible region and photocatalytic activity.
The constructions of heterojunction by combining a semiconductor with other semiconductors have attracted much research attention because of their perfect effectiveness in the separation of the photogenerated charge carriers and boosting the photocatalytic activity. In the past few years, a lot of significant findings have been described on the heterojunction of nano-/microarchitectures. Nano-Cu2O/NaTaO3 composite for the degradation of organic pollutants have also been successfully developed [13]. Nano-Cu2O/NaTaO3 composite exhibits highly enhanced photocatalytic activity in comparison to their individual counterpart. Furthermore, C3N4/NaTaO3 and C3N4/KTaO3 composite photocatalysts were also developed [40,41]. Loading of C3N4 is a good strategy to achieve the visible light photocatalytic activity (Figure 5). Photogenerated electron jumped from the VB to CB of C3N4 could unswervingly insert into the conduction band of NaTaO3 or KTaO3, making C3N4/NaTaO3 and C3N4/KTaO3 as visible light-driven photocatalyst. Both of the composites showed superior photocatalytic activity toward Rhodamine B degradation under visible light irradiation, being close to commercial P25. Yin and coworkers reported the preparation of novel C–NaTaO3–Cl–TiO2 composites via a facile solvothermal method. When C–NaTaO3 is joined with Cl–TiO2 to construct a core shell configuration, the visible light-induced degradation activity toward NOx of the catalysts under visible light irradiation could be highly improved because of the suppression of the recombination of photogenerated charge carriers [42]. Zaleska et al. prepared a series of novel binary and ternary composite photocatalysts based on the combination of KTaO3, CdS and MoS2 semiconductors via hydro/solvothermal precursor route. They found that the highest photocatalytic activity toward phenol degradation under both UV-Vis and visible light irradiation and superior stability in toluene removal was observed for ternary hybrid obtained by calcination of KTaO3, CdS and MoS2 powders at the 10: 5: 1 molar ratio [43].
Schematic illustration of the photocatalytic degradation process of RhB by visible light-irradiated C3N4/NaTaO3 or C3N4/KTaO3.
As one of the most important factors, surface area also imposes a big effect on the photocatalytic activity of the semiconductors. The majority of photocatalytic reactions occur at semiconductor surfaces, and therefore the photocatalytic activities of semiconductor oxides are usually greatly improved by the increase in surface area [44]. To further improve the surface area, nanocrystalline NaTaO3 thin films with ordered three-dimensional mesoporous and nanostick-like constructions were successfully produced by PIB-b-PEO polymer-based sol–gel method. NaTaO3 prepared at 650οC exhibits a BET surface area of about 270 m2cm–3, which is much larger than the ever reported values [45]. These nanocrsytalline mesoporous NaTaO3 samples show both enhanced ultraviolet light photocatalytic activity and can keep steady performance. A confined space synthesis process was also used for preparing colloidal array of NaTaO3 by using three-dimensional mesoporous carbon as the hard template. This method brings about the creation of a colloidal collection of mesoporous NaTaO3 particles (20 nm). After NiO loading, the mesoporous NaTaO3 nanoparticles showed photocatalytic activity for overall water splitting more than three times as high as non-structured bulk NaTaO3 particles [46]. A carbon modified NaTaO3 mesocrystal nanoparticle was also successfully synthesized by a one-pot solvothermal method by employing TaCl5, NaOH and glucose as the starting materials and distilled H2O/ethylene glycol mixed solution as a reaction solvent. The as-synthesized mesocrystal nanoparticles exhibited a high specific surface area of 90.8 m2g–1 with large amounts of well-dispersed mesopores in the particles. The carbon-modified NaTaO3 mesocrystal demonstrated excellent efficiency for continuous NO gas destruction under visible light irradiation, which is considerably superior to those of the unmodified NaTaO3 specimen and commercial Degussa P25, owning to large specific surface area, high crystallinity and visible light absorption [47].
As well documented in previous literatures, co-catalyst introduces two positive factors into the photocatalyst, including promotion on the separation of photogenerated charge carriers and construction of active sites for reduction and/or oxidation reaction. Several noble metals have been commonly used as co-catalysts for photocatalytic applications. For example, water splitting activity of NaTaO3:La was improved when Au was loaded either by photodeposition method or by impregnation method. Moreover, Au/NaTaO3:La prepared by impregnation method exhibits much higher and more stable photocatalytic activity toward water splitting due to the fact that O2 reduction on photodeposited Au co-catalyst was more efficient than that of impregnated Au co-catalyst [48]. Besides Au nanoparticles, Pt is also frequently used as co-catalyst for increasing the photocatalytic activity of alkali tantalates. With the deposition of Pt nanoparticles as co-catalyst, rare earth (including Y, La, Ce and Yb) doped NaTaO3 exhibits a clear improvement of the hydrogen evolution, which is due to the fact that Pt nanoparticles act as electron scavengers reducing the photogenerated charge carrier recombination rate and facilitating the electron move to metal sites from the CB of NaTaO3, being as the catalytic center for hydrogen generation [49]. Moreover, Pd nanoparticles are also used as a co-catalyst for H2 production from water containing electron donor species. Su et al. prepared novel Pd/NiO core/shell nanoparticles as co-catalyst, which are placed on the surface of La doped NaTaO3 photocatalyst. It is noted that Pd nanoparticles are more effective for H2 generation from water containing methanol, while Pd/NiO core/shell nanoparticles exhibit a higher H2 generation by splitting pure water. The presence of NiO not only provides hydrogen evolution sites and suppresses the reverse reactions on Pd-based catalysts but also improves the stability of the Pd nanoparticles on the La doped NaTaO3 surfaces [50]. In another case, when RuO2 (1 wt.%) was introduced as co-catalyst, the ability for H2 generation of NaTaO3 prepared by an innovative solvo-combustion reaction was improved significantly, reaching around 50 mmol of H2 after 5 h, which is the best of other reports in literature [51].
