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New Developments in Nanosensors for Pharmaceutical Analysis
Автор: Academic Press
Активность, связанная с книгой
Начать чтениеДлина: 889 стр.9 ч
- Издатель:
- Academic Press
- Издано:
- May 22, 2019
- ISBN:
- 9780128163788
- Формат:
- Книге
Описание
New Developments for Nanosensors in Pharmaceutical Analysis presents an overview of developments in nanosensor usage in pharmaceutical analysis, thereby helping pharmaceutical companies attain reliable, precise, and accurate analysis of pharmaceuticals.
This book presents very simple, precise, sensitive, selective, fast, and relatively inexpensive methods for pre-treatment, prior to analysis. These methods may be considered for further application in clinical studies and assays. The book includes the manufacturing of sensors for pharmaceutical analysis at nano- or smaller scales, and gives simple and relatable designs for the fabrication of sensors. Twelve chapters cover an introduction to the topic, immobilization techniques, mechanism effect of nanomaterials on structure, optical nanosensors for pharmaceutical detection, chemical nanosensors in pharmaceutical analysis, noble metal nanoparticles in electrochemical analysis of drugs, photo-electrochemical nanosensors for drug analysis, molecularly imprinted polymer based nanosensors for pharmaceutical analysis, nanomaterials for drug delivery systems, nanomaterials enriched nucleic acid-based biosensors, nanosensors in biomarker detection, and nanomaterials-based enzyme biosensors for electrochemical applications.
Presents nanosensor types, synthesis, immobilizations and applications in different fields Gives simple repeatable designs for the fabrication of sensors for pharmaceutical analysis Details how to carry out sensitive analysis of pharmaceuticals using nanosensors Describes how to synthesize and immobilize nanosensors, and how nanosensors can be applied in drug assay Proposes innovative ways to optimize pharmaceutical processes with nanosensorsАктивность, связанная с книгой
Начать чтениеСведения о книге
New Developments in Nanosensors for Pharmaceutical Analysis
Автор: Academic Press
Длина: 889 стр.9 ч
Описание
New Developments for Nanosensors in Pharmaceutical Analysis presents an overview of developments in nanosensor usage in pharmaceutical analysis, thereby helping pharmaceutical companies attain reliable, precise, and accurate analysis of pharmaceuticals.
This book presents very simple, precise, sensitive, selective, fast, and relatively inexpensive methods for pre-treatment, prior to analysis. These methods may be considered for further application in clinical studies and assays. The book includes the manufacturing of sensors for pharmaceutical analysis at nano- or smaller scales, and gives simple and relatable designs for the fabrication of sensors. Twelve chapters cover an introduction to the topic, immobilization techniques, mechanism effect of nanomaterials on structure, optical nanosensors for pharmaceutical detection, chemical nanosensors in pharmaceutical analysis, noble metal nanoparticles in electrochemical analysis of drugs, photo-electrochemical nanosensors for drug analysis, molecularly imprinted polymer based nanosensors for pharmaceutical analysis, nanomaterials for drug delivery systems, nanomaterials enriched nucleic acid-based biosensors, nanosensors in biomarker detection, and nanomaterials-based enzyme biosensors for electrochemical applications.
Presents nanosensor types, synthesis, immobilizations and applications in different fields Gives simple repeatable designs for the fabrication of sensors for pharmaceutical analysis Details how to carry out sensitive analysis of pharmaceuticals using nanosensors Describes how to synthesize and immobilize nanosensors, and how nanosensors can be applied in drug assay Proposes innovative ways to optimize pharmaceutical processes with nanosensors- Издатель:
- Academic Press
- Издано:
- May 22, 2019
- ISBN:
- 9780128163788
- Формат:
- Книге
Связано с New Developments in Nanosensors for Pharmaceutical Analysis
Отрывок книги
New Developments in Nanosensors for Pharmaceutical Analysis
toxins.
Preface
Sibel A. Ozkan*; Afzal Shah†, * Ankara University, Ankara, Turkey, † University of Bahrain, Sakhir, Bahrain
Nanosensors are emerging as promising tools for the analysis of pharmaceuticals and biological molecules. Nanosensing devices are bestowed with superior qualities of selectivity, sensitivity, affordability, and fast detection ability. They are preferred in diverse fields, such as the environmental, agricultural, forensic, medical, and industrial sectors. Compared to other old-fashioned sensors, nanosensors possess several advantageous features, such as ultrasensitivity, portability, real-time detectability, and user friendliness. In the literature, many techniques, including top-down lithography, self-assembled layers, and bottom-up assembly have been reported for the fabrication of nanosensors. By adopting smart strategies, materials can be ordered into nanotubes, nanowires, nanofibers, graphenes, fullerenes, nanorods, nanocomposites, metal nanoparticles, and nanostructured polymers for use in the development of nanosensors. All these nanomaterials have high surface area/volume ratio and display excellent catalytic activities. Moreover, they are associated with high mechanical strength and attractive electrical and chemical features. Biological molecules, such as proteins and nucleic acids, can be detected by nanosensors as linked receptors on sensor surfaces. Thus, the development of nanosensors is very important for the analysis of pharmaceuticals, biological molecules, and disease biomarkers.
