Important parameters of carbon materials of different dimensionalities [6].
\\n\\n
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Barely three months into the new year and we are happy to announce a monumental milestone reached - 150 million downloads.
\n\nThis achievement solidifies IntechOpen’s place as a pioneer in Open Access publishing and the home to some of the most relevant scientific research available through Open Access.
\n\nWe are so proud to have worked with so many bright minds throughout the years who have helped us spread knowledge through the power of Open Access and we look forward to continuing to support some of the greatest thinkers of our day.
\n\nThank you for making IntechOpen your place of learning, sharing, and discovery, and here’s to 150 million more!
\n\n\n\n\n'}],latestNews:[{slug:"intechopen-supports-asapbio-s-new-initiative-publish-your-reviews-20220729",title:"IntechOpen Supports ASAPbio’s New Initiative Publish Your Reviews"},{slug:"webinar-introduction-to-open-science-wednesday-18-may-1-pm-cest-20220518",title:"Webinar: Introduction to Open Science | Wednesday 18 May, 1 PM CEST"},{slug:"step-in-the-right-direction-intechopen-launches-a-portfolio-of-open-science-journals-20220414",title:"Step in the Right Direction: IntechOpen Launches a Portfolio of Open Science Journals"},{slug:"let-s-meet-at-london-book-fair-5-7-april-2022-olympia-london-20220321",title:"Let’s meet at London Book Fair, 5-7 April 2022, Olympia London"},{slug:"50-books-published-as-part-of-intechopen-and-knowledge-unlatched-ku-collaboration-20220316",title:"50 Books published as part of IntechOpen and Knowledge Unlatched (KU) Collaboration"},{slug:"intechopen-joins-the-united-nations-sustainable-development-goals-publishers-compact-20221702",title:"IntechOpen joins the United Nations Sustainable Development Goals Publishers Compact"},{slug:"intechopen-signs-exclusive-representation-agreement-with-lsr-libros-servicios-y-representaciones-s-a-de-c-v-20211123",title:"IntechOpen Signs Exclusive Representation Agreement with LSR Libros Servicios y Representaciones S.A. de C.V"},{slug:"intechopen-expands-partnership-with-research4life-20211110",title:"IntechOpen Expands Partnership with Research4Life"}]},book:{item:{type:"book",id:"6116",leadTitle:null,fullTitle:"Modelling, Simulation and Identification",title:"Modelling, Simulation and Identification",subtitle:null,reviewType:"peer-reviewed",abstract:"Modeling, simulation and identification has been actively researched in solving practical engineering problems. 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\r\n\tThe purpose of this book will be to make an inroad into the field of risk management. The field of risk management is important in the current conditions of environmental dynamics. This book will address risk management in tangential areas: Risk management in various fields of activity, sustainability, and the circular economy and leadership.
\r\n\tRisk management aims to develop an efficient organizational development environment through risk planning, assessment, analysis, and control. This process will apply in all areas of activity, and the evaluation framework is the same regardless of the field. This volume will aim to appeal to chapters that address methods, models, evaluation frameworks, benefits, barriers, and other dimensions of risk management.
\r\n\tSustainability and the circular economy are approaches approached by many companies and have become activities of global interest. Protecting the environment, streamlining the consumption of organizational resources, reducing the amount of waste generated, and other activities are objectives of these efforts. The circular economy contributes to the sustainable development of the company or country and the achievement of the global objectives of sustainable development. This book will aim to collect various studies for organizational and global sustainability.
\r\n\tLeadership has become a globally desirable approach that can help improve organizational competitiveness and reduce organizational risks. Risks and barriers in risk-free management can be well managed through effective organizational leadership. This book will aim to bring together chapters that explore different areas of leadership.
Carbon is an abundant element playing a major role in the chemistry of life [1]. Some of the advantageous properties of carbon-based electrodes include wide potential windows, fairly inert electrochemistry, and good electrocatalytic activity for many redox reactions [2]. Various carbon allotropes including diamond (the carbon atoms are bonded together in a tetrahedral lattice arrangement, 3D), graphite (the carbon atoms are bonded together in sheets of a hexagonal lattice, 3D), graphene (2D), carbon nanotubes (single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT), 1D), and fullerenes (the carbon atoms are bonded together in spherical, tubular, or ellipsoidal formations, 0D) have very different physical and electrochemical properties from each other (see Table 1 and Figure 1) [2-4]. The advents of sp2 and/or sp3 hybridized structures, such as fullerenes, carbon nanotubes, and conducting diamond, provide a route for surface modification and are very beneficial to electrochemical research, especially electrocatalysis [2]. The former 3D allotropes have been known and widely used for centuries whereas fullerenes and nanotubes have been only discovered and studied in the last two decades. With the exception of diamond, it is possible to think of fullerenes, nanotubes, and graphite as different structures built from the same hexagonal array of sp2 carbon atoms, namely, graphene [3].
Different allotropes of carbon.
Graphene consists of a single sheet of carbon atoms that bind with each other in a honeycomb lattice. Graphene sheets are one-atom thick and 2D layers of sp2-bonded carbon [4]. It is the basic building block for graphitic materials of all other dimensionalities. Graphene can be wrapped up into spherical shape to form 0D fullerenes (buckyballs), rolled into a cylindrical shape to form 1D nanotubes or stacked in layers to form 3D graphite as illustrated in Figure 2 [1, 3, 5-8]. The electronic structure of graphene sheets, individual layers of graphite, was first discussed by Wallace in 1947 [2]. Boehm and co-workers separated thin lamellae of carbon by heating and chemical reduction of graphite oxide in 1962 [6]. Until 2004, single layers of graphite were believed to be thermodynamically unstable under ambient conditions [2, 6]. Since the historical observation of single layer graphene in 2004 by two Nobel Laureates in physics, Prof. Andre Geim and Prof. Konstantin Novoselov, this atomically thin carbon film has received ever increasing attention and become the hottest topics and a rapidly “rising star” on the horizon of materials science and condensed-matter physics attracting enormous interests [8-10]. This revolutionary discovery has added a new dimension of research in the fields of physics, chemistry, biotechnology, and materials science [6]. Technologists and materials scientists have rapidly grabbed some of the assets of graphene and are already exploring the ways of incorporating graphene into applied devices and materials [3].
Basis of all graphitic forms. Graphene is a 2D building material for carbon materials of all other dimensionalities. It can be wrapped up into 0D buckyballs, rolled into 1D nanotubes or stacked into 3D graphite [
\n\t\t\t\t | \n\t\t\t0D | \n\t\t\t1D | \n\t\t\t2D | \n\t\t\t3D | \n\t\t
\n\t\t\t\t | \n\t\t\tFullerene | \n\t\t\tNanotube | \n\t\t\tGraphene | \n\t\t\tDiamond | \n\t\t
\n\t\t\t\t | \n\t\t\tsp2\n\t\t\t | \n\t\t\tsp2\n\t\t\t | \n\t\t\tsp2\n\t\t\t | \n\t\t\tsp3\n\t\t\t | \n\t\t
\n\t\t\t\t | \n\t\t\t1.72 | \n\t\t\t1.2-2.0 | \n\t\t\t2.26 | \n\t\t\t3.515 | \n\t\t
\n\t\t\t\t | \n\t\t\t1.40 (C=C) 1.46 (C-C) | \n\t\t\t1.44 (C=C) | \n\t\t\t1.42 (C=C) | \n\t\t\t1.54 (C-C) | \n\t\t
\n\t\t\t\t | \n\t\t\tSemiconductor Eg = 1.9 eV | \n\t\t\tMeta/semiconductor Eg =~ 0.3-1.1 eV | \n\t\t\tZero-gap semiconductor | \n\t\t\tInsulator | \n\t\t
Important parameters of carbon materials of different dimensionalities [6].
Graphene, a monolayer of sp2-bonded carbon atoms arranged in a honeycomb lattice, has attracted tremendous attention from both the theoretical and experimental scientific communities in recent years because of its unique nanostructure and extraordinary properties [11, 12]. It has become a novel and very promising material for nanoelectronics, nanocomposites, optoelectronic devices, electrochemical supercapacitor devices, fabricated field-effect transistors, drug delivery systems, solar cells, memory devices, and constructed ultrasensitive chemical sensors such as pH sensors, gas sensors, biosensors, etc. [6, 11, 12]. The rapid adoption of graphene as a material of interest lies in its actual availability by a range of techniques and methods and may also be principally because monolayer and few-layer graphene possess a diverse set of unusual properties. These properties happen to be matching the short-comings of other materials, such as carbon nanotubes, graphite, or indium tin oxide (ITO) that have been studied and used for some time [3]. In the following points, we will give an exhaustive account of the unique physical and chemical properties of graphene.
Graphene implies large theoretical specific surface area (~ 2630 m2 g-1, for single-layer graphene), exhibiting high electrocatalytic activities and ultrahigh loading capacity for biomolecules and drugs [6, 8, 13].
Graphene is a unique bendable material with excellent mechanical flexibility and high crystallographic quality. It is strictly 2D and stable under ambient conditions [6, 11, 14].
Graphene exhibits high optical transparency [6, 11] with an absorption of ~ 2.3% toward visible light [15]. Indeed, in the visible range, thin graphene films have a transparency that decreases linearly with the film thickness. For 2-nm thick films, the transmittance is higher than 95% and remains above 70% for 10-nm thick films. This optical characteristic combined with the excellent conductivity of graphene-based materials holds promises as a replacement to the cost-raising standard ITO [3].
The breaking strength of graphene is 200 times higher than steel making it the strongest material ever tested. Graphene exhibits high values of Young’s modulus (~1.1 Tpa) [6, 11].
It is one of the thinnest known materials. The carbon atoms are densely packed in a honeycomb crystal lattice with a bond length of 0.141 nm. Different research groups have measured the thickness of graphene from 0.35 nm to 1.00 nm. Novoselov et al. have determined platelet thicknesses of 1.00–1.60 nm [6].
It is well established that the superior properties of graphene are associated with its single layer [6]. Figure 3 (a) shows the honeycomb lattice of graphene that is formed by a triangular lattice with a basis of 2 atoms per unit cell. Each atom has four valence electrons: one
It exhibits excellent room temperature electrical conductivity (~ 7200 S.m-1) [6, 11] with amazing intrinsic mobilities of ~ 200,000 cm2V-1s-1. The room temperature thermal conductivity values have been determined to be ~ (4.84 ± 0.44)×103 to (5.30 ± 0.48)×103 WmK-1 for single-layer graphene [5, 6, 16].
One of the factors that made graphene so attractive in the research field is its low energy dynamics of electrons. The 2D crystal of
Graphene exhibits strong adsorptive capability [12] since every atom in a graphene sheet is a surface atom thus molecular interaction and electron transport through graphene can be highly sensitive to adsorbed molecules [17]. The unique electrochemical responses of graphene to target molecules are from the planar geometric structure and special electronic character of graphene [10].
Easy synthesis, low cost, and non-toxicity of graphene make this material a promising candidate for many technological applications [5, 16].
Graphene is an ideal material for various applications because of its very large 2D electrical conductivity, large surface area, and low cost. In comparison with carbon nanotubes (CNTs), two advantages of graphene are obvious as follows:
Graphene does not contain metallic impurities as CNTs do. In many cases, such impurities dominate the electrochemistry of CNTs and lead to misleading conclusions.
The production of graphene can be achieved using graphite that is cheap and accessible [18].
(a) Honeycomb lattice of graphene showing two triangular sublattices A and B. (b) Linear energy bands in the honeycomb lattice close to the Dirac point [
The rapid adoption of graphene as a material of interest lies in its actual availability by a range of techniques and methods [3, 5]. In 2004, Geim and coworkers first reported graphene sheets prepared by mechanical exfoliation (repeated peeling) of highly oriented pyrolytic graphite. This method, which is called the “scotch-tape” method, is still widely used in many laboratories to obtain pristine perfect structured graphene layer(s) for basic scientific research and for making proof-of-concept devices [18, 19]. However, this method is not suitable for the large-scale production of graphene necessary to fulfill the requirements in different areas. A large amount of recent effort has been devoted to develop methods to synthesize graphene at large scale for practical electronic applications. These methods include mechanical exfoliation and cleavage of natural graphite, chemical vapor deposition on metals, electric arc discharge, epitaxial growth on electrically insulating surfaces, unzipping of carbon nanotubes, solution-based chemical approaches (chemical or thermal reduction of graphite oxide), and thermal decomposition of SiC wafer under ultrahigh vacuum conditions [2, 5, 6, 19].
Chemical vapor deposition (CVD) is a simple, scalable, and cost-efficient method to prepare single and few-layer of graphene on various substrates. It opens a new route to large-area production of high-quality graphene films for practical applications [20-23]. In general, CVD techniques involve the decomposition of fluid (gas and liquid sprays) at high temperature to form either thin films on substrates or powders through filters. There are many forms of CVD like hot wire CVD, thermal CVD [24], plasma-enhanced CVD [25], radio-frequency CVD, and ultrasonic spray pyrolysis. Evaporated Ni film on SiO2/Si wafers or copper foils are ideal substrates for graphene synthesis. Synthesis of graphene on Ni supported on Si/SiO2 wafers facilitated the breakthrough approach for large-scale graphene. This is attributed to the excellent geometrical fit of the ordered graphene/graphite phase of carbon to the crystalline metal surface that is provided by Ni films. Another reason is the convenient interactions that favor bond formation between carbon atoms at specific conditions. Carbon atoms dissolve into the Ni crystalline surface and they arrange epitaxially on the Ni (111) surface to form graphene at certain temperatures (Figure 4). CVD synthesis of graphene can be carried out at ambient pressure or vacuum by systematically varying parameters such as gas composition and flow rate, temperature, and deposition time [4, 19]. The carbon precursor in CVD is methane [26-29]. By using diluted methane, single and few-layers of graphene (less than 5 layers) were grown, while using concentrated methane results in multilayer growth [4]. Other carbon precursors can be used in CVD such as ethanol [30], isopropanol [27], ethylene, acetylene, and others [4].
Schematic representation of the atomic arrangement of the hexagonal lattice of the (111) face of nickel (blue spheres) and how carbon atoms (gray spheres) would arrange on the Ni (111) surface to form graphene [
The method of unzipping single-walled carbon nanotubes to form monolayer graphene has been reported recently accomplishing by harsh acids and the right thermodynamic conditions (Figure 5) [31]. Recently, Dai and coworker have taken a unique approach to fabricate graphene nanoribbons (GNRs) with well-controlled dimensions. Based on the concept that CNTs are considered to be GNRs rolled up into seamless tubes and the fact that the size of CNTs has been well controlled, Dai’s group developed a method to produce GNRs through controlled unzipping of CNTs using the Ar plasma etching method. Shimizu and coworkers produced GNRs through the oxidization and longitudinal unzipping of MWCNTs in concentrated sulfuric acid followed by treatment with KMnO4 [32]. Another approach involved the preparation of longitudinal unzipped MWCNTs by controlled oxidation and intercalation through reaction with concentrated H2SO4 and HNO3 at room temperature in order to control the reaction rate. The unzipped MWCNTs are thermally treated up to 1000ºC and 2500ºC in an inert atmosphere to exfoliate and reduce the edge defects. The sonication process is responsible for chemo-mechanical breaking and the separation of multi-layer nanoribbons [33]. Furthermore, graphene nanoribbons were synthesized by the oxidative unzipping of SWCNTs using a mixture of concentrated HNO3/H2SO4 in a 1:3 volume ratio followed by 8 hours of ultrasonic treatment performed at 50 W at 45ºC [34]. In addition, catalytic unzipping of single-, double-, and multi-walled carbon nanotubes (SWCNTs, DWCNTs, and MWCNTs) in the presence of Pd nanoparticles and an oxygen-containing liquid medium yielding few layer graphene sheets was performed under microwave irradiation [35].
Modelling illustration of the SWCNT unzipped into monolayer graphene [
Arc discharge is a versatile and low-cost method for producing various kinds of carbon nanomaterials. Compared to other methods, the graphene sheets synthesized by arc discharge method have merits of good dispersibility in organic solvent, few defects, and high thermal stability [36]. In the arc discharge technique, graphite rods (purity: 99.99 %) are used as electrodes for high voltage arcing. At extremely high voltages between the electrodes that are separated by very small distances, very high electric fields can be produced leading to instantaneous sparks like in a welding process. The fall-out during the discharge process is the end product that contains the carbon nano-structures [31]. To prepare pure few-layered graphene, a direct current arc discharge of graphite evaporation was carried out in a water-cooled stainless steel chamber filled with different buffer gases after evacuating the chamber by a mechanical pump [31, 36]. When the arc discharge process ended, the generated soot was collected under ambient conditions. The soot deposited on the inner and top wall of the reaction chamber was only collected in order to exclude relatively heavy products (amorphous carbon nanoparticles or multi-layered graphene sheets) dropped to the bottom of the chamber during the arc discharge process [36]. Different discharge atmospheres may induce different chemical bonds that cause the prepared graphene sheets to have different properties. Direct current hydrogen arc discharge evaporation of pure graphite electrodes in various gas mixtures can be used to mass-produce high-crystalline few-layer graphene sheets [40]. Various gas mixtures were reported such as H2, He, mixture of H2 and He, mixture of NH3 and He, and mixture of CO2 and He to synthesize few-layered graphene sheets with high electrical conductivity [36-38]. On the other hand, a novel method for the large-scale production of graphene flakes in an arc discharge enhanced with a specially shaped magnetic field and a custom-designed catalyst was reported [39].
Graphene oxide (GO) was synthesized by the strong oxidation of flake graphite using acid via Hummers’ method [40, 41] or modified Hummers’ method [42-44]. GO, an oxidized form of graphene, is decorated by hydroxyl and epoxy functional groups on the hexagonal network of carbon atoms with carbonyl and carboxyl groups at the edges. GO is highly hydrophilic and forms stable aqueous colloids due to the large number of oxygen-containing functional groups as well as the repulsive electrostatic interactions at the edges of the platelets [41, 45]. It was reported that GO can be reduced via thermal, chemical, electrochemical, and laser-scribing methods.
The thermal method is believed to be a green method in which no hazardous reductants are used. This process requires heating up to 1050°C in an oven under argon gas, up to 800°C under hydrogen gas, or up to 700°C in a quartz tube. The thermal reduction of GO was accompanied by the elimination of epoxy and carboxyl groups in the forms of O2, CO, CO2, and H2O as predicted from thermogravimetry data [46-48]. Recently, graphene sheets were prepared by a solvothermal reduction of GO suspension in water, octadecylamine, butanol, or N,N-dimethylacetamide [46]. Wei Huang synthesized high-performance graphene nanosheets by thermal reduction of GO under ethanol atmosphere at 900°C. This method can effectively remove the oxygen-containing functional groups and restore its graphic structure compared to the ones obtained using hydrazine or hydrogen. It can provide a simple, low-cost, and high yield approach for the preparation of high performance graphene nanosheets [49]. Furthermore, graphene sheets with different reduction levels were produced through thermal reduction of GO in the temperature range of 200–900°C under N2 atmosphere for supercapacitor applications [50, 51]. Thermal reduction can produce few layer graphene with less agglomeration, higher specific surface area, and higher electrical conductivity compared to other reduction routes [51].