Due to too much scarcity and expense of noble metal co-catalyst to apply for wider scope solar energy applications, the development of high-efficiency and low-cost noble-metal-free co-catalysts is acutely necessary. Lately, co-catalysts composed of earth abundant elements have been explored extensively to replace noble metal co-catalysts for solar energy applications [52]. NiO is a p-type semiconductor with a band gap energy ranging within 3.5–4.0 eV, which is widely used as the co-catalyst of tantalates-based semiconductors for enhancing photocatalytic activity [53]. In the case of NiO/NaTaO3:La photocatalyst with high photocatalytic reactivity, NiO acts as co-catalyst loading as ultrafine NiO particles, which possesses characteristic absorption bands at 580 and 690 nm, The ultrafine NiO particles were highly active for hydrogen evolution as well as Pt of an excellent co-catalyst [12]. A detailed study on the structural features of NiO nanoparticles indicated that the interdiffusion of Na+ and Ni2+ cations created a solid–solution transition zone on the outer sphere of NaTaO3. The high photocatalytic activity resulting from a low NiO loading suggests that the interdiffusion of cations heavily doped the p-type NiO and n-type NaTaO3, reducing the depletion widths and facilitating charge transfers through the interface barrier [54]. Besides NiO, Ni metallic nanoclusters were also used as co-catalyst. For instance, a series of nickel-loaded LaxNa1–xTaO3 photocatalysts was synthesized by a hydrogen peroxide-water based solvent method. Systematical investigation indicated that the activity of hydrogen generation from pure water is in sequence: Ni/NiO > NiO > Ni, whereas the activity sequence with respect to aqueous methanol is: Ni > Ni/NiO > NiO. Ni metallic nanoclusters exhibit the most active sites and facilitate the formation of hydrogen from aqueous methanol. In the case of Ni/NiO core/shell structure, Ni metallic nanoclusters induce the migration of photogenerated electrons from the bulk to catalyst surface, while NiO acts as H2 evolution site and prevents water formation from H2 and O2 [55].
Molecular co-catalyst engineering have received much research attention in recent years. In a molecular/semiconductor hybrid system, the noble-metal-free molecular complex as co-catalyst can not only facilitate the charge separation but also help us to understand the mechanisms of hydrogen evolution and carbon dioxide reduction at molecular level [56]. Although the study on molecular sensitized alkali tantalates is limited, an excellent research has been done by Hong and coworkers. In this case, by using a molecular co-catalyst [Mo3S4]4+, the photocatalytic activity of NaTaO3 was significantly improved. The hydrogen production rate is about 28 times higher than pure NaTaO3 because [Mo3S4]4+ clusters can provide a large number of effective active sites for hydrogen evolution and the matching of the conduction band of NaTaO3 and the reduction potential of [Mo3S4]4+ also acts as one of the major determinants for the enhancement of the photocatalytic activity [57].
Solid-state reaction method and hydrothermal method are used routinely to synthesize alkaline earth and transition metal tantalates. Almost all the alkaline earth and transition metal tantalates can be obtained by high-temperature solid-state method using Ta2O5 and other salts as starting materials. For instance, Sr2Ta2O7 [58], Sr0.8Bi2.2Ta2O9 [59], Bi2SrTa2O9 [60] H1.81Sr0.81Bi0.19Ta2O7 [61], Ba(Zn1/3Ta2/3)O3 [62], Ba(Mg1/3Ta2/3)O3 [63], Ba4Ta2O9 [64] and Ba5Ta4O15 [65] have been synthesized successfully by this method, which show prospects in many application including photocatalytic semiconductor, solar cells and electronic device. The high-temperature treatment of traditional solid-state reaction will increase the size of particles and thus decrease the surface area. Sr2Ta2O7 photocatalysts of layered perovskite structures gotten from the solid state reaction had better activity which is mainly because of their more negative conduction band. H2ATa2O7 (A = Sr or La2/3) [66] and LiCa2Ta3O10 [67] were reported to be obtained by similar way with extra alkali, which can supply the loss at high temperature to suppress defects formation. This makes the crystal structure grow well and has better catalytic efficiency than others synthesized with a theoretical ratio in most cases. This improved solid-state reaction method would efficiently inhibit the recombination of photocarrier to enhance the photocatalytic activity. A new polymerizable complex technique is one of the preparation methods of alkaline earth tantalates, which has a relative moderate condition. This method includes the provision of Ta-base compound and then come into being the sticky sol–gel, after the treatment at 600–700 °C. Comparing with solid-state method, the tantalate-based photocatalysts synthesized by a polymerizable complex way often have greater crystallinity and better crystal size, which will lead to remarkably increase the photocatalytic efficiency [68]. Comparing with solid-state method, hydrothermal method has been widely used in synthesizing perovskite tantalates with very lower reaction temperature. Lots of alkaline earth tantalate could be prepared by the hydrothermal method exhibiting higher activity. In 2006, Zhu and coworkers synthesize monomolecular-layer Ba5Ta4O15 nanosheets by hydrothermal method [65], which show enhanced activity ten times better than that of solid-state method-derived Ba5Ta4O15 particles in photodegradation reactions of Rhodamine B solution. Perovskite Ca2Ta2O7 has also been synthesized by hydrothermal process in aqueous KOH solution at 373 K for 120 h, which shows photocatalytic water splitting activity under UV-light irradiation [69]. Moreover, sol–gel route, as a common way to prepare the nanomaterials, also can be used for preparation of some perovskite tantalates. One typical case is that the ferroelectric SrBi2Ta2O9 [70] and SrBi2Ta2O9 nanowires [71] were synthesized using ethylene glycol as solvent, which showed greater dielectric and ferroelectric properties than the ceramics prepared by the solid-state reactions owning to a denser and more homogeneous microstructure with a better distribution of grain orientations. Sol–gel method is also used to prepare metastable phase like Sr0.5TaO3 nanosheets [72] with photocatalytic activities of water splitting under ultraviolet light irradiation. Several transition metal tantalates with perovskite structure can also be synthesized by these methods, including AgTaO3 [73], LaTaO4 [74], H2La2/3Ta2O7 [75] and so forth.
For ideal perovskite alkaline earth and transition metal tantalates, the cubic-symmetry structure has the Ta atom in 6-fold coordination, surrounded by an octahedron of oxygen atoms, and the alkaline earth or transition metal cation in 12-fold cuboctahedral coordination (Figure 6). The relative ion size requirements for stability of the cubic structure are quite stringent, so slight buckling and distortion can produce several lower-symmetry distorted versions, in which the coordination numbers of cations are reduced. [77] But in fact, almost all perovskite alkaline earth and transition metal tantalates have compound perovskite structures covering two different cations at Ta site in TaO6 octahedra or at cation site in 12-fold cuboctahedral coordination. This led to the chance of alternatives between ordered and disordered. Crystal structure is a very important factor manipulating the band gaps of perovskite tantalates containing the following aspects: (1) the bond angle of tantalum and oxygen ions of octahedra units; (2) the interlayer spacing of the perovskite; (3) the interaction between perovskite layers; (4) the polarization ability of cations at the interlayer toward the oxygen ions of octahedra facing the interlayer. Some of alkaline earth and transition metal tantalates with layered perovskite exhibited outstanding photo catalytic activity, including Ba5Ta4O15, H1.81Sr0.81Bi0.19Ta2O7, SrBi2Ta2O9, LaTaO4, H2La2/3Ta2O7 and Sr0.5TaO3 reported by many groups [61,65,70,72,74,75]. This kind of perovskite composites are promising materials with multiple elements, perovskite framework and layer-like structures, which can be classified into three category structures by the different interlayer structure. On the other hand, it has been reported that some perovskite alkaline earth tantalates with double-perovskite structure also show photocatalytic activity under ultraviolet light irradiation [79]. And some transition metal tantalates have simple cubic perovskite-type structure like AgTaO3, Ba3ZnTa2O9, Sr2GaTaO6 [80] and NaCaTiTaO6, NaCaTiNbO6, NaSrTiTaO6 and NaSrTiNbO6 [81].