The aim of this book is to introduce recent progress in the fabrication of nanosensors for the sensitive and selective detection of drug active compounds. The interaction of pharmaceuticals and nucleic acid has been discussed in detail. This book contains twelve contemporary chapters, which have been shared with readers, researchers, and students. All chapters emphasize recent nanosensor developments in different fields. In the first chapter, an overview of nanomaterials is presented to situate electrochemical methods in their analytical context. The following chapter includes the immobilization techniques of nanomaterials. Chapter 3 contains the mechanism effect of nanomaterials on the structure. In Chapter 4, optical nanosensors for pharmaceutical detection are described in detail. Subsequent chapters are summarized as chemical nanosensors in pharmaceutical analysis (Chapter 5), noble metal nanoparticles in electroanalytical studies of drugs (Chapter 6), photoelectrochemical-based nanosensors (Chapter 7), and molecularly imprinted polymer-based nanosensors for pharmaceuticals (Chapter 8). Recent developments in the field of nanomaterials for drug delivery systems are summarized in Chapter 9. In Chapters 10 and 11, details of nanomaterials-enriched nucleic acid-based biosensors and nanosensors in biomarker detection are presented. The last chapter (Chapter 12) offers valuable information about nanomaterials-based enzyme biosensors for electrochemical applications.
We believe that this book will be very useful for researchers working in the areas of chemistry, pharmacy, nanomaterials, and biochemistry. New, fast, portable, and easy-to-use devices that involve nanosensors can be modified according to the information presented in this book. Readers from various fields will likely find new ideas and approaches to solve typical nanosensor and nanomaterial problems. Moreover, it will be helpful in the development of environmental sensors and agricultural and food sensors as modern techniques.
The completion of this book could not have been possible without help, inspiration, and encouragement from many people. Last, but not the least, we warmly acknowledge the gracious support of our families, and we are very grateful to them for their assistance throughout the entire process of writing and editing.
We would like to specially thank Dr. Glyn Jones, our project manager, Tracy Tufaga, and our publisher Elsevier, for their support during the publishing of this book.
Finally, we would like to express our sincere gratitude to the leading authors, who accepted our invitation to join us and dedicated their valuable time and efforts to guarantee the success of this book.
Chapter 1
Introduction to Nanosensors
Faiza Jan Iftikhar⁎,†; Afzal Shah⁎,‡; Mohammad Salim Akhter‡; Sevinc Kurbanoglu§; Sibel A. Ozkan§ ⁎ Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan
† NUTECH School of Applied Sciences and Humanities, National University of Technology, Islamabad, Pakistan
‡ Department of Chemistry, College of Science, University of Bahrain, Sakhir, Bahrain
§ Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey
Abstract
Sensors are devices that detect a physical, chemical, or biological stimulus and give a response in the form of a measurable signal. The increasing number of applications for sensing technologies has increased the need for the development of a variety of new sensors with far better performance. Nanoparticles are at the forefront in the fabrication of high-throughput nanosensors for applications ranging from pharmaceuticals to signature nano-based platforms that profile different therapeutic drugs, selective chemicals, and bioassays to environmental analysis by modifying the surface of the electrode for electrochemical detection, offering high sensitivity and selectivity. In this chapter, we will discuss the sensing enhancement impact of a number of nanoparticles, including metals, oxides, and semiconductor-based nanoparticles, mostly employing carbon-based nanoparticles (CNTs, graphene, fullerenes, carbon nanodots, nanowires, and nanodiamonds), dendrimers, and composite nanoparticles on multiple sensors, such as electrochemical, optical, and photoelectrochemical sensors. Moreover, this chapter will offer an introduction to recent developments in the design of nanosensors for trace-level multidrug detection with reproducible results. The ability of electrodes modified with nanomaterials for multianalyte screening and rapid toxicity testing will also be discussed. Moreover, owing to the unique oxidation or reduction potential of every drug, the selectivity of electrochemical sensing platforms based on nanomaterials for the detection of drugs and their metabolites will be highlighted.