GO formation was followed by subsequent chemical reduction with a reducing agent such as hydroquinone, sodium borohydride, hydrazine, and hydrazine with NH3 [42, 47, 52]. Hydrazine hydrate was proved to be the best reducing agent for the chemical reduction of GO into graphene and very thin graphene-like sheets were obtained. Moreover, the hydrazine treatment resulted in the formation of unsaturated and conjugated carbon atoms, which in turn imparts electrical conductivity of the graphene sheets [41]. These reducing agents, particularly hydrazine, are highly toxic, explosive, and their use should be with extreme care and minimized [42, 52]. The chemical reduction may also leave some residual epoxide groups on the reduced GO sheets leading to some loss in electron mobility [52]. On the basis of these observations, a new approach was employed to develop a “green” synthesis method for the production of graphene by using environmentally friendly reducing agents such as vitamin C [44], reducing, sugars and l-glutathione under mild conditions [42].
On the other hand, the chemical reduction methods of exfoliated GO with reducing agents such as hydrazine hydrate provide a promising approach for the efficient large-scale production of chemically converted graphene (CCG) sheets. However, in most cases heating to nearly 100ºC over several hours is required. A novel, facile, convenient, and scalable method for the synthesis of CCG sheets as well as metallic and bimetallic nanoparticles supported on the CCG sheets using a simple household microwave oven was utilized [53-56]. It was reported that graphene is a good microwave-absorbing material and can reach a high temperature in minutes [57]. Microwave irradiation (MWI) has been demonstrated for the synthesis of a variety of nanomaterials with controlled size and shape without the need for high temperature or high pressure. The main advantages of MWI over other conventional heating methods are (i) rapid reaction velocity, (ii) clean and energy efficient, and (iii) uniform heating of the reaction mixture [47, 58-60]. Due to the difference in the solvent and reactant dielectric constants, selective dielectric heating can provide significant enhancement in the transfer of energy directly to the reactants causing an instantaneous internal temperature rise. Dried GO was sonicated in deionized water until homogenous dispersion was obtained. After that it was placed inside a conventional microwave after adding 100 µl of a reducing agent [hydrazine hydrate, ethylenediamine, or ammonium hydroxide] in 30 s cycles for a total reaction time of 60 s. A black color was obtained indicating the complete chemical reduction to graphene. The graphene sheets were separated by using centrifuge operated at 5000 rpm for 15 min and dried overnight under vacuum [53]. Microwave-assisted methods allowed the rapid chemical reduction of GO using a variety of reducing agents in either aqueous or organic media. By using this method, many types of metallic and bimetallic nanoparticles can be dispersed on the graphene sheets via simultaneous reduction of GO and a variety of metal salts to create novel nanocatalysts supported on the large surface area of the thermally stable 2D graphene [61]. Moreover, this method provides a low-cost approach to the facile production of nanoparticles/graphene composites on a large scale for applications [57, 61, 62].
As pointed out by Kaner and co-workers, both chemical and thermal reduction techniques have some obvious drawbacks, namely, the highly toxic reductant hydrazine, lack control of the film thickness, and the incompatibility of the thermal reduction process under some conditions. Thus, the electrochemical method was adopted as an effective and controllable alternative technique for the modification of electronic states [63]. It has drawn great attention due to its fast and green nature [17, 52]. This is done by adjusting the external power source to change the Fermi energy level of the electrode surface that reduces GO in the presence of direct current bias [63]. Typically, the electrochemical synthesis of graphene was carried out via two steps, namely, GO being first assembled on the electrodes by solution deposition methods then being subjected to electrochemical reduction by scanning the potential (cyclic voltammetry) [45, 47, 52, 64, 65] or by applying constant potential (bulk electrolysis) [66, 67]. Another approach was achieved via a one-step technique in which graphene films can be prepared on electrodes directly from GO dispersions by simultaneous electrodeposition and electroreduction [17]. The reduction of GO can be confirmed from the color of GO electrodes that changes from yellow (before reduction) to black (after reduction) [64], involving the reduction of the high number of functional groups present in the GO sheets such as OH, COOH, and epoxides [52].
The properties of electrochemically converted graphene (ECG) are quite different from other nanostructured carbons (CNTs) and even different from CCG. The morphology of CCG and ECG on glassy carbon sheet was characterized by high field emission-scanning electron microscopy (FE-SEM) (Figure 6 (A, B)), respectively. The micrographs show that CCG sheets are rippled and crumpled with a dimension of several nm to few μm while ECG sheets are more homogeneous and more compact on the surface than CCG [66]. ECG exhibits greatly enhanced activity for the electrocatalytic reduction of O2 and H2O2 and much higher electrochemical capacitance for potential application in ultracapacitors [64]. Moreover, the ECG coating is very stable as a result of its poor insolubility in common solvents [17].
SEM images using FE-SEM for a) CCG, b) ECG [
Compared to chemical and thermal methods, pulsed laser irradiation reduction is simple, rapid (shorten the reaction time from several hours to few minutes), energy efficient, and free from poisonous material and high temperature. Also, the pulsed laser reduction of GO in solution makes it particularly attractive for producing graphene composites by pre-mixing with other materials [68]. Moreover, Feng-Shou Xiao fabricated graphene microcircuits by direct reduction and patterning of GO films using femtosecond laser representing well-conductivity for electrical applications [69]. Recently, Kaner and co-workers prepared graphene using standard laser-scribing technology more typically used to etch labels and images onto DVDs. Initially, a thin film of GO dispersed in water was drop-cast onto a flexible substrate (a DVD covered with a layer of plastic). Irradiation of the film with an infrared laser inside an inexpensive commercially available light scribe CD/DVD optical drive reduces the GO to laser-scribed graphene (LSG), as indicated by the change in film color from golden brown to black. Analysis of cross sections of the film with scanning electron microscopy showed that the initially stacked GO sheets were converted into well-exfoliated LSG sheets without any sticking together through laser irradiation [70].
GO contains oxygen functional groups such as epoxides, OH, and COOH that make it hydrophilic and well dispersed in water. However, GO is incompatible with most organic polymers [52]. It is well established that the superior properties of graphene are associated with its single layer. However, the fabrication of single-layer graphene is difficult at ambient temperature. Graphene sheets with a high specific surface area tend to form irreversible agglomerates or even restack to form graphite through π–π stacking and van der Waals interactions if the sheets are not well separated from each other. Aggregation can be reduced by the attachment of other small molecules or polymers to the graphene sheets. The presence of hydrophilic or hydrophobic groups prevents aggregation of graphene sheets by strong polar–polar interactions or by their bulky size. The attachment of functional groups to graphene also aids in dispersion in a hydrophilic or hydrophobic media as well as in the organic polymer [6, 52]. Furthermore, the oxidized rings of functionalized and defective graphene sheets contain abundant C–O–C (epoxide) and C–OH groups while the sheets are terminated with C–OH and –COOH groups. Defects of graphene may change its electronic and chemical properties. The functionalized and defective graphene sheets are more hydrophilic and can be easily dispersed in solvents with long-term stability [12]. Moreover, they are more easily produced in mass quantities as compared with the carbon nanotubes [12, 16, 52]. They may be used to prepare some novel graphene-based nanocomposite films that could facilitate the further manipulation and processing of these materials for developing novel electronic devices such as chemical sensors, biosensors [12], cellular imaging, and drug delivery [52]. On the other hand, various polymer and nanoparticle (metal, metal oxide, semiconductor) composites have been developed based on the unique properties of graphene. The bulk production of GO and graphene has given opportunities to explore this flat structure of carbon with polymer and nanoparticles in composites [32]. Pristine graphene is a hydrophobic material and has no appreciable solubility in most solvents. Nevertheless, the processing of graphene composites concerns itself foremost with the solubilization of graphene. To improve the solubility of graphene, different functional groups have been attached to the carbon backbone by chemical modification, covalent or non-covalent functionalization [15].
Covalent modification: The structural alteration can take place at the end of the sheets and/or on the surface. Surface functionalization is associated with rehybridization of one or more sp2 carbon atoms of the carbon network into the sp3 configuration accompanied by simultaneous loss of electronic conjugation. Covalent functional groups can attach to the surface through the reaction between the functional groups (-OH, -COOH, -CO) present on the GO and reduced graphene oxide (rGO) surfaces and edges [15, 32]. The covalent modification of graphene can be achieved in four different ways: nucleophilic substitution, electrophilic addition, condensation, and addition [6].
Non-covalent modification: It is based on the van der Waals force or the π–π interaction between reduced graphene oxide (rGO) and stabilizers that not only gives less negative impact on the structure of graphene and its derivatives, but also provides the feasibility to tune their solubility and electronic properties [15, 32].
Graphene has recently attracted tremendous interest because of its unique thermal, mechanical, and electrical properties. One of the promising applications of graphene is electrochemical sensing. Since every atom in a graphene sheet is a surface atom, molecular interaction and thus electron transport through graphene can be highly sensitive to adsorbed molecules [17, 71]. Graphene is a strictly 2D material and as such enables devices based on graphene to have an identical performance on a large scale. In addition, with the 2D structure, the monolayer graphene has its whole volume exposed to the environment that can maximize the sensing effect. The principle of graphene devices is based on changes in device conductance due to chemical or biological species adsorbed on the surface of graphene acting as electron donors or acceptors [19]. On the other hand, graphene-based nanomaterials have recently shown fascinating applications in electrochemical sensors and biosensors. Owing to the extraordinary electronic transport property and high electrocatalytic activity of graphene, the electrochemical reactions of analyte are greatly promoted on graphene film resulting in enhanced voltammetric response. Moreover, the electrochemical properties of graphene can be effectively modified by integration with other functional nanomaterials such as catalyst nanoparticles to produce versatile electrochemical sensing performance. Comparing with CNTs, graphene has shown the advantages of high conductivity, ease of production and function, good biocompatibility, and abundance of inexpensive source material [71, 72]. Thus, graphene was a good candidate of advanced electrode materials and could be combined with other functional materials to fabricate the sensing interface for electroanalysis [8, 10].
Graphene has potential use in gas sensors owing to its 2D structure with extremely high surface area. Gas sensing by graphene generally involves the adsorption and desorption of gaseous molecules (which act as electron donors or acceptors) on the graphene surface leading to change in the conductance of graphene. The high sensitivity of graphene toward different gaseous molecules has led to its use as gas sensor for hydrogen, H2O, CO, NH3, NO2, Cl2, ethanol, I2, and O2 [73]. Graphene/ZnO hybrid [74] and reduced graphene oxide (rGO) [75] were utilized as highly efficient gas sensors. Qingkai Yu et al. synthesized Pd-decorated graphene films to be used as hydrogen sensor. This gas sensor was fabricated on graphene film with a 1 nm Pd film deposited for hydrogen detection in the concentration range of 25–10,000 ppm. H2 sensor based on Pd-decorated graphene films showed high sensitivity, fast response, and good recovery and can be used with multiple cycles [19]. Besides, Gupta et al. prepared a nanocomposite film based on poly(methyl methacrylate) (PMMA), rGO, and PMMA/rGO to be used as NH3 gas sensor. The sensor performance in terms of selectivity and sensitivity was much better in the case of PMMA/rGO nanocomposite compared to the individual layers of rGO or PMMA [76]. On the other hand, an acetylene gas sensor was fabricated by synthesizing Ag-loaded ZnO-rGO hybrid via a facile chemical route (Figure 7). A well-structured crystalline nature and mixed phases of Ag, graphene (Gr), and ZnO was obtained. The morphological characterization revealed that particle-like nanostructures of ZnO and Ag were well distributed and closely distributed onto the surface of thin-layer RGO sheets. A low detection limit of 1 ppm, fast response of 25 s, recovery of 80 s, and good repeatability were obtained [77].
Schematic diagram of the fabricated sensor device [
Metal ions such as lead, cadmium, silver, mercury, and arsenic have severe environmental and medical effects so that they require careful monitoring. Therefore, the development of a sensitive and selective detection method would benefit both the environmental and food chemists [5, 73]. A novel stannum film/poly(p-aminobenzene sulfonic acid, p-ABSA)/graphene composite modified glassy carbon electrode (GCE) was used for sensitive determination of trace Cd2+ ions by square wave anodic stripping voltammetry. Graphene layer presents enhanced electron transfer and enlarged specific surface area. The resulting matrix offers a good stripping performance for the analysis of Cd2+ in the linear range from 1.0 to 70.0 μg L-1 with a detection limit of 0.05 μg L-1 [78]. Furthermore, Erkang Wang used graphene nanosheets dispersed in Nafion (Nafion-G) solution in combination with in situ plated bismuth film electrode for fabricating the enhanced electrochemical sensing platform for Pb2+ and Cd2+ by differential pulse anodic stripping voltammetry. The prepared Nafion-G composite film exhibited improved sensitivity for the metal ion detections and alleviated the interferences as a result of the synergistic effect of Nafion-G. The stripping current signal is greatly enhanced and well distinguished on graphene electrodes with a wide linear range and 0.02 µg L−1 detection limit for both ions (Figure 8) [5, 79]. Moreover, various modified surfaces were constructed for the sensitive and simultaneous determination of Pb2+ and Cd2+ such as graphene/polyaniline/polystyrene nanoporous fiber [80] and graphene/ionic liquid/bismuth film composite modified screen-printed electrodes [81], functionalized graphene (GNSPF6) with potassium hexafluorophosphate [82], and a hybrid nanocomposite of one-dimensional MWCNTs and graphene sheets [83]. Large surface area, good ionic and electronic conductivity, wide electrochemical window, as well as high stability, sensitivity, low detection limit, and applicability in real samples are the obvious characteristics of the proposed sensors. On the other hand, functionalized graphene sheets were fabricated and used for simultaneous removal of high concentration of inorganic species of arsenic (both trivalent and pentavalent) and sodium from aqueous solution using a supercapacitor-based water filter. Also, they were utilized for the desalination of sea water. High adsorption capacity for both inorganic species of arsenic and sodium along with the desalination ability of a graphene based supercapacitor provides a solution for a commercially feasible water filter. Additionally, the cost effective production of graphene sheets and better performance compared to other adsorbents like CNTs provides a platform for the development of commercially feasible supercapacitor-based water filter [84]. Furthermore, rGO–lead dioxide composite was presented as an excellent material for the detection of a low level of arsenic with a low detection limit of 10 nM. This study opens up the possibility of using the composite for simultaneous detection of arsenic and lead [85]. Furthermore, Zhuangjun Fan synthesized a type of graphene nanosheet/δ-MnO2 (GNS/MnO2) composite by a microwave-assisted method to be used as an adsorbent for the removal of nickel ions from waste water [86].
Striping voltammograms for the different concentrations of Cd2+ and Pb2+ on an in situ plated Nafion-G-BFE (bismuth film electrode) in solution containing 0.4 mg L-1 Bi3+ [
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
Nafion/TiO2–graphene nanocomposite | \n\t\t\t1-100 μM | \n\t\t\t210 nM | \n\t\t\t[7] | \n\t\t
Electrochemically reduced and deposited graphene onto GCE | \n\t\t\t5.0 nM-800 μM | \n\t\t\t2.13 nM | \n\t\t\t[91] | \n\t\t
Electrochemically reduced graphene loaded nickel oxides (Ni2O3–NiO) nanoparticles coated onto GCE | \n\t\t\t0.04-100 μM | \n\t\t\t0.02 μM | \n\t\t\t[92] | \n\t\t
Poly(4-aminobenzoic acid)/electrochemically reduced graphene oxide composite film modified GCE | \n\t\t\t0.1–65 μM | \n\t\t\t0.01 μM | \n\t\t\t[93] | \n\t\t
Examples of modified electrodes for ACOP detection.
Paracetamol or acetaminophen (ACOP) is a long-established and one of the most extensively employed “over the counter” drugs in the world. It is non-carcinogenic and an effective substitute for aspirin for patients with sensitivity to aspirin. It is used to reduce fever, cough, and cold and reduce mild to moderate pain. It is also useful in osteoarthritis therapy, protects hardening of arteries, relieves asthma patients, and protects against ovarian cancer. So it is very important to establish a simple, fast, sensitive, and accurate detection method for ACOP [87, 88]. Yuehe Lin et al. presented an electrochemical sensor for ACOP based on the electrocatalytic activity of functionalized graphene. Graphene-modified GCE obviously promotes the sensitivity of the determination of paracetamol with a low detection limit of 32 nM and a satisfied recovery from 96.4% to 103.3% [12]. Moreover, SWCNTs [89] or MWCNTs [90] graphene nanosheet nanocomposite modified GCE (SWCNTs-GNS/GCE or MWCNTs-GNS/GCE) was utilized as a novel, simple, and highly selective electrochemical sensor for tyrosine and paracetamol. The proposed sensor exhibited perfect characteristics like high effective surface area, high porosity, more reactive sites, excellent electrochemical catalytic activity, and applicability in human blood serum and pharmaceutical samples. Very low detection limits of 0.19 μM and 0.10 μM were obtained for tyrosine and paracetamol, respectively [90]. Table 2 contains examples of various modified electrodes for ACOP detection [7, 91-93].
Catecholamines are a class of neurotransmitters and their detection in the human body has been of great interest to neuroscientists. They include dopamine (DA), epinephrine (EP), and norepinephrine (NE) playing important roles in various biological, pharmacological, and physical processes. They are widely distributed in the mammalian central nervous system for message transfer [94, 95].
EP, a hormone secreted by the medulla of adrenal glands, is an important catecholamine inhibitory neurotransmitter. The presence of EP in the body affects the regulation of blood pressure and the heart rate, lipolysis, immune system, and glycogen metabolism. Low levels of EP have been found in patients with Parkinson’s disease. Therefore, the quantitative determination of EP in different human fluids such as plasma and urine is important for developing nerve physiology, pharmacological research, and life science [96]. Xiaoli Zhang fabricated graphene/Au nanocomposites modified GCE (GR/Au/GCE) for the detection of EP with high sensitivity. The oxidation of EP at this modified electrode occurred at less positive potentials than on bare GCE. In addition, the oxidation peaks of EP and ascorbic acid (AA) were separated from each other by approximately 180 mV. At the same time, this electrode also showed favorable electrocatalytic activity toward some other small biomolecules (such as DA, b-nicotinamide adenine dinucleotide, and uric acid) suggesting the potential applications of GR/Au nanocomposites for constructing biosensors [97]. Moreover, GR modified Pd was prepared to be used as a voltammetric sensor for NE, an important neurotransmitter. GR as well as Pd nanoparticles presented perfect characteristics for the proposed sensor-like excellent electrocatalytic activity for the oxidation of NE in terms of remarkable enhancement in the peak current and lowering of peak potential. Also, low detection and quantification limits were obtained that were 67.44 nM and 224.8 nM, respectively. The application of the proposed sensor in pharmaceutical dosage forms and human urine samples in the presence of high concentration of uric acid was achieved with excellent recovery results [98].