General structure of perovskite and layered perovskite [76].
Introducing external ions into crystal structure has been generally approved as a positive way to improve the visible-light photocatalytic activity of semiconductors with larger band gaps. For nitrogen-doped layered oxide Sr5Ta4O15–xNx, the extension of the visible light absorption has been ascribed to the substitution of nitrogen for oxygen atoms as well as the formation of Ta–N bonds. The N 2p states mixed with pre-existing O 2p states shift the valence band maximum upward and result in wide visible light absorption [82]. A slight N dopant led to hinder the recombination of photo-generated charge pairs. N-doped Ba5Ta4O15 also displays a brilliant photocatalytic activity under solar condition. The doping resulted in a significant narrowing of the band gap from 4.06 eV to ca. 1.76 eV, indicating that it can use more visible light [83]. Furthermore, Sun et al. investigated affection of band gap doping with several metal and non-metal by DFT calculation [84]. It is found that, in most perovskite cases, the valence band levels were shifted upwards, in which the maximum contribution to valence band maximum comes from the p orbitals of the dopant anions, which shift. On the other hand, the dopant cations shift the CB level downwards because the CBM is chiefly governed by the d orbitals of foreign cations. This conclusion was applicable to perovskite structure tantalates system (Figure 7) directly by Liu and coworkers [85].
The electronic band edge positions with respect to the water reduction and oxidation potential levels for the pure and doped Sr2Ta2O7 systems [85].
Multi-component semiconductor combination tactic shows effectivity to improve photocatalytic activity by separation of the photo-generated charge carriers with a formation of a heterojunction structure. Heterojunction structure is the interface that is located at two areas of different crystalline semiconductors. This kind of material has to consider the following points, including near crystal structure, similar interatomic spacing and close coefficient of thermal expansion. Otherwise, they should have discrepant band gap values, which is exact contrary to a homojunction. It is benefited to regulate the electronic energy bands. To promote the redox ability and photocatalytic activity, composite photocatalysts involving two or more components were extensively studied. One type of such composites is usually constructed by coupling semiconductors with larger band gap for the purpose of the higher redox ability. A charming work is the Ba5Ta4O15/Ba3Ta5O15 composite reported by Roland Marschall et al., which synthesized through the sol–gel method showed brilliant activities in OH radical generation and photocatalytic hydrogen production [86]. The outstanding activity is expected to come from enhanced charge carrier separation. In 2011, Wang and coworkers present Pt-loaded graphene-Sr2Ta2O7–xNx (Figure 8) with enlarged visible light absorption region and enhanced photocatalytic hydrogen generation [87].
Schematic diagram for Pt-loaded graphene-Sr2Ta2O7–xNx photocatalyst under simulated solar light irradiation [87].
Transition metals and their oxides are usually used as practical co-catalysts for photocatalysis. The role of the co-catalysts attached on the surface of the semiconductor material is particularly significant. It increases the overall photocatalytic activity by helping to separate charge pairs, which can work for both bulk and surface electron/hole pathway. The chemical reaction that took place at surface is promoted by the co-catalysts. Various metals and oxides loaded on the surface of semiconductor show different effects. In most photocatalytic water splitting systems, several metals like Au and Pt can accelerate the rate of reduction of hydrogen observably [88,89]. On the other hand, some oxides like NiO, NiOx and RuO2 can promote the rates of both hydrogen and oxygen production [90–92]. Among them, NiOx exhibited highest activity in photocatalytic process [78]. As a hydrogen evolution site, the co-catalyst has to extract the photogenerated electrons from the CB of host materials. Thus, the conduction band level of co-catalyst should be below that of photocatalyst. In addition, photocatalytic water splitting is sensitive to the deposition methods of co-catalysts. Kudo et al. reported that photocatalysts show diversity in photocatalytic water splitting with different deposition methods [59]. Moreover, transition-metal sulfides like MS (M = Ni, Co, Cu) have also been developed as co-catalysts to improve the photocatalytic activity. These sulfides have the same effects with other co-catalysts in reaction process [93].
Tantalate-based perovskite semiconductors are well known for their wide spread applications in photocatalysis, ionic conductors, luminescence host materials and ferroelectric ceramics. Drawbacks of wide band gap and low charge separation efficiency inhibit the further development of tantalate-based perovskite semiconductors as superior photocatalysts. The combination of various strategies, such as doping, heterojunction and co-catalyst engineering, induces a thrilling beginning for exploring visible light active and highly efficient photocatalysts for solar energy applications. However, the studies on tantalate-based perovskite semiconductors are currently unsystematic. Meanwhile, the as-mentioned strategies and the derived photocatalytic systems with high efficiency and stability still need to be further developed.
This work is financially supported by the National Natural Science Foundation of China (Grants 21267014, 21367018, 21563021), the Project of Scientific and Technological Innovation Team of Inner Mongolia University (12110614), Fund of Key Laboratory of Optoelectronic Materials Chemistry and Physics, Chinese Academy of Sciences (2008DP173016-1410).
Electrochemical impedance spectroscopy (EIS) is a usually described as a potent (if not the most powerful) electrochemical analytical technique. The history of EIS goes back to the late nineteenth century, thanks to the foundations established by Heaviside on his work on the linear systems theory (LST). By the end of the same century, the success achieved by Warburg to broaden the conception of impedance to the electrochemical systems (ES) came to the scene. It was close to the middle of the twentieth century, when the EIS started to realize its potential! That came with the invention of the potentiostat in the 1940s, followed by the frequency response analyzers in the 1970s. This progress has led to the application of EIS chiefly in investigation of corrosion mechanisms [1, 2, 3].
Later on, this has opened the doors for realms of applications of EIS. Applications encompassed electrocatalysis and energy [3, 4, 5]; characterization of materials, e.g. corrosion phenomenon surveillance [6, 7]; and depiction of quality of coatings [8], exploring mechanisms of processes such as electrodeposition and electro-dissolution [9, 10], food and drug analysis [11, 12, 13], detection of biomarkers [14, 15], and water analysis [16, 17].