Keywords
Nanomaterials; Metal oxide based NPs; Carbon based NPs; Sensitivity; Selectivity; Electrochemical sensors
1 Introduction
Improving nano-sensing technology is at the heart of electrochemical detection strategies that offer effective, economical, time-saving, on-site monitoring amongst a large pool of analytes, such as heavy metal ions, food contaminants, such as melamine and aflatoxin, clinical toxins, such as cholera toxin and dopamine, and cancer and other disease markers, to name just a few cases with promising results. Nanostructured materials have at least one dimension of single or multiple phase that is less than 100 nm in size. Sensors based on nanoparticles rely on focusing on nanoscale dimensions, thus enhancing the optical and electronic properties due to a significant increase in the number of atoms at the surface of the material rather than the bulk. Hence, the interesting and unexpected properties are due to a large surface area, which translates into manipulating the material at the molecular or atomic level, in order to deploy it in different applications, ranging from heath diagnostics and cancer treatment to environmental analysis to clean energy. Due to their small size, nanoparticles can confine electrons to produce quantum effects and display an exquisite array of optical colors. Other size-dependent properties may include super paramagnetism in magnetic materials and surface plasmon resonances in noble metal particles. This property was utilized by artists in medieval times, who were unaware at that time of the existence of nanoparticles and their chemistry, for sculptures and churches. Nanoparticles found use in red wine glass in mosaics, with the color arising from AuNPs of 20 nm size. Orange glass got its color from 80 nm AuNPs, while Ag and Pt had their own unique colors depending on the size of the nanoparticles (Cullum, Griffin, & Vo-Dinh, 2002; De Castro Bueno, Garcia, Steffens, Deda, & Leite, 2017; Horikoshi & Serpone, 2013; Pérez-López & Merkoçi, 2011; Zhu, Yang, Li, Du, & Lin, 2014).
The application of nanotechnology provides a formidable toolbox and it can only be deployed effectively once we understand what each tool stands for. Signal amplification by electrochemical sensors and biosensors based on functional materials, such as nanosensors, can greatly improve their sensitivity and selectivity. The choice of appropriate electrode material for electrochemical detection is important in developing high-performance sensing platforms. These functional nanomaterials are not only responsible for synergism to enhance signal transduction for catalytic activity and biocompatibility but also to amplify recognition events, leading to many applications for devices based on electrochemical methods. Moreover, these functional nanostructured materials provide effective sites for immobilization at the surface of matrices. In this chapter, the unique and inherent features of nanomaterials coupled with electrochemical methods for improved sensing response and disease diagnosis are highlighted (Cullum et al., 2002; De Castro Bueno et al., 2017; Pérez-López & Merkoçi, 2011; Zhu et al., 2014).
2 Nanoparticles in Nanosensors and Their Broad Applications
Nanoparticles, which are ultimately released into the environment, may be divided into natural, engineered, and incidental NPs based on their dimensions. Natural NPs may originate from biotic and abiotic factors and may include organic matter, volcanic dust, minerals from weathering, clays, microbial actions, and metal oxides (Morales-Díaz et al., 2017), while engineered NPs have a specific shape, size, and surface morphology designed for specific applications. These include TiO2, SiO2, and FeOx and are used in a wide variety of consumer applications (Piccinno, Gottschalk, Seeger, & Nowack, 2012). Anthropogenic incidental involuntary production of NPs as a by-product of the combustion of fuels and other combustion activities, from production and manufacturing facilities, and from agricultural practices are classified as incidental NPs and have far-reaching and even drastic effects on the environment and health (Zumwalde & Hodson, 2009). In addition to size and type, the shape of nanoparticles can be engineered and controlled. Besides, the shape of the nanoparticles can be determined by the ratio of the metal salt, appropriate solvent, and reducing agent during the synthesis step. Generally, a high ratio of, for example, Au, in comparison with other ingredients will result in larger nanoparticles. Moreover, by changing the conditions during synthesis, such as the temperature and pressure, other shapes can be formed, such as nanorods or other complex structures. The variety of NP shapes is used in a broad range of applications in areas in which NPs have desirable optical properties and suitable pore structures to potentially hold drugs for targeted drug delivery. An important aspect in nanoparticles is to encapsulate nanoparticles or to modify the surface of nanoparticles with a wide variety of molecular ligands, including alkyl-based molecular linkers, akanethiolates, arenethiolates, sugars, phospholipids, DNA, and dialkyl disulfides. Encapsulation is extremely important to protect nanoparticles from agglomeration and to avoid losing the special features of NPs, as well as to provide surface protection that helps in achieving specific properties; for example, by using a longer protecting ligand, the distance between the NPs can be larger, which affects the amount of analyte absorbed in sensing applications (Gupta & Gupta, 2005; Jamieson et al., 2007; Samia, Dayal, & Burda, 2006; Sassolas, Blum, & Leca-Bouvier, 2012).