On the other hand, DA, ascorbic acid (AA), and uric acid (UA) are compounds of great biomedical interests playing determining roles in human metabolism. DA is one of the crucial catecholamine neurotransmitters playing an important role in the function of central nervous, renal, hormonal, and cardiovascular systems. Thus, a loss of DA-containing neurons may lead to neurological disorders such as Parkinsonism and schizophrenia [94, 95, 99]. AA (vitamin C), an antioxidant, is a vital vitamin in human diet existing in both animal and plant kingdoms. It has been used for the prevention and treatment of the common cold, mental illness, infertility, and cancer and in some clinical manifestations of human immunodeficiency virus infections. UA is the primary end product of purine metabolism. The extreme abnormalities of UA levels in the body are symptoms of several diseases including gout, hyperuricemia, and Lesch–Nyhan. Therefore, simultaneous detection of DA, AA, and UA is a challenge of critical importance not only in the field of biomedical chemistry and neurochemistry but also for diagnostic and pathological research [94, 95]. Feng Li et al. prepared a graphene doped carbon paste electrode (CPE) by the addition of graphene into the carbon paste mixture for the successful determination of AA. This sensor showed an excellent electrocatalytic oxidation activity toward AA with a lower overvoltage, pronounced current response, and good sensitivity. The proposed sensor exhibited a rapid response to AA within 5 s and a good linear calibration plot from 0.1 to 106 µM with low detection limit of 70 nM [8]. On the other hand, Jinghong Li et al. synthesized graphene chemically by the Hummers and Offeman method and the graphene-modified electrode was applied for the selective determination of DA in the linear range of 5–200 µM in a large excess of AA. Selective detection was realized in completely eliminating AA based on the unique planar structure of graphene. The interesting performance of graphene to DA and AA may be correlated with the following reasons:
The high quality of the sp2 conjugated bond in the carbon lattice, graphene is highly conductive and shows metallic conductance even in the limit of zero carrier density. The unusual density of electronic states of graphene affects its electrochemical reactivity.
Molecular structures of DA and AA are distinct from each other. The π–π interaction between the phenyl structure of DA and 2D planar hexagonal carbon structure of graphene makes the electron transfer feasible. AA oxidation is inactive most likely because of its weak π–π interaction with graphene [10].
Several sensors were utilized for the simultaneous determination of DA and AA such as graphene modified electrode [100], graphene sheets/Congo red-molecular imprinted polymers [101], and Pt nanoparticles/polyelectrolyte-functionalized ionic liquid/graphene sheets [102]. On the other hand, TiO2–graphene nanocomposite modified GCE exhibited remarkable electron transfer kinetics, electrocatalytic activity, and selective determination of DA in the presence of UA and AA. Differential pulse voltammetry (DPV) peaks of DA, AA, and UA are well resolved with peak potentials at 108 mV, 272 mV, and 403 mV for AA, DA, and UA, respectively. The separation of DPV peak potentials for AA–DA and DA–UA are calculated to be 164 mV and 131 mV, respectively, which are large enough to determine DA selectively [103]. Several electrochemical sensors based on graphene-modified surfaces were employed for the simultaneous determination of DA, AA, and UA like polystyrene-grafted-graphene hybrid [104] and nafion covered core–shell structured Fe3O4@graphene nanospheres (GNs) [105] modified GCE, graphene-AuAg (Au/Gr-AuAg) composite modified gold electrode [106], Au nanoplates and rGO modified GCE (Au/rGO/GCE) [107], three-dimensional reduced graphene oxide (3D-rGO) material [108], water-soluble sulfonated graphene [109], ferulic acid functionalized electrochemically reduced graphene [110], graphene/nickel hydroxide composite [111], and well-defined flower-like graphene-nanosheet clusters (f-RGO) modified GCE [112]. In addition, Pd–Pt bimetallic nanoparticles anchored on functionalized rGO nanomaterials [113], electrochemically reduced graphene oxide (ERGO) [114], nitrogen-doped graphene (NG) [115], and tryptophan-functionalized graphene nanocomposite (Trp-GR) [116] were fabricated for the simultaneous detection of DA, AA, and UA and multi-walled carbon nanotubes (MWNTs) bridged mesocellular graphene foam (MGF) nanocomposite (MWNTs/MGF) modified GCE for the simultaneous determination of DA, AA, UA, and tryptophan [117]. As well, graphene (Gr)/copper(II) phthalocyanine-tetrasulfonic acid tetrasodium salt/polyaniline nanocomposites [118] and NiO nanoparticles-graphene composite film were employed as electrochemical sensors for the selective determination of AA in the presence of DA and UA [118] and in the presence of folic acid [119], respectively.
On the other hand, serotonin (5-hydroxytryptamine, 5-HT) is an important neurotransmitter and it is important to sensitively determine its concentration. A double-layered membrane of rGO/polyaniline nanocomposites and molecularly imprinted polymers embedded with Au nanoparticles was employed as an electrochemical sensor for 5-HT. The prepared sensor displayed obvious selectivity to 5-HT and a low detection limit of 11.7 nM in the linear range of 0.2–10.0 μM [120]. Moreover, graphene nanosheets [121] and graphene grafted poly(lactic acid) with Pd nanoparticles [122] were applied as 5-HT sensor showing high sensitivity, good selectivity, low detection limit, fast response time, and stability. In addition, electrochemically reduced GO-P (graphene oxide and 5,15-pentafluorophenyl-10,20-p-aminophenyl porphyrin) was employed as an electrochemical sensor for the simultaneous and selective determination of DA and 5-HT in the presence of AA. The detection limits of DA and 5-HT were 35 nM and 4.9 nM, respectively [123].
Levodopa (LD), an important neurotransmitter, was determined at modified CPE modified with graphene (GR), 1-(6,7-dihydroxy-2,4-dimethylbenzofuran-3-yl) ethanone (DE), and ionic liquid (IL) (GR–DE–IL/CPE). GR–DE–IL/CPE showed enhanced electrocatalytic activity toward LD with a lower oxidation potential and good electrochemical performance with higher conductivity and lower electron transfer resistance. Very low detection limit of 5.0 nM in the linear range of 0.015 to 1000 μM was obtained [124]. An assembly of rGO, Au nanoparticles, and 2-(3,4-dihydroxy phenyl) benzothiazole [125] and graphene nanosheets modified GCE [126] and reduced graphene nanoribbons modified carbon screen-printed electrode [127] were employed for the simultaneous determination of LD, UA and folic acid, LD and carbidopa and AA, LD and UA, respectively.
Graphene has the great potential for distinguishing a diverse range of aromatic isomers. Chengbin Liu et al. had utilized graphene modified electrode (EG/GCE) for the simultaneous detection of hydroquinone HQ (1,4-dihydroxybenzene) and catechol CC (1,2-dihydroxybenzene). It showed enhanced electron transfer properties, good potential separation of oxidation peaks between HQ and CC (about 110 mV), wide linear concentration ranges, low detection limits, excellent reproducibility and stability, and high resolution capacity to the HQ and CC isomers [17]. On the other hand, a highly stable (pyridine-NG) was used as an electrochemical sensor for simultaneous determination of HQ and CC. Excellent electrocatalysis of pyridine-NG for simultaneous determination of HQ and CC was achieved due to the π–π interactions between the benzene ring of CC and graphene layer and the hydrogen bonds formed between hydroxyl in HQ molecule and pyridinic nitrogen atoms within graphene layers, especially the less density distribution of π electron cloud in pyridinic-NG in acidic condition [128]. Several novel sensors like poly(3,4-ethylenedioxythiophene)/nitrogen-doped graphene composite [129], MWCNTs-poly(diallyldimethylammonium chloride)-graphene [130], and laser reduced graphene [131] modified GCE were fabricated for the simultaneous detection of CC and HQ with low detection limit, high sensitivity, excellent potential peak separation, and anti-interference ability. Table 3 contains examples of modified electrodes for HQ and CC detection [132-135].
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
Graphene and TiO2 nanocomposite | \n\t\t\t0.5–100 µM | \n\t\t\t0.082 µM | \n\t\t\t0.5–100 µM | \n\t\t\t0.087 µM | \n\t\t\t[132] | \n\t\t
Electrochemically reduced graphene oxide- MWCNTs and terthiophene | \n\t\t\t--- | \n\t\t\t35 nM | \n\t\t\t--- | \n\t\t\t4.9 nM | \n\t\t\t[133] | \n\t\t
1D MWCNTs and 2D graphene modified GCE using 1-butyl-3-methyl-imidazolium hexafluoro-phosphate ionic liquid | \n\t\t\t--- | \n\t\t\t0.1 μM | \n\t\t\t--- | \n\t\t\t0.06 μM | \n\t\t\t[134] | \n\t\t
Au nanoparticle and graphene composite film modified carbon ionic liquid electrode | \n\t\t\t0.06-800 µM | \n\t\t\t0.018 µM | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[135] | \n\t\t
Examples of modified electrodes for HQ and CC detection.
Morphine, noscapine, and heroin are three major alkaloids in heroin samples. Morphine and noscapine that are directly extracted from poppy are the most abundant constituents in opium. The widespread use of illicit drugs has led to an increased effort toward developing and improving methods for their determination in biological samples, which is still a very challenging task. Graphene nanosheets (GNSs) modified GCE was employed for the simultaneous determination of morphine, noscapine, and heroin exhibiting excellent electrocatalytic activity at reduced overpotentials in wide pH range. Fast response time, high sensitivity and stability, low cost, low detection limit, and ease of preparation method without using any specific electron-transfer mediator or specific reagent are the advantages of the proposed sensor [136]. In addition, electrochemically reduced MWNTs-doped GO (ER-MWNTs-doped-GO) composite film modified GCE was employed as morphine sensor combining the excellent conductivity of MWNTs and ER-GO with the film forming properties of GO [137]. Also, rGO–Pd (rGO–Pd) hybrid had higher current response toward morphine oxidation compared to the unmodified rGO with a low detection limit of 12.95 nM [138].
On the other hand, graphene and Nafion film modified GCE was fabricated for the detection of codeine displaying an excellent analytical performance and enhanced applicability for codeine detection in urine samples and cough syrup. The high electrocatalytic activity of the proposed sensor toward codeine was attributed to the outstanding electric conductivity of graphene and the high codeine loading capacity on the electrode surface [139]. Furthermore, a nanocomposite of Gr and CoFe2O4 nanoparticles modified CPE was proved to be an ultrasensitive electrochemical sensor for codeine and ACOP with low detection limits of 0.011 and 0.025 μM, respectively. The proposed method was free from interference effects of glucose, ascorbic acid, caffeine, naproxen, alanine, phenylalanine, glycine, and others [140]. On the other hand, rapid and simultaneous determination of tramadol and ACOP was achieved based on NiFe2O4/graphene nanoparticles modified CPE with a low detection limit of 0.0036 and 0.0030 μM, respectively [141]. Table 4 contained a summary of some modified electrodes for drug sensing.
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
Graphene nanosheets modified GCE | \n\t\t\tmorphine, noscapine and heroin | \n\t\t\tup to 65, 40 and 100 μM, respectively | \n\t\t\t0.4, 0.2 and 0.5 μM, respectively | \n\t\t\t[136] | \n\t\t
electrochemically reduced MWNTs-doped GO modified GCE | \n\t\t\tmorphine | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[137] | \n\t\t
rGO–Pd modified GCE | \n\t\t\tmorphine | \n\t\t\t0.34-12 μM | \n\t\t\t12.95 nM | \n\t\t\t[138] | \n\t\t
graphene and Nafion film modified GCE | \n\t\t\tcodeine | \n\t\t\t5 × 10−8 to 3 × 10−5 M | \n\t\t\t15 nM | \n\t\t\t[139] | \n\t\t
a nanocomposite of Gr and CoFe2O4 nanoparticles modified CPE | \n\t\t\tcodeine and ACOP | \n\t\t\t0.03 to 12.0 μM for both | \n\t\t\t0.011 μM and 0.025 μM, respecively | \n\t\t\t[140] | \n\t\t
NiFe2O4/graphene nanoparticles modified CPE | \n\t\t\ttramadol and ACOP | \n\t\t\t0.01–9 μM | \n\t\t\t0.0036 and 0.0030 μM, respectively | \n\t\t\t[141] | \n\t\t
Examples of modified electrodes for drug detection.
B-nicotinamide adenine dinucleotide (NAD) and its reduced form (NADH) are a cofactor of many dehydrogenases, which have received considerable interest in developing amperometric biosensors, biofuel cells, and bioelectronic devices [2, 5, 18, 73]. The oxidation of NADH serves as the anodic signal and regenerates the NAD cofactor, which is of great significance in biosensing important substrates such as lactate, alcohol, or glucose. Problems inherent to such anodic detection are the large overvoltage for NADH oxidation and surface fouling associated with the accumulation of reaction products. Graphene shows promise in addressing these problems [73, 142]. Jinghong Li studied the oxidation of NADH at GCE and reduced graphene sheet films (rGSF)/GC. The oxidation of NADH occurs at bare GC electrode at 0.75 V vs. Ag/AgCl, which decreased to 0.42 V at rGSF/GC [2]. Table 5 contained examples of several sensors for the sensitive and selective determination of NADH with low detection limit.
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
methylene green functionalized graphene modified GCE | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[5] | \n\t\t
ionic liquid functionalized graphene modified GCE | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[73] | \n\t\t
chemically reduced graphene oxides modified GCE | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[18] | \n\t\t
graphene assembled electrode modified GCE | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[142] | \n\t\t
electroreduced graphene oxide and polythionine modified GCE | \n\t\t\t0.01–3.9 mM | \n\t\t\t0.1 μM | \n\t\t\t[144] | \n\t\t
nitrogen-doped graphene modified GCE | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[145] | \n\t\t
graphene–Au nanorods hybrid nanosheets modified GCE | \n\t\t\t5 to 377 µM | \n\t\t\t1.5 μM | \n\t\t\t[146] | \n\t\t
Au nanoparticles /reduced graphene oxide nanocomposites modified GCE | \n\t\t\t50 nM to 500 µM | \n\t\t\t1.13 nM | \n\t\t\t[147] | \n\t\t
graphene paste electrode modified GCE | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[148] | \n\t\t
GCE modified with deoxyribonucleic acid, graphene methylene blue | \n\t\t\t10 μM to 1.50 mM | \n\t\t\t1.0 μM | \n\t\t\t[143] | \n\t\t
Examples of modified electrodes for NADH detection.
Electrochemical DNA sensors offer high sensitivity, good selectivity, and low cost for the detection of selected DNA sequences or mutated genes associated with human disease and promise to provide a simple, accurate, and inexpensive platform of patient diagnosis. Electrochemical DNA sensors also allow device miniaturization for samples with a very small volume. Among all kinds of electrochemical DNA sensors, the one based on the direct oxidation of DNA is the simplest [5, 13]. Zhou et al. reported an electrochemical DNA sensor based on CR-GO. The current signals of the four free bases of DNA (i.e., guanine (G), adenine (A), thymine (T) and cytosine (C)) on the CR-GO/GC electrode are all separated efficiently indicating that CR-GO/GC can simultaneously detect four free bases but neither graphite nor GCE can. This is attributed to the antifouling properties and the high electron transfer kinetics for bases oxidation on CR-GO/GC electrode resulting from a high density of edge-plane-like defective sites and oxygen containing functional groups on CR-GO. These functional groups are beneficial for accelerating electron transfer between the electrode and species in solution providing many active sites. CR-GO/GC is also able to efficiently separate all four DNA bases in both single-stranded DNA (ssDNA) and double-stranded DNA (ds-DNA), which are more difficult to oxidize than free bases at physiological pH without the need of a prehydrolysis step. This is attributed to the unique physicochemical properties of CR-GO (the single sheet nature, high conductivity, large surface area, antifouling properties, high electron transfer kinetics, etc.) [5, 73]. Furthermore, a zinc sulfur-coated poly (3,4-ethylenedioxythiophene)-reduced graphene oxide hybrid film was developed for the simultaneous determination of three deoxyribonucleic acid (DNA) bases: G, A, and T. This electrochemical sensor displayed a good photoelectronic effect and the peak currents of G, A, and T increased obviously. The proposed sensor was successfully applied to the analysis of G, A, and T contents in real-life samples such as herring sperm DNA samples, milk powder, and urine sample from human beings with satisfactory results [149]. As well, an electrochemical DNA biosensor for the detection of ssDNA sequence related to transgenic maize MON810 was fabricated based on electrochemical reduced graphene (ERG) modified carbon ionic liquid electrode (CILE) and methylene blue (MB). The presence of ERG increased the adsorption amounts of probe ssDNA sequence on the electrode resulting in the enhancement of the reduction peak current of MB that used as the hybridization indicator. Under optimal conditions, the linear range of ssDNA sequences was 1.0 × 10−11 to 1.0 × 10−6 M with the detection limit of 4.52 × 10−12 mol/L [150]. In addition, the simultaneous determination of adenine and guanine was achieved at the ionic liquid-functionalized graphene-modified carbon paste electrode (IL-graphene/CPE) with very low detection limits of 65 nM for guanine and 32 nM for adenine [13]. Moreover, TiO2-graphene nanocomposite modified GCE exhibited high electrocatalytic activity, wide linear range, and low detection limit for the simultaneous determination of adenine and guanine. The excellent performance of this electrochemical sensor was attributed to the high adsorptivity and conductivity of TiO2-graphene nanocomposite providing an efficient microenvironment for the electrochemical reaction of these purine bases [151]. On the other hand, a graphene-based electrochemical DNA sensor was developed for the detection of low concentrations of breast cancer-related BRCA1 gene. The sensor was stable, reproducible, and sensitive and it could detect up to 1 femtomolar BRCA1 gene (5.896 femtogram/ml) [152]. Moreover, a graphene sheets/polyaniline/gold nanoparticle based DNA sensor was employed for the electrochemical determination of BCR/ABL fusion gene in chronic myelogenous leukemia. Under optimum conditions, the DNA sensor exhibited a detection limit as low as 2.11 pM (S/N=3) with an excellent differentiation ability. It has been applied for assay of BCR/ABL fusion gene from real samples with satisfactory results [153]. Also, a riboflavin electrochemical sensor based on homoadenine single-stranded DNA/molybdenum disulfide–graphene nanocomposite modified gold electrode was fabricated. This sensor possessed a wide linear range from 0.025 to 2.25 μM with a low detection limit of 20 nM [154]. A brief summary of DNA biosensors is given in Table 6.
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
zinc sulfur-coated poly (3,4-ethylenedioxythiophene)-reduced graphene oxide hybrids film | \n\t\t\tguanine, adenine and thymine | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[149] | \n\t\t
Chemically reduced graphene oxide modified GCE | \n\t\t\tguanine, adenine, thymine and cytosine | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[5, 73] | \n\t\t
electrochemical reduced graphene modified carbon ionic liquid electrode and methylene blue | \n\t\t\tssDNA sequence related to transgenic maize MON810 | \n\t\t\t1.0 × 10−11 to 1.0 × 10−6 M | \n\t\t\t4.52 × 10−12 mol/L | \n\t\t\t[150] | \n\t\t
ionic liquid-functionalized graphene modified carbon paste electrode | \n\t\t\tadenine and guanine | \n\t\t\t--- | \n\t\t\t65 nM and 32 nM for guanine and adenine, respectively | \n\t\t\t[13] | \n\t\t
TiO2-graphene nanocomposite modified GCE | \n\t\t\tadenine and guanine | \n\t\t\t0.5–200 μM | \n\t\t\t0.10 and 0.15 μM for adenine and guanine, respevtively | \n\t\t\t[151] | \n\t\t
graphene-based electrochemical DNA sensor | \n\t\t\tbreast cancer-related BRCA1 gene | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[152] | \n\t\t
graphene sheets/polyaniline/gold nanoparticles based DNA sensor | \n\t\t\tBCR/ABL fusion gene in chronic myelogenous leukemia | \n\t\t\t--- | \n\t\t\t2.11 pM | \n\t\t\t[153] | \n\t\t
homoadenine single-stranded DNA/molybdenum disulfide–graphene nanocomposite modified gold electrode | \n\t\t\triboflavin | \n\t\t\t0.025 to 2.25 μM | \n\t\t\t20 nM | \n\t\t\t[154] | \n\t\t
Examples of modified electrodes for DNA detection.