It is noteworthy to mention that impedance spectroscopy (IS), depending on the material used, the device, and the system or process to be studied, has two main categories: EIS (the topic of this chapter) and dielectric IS. A major difference is that EIS applies to systems/materials involving chiefly ionic conduction, in contrast to electronic conduction in the case of dielectric IS. Therefore, it can be observed from the fields of EIS applications that EIS usually applies to systems like electrolytes (solid/liquid), polymers, and glasses [18, 19, 20, 21].
In general, EIS measurements involve the application of an alternating current (AC) voltage or current to the system under investigation, followed by measurement of the response in the form of AC current (or voltage) as a function of frequency. Measurements are usually performed using the potentiostat, and the measured response is analyzed using a frequency response analyzer (FRA) [18]. By and large, three factors make EIS exceptionally attractive in terms of applications:
Capability to explore the ES at relatively low frequencies using the minimal perturbation that in turn serves to keep the kinetic information of the system under investigation at near zero conditions (steady state). Therefore, EIS is said to be a steady-state and nondestructive technique. The majority of the electrochemical techniques, however, involve an application of large perturbation for sensing the membrane/electrolyte interface, with the purpose of obtaining mechanistic data following the driving of the reaction to a state that is far from equilibrium [3].
Feasibility of implementation of EIS into the system to be measured.
The usefulness of data obtained in characterizing the studied ES, where EIS provides on-site data on the relaxation data over a range of frequencies, from as low as 10−4 Hz and up to 106 Hz.
A combination of the three advantages led to the wide use of EIS as previously mentioned.
The current chapter throughout the following sections is investigating the applications of EIS in a variety of matrices, mainly in food, drug, and water analysis, and the recent advances in these fields as well as comparisons between EIS and other electroanalytical approaches applied for the same purposes.
Throughout the current chapter, readers will be exposed to the different analytical techniques, especially the electrochemical-based approaches, which are generally used for detection of pollutants in food, drug, and water.
Readers will be more focused on the applications of EIS in specific. A comparison between EIS and the other techniques commonly used in water and food analysis will be exhibited.
The safety, quantity, and the quality of food and water are becoming worldwide concerns. Water is the most crucial source for human development. With the advancement of human life, uncountable contaminants are intimidating the aquatic system. These intimidations include but not limited to automation/industrialization, widespread use of chemicals, increased population, and suburbanization. Subsequently, water pollution is becoming a significant health and environmental concern.
By and large, the safety of food and water is influenced by contaminants. Among these pollutants, heavy metals, elevated anions (sulfates, phosphates, fluoride, etc.), dyes, agricultural waste, pesticides, drugs, and pharmaceuticals are the most common. Heavy metals, in specific, are widely used in many industrial, domestic, and agricultural applications, and they are nondegradable, an issue that raises the concern about their potential influence on public health, water systems, and the ecosystem in general. As, Cd, Cr, Pb, and Hg have been reported to be the highest systemic toxicant elements.
According to the US EPA and the International Agency for Research on Cancer (IARC), these toxic elements are probable to be carcinogenic. Moreover, accumulation of Pb, Cd, and Hg in the human body over time can cause serious health problems [22, 23, 24, 25, 26].
Similarly, food, leather, and textile industries discharge huge amounts of polluted wastes. With the various structures of the chemicals used in these industries, numerous problems develop. Dyes, a key water pollutant and even if discharged as traces (as low as 1 ppm), would color large volumes of water. Reports show that amount of dyes as huge as 7 × 105 tons per annum are being produced annually, demonstrating the magnitude of the problem. Released dyes do not only affect the aquatic beings but also the human health. Their impact includes carcinogenicity, mutagenicity, poisoning, disturbance of the metabolism in aquatic bodies, etc. [27, 28].
On the other hand, and representing a significant category of aquatic pollutants, pharmaceutically active materials (PhAMs) are usually released into the aquatic systems from different sources, including but not limited to the effluents of the manufacturing sites and hospitals, illegal disposal, veterinary applications, and landfill leachate. Daily use by humans and the subsequent conversion of PhAMs into various metabolites with variable chemical structures is also a major source. The fate of these metabolites, and probably their parent drug compound, is usually the wastewater [29, 30, 31, 32, 33].
The increasing understanding of the assembly of the food chain and the probability of infection of human with these resilient microorganisms, either directly or via the food chain, has explained largely the spread of these species. Therefore, the process of food production and commercialization is posing rigorous regulations nowadays. Different societies, such as the Food and Drug Administration (US FDA), European Union (EU), and World Health Organization (WHO) in collaboration with the Food and Agriculture Organization of the United Nations (FAO) creating the FAO/WHO Codex Alimentarius Commission (CAC), are setting up standards for the maximum residue levels (MRLs) permissible in raw and processed food products of animal or poultry origin. Yet, any food product that would conform to these criteria and the preceding risk assessments cannot be banned by countries of the World Trade Organization (WTO) [34, 35, 36, 37, 38].
The elevating concerns on food and water safety and the existence of these materials at relatively low concentrations have created the need to find sturdy as well as sensitive detection and removal/remediation technologies. Detection technologies included traditional techniques such as spectrophotometry, spectrofluorimetry, atomic absorption spectrometry (AAS), as well as electrochemical and the more sophisticated chromatographic approaches [27, 28, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49]. Each of these techniques has its pros and cons.
Electrochemical techniques are among the widely used techniques for detection of pollutants in food and water analyses. The following subsections will be focused on the electrochemical approaches and EIS in specific in detection of contaminants in water and food samples.
As an analytical approach, electroanalysis offers many advantages including but not limited to simplicity, sensitivity, specificity, and applicability in various matrices and cost-effectiveness. These advantages are of specific importance when it comes to detection of drugs and pharmaceuticals, especially in food and water samples as well as in quality control (QC) and quality assurance (QA) laboratories. According to the signal being measured (voltage/potential, current, conductance, impedance), electroanalytical techniques can be categorized into potentiometric, amperometric, conductometric, and impedimetric techniques. Subcategories for each technique also exist, and coupling with other technologies has been investigated.
Sensors, and in particular those based on the classical potentiometric technique, or the new polyion, galvanostatic, or voltammetric sensing mechanisms, now possess the foothold in analytical chemistry. Offering irresistible advantages, on the in vitro scale, such as operation simplicity, sturdiness, and remarkable sensitivity hitting nine orders of magnitude, selectivity, and functionality over wide range of matrices, suitability for on-line or real-time analyses, and most prominently their liability for miniaturization, make the use of sensors indispensable [50, 51, 52, 53].