2.1 Metal-Based Nanoparticles and Their Broad Applications
NPs based on metal oxides have a broad range of biomedical applications and they find use in sensors, catalysis, environmental remediation, and energy technology (Fernández-García & Rodriguez, 2011; Osgood, Devaguptapu, Xu, Cho, & Wu, 2016; Polshettiwar, Baruwati, & Varma, 2009). Such NPs have been given considerable attention due to their high chemical activity as well as specificity for reactions and product formation. They behave as unique versatile materials that are intensely affected by the choice of synthesis method, which controls their size and morphology. These are important parameters for tuning the catalytic activity and surface area enhancement. In the past few years, metal oxides have been employed as highly selective catalysts for organic substrates used for industrial applications (Akbari et al., 2018). Hence, optimization of the catalyst is an important step toward increasing its selectivity for reactants and product formation, while adopting green synthetic chemistry for a sustainable future is a topic of increasing interest amongst researchers (Anastas & Eghbali, 2010; Anastas & Kirchhoff, 2002; Anastas, Kirchhoff, & Williamson, 2001). Moreover, noble metals, such as Pt, PtRu, PtSn, Pd, Au, Ru, and Ag, can be used with carbon-based nanomaterials to prepare nanohybrids for applications in heterogeneous catalysis, fuel cells, and chemo/biosensors (Wu, Kuang, Zhang, & Chen, 2011) (Fig. 1).
Fig. 1 Brief summary of the preparation and application of noble metal NP/CNT nanohybrids. Reprinted with permission from the publisher (Wu, B., Kuang, Y., Zhang, X., & Chen, J. (2011). Noble metal nanoparticles/carbon nanotubes nanohybrids: Synthesis and applications. Nano Today, 6(1), 75–90).
Similarly, MoOx possesses a unique structure, which has attracted a lot of attraction in the field of sensors (Liang et al., 2005; Malikov & Mikhailov, 1997; Prasad et al., 2003). However, much less is reported regarding its catalytic activity (Katrib, Mey, & Maire, 2001; Song et al., 2002). Hence, MoOx doped with Fe for oxidation of Olefin has been reported using a hydrothermal method of synthesis (Bento, Sanches, Medina, Nunes, & Vaz, 2015; Bento, Sanches, Vaz, & Nunes, 2016). Moreover, MoO3 doped with magnetic Fe2O3 with a core shell architecture and coated with glucose to prevent aggregation of Fe2O3 NPs has been reported to demonstrate outstanding catalytic performance and selectivity for epoxide product formation (Zhang, Hu, Zhong, Yan, & Chen, 2014). Similarly, heterogeneous catalyst WOx NPs dispersed on supports, such as mesoporous silica: SBA-15, MCM-48, and MCF, having a high surface area, leads to enhanced catalytic performance (Gao et al., 2008; Herrera et al., 2006; Koo, Kim, & Chang, 2005). Tungsten doped with different metals, W-X/SnO2 where X are different metals with a strong dependence on the additive X, have been reported to act as useful catalysts (Keigo et al., 2011). Similarly, NPs of iron oxide have been widely used, owing to their low toxicity, good dispensability, and easy separation due to their magnetic properties and for which recovery of the catalyst is feasible. Iron oxide NPs are mostly capped by silica-based agents to prevent their aggregation. Free Fe2O3 is very rarely reported for its application as a catalyst, however, bulk Fe2O3 and nano Fe2O3 with different sizes of NPs have been reported (Feng et al., 2007). Diverse morphologies, such as nanofibers and nanotubes of TiO2, have been used as catalyst promoters for Fe2O3 NPs for catalytic activity (Nafria et al., 2013). Cobalt oxide finds wide applications in sensing, electrochemical investigations, and catalysis (Cantalini, Post, Buso, Guglielmi, & Martucci, 2005; Poizot, Laruelle, Grugeon, Dupont, & Tarascon, 2000; Solsona et al., 2008). The size and morphology of catalysts play important roles in deciding the catalytic activity and selectivity. Different CuO NPs are prepared by the hydrothermal method. Similarly, CuO is one of the most important transition metal oxides (Soleimani & Taheri, 2017). Different morphologies have been prepared by different synthesis methods (Cao et al., 2003; Liu & Zeng, 2004; Ng & Fan, 2007; Xiao, Fu, Zhu, Li, & Yang, 2007; Xu, Chen, Jiao, & Xue, 