Increasing attention has been focused on the development of immunoassay because it has become a major analytical tool in clinical diagnosis. In immunoassay, the determination of cancer markers associated with certain tumors in patients plays an important role in diagnosing cancer diseases. Carcinoembryonic antigen (CEA) is one of the most extensively used tumor markers. An elevated CEA level in serum may be an early indication of lung cancer, ovarian carcinoma, colon cancer, breast cancer, and cystadenocarcinoma. Hence, Sheng Yu used gold nanoparticles (AuNPs), reduced graphene oxide (R-GO) and poly(L-Arginine) composite material modified CILE as the platform for the construction of a new electrochemical CEA immunosensor. The poly(L-Arginine)/R-GO composite film was used to modify CILE to fabricate Arg/R-GO/CILE through electropolymerization of L-Arginine on R-GO/CILE. AuNPs were adsorbed on the modified electrode to immobilize the CEA antibody and to construct the immunosensor. By combining the specific properties such as the biocompatibility and big surface area of AuNPs, the excellent electron transfer ability of R-GO and the high conductivity of CILE, the synergistic effects of composite increased the amounts of CEA antibody adsorbed on the electrode surface resulting in the greatly increase of the electrochemical responses. The proposed immunosensor showed good reproducibility, selectivity, low detection limit, and acceptable stability [155]. As well, ultrathin Au-Pt nanowire-decorated thionine/reduced graphene oxide (AuPtNWs/THI/rGO) [156] and Au nanoparticles–graphene–chitosan nanocomposite cryogel electrode [157] were developed for CEA detection showing high sensitivity, reproducibility, stability, and applicability in real samples (Table 7). Moreover, Jiadong Huang developed an ultrasensitive electrochemical immunosensor based on nanogold particles (nano-Au), Prussian Blue (PB), polyaniline/poly(acrylic acid) (PANI (PAA)), and Au-hybrid graphene nanocomposite (AuGN) for the detection of salbutamol (SAL). SAL is the most widely used β2-adrenergic receptor agonist that induces bronchodilation making it highly useful for curing bronchial asthma, chronic obstructive pulmonary disease, and other allergic diseases associated with respiratory pathway. Nano-Au, PB, and PANI (PAA)-incorporated film was used to enhance the electroactivity, stability, and catalytic activity for hydrogen reduction of the electrode. AuGN was used to immobilize chitosan, nano-Au, and horseradish peroxidase–anti-SAL antibody (HRP–AAb). The resulting nanostructure (AuGN–HRP–AAb) was used as the label for the immunosensor. This is attributed to the high surface-to-volume ratio of graphene that allows the immobilization of a high level of chitosan, nano-Au, and HRP–AAb and its good electrical conductivity that can improve the electron transfer among HRP, H2O2, and electrode. The proposed immunosensor showed low detection limit, excellent selectivity, good reproducibility, long-term stability, and high accuracy [158]. Furthermore, the synergistic effect between graphene sheet (GS) and cobalt hexacyanoferrate nanoparticle (CoNP) was investigated showing that the electroactivity of CoNP was greatly enhanced in the presence of GS due to the great electron-transfer ability of GS. A label-free electrochemical immunosensor for the sensitive detection of prostate specific antigen (PSA), it was widely used in prostate cancer diagnosis and screening, was fabricated. Molecule 1-pyrenebutanoic acid, succinimidyl ester (PBSE) was adsorbed onto GS and the colloidal solution containing GS–CoNP–PBSE was added onto the GCE surface to form a stable thin film with high electroactivity. After anti-PSA antibody was conjugated onto PBSE, the modified electrode could be used as an amperometric immunosensor for the detection of PSA. This immunosensor has the advantages of high sensitivity with a low detection limit of 0.01 ng/mL, good selectivity, and stability and could become a promising technique for cancer marker detection [159]. In addition, highly conductive graphene (GR)-gold (Au) composite modified electrode [160] and amino-functionalized graphene sheet–ferrocenecarboxaldehyde composite materials (NH2-GS@FCA) and silver hybridized mesoporous silica nanoparticles (Ag@NH2-MCM48) [161] were utilized as PSA immunosensor displaying an enhanced electron transfer and high sensitivity toward PSA (Table 7). On the other hand, ultrasensitive electrochemical immunosensor for carbohydrate antigen 19-9 was developed using Au nanoparticles functionalized porous graphene (Au-PGO) as sensing platform and Au@Pd core shell bimetallic functionalized graphene nanocomposites (Au@Pd-Gra) as signal enhancers [162]. Moreover, an electrochemical immunosensor for the sensitive detection of carbohydrate antigen 15-3 (CA15-3) was fabricated based on ionic liquid functionalized graphene and Cd2+-functionalized nanoporous TiO2. The good performance of the immunosensor was attributed to (i) high surface-to-volume ratio of graphene, (ii) excellent biocompatibility and electron transfer rate originating from ionic liquid functionalized graphene, and (iii) the highly specific surface area of nanoporous TiO2 facilitating the adsorption of a high amount of Cd2+ for signal amplification [163].
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
gold nanoparticles, reduced graphene oxide and poly(L-Arginine) composite material modified CILE | \n\t\t\tCarcinoembryonic antigen (CEA) | \n\t\t\t0.5 to 200 ng mL− 1\n\t\t\t | \n\t\t\t0.03 ng mL− 1\n\t\t\t | \n\t\t\t[155] | \n\t\t
ultrathin Au-Pt nanowire-decorated thionine/reduced graphene oxide | \n\t\t\tCEA | \n\t\t\t50 fg/mL to 100 ng/mL | \n\t\t\t6 fg/mL | \n\t\t\t[156] | \n\t\t
Au nanoparticles–graphene–chitosan nanocomposite cryogel electrode | \n\t\t\tCEA | \n\t\t\t1.0 × 10−6 to 1.0 ng/mL | \n\t\t\t2.0 × 10−7 ng/mL | \n\t\t\t[157] | \n\t\t
nanogold particles, Prussian Blue, polyaniline/poly(acrylic acid) and Au-hybrid graphene nanocomposite | \n\t\t\tsalbutamol | \n\t\t\t0.08 ng/mL and 1000 ng/mL | \n\t\t\t0.04 ng/mL | \n\t\t\t[158] | \n\t\t
graphene sheet and cobalt hexacyanoferrate nanoparticle | \n\t\t\tprostate specific antigen (PSA) | \n\t\t\t--- | \n\t\t\t0.01 ng/mL | \n\t\t\t[159] | \n\t\t
graphene-gold composite modified electrode | \n\t\t\tPSA | \n\t\t\t0–10 ng/mL | \n\t\t\t0.59 ng/mL | \n\t\t\t[160] | \n\t\t
amino-functionalized graphene sheet–ferrocenecarboxaldehyde composite materials and silver hybridized mesoporous silica nanoparticles | \n\t\t\tPSA | \n\t\t\t0.01–10.0 ng/mL | \n\t\t\t2 pg/mL | \n\t\t\t[161] | \n\t\t
Au nanoparticles functionalized porous graphene and Au@Pd core shell bimetallic functionalized graphene nanocomposites | \n\t\t\tcarbohydrate antigen 19-9 | \n\t\t\t0.015 to 150 U/mL | \n\t\t\t0.006 U/mL | \n\t\t\t[162] | \n\t\t
ionic liquid functionalized graphene and Cd2+-functionalized nanoporous TiO2\n\t\t\t | \n\t\t\tcarbohydrate antigen 15-3 | \n\t\t\t0.02–60 U/mL | \n\t\t\t0.008 U/mL | \n\t\t\t[163] | \n\t\t
Examples of modified electrodes used as immunosensors.
Hemoglobin (Hb) is the most important part of blood responsible for transporting O2 throughout the circulatory system. Change of Hb concentration in blood can cause several diseases and even death. Therefore, accurate determination of Hb content in blood is medically very essential [73]. Chunming Wang and Jun-Jie Zhu synthesized functionalized graphene nanosheets (PDDA-G) with poly(diallyldimethylammonium chloride) (PDDA) and used to combine with room temperature ionic liquid (RTIL). The resulting RTIL/PDDA-G composite displayed an enhanced capability for the immobilization of Hb to realize its direct electrochemistry. The proposed biosensor showed a fast direct electron transfer of Hb. Moreover, the RTIL/PDDA-G based biosensor exhibited excellent electrocatalytic activity for the detection of nitrite with wide linear range and low detection limit. The present strategy definitely paves a way for the functionalization of graphene sheets with good biocompatibility and solubility, thus provides a novel and promising platform for the study of the biological application of graphene [164]. Moreover, Ke-Jing Huang fabricated a promising biosensor, hemoglobin (Hb)/chitosan (Chit)–ionic liquid (IL)–ferrocene (Fc)/graphene (Gr)/GCE, that exploited the synergistic beneficial characteristics of Fc, Gr, and IL for Hb detection. The proposed biosensor showed a strong electrocatalytic activity toward the reduction of H2O2, which could be attributed to the favored orientation of Hb in the well-confined surface as well as the high electrical conductivity of the resulting Chit–IL–Fc/Gr inorganic hybrid composite. The developed biosensor exhibited a fast amperometric response, a good linear response toward H2O2 over a wide range of concentration, and a low detection limit of 3.8 µM. High sensitivity and stability, technically simple, and the possibility of preparation at short period of time are of great advantage of the developed biosensors [165]. Moreover, GR and Mg2Al layered double hydroxide composite was prepared and used for the immobilization of Hb on a CILE to obtain an electrochemical biosensor exhibiting electrocatalytic reduction to trichloroacetic acid [166]. As well, a biocompatible biosensor based on immobilized Hb on carboxymethyl cellulose functionalized reduced graphene oxide (rGO) nanocomposite was developed. The proposed Hb biosensor exhibited excellent bioelectrocatalytic activity toward the reduction of NO and H2O2. This biosensor opened up a promising platform for protein immobilization and biosensor preparation [167]. Also, a mediator-free biosensor was fabricated by the immobilization of Hb on TiO2NPs–rGO with a double-layered structure. TiO2NPs–rGO nanocomposite was an excellent matrix for immobilization and biocompatibility for redox protein presenting good protein bioactivity and stability. The direct electron transfer of Hb is facilitated due to the special double-layered structure of TiO2NPs–rGO. The prepared biosensor showed good performance for H2O2 detection with a low detection limit of 10 nM in the linear range of 0.1–140 μM [168]. On the other hand, a novel biocompatible sensing strategy based on a graphene (GR), ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4) and chitosan (CTS) composite film for the immobilization of myoglobin (Mb) was adopted. The CTS–Mb–GR–IL modified electrode exhibited an excellent enzyme-like catalytic activity for the reduction of trichloroacetic acid [169]. Another nanocomposite based on Pt nanoparticle decorated GR nanosheet was developed for the direct electrochemistry and electrocatalysis of Mb. GR–Pt nanocomposite was integrated with Mb on the surface of CILE. Nafion/Mb–GR–Pt/CILE electrochemical biosensor had potential applications for the electrocatalytic reduction of trichloroacetic acid in the linear range of 0.9 to 9.0 mM with the detection limit of 0.32 mM [170]. Moreover, 1-hexylpyridinium hexafluorophosphate based CILE was used as a substrate for the in situ electrodeposition of GR and nickel oxide (NiO) to get NiO/GR/CILE. Nafion/Mb/NiO/GR/CILE electrochemical sensor was constructed by the immobilization of Mb on the surface of NiO/GR/CILE with a Nafion film. The presence of the NiO/GR nanocomposite on the electrode promoted the direct electron transfer of Mb. A third-generation electrochemical Mb biosensor based on NiO/GR/CILE was constructed for the electrocatalytic reduction of trichloroacetic acid and H2O2 [171]. Table 8 contained a brief summary of some hemoglobin and myoglobin biosensors.
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
poly(diallyldimethylammonium chloride) functionalized graphene nanosheets combined with room temperature ionic liquid and modified with Hb | \n\t\t\tnitrite | \n\t\t\t0.2 to 32.6 μM | \n\t\t\t0.04 μM | \n\t\t\t[164] | \n\t\t
Hb/chitosan–ionic liquid–ferrocene/graphene/GCE | \n\t\t\tH2O2\n\t\t\t | \n\t\t\t50 μM to 1200 μM | \n\t\t\t3.8 µM | \n\t\t\t[165] | \n\t\t
Hb/ GR and Mg2Al layered double hydroxide composite | \n\t\t\ttrichloroacetic acid | \n\t\t\t1.6 to 25.0 mM | \n\t\t\t0.534 mM | \n\t\t\t[166] | \n\t\t
immobilized Hb on carboxymethyl cellulose functionalized reduced graphene oxide (rGO) nanocomposite | \n\t\t\tNO and H2O2\n\t\t\t | \n\t\t\t0.864 μM-19.8 μM and 0.083–13.94 μM for NO and H2O2, respectively | \n\t\t\t0.37 μM and 0.08 μM for NO and H2O2, respectively | \n\t\t\t[167] | \n\t\t
Hb/ TiO2NPs–rGO | \n\t\t\tH2O2\n\t\t\t | \n\t\t\t0.1–140 μM | \n\t\t\t10 nM | \n\t\t\t[168] | \n\t\t
myoglobin (Mb)/graphene , 1-ethyl-3-methyl-imidazolium tetrafluoroborate and chitosan composite film | \n\t\t\ttrichloroacetic acid | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[169] | \n\t\t
Mb/ Pt nanoparticle decorated GR nanosheet | \n\t\t\ttrichloroacetic acid | \n\t\t\t0.9 to 9.0 mM | \n\t\t\t0.32 mM | \n\t\t\t[170] | \n\t\t
Nafion/Mb/NiO/GR/1-hexylpyridinium hexafluorophosphate CILE | \n\t\t\ttrichloroacetic acid and H2O2\n\t\t\t | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[171] | \n\t\t
Examples of modified electrodes used as Hemoglobin and Myoglobin Biosensors.
Glucose biosensors are becoming increasingly important due to their applications in biological and chemical analyses, clinical detection, and environmental monitoring. The immobilization of enzymes on electrodes is generally the first step in fabrication attracting significant efforts because enzymes are highly selective and quickly responsive to specific substrates. Glucose oxidase (GOD) is employed as the enzyme in most of the glucose biosensors. It catalyzes the electron transfer from glucose to oxygen accompanied by the production of gluconolactone and hydrogen peroxide. The quantification of glucose can be achieved via electrochemical detection of the enzymatically liberated H2O2 [172]. Hua Zhang proposed a direct electrochemical method to reduce single-layer GO adsorbed on the 3-aminopropyltriethoxysilane (APTES) modified GCE. The reduced GO was modified with GOD and the obtained GCE-APTES-rGO-GOD was successfully used to detect glucose opening up a potential application in biosensing [52]. In addition, a bionanocomposite film consisting of GOD/Pt/functional graphene sheets/chitosan (GOD/Pt/FGS/chitosan) was employed for glucose sensing. With the electrocatalytic synergy of FGS and Pt nanoparticles to H2O2, a sensitive biosensor with a detection limit of 0.6 µM for glucose was achieved displaying good reproducibility, long-term stability, and anti-interfering ability from AA and UA. The large surface area and good electrical conductivity of graphene suggests that graphene is a potential candidate as a sensor material [173]. Also, AuNPs–graphene nanocomposite was prepared and its electrocatalytic activity toward glucose oxidation was investigated. The results indicated that AuNPs–graphene nanocomposite had a higher catalytic activity than AuNPs or graphene alone indicating the synergistic effect of graphene and AuNPs [174]. Furthermore, Li Niu developed a novel glucose biosensor based on graphene/AuNPs/chitosan at gold electrode exhibiting good electrocatalytic activity toward H2O2 and O2. With GOD as a model, the graphene/AuNPs/GOD/chitosan composite-modified electrode was constructed through a simple casting method. The resulting biosensor exhibited good amperometric response to glucose with linear range, good reproducibility, and low detection limit of 180 µM [175]. Also, amperometric glucose biosensors were fabricated by using Pt–Au and Au nanoparticle spacers decorated functionalized graphene (f-G) nanosheets. The immobilization of GOD over nafion-solubilized metal nanoparticles dispersed graphene f-G-(Pt–Au) and f-G-(Au) electrodes has been achieved by physical adsorption. The resultant bioelectrode retains its biocatalytic activity offering fast and sensitive glucose quantification. The fabricated f-G-(Au) based glucose biosensor exhibited best sensing performance with a linear response up to 30 mM with an excellent detection limit of 1 µM [172]. Moreover, a dual biosensor platform based on hemin-functionalized graphene nanosheets (H-GNs) was presented. The nanomaterial combines the features of both graphene (high conductivity and surface area) and hemin (excellent catalysis and intrinsic peroxidase-like activity). Based on these features, the simple, economical, and highly sensitive amperometric and colorimetric biosensors for H2O2 and glucose have been developed. The detection limits for H2O2 and glucose reached 0.2 µM and 0.3 µM by the amperometric method, respectively. By the colorimetric methods, the detection limits for H2O2 and glucose were as low as 20 nM and 30 nM, respectively. The rapid, simple, and sensitive sensing platform showed great promising applications in the pharmaceutical, clinical, and industrial detection of H2O2 and glucose [176]. Also, GCE modified with electrochemically reduced graphene oxide/sodium dodecyl sulfate (GCE/ERGO/SDS) was further modified with GOD to be used as an enzymatic glucose biosensor with a low detection limit of 40.8 μM [177]. On the other hand, graphene functionalized with poly(diallyldimethylammonium chloride) (PDDA) can be used as non-enzymatic H2O2 biosensor showing enhanced electrocatalytic activity toward H2O2 reduction. As well, this modified surface can be used as an enzymatic glucose sensor by the immobilization of the negatively charged GOD onto the positively charged PDDA-G matrix through electrostatic interaction. GOD/PDDA-G bionanocomposite can detect glucose with a low detection limit of 8 µM in the linear range of 0.02 to 1.8 mM [178]. In addition, a graphene and cobalt oxide nanoparticle composite was employed as non-enzymatic H2O2 and enzymatic glucose biosensor [179]. Several modified surfaces were utilized as non-enzymatic H2O2 biosensors, which were summarized in Table 9. On the other hand, a stable and sensitive non-enzymatic glucose biosensor based on CuO and rGO nanocomposite was developed. The proposed biosensor presented a high sensitivity of 2221 µA/mM.cm2 and a wide linear range from 0.4 µM to 12 mM toward glucose with good selectivity and stability. The TEM of rGO sheets showed a typical wrinkled and crumpled shape with thin layers. Upon CuO modification, there is a uniform distribution of rod-like nanoparticles with an average length of 20–30 nm on the surface of rGO indicating the successful synthesis of CuO-rGO nanocomposite [186]. Also, Ni(OH)2/electroreduced graphene oxide-MWCNTs film was employed as non-enzymatic H2O2 and glucose biosensors [187].