Figure 1 shows an illustration of ISE (ion-selective electrode) potentiometric sensor and generation of potential across the different phase boundaries.
Schematic illustration of ISE cell assembly and the generation of EMF across different phase boundaries.
The sensing mechanism especially if the target analyte is a biomolecule depends on tailoring the surface of the sensor with a bio-receptor that can selectively bind to the target bio-analyte. Following the adsorption of the bio-analyte from the solution on the surface of the probe, a change in the electrochemical signal can be observed and measured. Such a change is correspondingly dependent on the bio-analyte concentration.
Figure 2 shows a schematic illustration of the sensing mechanism in plastic microfluidic channels. The left panel shows the generation of streaming potential, ΔE, as a result of pressure-driven flow and surface charge at the electric double layer (EDL). The right panel shows a sensogram with signal inversion upon adsorption of the analyte. The bottom graph shows the pulsed streaming potentials as a function of heparin with immobilized protamine.
Schematic illustration of the generation of streaming potential as a result of pressure-driven flow and surface charge at the electric double layer (EDL)—left upper panel. The right panel shows a sensogram with signal inversion upon adsorption of the analyte. The bottom graph shows the pulsed streaming potentials as a function of heparin with immobilized protamine on a surface of a cyclo-olefin copolymer (COC) microchannel. Data points were fitted using Langmuir isotherm. Graphs are replicated from the authors’ own work with permission from Copyrights@ American Chemical Society (ACS) [45].
EIS as an electrochemical technique entails measurement of the change in the charge transfer resistance (Rct) following the interactions between the analyte and the receptor and the consequent change in the interfacial electron transfer kinetics. The following sections will be dealing with the application for EIS for sensing different target analytes in different matrices [53, 54].
The effects of presence of the PhAMs either in waste and drinking water or even in wastewater treatment plants (WWTPs) are still inarticulate. However, what is well understood is that the impact extends to humans and animal’s health, the aquatic environment, and in the long run the ecosystem. This effect is greatly dependent on the released dose of the PhAMs as well as their pharmacological effects. The issue becomes of concern when we know that the metabolites might be of a higher risk than the parent drug compound. At the microbial level, microorganisms upon prolonged exposure to anti-infectives, for example, become more tolerant, and new strains, which cannot be cured using the conventional antimicrobials, are now in the scene [55, 56, 57].
EIS, being capable of detecting as low as 10−12 M of the target analyte, is widely used in drug analysis. Several drug categories were analyzed using EIS. Table 1 shows some examples of drugs analyzed using EIS, as well as the matrices and type of electrode used together with the sensing interface, sensing strategy (label-free or labelled), and limit of detection (LoD).
Target drug | Sensing interface | Electrode | Matrix | Sensing measurement method and strategy | LoD | Ref |
---|---|---|---|---|---|---|
Raloxifene | Nd2O5 NPs@GO/GCE | GCE | ND Serum and urine | EIS CV Amperometry (Label-free) | ND ND 18.43 nM | [58] |
OTC | Aptasensor (Fe3O4@mC900) | GCE | Milk samples | EIS (Label-free) | 0.027 pg mL−1 | [59] |
TET | Aptasensor 1: CPE/OA/anti-TET Aptasensor 2: MBCPE/Fe3O4NPs/OA/anti-TET | CPE MBCPE | Tablets, milk, honey, and serum | EIS (Label-free) | 10−1–10−7 M 3.0 × 10−13 M | [60] |
TOB | Aptasensor/ SnOx@TiO2@mC | GCE | Urine and serum | EIS (Label-free) | 0.01 nM | [61] |
Chloramphenicol | Au/N-G | GCE | Eye drops | EIS (Label-free) | 0.59 μM | [62] |
Sulphamethoxazole | MIP-decorated Fe3O4 MNPs | SPCE | Seawater | EIS (Label-free) | 0.001 nM | [63] |
17β-estradiol | Au nanoparticle-thiolated protein G-scaffold | Au | Serum | EIS (Label-free) | 26 pg mL−1 | [64] |
BPA | AuNPs/PB/CNTs-COOH/GCE | GCE | Water | EIS (Labelled detection) | 0.045 pM | [65] |
P4 | ssDNA/Au | Au | Tap water | EIS (Labelled detection) | 0.90 ng mL−1 | [66] |
Applications of EIS in analysis and characterizations of different drug materials in variable matrices.
The electrochemical properties of raloxifene, an important chemotherapeutic agent, were assessed using different techniques including EIS. Three electrodes were tested for this investigation: (1) bare screen-printed carbon electrode (SPCE), (2) graphene oxide (GO)/glassy carbon electrode (GCE), and (3) neodymium sesquioxide nanoparticles Nd2O5 NPs@GO/GCE. The target was to assess the interface properties of these electrodes. Results showed that the Rct of the third electrode was much smaller than the other electrodes. Other electrochemical techniques such as cyclic voltammetry (CV) were used in the same work [58].
Other examples included the determination of an important class of PhAMs, which is antibiotics, a subclass of antimicrobials. Label-free detection of oxytetracycline (OTC) in milk samples was performed using a mixture of iron oxide and mesoporous carbon (Fe3O4@mC) together with nanocomposites made of Fe(II)-based metal-organic frameworks (525-MOF) by calcination at different temperatures. The sensor showed a very high sensitivity with a LoD = 0.027 pg mL−1 and a linear range of 0.005–1.0 ng mL−1. Moreover, the fabricated aptasensor showed a high selectivity for oxytetracycline in the presence of similar drugs like tetracycline, doxycycline, and chlortetracycline [59].
Similarly, label-free detection of tetracycline (TET) was performed using two aptasensors made of carbon paste electrode (CPE) with oleic acid (OA) and a magnetic bar carbon paste electrode (MBCPE) with Fe3O4 magnetic nanoparticles and oleic acid (OA) following the modification of electrode surfaces using anti-TET. The LoD were 1.0 × 10−12 to 1.0 × 10−7 M and 3.0 × 10−13 M for the two aptasensors, respectively, and the sensors were applied to pharmaceutical formulations, serum samples, as well as food products (milk and honey) [60].
A sensor based on nanocomposites of mC with SnOx and TiO2 nanocrystals was used to determine tobramycin (TOB) in urine and serum samples selectively and in the presence of kanamycin, oxytetracycline, and doxycycline. The aptasensor showed an excellent sensitivity with a LoD of 0.01 nM [61].