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
GOD modified reduced GO adsorbed on the 3-aminopropyltriethoxysilane (APTES) modified GCE | \n\t\t\tenzymatic glucose | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[52] | \n\t\t
GOD/Pt/functional graphene sheets/chitosan | \n\t\t\tenzymatic glucose | \n\t\t\t--- | \n\t\t\t0.6 µM | \n\t\t\t[173] | \n\t\t
AuNPs–graphene nanocomposite | \n\t\t\tenzymatic glucose | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[174] | \n\t\t
graphene/AuNPs/GOD/chitosan composite-modified electrode | \n\t\t\tenzymatic glucose | \n\t\t\t2 to 10 mM | \n\t\t\t180 µM | \n\t\t\t[175] | \n\t\t
GOD modified Pt–Au and Au nanoparticle spacers decorated functionalized graphene (f-G) nanosheets | \n\t\t\tenzymatic glucose | \n\t\t\tup to 30 mM | \n\t\t\t1 µM | \n\t\t\t[172] | \n\t\t
hemin-functionalized graphene nanosheets (H-GNs) | \n\t\t\tH2O2 and glucose | \n\t\t\t--- | \n\t\t\t0.2 µM for H2O2 and 0.3 µM for glucose | \n\t\t\t[176] | \n\t\t
GCE modified with electrochemically reduced graphene oxide/sodium dodecyl sulfate and GOD | \n\t\t\tenzymatic glucose | \n\t\t\t--- | \n\t\t\t40.8 μM | \n\t\t\t[177] | \n\t\t
graphene functionalized with poly(diallyldimethylammonium chloride) | \n\t\t\tNon-enzymatic H2O2 and enzymatic glucose | \n\t\t\t0.02 to 1.8 mM | \n\t\t\t8 µM | \n\t\t\t[178] | \n\t\t
graphene and cobalt oxide nanoparticle composite | \n\t\t\tnon-enzymatic H2O2 and enzymatic glucose | \n\t\t\t0.5 mM to 16.5 mM for glucose. 0.2 to 211.5 μM for H2O2\n\t\t\t | \n\t\t\t0.06 μM for H2O2\n\t\t\t | \n\t\t\t[179] | \n\t\t
prussian blue nanocubes on nitrobenzene-functionalized reduced graphene oxide | \n\t\t\tnon-enzymatic H2O2\n\t\t\t | \n\t\t\t1.2 μM to 15.25 mM | \n\t\t\t0.4 μM | \n\t\t\t[180] | \n\t\t
layer-by-layer deposited low dimensional building blocks of graphene-prussian blue onto graphite screen-printed electrodes | \n\t\t\tnon-enzymatic H2O2\n\t\t\t | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[181] | \n\t\t
Ag nanoparticles/graphene nanosheet | \n\t\t\tnon-enzymatic H2O2\n\t\t\t | \n\t\t\t0.1 to 100 mM | \n\t\t\t0.5 μM | \n\t\t\t[61] | \n\t\t
prussian blue-graphene modified GCE | \n\t\t\tnon-enzymatic H2O2\n\t\t\t | \n\t\t\t10–1440 μM | \n\t\t\t3 μM | \n\t\t\t[182] | \n\t\t
graphene/Nafion/azure I/Au nanoparticles composites modified GCE | \n\t\t\tnon-enzymatic H2O2\n\t\t\t | \n\t\t\t30 μM to 5 mM | \n\t\t\t10 μM | \n\t\t\t[183] | \n\t\t
rGO and Fe3O4 nanocomposites | \n\t\t\tnon-enzymatic H2O2\n\t\t\t | \n\t\t\t0.1 mM to 6 mM | \n\t\t\t3.2 µM | \n\t\t\t[184] | \n\t\t
cationic polyelectrolyte-functionalized ionic liquid decorated graphene sheets nanocomposite | \n\t\t\tnon-enzymatic H2O2\n\t\t\t | \n\t\t\t--- | \n\t\t\t--- | \n\t\t\t[185] | \n\t\t
CuO and rGO nanocomposite | \n\t\t\tnon-enzymatic glucose | \n\t\t\t0.4 µM to 12 mM | \n\t\t\t--- | \n\t\t\t[186] | \n\t\t
Ni(OH)2/electroreduced graphene oxide-MWCNTs film | \n\t\t\tnon-enzymatic H2O2 and non-enzymatic glucose | \n\t\t\t10-1500 µM and 10 µM-9050 µM for glucose and H2O2, respectively | \n\t\t\t2.7 µM and 4.0 µM for glucose and H2O2, respectively | \n\t\t\t[187] | \n\t\t
Examples of modified electrodes used as Glucose and H2O2 Biosensors.
Graphene exhibits a unique chemical structure and outstanding properties making it very attractive for various engineering applications. Graphene and graphene-based materials have a profound impact on electroanalysis, electrocatalysis, sensors, and biosensors. In sensing applications, graphene-based materials featured with good conductivity and large specific surface area have demonstrated accurate, rapid, selective, sensitive, and even single-molecular sensing abilities. Graphene-based materials are ideally used as gas sensors, electrochemical sensors for heavy metal ions, immunosensors and NADH, DNA, catecholamine neurotransmitters, paracetamol, glucose, H2O2, hemoglobin, and myoglobin biosensors. Future investigations on graphene-based sensing platforms, combined with versatile sensing strategies, are expected to continuingly lower the detection threshold.
Figure number (in chapter) | \n\t\t\tFigure Source (reference number) | \n\t\t\tPermission number | \n\t\t
2 | \n\t\t\t[6] | \n\t\t\t3556440341708 | \n\t\t
3 | \n\t\t\t[1] | \n\t\t\t3556440556169 | \n\t\t
4 | \n\t\t\t[4] | \n\t\t\tOpen access | \n\t\t
5 | \n\t\t\t[31] | \n\t\t\tOpen access | \n\t\t
6 | \n\t\t\t[66] | \n\t\t\tOpen access | \n\t\t
7 | \n\t\t\t[77] | \n\t\t\t3556441025155 | \n\t\t
8 | \n\t\t\t[79] | \n\t\t\t3556441165370 | \n\t\t
Table 1 | \n\t\t\t[6] | \n\t\t\t3556460926032 | \n\t\t
Climate change is already present and will continue to change, affecting societies and the environment [1]. This occurs directly through changes in hydrological systems that are influencing water availability, water quality, and extreme events, and indirectly through changes in water demand, which in turn can have impacts on energy production, social and environmental damages, food security and the economy, among others [2]. On the other hand, communities have increased pressure on water resources, seeking new alternatives to mitigate the lack of this vital element. Among these alternatives is desalination technology, which is a solution to this problem [3], considering that the planet earth is 97.3% saltwater [4] and 2.5% freshwater [5]. However, in spite of being a solution that is becoming more and more common, this technology generates some environmental problems. On the one hand, it generates a product water or desalinated water that can be treated to be suitable for human consumption or irrigation, adding the necessary minerals, and on the other hand, a saline stream called brine that is generally disposed of in the sea, causing serious environmental problems [6]. It is estimated that for every 1 m3 of desalinated water, between 0.3 and 1 m3 of brine is generated [7]. Considering that the global product water capacity from seawater desalination plants as of 2020 was 9.72 × 109 m3/d [4] and according to the above estimate, in the same year, there have been between 2.92 × 109 and 9.72 × 109 m3 d−1 of brine. According to Ihsanullah 2021, reusing and recycling brine is presented as a good alternative to minimize the negative impacts it produces, being favorable on a small scale. However, he indicates that more work is needed to assess the feasibility of brine treatment in commercial or larger desalination plants [8].
On the other hand, today’s economy is based on a circular model, which assumes that resources are abundant and that one must “take-make-consume-reuse.” Therefore, given the large amount of brine produced today, reutilization is a matter of principle that is strongly linked to the circular economy [9]. In that sense, wastewater such as brine is a valuable water, energy, and material resource; therefore, it is essential to manage its use and final disposal, following strategies of reduction, reuse, recycling, recovery, restoration, and regeneration, among others of the circular economy [10]. In addition, it is worth noting that the idea of circular economy through business models that encourage reuse and recycling can be very relevant for arid regions [11], where water is a valuable resource for basic needs such as drinking and sanitation, or for irrigation.
The agricultural sector uses 70% of the world’s water and is one of the most important sectors for human beings. According to the WHO, it is estimated that by the year 2050, the demand for food products will be approximately 70% higher than today, as a result of population growth [12]. On the other hand, FAO, in its reports “The State of Food and Agriculture,” indicates that 1.2 million people live in agricultural areas with high levels of water stress and 520 millions of them live in rural areas [13]. In addition, special attention is paid to agri-food systems, where food-producing families engaged in small-scale agriculture are increasingly being put to the test due to the lack of water for irrigation [14]. These potential effects on agriculture are mainly due to climate change, which could lead to regions with increased salinization and desertification in arid areas of South American countries such as Chile and Brazil [15].
The Arica and Parinacota region is located in northern Chile and has arid characteristics. Although this region has available water resources such as the Lluta River or Camarones River, this water is limited and of poor quality due to high concentrations of arsenic, boron, and total dissolved solids (TDSs) [16] that exceed standards such as NCh 409.Of1.2005 for “drinking water” [17] or NCh 1333.Of1978mod1989 “water for irrigation” [18]. This condition limits their use to only a few crops such as corn, tomatoes, alfalfa, among others. Also, the soils of the Lluta Valley and the Camarones Valley, where these rivers are located, are affected by the poor quality of their waters, causing a lack of crop diversification [19]. This condition considerably affects the agricultural and livestock production sector and the local community. One of the most important crops in this region is alfalfa production, which is the main feed for bovines and goats [16]. On the other hand, there is
Consequently, to mitigate this lack of water in quantity and quality, research on desalination technologies for water production is being carried out at the Universidad de Tarapacá (Arica and Parinacota region). To this end, a desalination plant has been implemented for the production of drinking water or irrigation. However, one of the problems generated by this type of plant was what to do with the brine produced. Considering this question, this work is expected to evaluate the use of brine for the production of halophytes (
Desalination is a process of removing dissolved salts and other minerals from seawater or brackish water, resulting in freshwater and a subproduct called brine [21, 22]. Seawater desalination is an alternative that can extend water supplies beyond what is available in the hydrological cycle, with a constant and climate-independent supply [23]. The main desalination technologies include thermal methods such as multistage flash distillation (MSF) and multi-effect distillation (MED) and within membrane methods, reverse osmosis (RO). These desalination technologies commercially cover almost 90% of the world market. RO processes lead with a 53% share, followed by thermal technologies with 33% [24], and RO is a technology that has lower energy requirements, low complexity and, therefore, lower economic cost [25]. This technique requires electrical energy to activate a high-pressure pump, whereby the saline water is forced through semipermeable membranes to separate the freshwater (or product) from the saltwater (brine) [26]. However, despite the benefits offered by desalination, it is still an environmental challenge to consider the disposal of coproduced brine to mitigate the environmental impacts attributed to discharges into the environment. Generally, brine is discharged to the sewer or to the sea [27]. Currently, desalination technologies are also applied to treat the large amount of brine generated in these processes, which can be by electrodialysis [28] or by membrane distillation crystallization (MDC) [29], among other alternatives, in order to recover a greater volume of product water.
On the other part, being RO the most widely used technology, its performance depends largely on the type of membrane, which have a pore size <1 nm, allowing the passage of small molecules such as water and rejecting larger species such as Na+, K+, Cl−, or dissolved organic compounds. In that sense, there are several studies that seek to improve and optimize the membrane material to generate higher permeability, better selectivity, and anti-incrustant properties [30].
The most commonly used methods of brine disposal are i) discharge to the sea (surface and through multiport diffusers installed on the deep sea floor), ii) disposal in sewers (wastewater collection system, low cost and energy), iii) injections into deep wells (injected into porous subsurface rock formations), iv) injections into deep wells (injected into porous subsurface rock formations) (v) sewage disposal (wastewater collection system, low cost and energy), (vi) deep well injections (injected into porous subsoil rock formations), (vii) land applications (irrigation of salt-tolerant crops and grasses), and (viii) evaporation ponds (evaporation of brine in ponds, salts accumulate at the base of the pond) [7]. In addition, when selecting the disposal technology, it is important to consider the location, quality, and volume of the brines [31].
Among these applications, irrigation of crops with a concentrated solution of salts is a great solution in these times, considering that currently there is low-quality water available and that there is an increase in temperature worldwide, which is causing a greater demand for irrigation water [32], which is why having water, even if it is saline (brine), is a benefit to be considered.
Generally, the use of brine in sprinkler irrigation is common in parks, lawns, and golf courses, and also, in the cultivation of forage plants, which require low volumes of this solution. However, its use is limited for large volumes due to climatic conditions, plant size, seasonal demand, and depending on the stratigraphic and structural conditions where the subway aquifer is formed [33].
There are studies of halophyte plants such as
The means by which halophytes sequester salts and the degree of salt absorption differs according to plant species affect the efficiency of their use for remediation of affected soils. Halophytes have many productive applications: rehabilitating degraded lands, preventing desertification, providing firewood and timber, creating shade and shelter, and producing industrial crops and animal fodder. Halophytes can be grown on soils too saline for normal crops and pastures, from inland soils to soils near the sea, and thus can make a significant contribution to food security for living things [35].
Considering the above, it can be evaluated that this type of brine from desalination plants, when used in irrigation, presents advantages and disadvantages, which are described as follows:
Water availability (for irrigation).
No environmental impact if brine is used for irrigation.
Inland desalination plants compared to plants located in sectors avoid marine pollution.
Soil degradation or seepage into groundwater is avoided if brine is added directly through injection from deep wells.
Its use in aquaponics would allow to produce fish and at the same time to nourish the plants through an aquaculture recirculation system.
There are plants that are tolerant to salinity (halophytes).
Low capital cost by reusing the brine directly for irrigation of halophytes.
Allows remediation of saline soils.
Not all plants are tolerant to high salinity concentrations.
Risk of soil contamination if irrigated soils are microporous such as clay or silt soils.
Not applicable for large volumes.
One of the main problems in the installation of desalination plants is the cost of brine disposal, which is usually very high, ranging from 5 to 33% of the total cost of the desalination plant [7].
In addition, this cost depends on factors such as concentrate characteristics, treatment prior to disposal, disposal method, environmental regulations, location, concentrate volume, among others. It is also important to consider that the economic and environmental risks would be reduced if there is good management of brine use and final disposal. Así como también, es importante considerar que los riesgos económicos y ambientales se reducirían si existe una buena gestión del uso y disposición final de la salmuera [31].
It is worth mentioning that among the few existing regulations worldwide, the Mexican regulation is a good option to start controlling the start-up of desalination plants and their waste. In this regulation called “PROY-NOM-013-CON AGUA/SEMARNAT-2015: that establishes specifications and requirements for intake and discharge works to be complied with in desalination plants or processes that generate brackish or saline rejection water,” it indicates that it has 11 parameters and whose maximum limits include temperature, pH, total dissolved solids, turbidity, aluminum, copper, cadmium, among others. However, it does not refer to the main compound within the brine, NaCl [36].
Currently in Chile, there are no specific regulations related to desalination plants, as well as no regulatory system that considers the maximum concentration of brine expressed in NaCl, (mg L−1) or salinity (dimensionless), or for the temperature (°C) for its final disposal, there is only a guide with minimum technical guidelines for desalination projects related to the jurisdiction of the maritime authority prepared by DIRECTEMAR [37] which includes desalination projects that may or may not be submitted to the Evaluación de Impacto Ambiental (SEIA) [38]. Cornejo-Ponce, et al. 2020 [7] proposed that both salinity and temperature, which are essential parameters, should have their upper limits expressed as follows: for salinity, the concentration should be less than or equal to that of the receiving mass. For example, if discharged into the sea, it should be lower than the salinity of the sea (35 mg L−1), and for temperature, it should be considered approximately 2°C higher than that of the receiving mass, respecting the 2015 Paris agreement. In addition, once these parameters have been established, the different alternatives for their elimination can be evaluated.
The calculations involved in the desalination process (Table 1) and specifically for obtaining the amount of brine produced consider a concentration of feedwater Ca (Kg m−3), product water Cp (Kg m−3), and brine Cs (Kg m−3), as well as a flow rate of feedwater Qa (m3 h−1), product Qp (m3 h−1), and brine Qs (m3 h−1) [39, 40].
Item | Equation | Definition |
---|---|---|
Charge balance | ||
Rejection factor (R) | Corresponds to the rejection of salts from the membranes and in a membrane system, and it is the factor that determines the final quality of the product water of a distillation system. | |
Salt passage (SP) | It corresponds to the ratio between the salt concentration of the product and the feed, measured as a percentage. | |
Conversion (Y) | It corresponds to the percentage ratio between the permeate flow rate and the water flow rate entering the desalination process. | |
Concentration factor (CF) | Corresponds to the number of times the brine is concentrated with respect to the feedwater. |
The world is changing; the economic, environmental, and social challenges facing today’s society are becoming increasingly demanding. In this sense, the principle of the “circular economy” is a good way to make this approach more sustainable [39]. Whereas, over the past 10 years, private/public sector actors, governments, policy-makers, citizens, the media, and the scientific community have been working to make the world more sustainable [41], changing the economic model from extract-use-dispose to an extract-use-reuse model. Thus, the circular economy seeks that system resources, energy, and materials are reused several times, considering a minimum processing for each subsequent use, through a closed loop. In other words, turning waste into a resource is an essential part of increasing our efficiency and moving toward a more circular economy [8].
In relation to the circular economy in water, in addition to complying with the reuse of this good, its quality and quantity must be prioritized [42]. Therefore, evaluating brine disposal management measures is an alternative to consider, depending on factors such as: (a) the volume or quantity of the concentrate, (b) quality of the concentrate, (c) physical and geographic location of the discharge point, (d) capital and operational costs, among others [43].
In addition, it is worth mentioning that the Office of Agricultural Studies and Policies, 2019 [44], proposed 3 principles and 11 strategies of circular economy, based on the World Economic Forum, 2018. Each principle is related to the strategies defined as follows:
Design (R1): Integrate environmental impact in the development of products and services.
Reduce/Prevent (R2): Avoid use of unnecessary resources and prevent waste generation.
Optimize (R3): Maximize the usefulness of products, materials, resources, and assets.
Reuse/Distribute (R4): Take advantage of discarded or old products in good condition so that they fulfill their original function.
Repair (R5): Repair defective or old products to fulfill their original function.
Remanufacture (R6): Capture the value of components of discarded products to fulfill an original function, a new product.
Revaluate (R7): Transform discarded products, parts, or waste to condition a new function by capturing the value of materials.
Recycle (R8): Process materials to obtain products of equal or lower quality.
Recover (R9): Energy recovery by incineration of materials.
Regenerate (R10): Regenerate natural ecosystems to promote positive impact on the environment.
Supply (R11): Procure sustainable supply of inputs with the least environmental impact.
The use of brines in saline agriculture can be beneficial, as it reduces the current demand for food production and maximizes water resources and the use of saline soils in accordance with the three principles of the circular economy (optimizing resources, maximizing the utility of materials, and preserving natural capital).
Today, it is possible to find salt-tolerant crops such as halophytes. These plants have developed a series of physiological and morphological adaptations that allow their tolerance to salt, and although they represent only 2% of terrestrial plant species, their domestication and cultivation in a context of saline agriculture may be interesting to consider [45].