Chloramphenicol was also determined in eye drop formulations using N-doped graphene nano-sheet-Au NP composite (Au/N-G). The LoD was 0.59 μM, and the sensor showed a selectivity in the presence of interferences like oxytetracycline, chlortetracycline, ascorbic acid, and metronidazole [62]. Other applications included sulphamethoxazole using molecularly imprinted polymers (MIPs) decorated with Fe3O4 magnetic nanoparticles (MNPs) on SPCE [63].
Immunosensors for 17β-estradiol composed of Au electrode nanoparticle-thiolated protein G-scaffold. This structure has facilitated the anchoring of a mouse monoclonal anti-estradiol antibody. The LoD was 26 pg mL−1. As per the authors, square wave voltammetry (SWV) was more sensitive (18 pg mL−1) and required less time and effort compared to EIS [64].
Bisphenol A (BPA), a xenoestrogen with an estrogen-mimicking effect and that is widely used as a precursor in plastics industry, has been determined using a labelled aptasensor made of gold nanoparticles (AuNPs), Prussian blue (PB), and functionalized carbon nanotubes (AuNPs/PB/CNTs-COOH).
Determination of progesterone (P4) in water and other clinical samples was performed using single-stranded ssDNA aptamers with high binding affinity to P4 [66].
In addition to food contamination with antimicrobials and other drugs, bacteria and other pathogens like mycotoxins (secondary metabolites of microfungi) or chemicals such as pesticides are also other sources of food contamination. Food contamination can occur at any stage of food production, storage, or dissemination. Sicknesses caused by foodborne pathogens include symptoms such as diarrhea, nausea, vomiting, septicemia, meningitis, and even death [50, 53, 67, 68]. Pathogens include famous strains of bacteria such as different species of Salmonella (e.g., S. enteritidis and S. typhimurium), Escherichia coli (E. coli), and Staphylococcus aureus (S. aureus).
Table 2 shows examples of different bacterial strains that have been determined in food products using EIS-based aptamers.
Target | Sensing interface | Electrode | Matrix | Sensing method | LoD | Ref |
---|---|---|---|---|---|---|
Bacteria (LoD is measured as/CFU mL−1)* | ||||||
S. enteritidis | GNPs@SPCE | SPCE | Poultry products | EIS | 600 | [69] |
S. typhimurium | GNPs@SPCE | SPCE | Animal-based products | EIS | 600 | [70] |
Salmonella | GO+AuNPs@GCE | GCE | Pork meat | EIS | 3.0 | [71] |
Mycotoxins | ||||||
OTA | Diazonium modified-SPCE | SPCEs | Cocoa beans | EIS | 0.15 ng mL−1 | [72] |
OTA | Thiolated DNA aptamer | Au | Food products | EIS | 0.12–0.40 nM | [73] |
AFB1 | Cys-PAMAM-modified electrode | Au | Peanuts and corn snacks | EIS | 0.40 ± 0.03 nM | [74] |
Pesticides | ||||||
Acetamiprid | Ag-NG/GCE | GCE | Cucumber and tomatoes | EIS | 0.033 pM | [75] |
Applications of EIS in analysis of food and food products.
Colony-forming unit (CFU) mL−1.
A highly specific DNA—aptamer to S. enteritidis in pork products—was developed using gold NPs, i.e., modified SPCE (GNPs-SPCE). The developed aptasensor was selective towards S. enteritidis and showed a negative response towards mixture of other pathogens [69]. Similarly, the same electrode was used as a sensor for S. typhimurium [70]. The developed sensors were capable of differentiating between the targeted Salmonella species (S. enteritidis and S. typhimurium) and the other Salmonella.
Another Salmonella sensor was fabricated using a GO/Au NP-modified GCE. The sensor was applied for pork samples and achieved a LoD of 3.0 colony-forming unit (CFU mL−1) in this case [71] compared to 600 CFU mL−1 using the GNPs@SPCE aptasensors [69, 70].
The mycotoxin ochratoxin (OTA) has been determined in a variety of samples, e.g., in cocoa beans, using EIS aptasensor developed using a diazonium-coupling reaction mechanism for the immobilization of anti-OTA-aptamer on screen-printed carbon electrode (SPCE) [72]. EIS was also applied for the determination of OTA using a thiolated DNA aptamer immobilized by chemisorption to the surface of Au electrode [73]. Other mycotoxins, e.g., Aflatoxin B1 (AFB1) were detected using layer coating of cystamine (Cys), poly (amido-amine) dendrimers of generation 4.0 (PAMAM G4) and DNA aptamers (on Au electrode) specific to AFB1 [74].
Pesticides, e.g., acetamiprid, were determined in samples of vegetables (tomatoes and cucumber) using AgNP-modified nitrogen-doped graphene (AgNPs/NG). The designed aptasensor was sensitive, selective, and economical and did not require intricate labelling procedures [75].
Discharge of heavy metals (HMs) into the water bodies via industrial activities and other sources, e.g., mining, acid rain, agricultural waste, etc., denotes a worldwide challenge. As previously mentioned in this chapter, HMs and other emergent contaminants possess a significant influence on the environment and human health. The intensifying flux of HMs into aquatic environments and the properties of HMs (toxicity, degradation rates, accumulation, uptake, bioavailability, etc.) necessitate the presence of firm rules and action plans for monitoring, detoxification methodologies, and treatment technologies to keep their concentrations within the permitted levels [23, 24, 25, 26, 76].
Table 3 shows examples for the applications of EIS in determination of water contaminants such as HMs, pesticides, drugs, and pharmaceuticals.
Target | Sensing interface | Matrix | LoD | Ref |
---|---|---|---|---|
Heavy metals | ||||
Hg2+, Cd2+ | Arthrospira platensis cells (Spirulina) | Municipal wastewater | 10−20 M and 10−20 M | [77] |
Pb2+, Cd2+ | PET-SPE | Water | 1 nM for both metals | [78] |
Hg2+ | Cu2O@NCs | River water samples | 0.15 nM | [79] |
Pesticides and herbicides | ||||
Parathion-methyl | Arthrospira platensis cells (Spirulina) | Municipal wastewater | 10−20 M | [77] |
Paraoxon-methyl | Arthrospira platensis cells (Spirulina) | Municipal wastewater | 10−18 M | [77] |
Triazine | Arthrospira platensis cells (Spirulina) | Municipal wastewater | 10−20 M | [77] |
Acetamiprid | Ag-NG/GCE | Wastewater | 0.033 pM | [75] |
Drugs and pharmaceuticals | ||||
Sulphamethoxazole | MIP-decorated Fe3O4 MNPs@SPCE | Seawater | 0.001 nM | [63] |
BPA | AuNPs/PB/CNTs-COOH/GCE | Water | 0.045 pM | [65] |
P4 | ssDNA/Au | Tap water | 0.90 ng mL−1 | [66] |
Applications of EIS in analysis of water.