Among the halophyte plants is the forage shrub
Forage crop
In addition, there are studies in Brazil where they have cultivated forage plants irrigated with brine (obtained from RO), indicating that the yield for
To achieve the objective of this work, it is proposed to follow the following flow chart of the research methodology to be carried out (Figure 2). For this purpose, the use of water from the Luta River, feedwater to be treated in the reverse osmosis desalination plant, from which product water and brine are obtained, is considered. The latter is the subject of this publication. For this, according to the existing brine disposal factors, it is proposed as an alternative to minimize the potential environmental impacts to apply the 3 principles and 11 strategies of circular economy [44] for the cultivation of halophyte plants (
Methodology for the use of brine for the production of halophyte plants (proper elaboration).
In addition, the methodology is based on mathematical calculations to obtain information on flow rate and brine concentration, feed flow, among others, according to formulas in item 2.5 calculation of brine concentrate, considering the factors that influence brine disposal [43].
The reverse osmosis plant is located at the
The feedwater for the reverse osmosis plant was obtained from the Lluta River, which was transported by truck, in order to study real samples to generate information to support the rural communities that live in and use this water directly for their crops, limiting their diversification. The parameters used to determine the quality of the Lluta River feedwater were temperature, conductivity, pH, and total dissolved solids (TDSs). These were measured with a multiparameter apparatus (model HI 9828, HANNA Instruments, USA). The concentration of arsenic was also determined using the VARIAN FS 280 VGA 77 atomic absorption equipment with hydride generation and 950°C electrothermal blanket, which were analyzed according to international standards [49] at the Laboratorio de Investigación Ambiental de Zonas Áridas, LIMZA, of the Universidad de Tarapacá (Arica, Chile).
To evaluate the quality of the soil in the sector adjacent to the Lluta River, samples were taken to determine parameters such as, texture, organic matter, pH, electrical conductivity, arsenic, available phosphorus, and total nitrogen, which were analyzed according to international standards [49] and the recommended methods of analysis for Chilean soils of the Comisión de Normalización y Acreditación (CNA), 2004 [50] at the Laboratorio de Investigación Ambiental de Zonas Áridas, LIMZA, of the Universidad de Tarapacá (Arica, Chile).
The pilot plant under study in this work corresponds to a reverse osmosis desalination plant, Wave Cyber Vessels, Model 300E 4” Side Port Housing, with 300 PSI (21 bar) maximum pressure, 49°C maximum temperature, −7°C minimum temperature, and dimensions of 328.2 cm in length. The product water yield is 360 L h−1 and the rejection factor is 50% brine [51].
The feedwater passes through a water pump first passing through sand and activated carbon filters, respectively. The 5-micron cartridge filter retains sediment (sand, sludge, and oxidation particles) to obtain clean water, and the granular carbon filter retains bacteria, chlorine, odors, and organic chemicals.
Subsequently, by reducing salts and compounds that can clog the membrane, it enters the osmosis system where arsenic and salts are reduced (Figure 3).
Reverse osmosis plant (proper elaboration).
The use of brine as irrigation water for the cultivation of halophytes (
The Lluta River, located in the Lluta Valley, is a water system in which the physicochemical characteristics vary seasonally, mainly in summer due to the altiplanic summer rains. In addition, there are variations at different points along its course due to the presence of minor tributaries. The concentration of arsenic is notable, exceeding 29 times the value recommended by the WHO (10 mg L−1) [52]. Table 2 presents the physicochemical parameters of the Lluta River water.
Physicochemical parameters | Lluta River water values | NCh409/1.Of2005 drinking water | NCh1333. of 1978 Mod.1987 water for irrigation | Unit |
---|---|---|---|---|
pH | 7.69 | 6.5 – 8.5 | 6.0 – 9.0 | — |
Electrical conductivity | 1.52 | — | — | mScm−1 |
Temperature | — | 30 | °C | |
Chloride | 528.1 | 400 | 200 | mgL−1 |
Sulfate | 1,389 | 500 | 250 | mgL−1 |
Sodium | 31.15 | — | — | mgL−1 |
Magnesium | 41.14 | 125 | — | mgL−1 |
Calcium | 174.05 | — | — | mgL−1 |
Arsenic | 0.29 | 0.01 | 0.1 | mgL−1 |
Total dissolved solids | 1,981 | 1,500 | — | mgL−1 |
Physicochemical characterization of the Lluta River water (proper elaboration).
In the Lluta Valley, mainly only corn (
Texture | Organic matter (%m/m) | pH | Electrical conductivity (mScm−1) | Arsenic (mgkg-1) | Available phosphorus (mgkg−1) | Total nitrogen (mgkg-1) |
---|---|---|---|---|---|---|
53.5% sand 14.5% clay 32% silt | 1.80 | 6.88 | 2.34 | 276.6 | 26.5 | 0.61 |
Physicochemical characterization of the soil in the Lluta Valley (proper elaboration).
The calculation of the feed flow is made by means of Eq. (4), where Qp is 360 L h−1 and the conversion is 50%, obtaining Qa equal to 720 L h−1. With the optimum flow rates of feedwater and plant product water, the brine flow rate is obtained by means of a load balance (Ec. (1)), with Qs equal to 360 L h−1.
To estimate the concentration of salts, present in the brine, a theoretical calculation was made, considering that the plant has a yield equal to Y (%) = 50. Through (Ec. (5)), the concentration factor (CF) is obtained, whose result is 2. This value was used to characterize the brine, multiplying its value by the initial concentration of each parameter of the Lluta River water (Table 2), where the results are expressed in Table 4.
Physicochemical parameters | Values Brine | Unit |
---|---|---|
pH | 7.9 | — |
Electrical conductivity | 3.04 | mScm−1 |
Temperature | 22.0 | °C |
Chloride | 1,056.2 | mgL−1 |
Sulfate | 2,778 | mgL−1 |
Sodium | 62.30 | mgL−1 |
Magnesium | 82.28 | mgL−1 |
Calcium | 348.1 | mgL−1 |
Arsenic | 0.58 | mgL−1 |
Total dissolved solids | 2,962 | mgL−1 |
Theoretical characterization of the physicochemical parameters presents in the brine (proper elaboration).
The present proposal considers the use of brine obtained from the RO plant, from which 360 L h−1 are generated (Figure 4). If we consider that the plant will operate 12 hours a day for 20 days a month, we obtain 86,400 L h−1 of this saline liquid waste, which can be stored in a pond to be used for irrigation.
Diagram of reverse osmosis plant and the use of brine in the cultivation of forage plants (proper elaboration).
The soil conditions for the cultivation of the fodder plant should be a fallowed, tracked, and leveled soil, where a drip irrigation system is established, whose Polyvinyl chlorid, PVC, lines could be at a depth of 40 cm. The plants can be produced in a nursery until they reach a size of 20 cm and then transplanted in furrows 1.5 m apart, conditions established for a cultivable land of 1000 m2 [53]. In addition, the distance between plants should be 2.5 to 3 m because these forages generate a high volume of biomass [54]. It is proposed to cultivate 400 halophyte plants in a 1500 m2 plot, considering an irrigation of 6 hours per week and a volume of 75 L plant−1 week−1 [19].
The production obtained from
On the other hand, according to the comparison of the chemical analysis between alfalfa and
It should be noted that the proposed system for the production of halophytes from brine will use 31.319 kWh day−1 (11,431.435 kWh year−1) of electrical energy obtained from the photovoltaic system.
Considering the chemical properties of the soil, the components detailed in Table 3, the Lluta Valley soil corresponds to the United States Department of Agriculture (USDA) textural triangle, being classified as a sandy loam soil [56].
In addition, it is worth mentioning that this type of soil has an apparent density of 1.50 g cm−3, which indicates the space occupied by the pores in the soil in relation to the volume of water. In addition, these soils have a real density of 2.6 g cm−3.
For the determination of the total porosity of the soil (ξ), it is calculated according to the following equation (Ec. (6)) [57]:
Considering the equation x, we obtain a ξ =43% of total porosity.
This result indicates that they present spaces between the particles of 0.05–2 mm, increasing the size of the pore spaces between the particles and facilitating the drainage and aeration of the soil. This percentage also shows an adequate porosity for the development of halophyte plants. It is worth mentioning that halophyte plants are able to accumulate high concentrations of NaCl in their tissues, and there is information of 39% in a shrub [58]. In addition, the use of halophytes plants for phytoremediation appears as a cost-effective, noninvasive alternative to other methods used for contaminated soils [34].
Each plant has a certain tolerance to salinity, depending on the plant species, the soil, and the characteristics of the brine. In general, some plants can tolerate TDS concentrations of 500 mgL−1, and this is the case of halophytes that can be irrigated with a brine concentration higher than 2000 mgL−1 of TDS [58]. In general, soil texture is the main factor affecting the infiltration rate of soils, as well as soil depth, which makes the permeability characteristics of these different [59]. The soil under study has a sandy loam texture, whose infiltration rate is 0.8 to 1.2 cm h−1 (Table 6). This characteristic allows inferring that the soil for cultivation has a moderate infiltration rate, being optimal for drip irrigation [60].
Nutrients | Alfalfa | Optimum nutritional value for a dairy cow | |
---|---|---|---|
Dry matter, % | 89.7 | 88.1 | 20 |
Crude protein, % | 16 | 20.2 | 18 |
Metabolizable energy, Mcal kg−1 | 2.21 | 1.99 | 1.67–1.76 |
Texture class | Basic infiltration rate (cm h−1) |
---|---|
Fine sand | 1.2 a 1.9 |
Sandy loam soil | 0.8 a 1.2 |
Silty loam soil | 0.6 a 1 |
Clay | 0.2 a 0.5 |
Basic infiltration rate according to soil texture class [60].
On the other side, the capacity of the soil to retain water, called soil ponding capacity (PC), is another factor that influences infiltration, and in irrigation, it is always limited to a given depth (normally to the depth of roots). For the calculation of the ponding capacity (Ec. (7)), [61] was used, according to the data obtained in Table 7 at a depth of 40 cm, obtaining a value of 48 mm. It is important to mention that the field capacity (FC) is the water content of a soil after having been abundantly irrigated and having drained freely for 24 to 48 hours, and the permanent wilting point (PWP) is the soil moisture condition in which the plants are unable to absorb water or do so with extreme difficulty, experiencing irreversible wilting:
Texture | Ad Apparent density | FC Gravimetric soil water content at field capacity (%) | PWP Gravimetric soil water content at permanent wilting Point (%) |
---|---|---|---|
Sandy | 1.5–1.8 (1.65) | 6–12 (9.0) | 2–6 (4) |
Sandy loam | 1.4–1.6 (1.50) | 10–18 (14.0) | 4–8 (6) |
Loam | 1.0–1.5 (1.25) | 18–21 (19.5) | 8–12 (10) |
Clay loam | 1.1–1.4 (1.25) | 23–31 (27) | 11–15 (13) |
Sandy clay | 1.2–1.4 (1.30) | 27–35 (31) | 13–17 (15) |
Clayey | 1.1–1.4 (1.30) | 31–39 (35) | 15–19 (17) |
Physical properties for different textures [61].
The PC value obtained indicates that the soil can store in a depth of 40 cm a height of water equivalent to 48 mm. However, not all of this water is available to the crop, since crops have different minimum water balances, for example, like halophyte, in the case of alfalfa, and in general, they require approximately 60% of the available water capacity to maintain evapotranspiration and avoid water stress.
This proposal was applied to the present work (Table 8), mentioning that strategies R1 to R3 are relevant for the optimal performance and utilization of the RO plant energetically sustained with solar energy, and that its resulting by-products are used for irrigation. From strategy R5 to R8, the products can be maximized through valorization, considering that the “brines” are allowed to produce “food” for other species such as “cattle or goats.” In addition, membranes can be reused either by regenerating them or by using them to produce another type of membrane. As for strategies R10 and R11, they allow improving and preserving the natural ecosystem through the use of renewable energies, using the brine for irrigation, and reducing the use of conventional water.
Principles | Strategies | EC PRC |
---|---|---|
Plan for the optimal use of resources | R1 Design | The integrated design, which considers the use of photovoltaic panels to the reverse osmosis plant, allows to reduce the carbon footprint. In addition, the brine obtained from the RO process will be used to irrigate the |
R2 Reduce/Prevent | Avoiding the use of conventional electricity and using solar photovoltaic energy to generate electricity reduce greenhouse gases. Preventing brine from being disposed of in the sea or in sewage systems is a great relief for the environment and much better than using it to grow halophyte fodder crops for goats or bovines. | |
R3 Optimize | Considering that if we have brackish water (720 L h−1) and that when treated through RO, 50% product water (360 L h−1) and 50% brine (360 L h−1) are generated. The brine is generally disposed of in sewers, the sea or deep wells, but to maximize the resources, it is essential that the brine is used as irrigation water for halophyte plants, optimizing the use of feedwater by 100%. | |
Maximize the usefulness of materials at all times | R4 Reuse/Distribute | Not applicable. |
R5 Repair | Parts such as water or brine storage ponds will be repaired, or any parts of the RO plant that have technical problems will be repaired. In addition, membrane regeneration periods will be provided due to membrane saturation, typical in brackish water use. | |
R6 Remanufacture | The disused membranes will be used for applied research (new materials) and to generate new membranes in the laboratory LIMZA/UTA. | |
R7 Revaluate | This project valorizes brine for irrigation of halophyte plants, reducing water consumption for irrigation and therefore reducing the cost of water consumption. | |
R8 Recycle | Activated carbon bags are reused to store forage plants when they are available for animal consumption. | |
R9 Recover | Not applicable. | |
Preserve and improve the natural capital | R10 Regenerate | The cultivation of halophyte plants helps to preserve the local natural resource and thus avoid environmental damage by disposing of the brine, for example, in the sea. |
R11 Supply | The electrical energy photovoltaic consumption of the system to produce halophyte is 11,431.435 kWh per year sustained with conventional energy would produce approximately 1.5 tons of CO2 [62] |
Principles and strategies of the circular economy applied to the cultivation of halophytes with brine obtained from the RO plant [44] (proper elaboration).
Figure 5 is a proposal that considers three important components: 1. desalination plant, 2. photovoltaic system, and 3. halophyte cultivation. This integrated proposal would allow mainly rural communities to opt for the sustainable development of their products considering the circular economy in their processes.
Diagram of brine utilization in the cultivation of forage plants considering the principles of circular economy (proper elaboration).
Although, generally what is sought when implementing desalination plants is to obtain water for irrigation or human consumption; in this case, it is observed that the use of brine from this type of process serves for the cultivation of fodder plants. Therefore, environmental circularity would be achieved from the desalination plant by applying the different strategies of the circular economy.
Initially, the brine (R1) can be used for the cultivation of halophytes, reducing the consumption of irrigation water (R3 and R7). Subsequently, the fodder plant is used as feed for cattle and goats (R10 and R11), preserving the natural resource and reducing environmental pollution. It is worth mentioning that the valorization and consumption of animals fed with halophytes irrigated with brine should reduce production costs due to the water savings generated and the solar energy used as energy support for the system (R2).
Moreover, the desalination plant has parts that can be repaired (R5) or remanufactured (R6) or reevaluated (R7).
The combination of the adaptation of technologies with natural brackish water and solar energy in the area would help mitigate the effects of climate change. In other words, the use of brine is a proposal that provides another source of water for irrigation and reduces the greenhouse effect. The proposed system to produce
The use of brine in the cultivation of the halophyte plant
In addition to the environmental benefits, the integrated scheme used in the semiarid region of Arica and Parinacota would produce a new source of food for the agricultural sector, thus, diversifying the fodder for livestock in rural areas and adding value to a waste stream with potential contaminating effects.
The use of brine as irrigation water for halophilic plants is an option to consider compared to conventional forage crops such as alfalfa.
The circular economy can be considered as a valuable model to promote sustainable resource management, contributing to the construction of a vision for long-term sustainable development. Within this framework, the study complies with 9 of the 11 strategies of the circular economy.
The reverse osmosis technology produces a percentage of brine equal to that of the product water and researchers seek to improve and optimize the membranes to obtain more product water, in this particular case, it would not be necessary because the brine is used practically 100% in the irrigation of halophytes considering its cultivation in a sandy loam soil, with a pond capacity of 48 mm and a 43% of total porosity of the soil to be cultivated, introducing to this technology a new concept, circular economy, increasing its added value.
Finally, this study opens some potential opportunities for future research, such as the implementation of this type of projects in rural communities, considering the use of saline wastes as a source of water for irrigation, maintaining the circularity of RO desalination plants.
The authors thank the Solar Energy Research Center, SERC-Chile (ANID/FONDAP/15110019), proyecto UTA Mayor N° 8750-21 and Fondo de investigación estratégica en sequía (asignación rápida) año 2021, ANID, código FSEQ210016.
“The authors declare no conflict of interest.”
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\n\nCan collaboration be inspired by a publishing format? At IntechOpen, the answer is yes. The way the research is published, the way it is accessed, it’s all part of our mission to help academics make a greater impact by giving readers free access to all published work.