EIS has been applied for quantitative determination of HMs in water samples. In one of the investigations, a bi-enzymatic biosensor was constructed by immobilizing Arthrospira platensis cells (Spirulina) on gold interdigitated transducers. Consequently, phosphatase and esterase activities were inhibited by HMs and pesticides, respectively. This approach was used to determine Hg2+ and Cd2+ as well as parathion, paraoxon, and triazine pesticides, alone or in mixture with the HMs [77].
In another approach, a three-electrode sensor was printed on a polyethylene terephthalate film (PET) and was applied for impedimetric determination of Pb2+ and Cd2+ in water samples at nanomolar level [78]. An electrochemical DNA biosensor based on microspheres of cuprous oxide (Cu2O) and nano-chitosan (NC) was used for Hg2+ detection in river water samples with a LoD of 0.15 nM [79].
Other contaminants like pesticides and herbicides as well as drugs and pharmaceuticals were also determined using EIS [63, 65, 66, 75, 77] (Table 3).
The literature is rich in articles and reviews that investigate the applications of electrochemical impedance spectroscopy in detections of various contaminants such as heavy metals, drugs, and pharmaceuticals, as well as pesticides. The advantages that impedance spectroscopy introduces as an electrochemical technique are innumerable. High sensitivity, specificity, selectivity, no time or effort consumption, and being label-free are the major advantages reported in the majority of the surveyed literature. As the mentioned contaminants usually exist as traces in complicated matrices, impedance spectroscopy with the mentioned advantages was usually the electrochemical technique of choice for the detection of these contaminants in water, food, and drug matrices.
The authors declare no conflict of interest.
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\\n\\nThe Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\\n\\nThe Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\\n\\n4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\\n\\n5. TERMINATION
\\n\\n5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\\n\\nIn case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\\n\\n6. INTECHOPEN’S DUTIES AND RIGHTS
\\n\\n6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\\n\\n6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\\n\\n6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\\n\\n7. MISCELLANEOUS
\\n\\n7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\\n\\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\\n\\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\\n\\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\\n\\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\\n\\n7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\\n\\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\\n\\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\\n\\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
\\n\\nLast updated: 2020-11-27
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The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
\n\n1. DEFINITIONS
\n\nCorresponding Author: The Author of the Chapter who serves as a Signatory to this Agreement. The Corresponding Author acts on behalf of any other Co-Author.
\n\nCo-Author: All other Authors of the Chapter besides the Corresponding Author.
\n\nIntechOpen: IntechOpen Ltd., the Publisher of the Book.
\n\nBook: The publication as a collection of chapters compiled by IntechOpen including the Chapter. Chapter: The original literary work created by Corresponding Author and any Co-Author that is the subject of this Agreement.
\n\n2. CORRESPONDING AUTHOR'S GRANT OF RIGHTS
\n\n2.1 Subject to the following Article, the Corresponding Author grants and shall ensure that each Co-Author grants, to IntechOpen, during the full term of copyright and any extensions or renewals of that term the following:
\n\nThe aforementioned licenses shall survive the expiry or termination of this Agreement for any reason.
\n\n2.2 The Corresponding Author (on their own behalf and on behalf of any Co-Author) reserves the following rights to the Chapter but agrees not to exercise them in such a way as to adversely affect IntechOpen's ability to utilize the full benefit of this Publication Agreement: (i) reprographic rights worldwide, other than those which subsist in the typographical arrangement of the Chapter as published by IntechOpen; and (ii) public lending rights arising under the Public Lending Right Act 1979, as amended from time to time, and any similar rights arising in any part of the world.
\n\nThe Corresponding Author confirms that they (and any Co-Author) are and will remain a member of any applicable licensing and collecting society and any successor to that body responsible for administering royalties for the reprographic reproduction of copyright works.
\n\nSubject to the license granted above, copyright in the Chapter and all versions of it created during IntechOpen's editing process (including the published version) is retained by the Corresponding Author and any Co-Author.
\n\nSubject to the license granted above, the Corresponding Author and any Co-Author retains patent, trademark and other intellectual property rights to the Chapter.
\n\n2.3 All rights granted to IntechOpen in this Article are assignable, sublicensable or otherwise transferrable to third parties without the Corresponding Author's or any Co-Author’s specific approval.
\n\n2.4 The Corresponding Author (on their own behalf and on behalf of each Co-Author) will not assert any rights under the Copyright, Designs and Patents Act 1988 to object to derogatory treatment of the Chapter as a consequence of IntechOpen's changes to the Chapter arising from translation of it, corrections and edits for house style, removal of problematic material and other reasonable edits.
\n\n3. CORRESPONDING AUTHOR'S DUTIES
\n\n3.1 When distributing or re-publishing the Chapter, the Corresponding Author agrees to credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen. The Corresponding Author warrants that each Co-Author will also credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen, when they are distributing or re-publishing the Chapter.
\n\n3.2 When submitting the Chapter, the Corresponding Author agrees to:
\n\nThe Corresponding Author will be held responsible for the payment of the Open Access Publishing Fees.
\n\nAll payments shall be due 30 days from the date of the issued invoice. The Corresponding Author or the payer on the Corresponding Author's and Co-Authors' behalf will bear all banking and similar charges incurred.
\n\n3.3 The Corresponding Author shall obtain in writing all consents necessary for the reproduction of any material in which a third-party right exists, including quotations, photographs and illustrations, in all editions of the Chapter worldwide for the full term of the above licenses, and shall provide to IntechOpen upon request the original copies of such consents for inspection (at IntechOpen's option) or photocopies of such consents.
\n\nThe Corresponding Author shall obtain written informed consent for publication from people who might recognize themselves or be identified by others (e.g. from case reports or photographs).
\n\n3.4 The Corresponding Author and any Co-Author shall respect confidentiality rights during and after the termination of this Agreement. The information contained in all correspondence and documents as part of the publishing activity between IntechOpen and the Corresponding Author and any Co-Author are confidential and are intended only for the recipient. The contents may not be disclosed publicly and are not intended for unauthorized use or distribution. Any use, disclosure, copying, or distribution is prohibited and may be unlawful.
\n\n4. CORRESPONDING AUTHOR'S WARRANTY
\n\n4.1 The Corresponding Author represents and warrants that the Chapter does not and will not breach any applicable law or the rights of any third party and, specifically, that the Chapter contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy. The Corresponding Author warrants and represents that: (i) the Chapter is the original work of themselves and any Co-Author and is not copied wholly or substantially from any other work or material or any other source; (ii) the Chapter has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) they themselves and any Co-Author are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) they themselves and any Co-Author have not assigned and will not during the term of this Publication Agreement purport to assign any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\n\nThe Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\n\nThe Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\n\n4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\n\n5. TERMINATION
\n\n5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\n\nIn case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\n\n6. INTECHOPEN’S DUTIES AND RIGHTS
\n\n6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\n\n6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\n\n6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\n\n7. MISCELLANEOUS
\n\n7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\n\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\n\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\n\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\n\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\n\n7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\n\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\n\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\n\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
\n\nLast updated: 2020-11-27
\n\n\n\n
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I am also a member of the team in charge for the supervision of Ph.D. students in the fields of development of silicon based planar waveguide sensor devices, study of inelastic electron tunnelling in planar tunnelling nanostructures for sensing applications and development of organotellurium(IV) compounds for semiconductor applications. I am a specialist in data analysis techniques and nanosurface structure. I have served as the editor for many books, been a member of the editorial board in science journals, have published many papers and hold many patents.",institutionString:null,institution:{name:"Sheffield Hallam University",country:{name:"United Kingdom"}}},{id:"54525",title:"Prof.",name:"Abdul Latif",middleName:null,surname:"Ahmad",slug:"abdul-latif-ahmad",fullName:"Abdul Latif Ahmad",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"20567",title:"Prof.",name:"Ado",middleName:null,surname:"Jorio",slug:"ado-jorio",fullName:"Ado Jorio",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Universidade Federal de Minas Gerais",country:{name:"Brazil"}}},{id:"47940",title:"Dr.",name:"Alberto",middleName:null,surname:"Mantovani",slug:"alberto-mantovani",fullName:"Alberto Mantovani",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"12392",title:"Mr.",name:"Alex",middleName:null,surname:"Lazinica",slug:"alex-lazinica",fullName:"Alex Lazinica",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/12392/images/7282_n.png",biography:"Alex Lazinica is the founder and CEO of IntechOpen. After obtaining a Master's degree in Mechanical Engineering, he continued his PhD studies in Robotics at the Vienna University of Technology. Here he worked as a robotic 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 he co-founded and built the International Journal of Advanced Robotic Systems- world's first Open Access journal in the field of robotics. Starting this journal was a pivotal point in his career, since it was a pathway to founding IntechOpen - Open Access publisher focused on addressing academic researchers needs. Alex is a personification of IntechOpen key values being trusted, open and entrepreneurial. Today his focus is on defining the growth and development strategy for the company.",institutionString:null,institution:{name:"TU Wien",country:{name:"Austria"}}},{id:"19816",title:"Prof.",name:"Alexander",middleName:null,surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/19816/images/1607_n.jpg",biography:"Alexander I. Kokorin: born: 1947, Moscow; DSc., PhD; Principal Research Fellow (Research Professor) of Department of Kinetics and Catalysis, N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow.\r\nArea of research interests: physical chemistry of complex-organized molecular and nanosized systems, including polymer-metal complexes; the surface of doped oxide semiconductors. He is an expert in structural, absorptive, catalytic and photocatalytic properties, in structural organization and dynamic features of ionic liquids, in magnetic interactions between paramagnetic centers. The author or co-author of 3 books, over 200 articles and reviews in scientific journals and books. He is an actual member of the International EPR/ESR Society, European Society on Quantum Solar Energy Conversion, Moscow House of Scientists, of the Board of Moscow Physical Society.",institutionString:null,institution:{name:"Semenov Institute of Chemical Physics",country:{name:"Russia"}}},{id:"62389",title:"PhD.",name:"Ali Demir",middleName:null,surname:"Sezer",slug:"ali-demir-sezer",fullName:"Ali Demir Sezer",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/62389/images/3413_n.jpg",biography:"Dr. Ali Demir Sezer has a Ph.D. from Pharmaceutical Biotechnology at the Faculty of Pharmacy, University of Marmara (Turkey). He is the member of many Pharmaceutical Associations and acts as a reviewer of scientific journals and European projects under different research areas such as: drug delivery systems, nanotechnology and pharmaceutical biotechnology. Dr. Sezer is the author of many scientific publications in peer-reviewed journals and poster communications. Focus of his research activity is drug delivery, physico-chemical characterization and biological evaluation of biopolymers micro and nanoparticles as modified drug delivery system, and colloidal drug carriers (liposomes, nanoparticles etc.).",institutionString:null,institution:{name:"Marmara University",country:{name:"Turkey"}}},{id:"61051",title:"Prof.",name:"Andrea",middleName:null,surname:"Natale",slug:"andrea-natale",fullName:"Andrea Natale",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"100762",title:"Prof.",name:"Andrea",middleName:null,surname:"Natale",slug:"andrea-natale",fullName:"Andrea Natale",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"St David's Medical Center",country:{name:"United States of America"}}},{id:"107416",title:"Dr.",name:"Andrea",middleName:null,surname:"Natale",slug:"andrea-natale",fullName:"Andrea Natale",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Texas Cardiac Arrhythmia",country:{name:"United States of America"}}},{id:"64434",title:"Dr.",name:"Angkoon",middleName:null,surname:"Phinyomark",slug:"angkoon-phinyomark",fullName:"Angkoon Phinyomark",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/64434/images/2619_n.jpg",biography:"My name is Angkoon Phinyomark. I received a B.Eng. degree in Computer Engineering with First Class Honors in 2008 from Prince of Songkla University, Songkhla, Thailand, where I received a Ph.D. degree in Electrical Engineering. My research interests are primarily in the area of biomedical signal processing and classification notably EMG (electromyography signal), EOG (electrooculography signal), and EEG (electroencephalography signal), image analysis notably breast cancer analysis and optical coherence tomography, and rehabilitation engineering. I became a student member of IEEE in 2008. During October 2011-March 2012, I had worked at School of Computer Science and Electronic Engineering, University of Essex, Colchester, Essex, United Kingdom. In addition, during a B.Eng. I had been a visiting research student at Faculty of Computer Science, University of Murcia, Murcia, Spain for three months.\n\nI have published over 40 papers during 5 years in refereed journals, books, and conference proceedings in the areas of electro-physiological signals processing and classification, notably EMG and EOG signals, fractal analysis, wavelet analysis, texture analysis, feature extraction and machine learning algorithms, and assistive and rehabilitative devices. I have several computer programming language certificates, i.e. Sun Certified Programmer for the Java 2 Platform 1.4 (SCJP), Microsoft Certified Professional Developer, Web Developer (MCPD), Microsoft Certified Technology Specialist, .NET Framework 2.0 Web (MCTS). 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