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Although it has attracted great interests during last decades, it remains a challenging task and falls short of efficiency due to the nature of its data: high dimensionality, large in data size and updating continuously. With the advent of deep learning, new methods have been developed, especially Convolutional Neural Network (CNN) models. In this paper, we present a review of our time series CNN approaches including: (i) a data-level approach based on encoding time series into frequency-domain signals via the Stockwell transform, (ii) an algorithm-level approach based on an adaptive convolutional layer filter that suits the time series in hand, and (iii) another algorithm-level approach adapted to time series classification tasks with limited annotated data, which is a global, fast and light-weight framework based on a transfer learning technique with a source learning task similar or different but related to the target learning task. These approaches are implemented on identifying human activities including normal movements of typical subjects and disorder-related movements such as stereotypical motor movements of autistic subjects. Experimental results show that our approaches improve performance of time series classification.",book:{id:"8362",slug:"time-series-analysis-data-methods-and-applications",title:"Time Series Analysis",fullTitle:"Time Series Analysis - Data, Methods, and Applications"},signatures:"Lamyaa Sadouk",authors:[{id:"257943",title:"Ph.D.",name:"Lamyaa",middleName:null,surname:"Sadouk",slug:"lamyaa-sadouk",fullName:"Lamyaa Sadouk"}]},{id:"56653",doi:"10.5772/intechopen.70230",title:"Bayesian Hypothesis Testing: An Alternative to Null Hypothesis Significance Testing (NHST) in Psychology and Social Sciences",slug:"bayesian-hypothesis-testing-an-alternative-to-null-hypothesis-significance-testing-nhst-in-psycholog",totalDownloads:3438,totalCrossrefCites:14,totalDimensionsCites:19,abstract:"Since the mid-1950s, there has been a clear predominance of the Frequentist approach to hypothesis testing, both in psychology and in social sciences. Despite its popularity in the field of statistics, Bayesian inference is barely known and used in psychology. Frequentist inference, and its null hypothesis significance testing (NHST), has been hegemonic through most of the history of scientific psychology. However, the NHST has not been exempt of criticisms. Therefore, the aim of this chapter is to introduce a Bayesian approach to hypothesis testing that may represent a useful complement, or even an alternative, to the current NHST. The advantages of this Bayesian approach over Frequentist NHST will be presented, providing examples that support its use in psychology and social sciences. Conclusions are outlined.",book:{id:"5964",slug:"bayesian-inference",title:"Bayesian Inference",fullTitle:"Bayesian Inference"},signatures:"Alonso Ortega and Gorka Navarrete",authors:[{id:"203438",title:"Dr.",name:"Alonso",middleName:null,surname:"Ortega",slug:"alonso-ortega",fullName:"Alonso Ortega"},{id:"208842",title:"Dr.",name:"Gorka",middleName:null,surname:"Navarrete",slug:"gorka-navarrete",fullName:"Gorka Navarrete"}]},{id:"59936",doi:"10.5772/intechopen.75007",title:"Application of Principal Component Analysis to Image Compression",slug:"application-of-principal-component-analysis-to-image-compression",totalDownloads:1827,totalCrossrefCites:12,totalDimensionsCites:15,abstract:"In this chapter, an introduction to the basics of principal component analysis (PCA) is given, aimed at presenting PCA applications to image compression. Here, concepts of linear algebra used in PCA are introduced, and PCA theoretical foundations are explained in connection with those concepts. Next, an image is compressed by using different principal components, and concepts such as image dimension reduction and image reconstruction quality are explained. Also, using the almost periodicity of the first principal component, a quality comparative analysis of a compressed image using two and eight principal components is carried out. Finally, a novel construction of principal components by periodicity of principal components has been included, in order to reduce the computational cost for their calculation, although decreasing the accuracy.",book:{id:"6703",slug:"statistics-growing-data-sets-and-growing-demand-for-statistics",title:"Statistics",fullTitle:"Statistics - Growing Data Sets and Growing Demand for Statistics"},signatures:"Wilmar Hernandez and Alfredo Mendez",authors:null}],mostDownloadedChaptersLast30Days:[{id:"59209",title:"Utilization of Response Surface Methodology in Optimization of Extraction of Plant Materials",slug:"utilization-of-response-surface-methodology-in-optimization-of-extraction-of-plant-materials",totalDownloads:5470,totalCrossrefCites:64,totalDimensionsCites:97,abstract:"Experimental design plays an important role in several areas of science and industry. Experimentation is an application of treatments applied to experimental units and is then part of a scientific method based on the measurement of one or more responses. It is necessary to observe the process and the operation of the system well. For this reason, in order to obtain a final result, an experimenter must plan and design experiments and analyzes the results. One of the most commonly used experimental designs for optimization is the response surface methodology (RSM). Because it allows evaluating the effects of multiple factors and their interactions on one or more response variables it is a useful method. In this section, recent studies have been compiled which aim to extraction of plant material in high yield and quality and determine optimum conditions for this extraction process.",book:{id:"5856",slug:"statistical-approaches-with-emphasis-on-design-of-experiments-applied-to-chemical-processes",title:"Statistical Approaches With Emphasis on Design of Experiments Applied to Chemical Processes",fullTitle:"Statistical Approaches With Emphasis on Design of Experiments Applied to Chemical Processes"},signatures:"Alev Yüksel Aydar",authors:[{id:"218870",title:"Dr.",name:"Alev Yüksel",middleName:null,surname:"Aydar",slug:"alev-yuksel-aydar",fullName:"Alev Yüksel Aydar"}]},{id:"60864",title:"Statistical Methodology for Evaluating Business Cycles with the Conditions of Their Synchronization and Harmonization",slug:"statistical-methodology-for-evaluating-business-cycles-with-the-conditions-of-their-synchronization-",totalDownloads:1372,totalCrossrefCites:1,totalDimensionsCites:2,abstract:"The importance of the topic of business cycle research and their interaction is due to the fact that the cyclical nature of development is a universal feature of the market economy (regardless of the level of development of the country’s economy and the principles of its organization). In all cases, cyclical ups and downs depend not only on internal system cyclical processes and their factors in countries but also on the consequences of intercountry interaction. The ability to measure and predict business cycles, taking into account their mutual influence, is a prerequisite for the development of an adequate business policy of countries and their associations.",book:{id:"6703",slug:"statistics-growing-data-sets-and-growing-demand-for-statistics",title:"Statistics",fullTitle:"Statistics - Growing Data Sets and Growing Demand for Statistics"},signatures:"Elena Zarova",authors:null},{id:"60246",title:"Statistical Research of Investment Appeal of Russian Regions",slug:"statistical-research-of-investment-appeal-of-russian-regions",totalDownloads:1014,totalCrossrefCites:0,totalDimensionsCites:0,abstract:"In this chapter, the methodological results directed on realization statistical research of investment appeal of Russian regions are offered. Methodological basis of research is the method of the dynamic standard, index and the coefficient analysis and the method of paired comparisons. The results of the study: (1) the method of the dynamic standard for creation of statistical model of region investment appeal is offered; (2) the normative model of region investment appeal to measure the productivity of the realization of regions investment policy in Russia is created; (3) new factors of region investment appeal are investigated and (4) statistically valid conclusions are drawn and practical recommendations are made. The results of the study are addressed to the Ministry of Economic Development of the Russian Federation in order to justify the amount of federal targeted investment programs financing in Russian regions.",book:{id:"6703",slug:"statistics-growing-data-sets-and-growing-demand-for-statistics",title:"Statistics",fullTitle:"Statistics - Growing Data Sets and Growing Demand for Statistics"},signatures:"Burtseva Tatiana Alexsandrovna",authors:null},{id:"56460",title:"Application of Taguchi-Based Design of Experiments for Industrial Chemical Processes",slug:"application-of-taguchi-based-design-of-experiments-for-industrial-chemical-processes",totalDownloads:3222,totalCrossrefCites:27,totalDimensionsCites:54,abstract:"Design of experiment is the method, which is used at a very large scale to study the experimentations of industrial processes. It is a statically approach where we develop the mathematical models through experimental trial runs to predict the possible output on the basis of the given input data or parameters. The aim of this chapter is to stimulate the engineering community to apply Taguchi technique to experimentation, the design of experiments, and to tackle quality problems in industrial chemical processes that they deal with. Based on years of research and applications, Dr. G. Taguchi has standardized the methods for each of these DOE application steps. Thus, DOE using Taguchi approach has become a much more attractive tool to practicing engineers and scientists. And since the last four decades, there were limitations when conventional experimental design techniques were applied to industrial experimentation. And Taguchi, also known as orthogonal array design, adds a new dimension to conventional experimental design. 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She has been a faculty member at the University of California, Riverside in the School of Education since 2016. Her research focuses on translational studies to explore the reward system in ASD, as well as how anxiety contributes to social challenges in ASD. She also investigates how behavioral interventions affect neural activity, behavior, and school performance in children with ASD. She is also involved in the diagnosis of children with ASD and is a licensed clinical psychologist in California. 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He previously worked as a post-doctoral fellow at the Ben-Gurion University of Negev, Israel; University of the Free State, South Africa; and Central University of Technology Bloemfontein, South Africa. He obtained his Ph.D. in Organic Chemistry from Nagaoka University of Technology, Japan. He has published more than seventy-four journal articles and attended several national and international conferences as speaker and chair. Dr. Kendrekar has received many international awards. He has several funded projects, namely, anti-malaria drug development, MRSA, and SARS-CoV-2 activity of curcumin and its formulations. He has filed four patents in collaboration with the University of Central Lancashire and Mayo Clinic Infectious Diseases. His present research includes organic synthesis, drug discovery and development, biochemistry, nanoscience, and nanotechnology.",institutionString:"Visiting Scientist at Lipid Nanostructures Laboratory, Centre for Smart Materials, School of Natural Sciences, University of Central Lancashire",institution:null},{id:"428125",title:"Dr.",name:"Vinayak",middleName:null,surname:"Adimule",slug:"vinayak-adimule",fullName:"Vinayak Adimule",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/428125/images/system/428125.jpg",biography:"Dr. Vinayak Adimule, MSc, Ph.D., is a professor and dean of R&D, Angadi Institute of Technology and Management, India. He has 15 years of research experience as a senior research scientist and associate research scientist in R&D organizations. He has published more than fifty research articles as well as several book chapters. He has two Indian patents and two international patents to his credit. Dr. Adimule has attended, chaired, and presented papers at national and international conferences. He is a guest editor for Topics in Catalysis and other journals. He is also an editorial board member, life member, and associate member for many international societies and research institutions. His research interests include nanoelectronics, material chemistry, artificial intelligence, sensors and actuators, bio-nanomaterials, and medicinal chemistry.",institutionString:"Angadi Institute of Technology and Management",institution:null},{id:"284317",title:"Prof.",name:"Kantharaju",middleName:null,surname:"Kamanna",slug:"kantharaju-kamanna",fullName:"Kantharaju Kamanna",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/284317/images/21050_n.jpg",biography:"Prof. K. Kantharaju has received Bachelor of science (PCM), master of science (Organic Chemistry) and Doctor of Philosophy in Chemistry from Bangalore University. He worked as a Executive Research & Development @ Cadila Pharmaceuticals Ltd, Ahmedabad. He received DBT-postdoc fellow @ Molecular Biophysics Unit, Indian Institute of Science, Bangalore under the supervision of Prof. P. Balaram, later he moved to NIH-postdoc researcher at Drexel University College of Medicine, Philadelphia, USA, after his return from postdoc joined NITK-Surthakal as a Adhoc faculty at department of chemistry. Since from August 2013 working as a Associate Professor, and in 2016 promoted to Profeesor in the School of Basic Sciences: Department of Chemistry and having 20 years of teaching and research experiences.",institutionString:null,institution:{name:"Rani Channamma University, Belagavi",country:{name:"India"}}},{id:"158492",title:"Prof.",name:"Yusuf",middleName:null,surname:"Tutar",slug:"yusuf-tutar",fullName:"Yusuf Tutar",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/158492/images/system/158492.jpeg",biography:"Prof. Dr. Yusuf Tutar conducts his research at the Hamidiye Faculty of Pharmacy, Department of Basic Pharmaceutical Sciences, Division of Biochemistry, University of Health Sciences, Turkey. He is also a faculty member in the Molecular Oncology Program. He obtained his MSc and Ph.D. at Oregon State University and Texas Tech University, respectively. He pursued his postdoctoral studies at Rutgers University Medical School and the National Institutes of Health (NIH/NIDDK), USA. His research focuses on biochemistry, biophysics, genetics, molecular biology, and molecular medicine with specialization in the fields of drug design, protein structure-function, protein folding, prions, microRNA, pseudogenes, molecular cancer, epigenetics, metabolites, proteomics, genomics, protein expression, and characterization by spectroscopic and calorimetric methods.",institutionString:"University of Health Sciences",institution:null},{id:"180528",title:"Dr.",name:"Hiroyuki",middleName:null,surname:"Kagechika",slug:"hiroyuki-kagechika",fullName:"Hiroyuki Kagechika",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/180528/images/system/180528.jpg",biography:"Hiroyuki Kagechika received his bachelor’s degree and Ph.D. in Pharmaceutical Sciences from the University of Tokyo, Japan, where he served as an associate professor until 2004. He is currently a professor at the Institute of Biomaterials and Bioengineering (IBB), Tokyo Medical and Dental University (TMDU). From 2010 to 2012, he was the dean of the Graduate School of Biomedical Science. Since 2012, he has served as the vice dean of the Graduate School of Medical and Dental Sciences. He has been the director of the IBB since 2020. Dr. Kagechika’s major research interests are the medicinal chemistry of retinoids, vitamins D/K, and nuclear receptors. He has developed various compounds including a drug for acute promyelocytic leukemia.",institutionString:"Tokyo Medical and Dental University",institution:{name:"Tokyo Medical and Dental University",country:{name:"Japan"}}},{id:"94311",title:"Prof.",name:"Martins",middleName:"Ochubiojo",surname:"Ochubiojo Emeje",slug:"martins-ochubiojo-emeje",fullName:"Martins Ochubiojo Emeje",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/94311/images/system/94311.jpeg",biography:"Martins Emeje obtained a BPharm with distinction from Ahmadu Bello University, Nigeria, and an MPharm and Ph.D. from the University of Nigeria (UNN), where he received the best Ph.D. award and was enlisted as UNN’s “Face of Research.” He established the first nanomedicine center in Nigeria and was the pioneer head of the intellectual property and technology transfer as well as the technology innovation and support center. Prof. Emeje’s several international fellowships include the prestigious Raman fellowship. He has published more than 150 articles and patents. He is also the head of R&D at NIPRD and holds a visiting professor position at Nnamdi Azikiwe University, Nigeria. He has a postgraduate certificate in Project Management from Walden University, Minnesota, as well as a professional teaching certificate and a World Bank certification in Public Procurement. Prof. Emeje was a national chairman of academic pharmacists in Nigeria and the 2021 winner of the May & Baker Nigeria Plc–sponsored prize for professional service in research and innovation.",institutionString:"National Institute for Pharmaceutical Research and Development",institution:{name:"National Institute for Pharmaceutical Research and Development",country:{name:"Nigeria"}}},{id:"436430",title:"Associate Prof.",name:"Mesut",middleName:null,surname:"Işık",slug:"mesut-isik",fullName:"Mesut Işık",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/436430/images/19686_n.jpg",biography:null,institutionString:null,institution:{name:"Bilecik University",country:{name:"Turkey"}}},{id:"268659",title:"Ms.",name:"Xianquan",middleName:null,surname:"Zhan",slug:"xianquan-zhan",fullName:"Xianquan Zhan",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/268659/images/8143_n.jpg",biography:"Dr. Zhan received his undergraduate and graduate training in the fields of preventive medicine and epidemiology and statistics at the West China University of Medical Sciences in China during 1989 to 1999. He received his post-doctoral training in oncology and cancer proteomics for two years at the Cancer Research Institute of Human Medical University in China. In 2001, he went to the University of Tennessee Health Science Center (UTHSC) in USA, where he was a post-doctoral researcher and focused on mass spectrometry and cancer proteomics. Then, he was appointed as an Assistant Professor of Neurology, UTHSC in 2005. He moved to the Cleveland Clinic in USA as a Project Scientist/Staff in 2006 where he focused on the studies of eye disease proteomics and biomarkers. He returned to UTHSC as an Assistant Professor of Neurology in the end of 2007, engaging in proteomics and biomarker studies of lung diseases and brain tumors, and initiating the studies of predictive, preventive, and personalized medicine (PPPM) in cancer. In 2010, he was promoted to Associate Professor of Neurology, UTHSC. Currently, he is a Professor at Xiangya Hospital of Central South University in China, Fellow of Royal Society of Medicine (FRSM), the European EPMA National Representative in China, Regular Member of American Association for the Advancement of Science (AAAS), European Cooperation of Science and Technology (e-COST) grant evaluator, Associate Editors of BMC Genomics, BMC Medical Genomics, EPMA Journal, and Frontiers in Endocrinology, Executive Editor-in-Chief of Med One. He has\npublished 116 peer-reviewed research articles, 16 book chapters, 2 books, and 2 US patents. His current main research interest focuses on the studies of cancer proteomics and biomarkers, and the use of modern omics techniques and systems biology for PPPM in cancer, and on the development and use of 2DE-LC/MS for the large-scale study of human proteoforms.",institutionString:null,institution:{name:"Xiangya Hospital Central South University",country:{name:"China"}}},{id:"40482",title:null,name:"Rizwan",middleName:null,surname:"Ahmad",slug:"rizwan-ahmad",fullName:"Rizwan Ahmad",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/40482/images/system/40482.jpeg",biography:"Dr. Rizwan Ahmad is a University Professor and Coordinator, Quality and Development, College of Medicine, Imam Abdulrahman bin Faisal University, Saudi Arabia. Previously, he was Associate Professor of Human Function, Oman Medical College, Oman, and SBS University, Dehradun. Dr. Ahmad completed his education at Aligarh Muslim University, Aligarh. He has published several articles in peer-reviewed journals, chapters, and edited books. His area of specialization is free radical biochemistry and autoimmune diseases.",institutionString:"Imam Abdulrahman Bin Faisal University",institution:{name:"Imam Abdulrahman Bin Faisal University",country:{name:"Saudi Arabia"}}},{id:"41865",title:"Prof.",name:"Farid A.",middleName:null,surname:"Badria",slug:"farid-a.-badria",fullName:"Farid A. Badria",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/41865/images/system/41865.jpg",biography:"Farid A. Badria, Ph.D., is the recipient of several awards, including The World Academy of Sciences (TWAS) Prize for Public Understanding of Science; the World Intellectual Property Organization (WIPO) Gold Medal for best invention; Outstanding Arab Scholar, Kuwait; and the Khwarizmi International Award, Iran. He has 250 publications, 12 books, 20 patents, and several marketed pharmaceutical products to his credit. He continues to lead research projects on developing new therapies for liver, skin disorders, and cancer. Dr. Badria was listed among the world’s top 2% of scientists in medicinal and biomolecular chemistry in 2019 and 2020. He is a member of the Arab Development Fund, Kuwait; International Cell Research Organization–United Nations Educational, Scientific and Cultural Organization (ICRO–UNESCO), Chile; and UNESCO Biotechnology France",institutionString:"Mansoura University",institution:{name:"Mansoura University",country:{name:"Egypt"}}},{id:"329385",title:"Dr.",name:"Rajesh K.",middleName:"Kumar",surname:"Singh",slug:"rajesh-k.-singh",fullName:"Rajesh K. Singh",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/329385/images/system/329385.png",biography:"Dr. Singh received a BPharm (2003) and MPharm (2005) from Panjab University, Chandigarh, India, and a Ph.D. (2013) from Punjab Technical University (PTU), Jalandhar, India. He has more than sixteen years of teaching experience and has supervised numerous postgraduate and Ph.D. students. He has to his credit more than seventy papers in SCI- and SCOPUS-indexed journals, fifty-five conference proceedings, four books, six Best Paper Awards, and five projects from different government agencies. He is currently an editorial board member of eight international journals and a reviewer for more than fifty scientific journals. He received Top Reviewer and Excellent Peer Reviewer Awards from Publons in 2016 and 2017, respectively. He is also on the panel of The International Reviewer for reviewing research proposals for grants from the Royal Society. He also serves as a Publons Academy mentor and Bentham brand ambassador.",institutionString:"Punjab Technical University",institution:{name:"Punjab Technical University",country:{name:"India"}}},{id:"142388",title:"Dr.",name:"Thiago",middleName:"Gomes",surname:"Gomes Heck",slug:"thiago-gomes-heck",fullName:"Thiago Gomes Heck",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/142388/images/7259_n.jpg",biography:null,institutionString:null,institution:{name:"Universidade Regional do Noroeste do Estado do Rio Grande do Sul",country:{name:"Brazil"}}},{id:"336273",title:"Assistant Prof.",name:"Janja",middleName:null,surname:"Zupan",slug:"janja-zupan",fullName:"Janja Zupan",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/336273/images/14853_n.jpeg",biography:"Janja Zupan graduated in 2005 at the Department of Clinical Biochemistry (superviser prof. dr. Janja Marc) in the field of genetics of osteoporosis. Since November 2009 she is working as a Teaching Assistant at the Faculty of Pharmacy, Department of Clinical Biochemistry. In 2011 she completed part of her research and PhD work at Institute of Genetics and Molecular Medicine, University of Edinburgh. She finished her PhD entitled The influence of the proinflammatory cytokines on the RANK/RANKL/OPG in bone tissue of osteoporotic and osteoarthritic patients in 2012. From 2014-2016 she worked at the Institute of Biomedical Sciences, University of Aberdeen as a postdoctoral research fellow on UK Arthritis research project where she gained knowledge in mesenchymal stem cells and regenerative medicine. She returned back to University of Ljubljana, Faculty of Pharmacy in 2016. She is currently leading project entitled Mesenchymal stem cells-the keepers of tissue endogenous regenerative capacity facing up to aging of the musculoskeletal system funded by Slovenian Research Agency.",institutionString:null,institution:{name:"University of Ljubljana",country:{name:"Slovenia"}}},{id:"357453",title:"Dr.",name:"Radheshyam",middleName:null,surname:"Maurya",slug:"radheshyam-maurya",fullName:"Radheshyam Maurya",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/357453/images/16535_n.jpg",biography:null,institutionString:null,institution:{name:"University of Hyderabad",country:{name:"India"}}},{id:"418340",title:"Dr.",name:"Jyotirmoi",middleName:null,surname:"Aich",slug:"jyotirmoi-aich",fullName:"Jyotirmoi Aich",position:null,profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0033Y000038Ugi5QAC/Profile_Picture_2022-04-15T07:48:28.png",biography:"Biotechnologist with 15 years of research including 6 years of teaching experience. Demonstrated record of scientific achievements through consistent publication record (H index = 13, with 874 citations) in high impact journals such as Nature Communications, Oncotarget, Annals of Oncology, PNAS, and AJRCCM, etc. Strong research professional with a post-doctorate from ACTREC where I gained experimental oncology experience in clinical settings and a doctorate from IGIB where I gained expertise in asthma pathophysiology. A well-trained biotechnologist with diverse experience on the bench across different research themes ranging from asthma to cancer and other infectious diseases. An individual with a strong commitment and innovative mindset. Have the ability to work on diverse projects such as regenerative and molecular medicine with an overall mindset of improving healthcare.",institutionString:"DY Patil Deemed to Be University",institution:null},{id:"349288",title:"Prof.",name:"Soumya",middleName:null,surname:"Basu",slug:"soumya-basu",fullName:"Soumya Basu",position:null,profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0033Y000035QxIDQA0/Profile_Picture_2022-04-15T07:47:01.jpg",biography:"Soumya Basu, Ph.D., is currently working as an Associate Professor at Dr. D. Y. Patil Biotechnology and Bioinformatics Institute, Dr. D. Y. Patil Vidyapeeth, Pune, Maharashtra, India. With 16+ years of trans-disciplinary research experience in Drug Design, development, and pre-clinical validation; 20+ research article publications in journals of repute, 9+ years of teaching experience, trained with cross-disciplinary education, Dr. Basu is a life-long learner and always thrives for new challenges.\r\nHer research area is the design and synthesis of small molecule partial agonists of PPAR-γ in lung cancer. She is also using artificial intelligence and deep learning methods to understand the exosomal miRNA’s role in cancer metastasis. Dr. Basu is the recipient of many awards including the Early Career Research Award from the Department of Science and Technology, Govt. of India. She is a reviewer of many journals like Molecular Biology Reports, Frontiers in Oncology, RSC Advances, PLOS ONE, Journal of Biomolecular Structure & Dynamics, Journal of Molecular Graphics and Modelling, etc. She has edited and authored/co-authored 21 journal papers, 3 book chapters, and 15 abstracts. She is a Board of Studies member at her university. She is a life member of 'The Cytometry Society”-in India and 'All India Cell Biology Society”- in India.",institutionString:"Dr. D.Y. Patil Vidyapeeth, Pune",institution:{name:"Dr. D.Y. Patil Vidyapeeth, Pune",country:{name:"India"}}},{id:"354817",title:"Dr.",name:"Anubhab",middleName:null,surname:"Mukherjee",slug:"anubhab-mukherjee",fullName:"Anubhab Mukherjee",position:null,profilePictureURL:"https://intech-files.s3.amazonaws.com/0033Y0000365PbRQAU/ProfilePicture%202022-04-15%2005%3A11%3A18.480",biography:"A former member of Laboratory of Nanomedicine, Brigham and Women’s Hospital, Harvard University, Boston, USA, Dr. Anubhab Mukherjee is an ardent votary of science who strives to make an impact in the lives of those afflicted with cancer and other chronic/acute ailments. He completed his Ph.D. from CSIR-Indian Institute of Chemical Technology, Hyderabad, India, having been skilled with RNAi, liposomal drug delivery, preclinical cell and animal studies. He pursued post-doctoral research at College of Pharmacy, Health Science Center, Texas A & M University and was involved in another postdoctoral research at Department of Translational Neurosciences and Neurotherapeutics, John Wayne Cancer Institute, Santa Monica, California. In 2015, he worked in Harvard-MIT Health Sciences & Technology as a visiting scientist. He has substantial experience in nanotechnology-based formulation development and successfully served various Indian organizations to develop pharmaceuticals and nutraceutical products. He is an inventor in many US patents and an author in many peer-reviewed articles, book chapters and books published in various media of international repute. Dr. Mukherjee is currently serving as Principal Scientist, R&D at Esperer Onco Nutrition (EON) Pvt. Ltd. and heads the Hyderabad R&D center of the organization.",institutionString:"Esperer Onco Nutrition Pvt Ltd.",institution:null},{id:"319365",title:"Assistant Prof.",name:"Manash K.",middleName:null,surname:"Paul",slug:"manash-k.-paul",fullName:"Manash K. Paul",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/319365/images/system/319365.png",biography:"Manash K. Paul is a scientist and Principal Investigator at the University of California Los Angeles. He has contributed significantly to the fields of stem cell biology, regenerative medicine, and lung cancer. His research focuses on various signaling processes involved in maintaining stem cell homeostasis during the injury-repair process, deciphering the lung stem cell niche, pulmonary disease modeling, immuno-oncology, and drug discovery. He is currently investigating the role of extracellular vesicles in premalignant lung cell migration and detecting the metastatic phenotype of lung cancer via artificial intelligence-based analyses of exosomal Raman signatures. Dr. Paul also works on spatial multiplex immunofluorescence-based tissue mapping to understand the immune repertoire in lung cancer. Dr. Paul has published in more than sixty-five peer-reviewed international journals and is highly cited. He is the recipient of many awards, including the UCLA Vice Chancellor’s award and the 2022 AAISCR-R Vijayalaxmi Award for Innovative Cancer Research. He is a senior member of the Institute of Electrical and Electronics Engineers (IEEE) and an editorial board member for several international journals.",institutionString:"University of California Los Angeles",institution:{name:"University of California Los Angeles",country:{name:"United States of America"}}},{id:"311457",title:"Dr.",name:"Júlia",middleName:null,surname:"Scherer Santos",slug:"julia-scherer-santos",fullName:"Júlia Scherer Santos",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/311457/images/system/311457.jpg",biography:"Dr. Júlia Scherer Santos works in the areas of cosmetology, nanotechnology, pharmaceutical technology, beauty, and aesthetics. Dr. Santos also has experience as a professor of graduate courses. Graduated in Pharmacy, specialization in Cosmetology and Cosmeceuticals applied to aesthetics, specialization in Aesthetic and Cosmetic Health, and a doctorate in Pharmaceutical Nanotechnology. Teaching experience in Pharmacy and Aesthetics and Cosmetics courses. She works mainly on the following subjects: nanotechnology, cosmetology, pharmaceutical technology, aesthetics.",institutionString:"Universidade Federal de Juiz de Fora",institution:{name:"Universidade Federal de Juiz de Fora",country:{name:"Brazil"}}},{id:"219081",title:"Dr.",name:"Abdulsamed",middleName:null,surname:"Kükürt",slug:"abdulsamed-kukurt",fullName:"Abdulsamed Kükürt",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/219081/images/system/219081.png",biography:"Dr. Kükürt graduated from Uludağ University in Turkey. He started his academic career as a Research Assistant in the Department of Biochemistry at Kafkas University. In 2019, he completed his Ph.D. program in the Department of Biochemistry at the Institute of Health Sciences. He is currently working at the Department of Biochemistry, Kafkas University. He has 27 published research articles in academic journals, 11 book chapters, and 37 papers. He took part in 10 academic projects. He served as a reviewer for many articles. He still serves as a member of the review board in many academic journals. He is currently working on the protective activity of phenolic compounds in disorders associated with oxidative stress and inflammation.",institutionString:null,institution:{name:"Kafkas University",country:{name:"Turkey"}}},{id:"178366",title:"Dr.",name:"Volkan",middleName:null,surname:"Gelen",slug:"volkan-gelen",fullName:"Volkan Gelen",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/178366/images/system/178366.jpg",biography:"Volkan Gelen is a Physiology specialist who received his veterinary degree from Kafkas University in 2011. Between 2011-2015, he worked as an assistant at Atatürk University, Faculty of Veterinary Medicine, Department of Physiology. In 2016, he joined Kafkas University, Faculty of Veterinary Medicine, Department of Physiology as an assistant professor. Dr. Gelen has been engaged in various academic activities at Kafkas University since 2016. There he completed 5 projects and has 3 ongoing projects. He has 60 articles published in scientific journals and 20 poster presentations in scientific congresses. His research interests include physiology, endocrine system, cancer, diabetes, cardiovascular system diseases, and isolated organ bath system studies.",institutionString:"Kafkas University",institution:{name:"Kafkas University",country:{name:"Turkey"}}},{id:"418963",title:"Dr.",name:"Augustine Ododo",middleName:"Augustine",surname:"Osagie",slug:"augustine-ododo-osagie",fullName:"Augustine Ododo Osagie",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/418963/images/16900_n.jpg",biography:"Born into the family of Osagie, a prince of the Benin Kingdom. I am currently an academic in the Department of Medical Biochemistry, University of Benin. Part of the duties are to teach undergraduate students and conduct academic research.",institutionString:null,institution:{name:"University of Benin",country:{name:"Nigeria"}}},{id:"192992",title:"Prof.",name:"Shagufta",middleName:null,surname:"Perveen",slug:"shagufta-perveen",fullName:"Shagufta Perveen",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/192992/images/system/192992.png",biography:"Prof. Shagufta Perveen is a Distinguish Professor in the Department of Pharmacognosy, College of Pharmacy, King Saud University, Riyadh, Saudi Arabia. Dr. Perveen has acted as the principal investigator of major research projects funded by the research unit of King Saud University. She has more than ninety original research papers in peer-reviewed journals of international repute to her credit. She is a fellow member of the Royal Society of Chemistry UK and the American Chemical Society of the United States.",institutionString:"King Saud University",institution:{name:"King Saud University",country:{name:"Saudi Arabia"}}},{id:"49848",title:"Dr.",name:"Wen-Long",middleName:null,surname:"Hu",slug:"wen-long-hu",fullName:"Wen-Long Hu",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/49848/images/system/49848.jpg",biography:"Wen-Long Hu is Chief of the Division of Acupuncture, Department of Chinese Medicine at Kaohsiung Chang Gung Memorial Hospital, as well as an adjunct associate professor at Fooyin University and Kaohsiung Medical University. Wen-Long is President of Taiwan Traditional Chinese Medicine Medical Association. He has 28 years of experience in clinical practice in laser acupuncture therapy and 34 years in acupuncture. He is an invited speaker for lectures and workshops in laser acupuncture at many symposiums held by medical associations. He owns the patent for herbal preparation and producing, and for the supercritical fluid-treated needle. Dr. Hu has published three books, 12 book chapters, and more than 30 papers in reputed journals, besides serving as an editorial board member of repute.",institutionString:"Kaohsiung Chang Gung Memorial Hospital",institution:{name:"Kaohsiung Chang Gung Memorial Hospital",country:{name:"Taiwan"}}},{id:"298472",title:"Prof.",name:"Andrey V.",middleName:null,surname:"Grechko",slug:"andrey-v.-grechko",fullName:"Andrey V. Grechko",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/298472/images/system/298472.png",biography:"Andrey Vyacheslavovich Grechko, Ph.D., Professor, is a Corresponding Member of the Russian Academy of Sciences. He graduated from the Semashko Moscow Medical Institute (Semashko National Research Institute of Public Health) with a degree in Medicine (1998), the Clinical Department of Dermatovenerology (2000), and received a second higher education in Psychology (2009). Professor A.V. Grechko held the position of Сhief Physician of the Central Clinical Hospital in Moscow. He worked as a professor at the faculty and was engaged in scientific research at the Medical University. Starting in 2013, he has been the initiator of the creation of the Federal Scientific and Clinical Center for Intensive Care and Rehabilitology, Moscow, Russian Federation, where he also serves as Director since 2015. He has many years of experience in research and teaching in various fields of medicine, is an author/co-author of more than 200 scientific publications, 13 patents, 15 medical books/chapters, including Chapter in Book «Metabolomics», IntechOpen, 2020 «Metabolomic Discovery of Microbiota Dysfunction as the Cause of Pathology».",institutionString:"Federal Research and Clinical Center of Intensive Care Medicine and Rehabilitology",institution:null},{id:"199461",title:"Prof.",name:"Natalia V.",middleName:null,surname:"Beloborodova",slug:"natalia-v.-beloborodova",fullName:"Natalia V. Beloborodova",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/199461/images/system/199461.jpg",biography:'Natalia Vladimirovna Beloborodova was educated at the Pirogov Russian National Research Medical University, with a degree in pediatrics in 1980, a Ph.D. in 1987, and a specialization in Clinical Microbiology from First Moscow State Medical University in 2004. She has been a Professor since 1996. Currently, she is the Head of the Laboratory of Metabolism, a division of the Federal Research and Clinical Center of Intensive Care Medicine and Rehabilitology, Moscow, Russian Federation. N.V. Beloborodova has many years of clinical experience in the field of intensive care and surgery. She studies infectious complications and sepsis. She initiated a series of interdisciplinary clinical and experimental studies based on the concept of integrating human metabolism and its microbiota. Her scientific achievements are widely known: she is the recipient of the Marie E. Coates Award \\"Best lecturer-scientist\\" Gustafsson Fund, Karolinska Institutes, Stockholm, Sweden, and the International Sepsis Forum Award, Pasteur Institute, Paris, France (2014), etc. Professor N.V. Beloborodova wrote 210 papers, five books, 10 chapters and has edited four books.',institutionString:"Federal Research and Clinical Center of Intensive Care Medicine and Rehabilitology",institution:null},{id:"354260",title:"Ph.D.",name:"Tércio Elyan",middleName:"Azevedo",surname:"Azevedo Martins",slug:"tercio-elyan-azevedo-martins",fullName:"Tércio Elyan Azevedo Martins",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/354260/images/16241_n.jpg",biography:"Graduated in Pharmacy from the Federal University of Ceará with the modality in Industrial Pharmacy, Specialist in Production and Control of Medicines from the University of São Paulo (USP), Master in Pharmaceuticals and Medicines from the University of São Paulo (USP) and Doctor of Science in the program of Pharmaceuticals and Medicines by the University of São Paulo. Professor at Universidade Paulista (UNIP) in the areas of chemistry, cosmetology and trichology. Assistant Coordinator of the Higher Course in Aesthetic and Cosmetic Technology at Universidade Paulista Campus Chácara Santo Antônio. Experience in the Pharmacy area, with emphasis on Pharmacotechnics, Pharmaceutical Technology, Research and Development of Cosmetics, acting mainly on topics such as cosmetology, antioxidant activity, aesthetics, photoprotection, cyclodextrin and thermal analysis.",institutionString:null,institution:{name:"University of Sao Paulo",country:{name:"Brazil"}}},{id:"334285",title:"Ph.D. Student",name:"Sameer",middleName:"Kumar",surname:"Jagirdar",slug:"sameer-jagirdar",fullName:"Sameer Jagirdar",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/334285/images/14691_n.jpg",biography:"I\\'m a graduate student at the center for biosystems science and engineering at the Indian Institute of Science, Bangalore, India. I am interested in studying host-pathogen interactions at the biomaterial interface.",institutionString:null,institution:{name:"Indian Institute of Science Bangalore",country:{name:"India"}}},{id:"329248",title:"Dr.",name:"Md. Faheem",middleName:null,surname:"Haider",slug:"md.-faheem-haider",fullName:"Md. Faheem Haider",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/329248/images/system/329248.jpg",biography:"Dr. Md. Faheem Haider completed his BPharm in 2012 at Integral University, Lucknow, India. In 2014, he completed his MPharm with specialization in Pharmaceutics at Babasaheb Bhimrao Ambedkar University, Lucknow, India. He received his Ph.D. degree from Jamia Hamdard University, New Delhi, India, in 2018. He was selected for the GPAT six times and his best All India Rank was 34. Currently, he is an assistant professor at Integral University. Previously he was an assistant professor at IIMT University, Meerut, India. He has experience teaching DPharm, Pharm.D, BPharm, and MPharm students. He has more than five publications in reputed journals to his credit. Dr. Faheem’s research area is the development and characterization of nanoformulation for the delivery of drugs to various organs.",institutionString:"Integral University",institution:{name:"Integral University",country:{name:"India"}}},{id:"329795",title:"Dr.",name:"Mohd Aftab",middleName:"Aftab",surname:"Siddiqui",slug:"mohd-aftab-siddiqui",fullName:"Mohd Aftab Siddiqui",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/329795/images/system/329795.png",biography:"Dr. Mohd Aftab Siddiqui is an assistant professor in the Faculty of Pharmacy, Integral University, Lucknow, India, where he obtained a Ph.D. in Pharmacology in 2020. He also obtained a BPharm and MPharm from the same university in 2013 and 2015, respectively. His area of research is the pharmacological screening of herbal drugs/natural products in liver cancer and cardiac diseases. He is a member of many professional bodies and has guided many MPharm and PharmD research projects. Dr. Siddiqui has many national and international publications and one German patent to his credit.",institutionString:"Integral University",institution:null}]}},subseries:{item:{id:"1",type:"subseries",title:"Oral Health",keywords:"Oral Health, Dental Care, Diagnosis, Diagnostic Imaging, Early Diagnosis, Oral Cancer, Conservative Treatment, Epidemiology, Comprehensive Dental Care, Complementary Therapies, Holistic Health",scope:"\r\n\tThis topic aims to provide a comprehensive overview of the latest trends in Oral Health based on recent scientific evidence. Subjects will include an overview of oral diseases and infections, systemic diseases affecting the oral cavity, prevention, diagnosis, treatment, epidemiology, as well as current clinical recommendations for the management of oral, dental, and periodontal diseases.
",coverUrl:"https://cdn.intechopen.com/series_topics/covers/1.jpg",hasOnlineFirst:!0,hasPublishedBooks:!0,annualVolume:11397,editor:{id:"173955",title:"Prof.",name:"Sandra",middleName:null,surname:"Marinho",slug:"sandra-marinho",fullName:"Sandra Marinho",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRGYMQA4/Profile_Picture_2022-06-01T13:22:41.png",biography:"Dr. Sandra A. Marinho is an Associate Professor and Brazilian researcher at the State University of Paraíba (Universidade Estadual da Paraíba- UEPB), Campus VIII, located in Araruna, state of Paraíba since 2011. She holds a degree in Dentistry from the Federal University of Alfenas (UNIFAL), while her specialization and professional improvement in Stomatology took place at Hospital Heliopolis (São Paulo, SP). Her qualifications are: a specialist in Dental Imaging and Radiology, Master in Dentistry (Periodontics) from the University of São Paulo (FORP-USP, Ribeirão Preto, SP), and Doctor (Ph.D.) in Dentistry (Stomatology Clinic) from Hospital São Lucas of the Pontifical Catholic University of Rio Grande do Sul (HSL-PUCRS, Porto Alegre, RS). She held a postdoctoral internship at the Federal University from Jequitinhonha and Mucuri Valleys (UFVJM, Diamantina, MG). She is currently a member of the Brazilian Society for Dental Research (SBPqO) and the Brazilian Society of Stomatology and Pathology (SOBEP). 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