2007; Yu, Yu, Liu, & Mann, 2007; Zhang, Liu, Peng, Wang, & Li, 2006; Zhou, Kamiya, Minamikawa, & Shimizu, 2007). Aggregation and stability, which can limit the catalytic activity as oxidants, are some issues that need proper handling on unsupported CuO NPs. However, supported CuO NPs on Ag nanowires and SiO2 have been investigated (Scotti, Ravasio, Zaccheria, Psaro, & Evangelisti, 2013; Ye et al., 2012). The low catalytic activity of CuO on SiO2 can be overcome by a novel method of using alkali metals, such as Cs and K+, as promoters (He, Zhai, Zhang, Deng, & Wang, 2013). A novel bimetallic oxide system has been introduced, CuO-NiO/SBA-15, as an excellent catalyst by using the postgrafted ultrasonic method (Tang et al., 2016). Hybrid CuO NPs were investigated using core shell nano-architecture with magnetic Fe2O3 NPs as the core and mesoporous silica as the protective shell (Zhang et al., 2014). In one particular study, cerium oxide NPs were employed as environmentally friendly oxidizing catalysts (Deori, Gupta, Saha, Awasthi, & Deka, 2013). Cerium oxide nanoparticles (nanoceria) are also used as an electrode material in gas sensors, as oxide ion conductors in solid oxide fuel cells (SOFCs), and in biomedical applications (Culcasi et al., 2012; Dahle & Arai, 2015; Deori et al., 2013; Pulido-Reyes et al., 2015; Trovarelli, 1996; Wang & Lin, 2004). However, in order to make them soluble and biocompatible, CeO2 NPs are coated with a polymer, such as dextran, for antioxidant activity (Perez, Asati, Nath, & Kaittanis, 2008). Although nanoceria are being used for different applications, their toxicity has been a concern for the environment and for humans. They may cause in vitro or in vivo oxidative cell damage leading to cell death. Nanoceria have been synthesized in a number of ways, however, more emphasis is laid on their synthesis by green methods, such as by using Gloriosa superba L. leaf extract, Curvularia lunata culture filtrate, Aloe vera, and Acalypha indica plant leaf extract, as capping agents and, finally, using Hibiscus sabdariffa as a chelating agent (Arumugam et al., 2015; Kannan & Sundrarajan, 2014; Munusamy, Bhakyaraj, Vijayalakshmi, Stephen, & Narayanan, 2014; Priya, Kanneganti, Kumar, Rao, & Bykkam, 2014; Thovhogi, Diallo, Gurib-Fakim, & Maaza, 2015). These nanoceria acting as antioxidant NPs are found to have a profound effect on ROS when nanoceria were coated with Levan as a reductant and stabilizing agent (Kim & Chung, 2016). It was also found that nanoceria protected the neurons and cells from free radical damage depending on size of NPs. These nanoceria behave as ROS scavengers and can be used an alternative therapy to cancer and Alzheimer disease (Rajeshkumar & Naik, 2017).
2.1.1 Metal-Based NPs as Gas Sensors
Gas sensors sense changes in the electrical, optical, and junction properties of inorganic materials when they interact with gas molecules. Among the different types of gas sensors, sensors based on semiconductor metal oxides exhibit outstanding features with regards to sensitivity, response time, maintenance, portability, and cost (Dey, 2018). However, nanostructured materials offer a wide range of size-related effects due to large surface-to-volume ratios, displaying characteristic advantages for gas sensing with enhanced surface active sites. A gas sensor should be selective toward a gas in a gas mixture to be an efficient sensor. Likewise, the sensor response and recovery time, as well as being resistant to drift in the sensor response, are important parameters for gas sensors, as are the cost and fabrication (Mehta, Singh, & Khanuja, 2011).
A number of synthesis methods are used, such as the sol-gel method, solid state reactions, the wet chemical route, spin coating, and laser ablation. Different size ranges for SnO2 for sensing different gas molecules, such as NH3, H2CO, CH4, and ethanol, have been investigated by controlling the size with annealing, temperature, additives, doping, and capping agents, among others, which suggests that sensitivity increases with decreasing particle size, as can also be seen for indium oxide, which is able to sense oxidizing and reducing gases (Cavicchi, Walton, Aquino-Class, Allen, & Panchapakesan, 2001; Dolbec & El Khakani, 2007; Gagaoudakis et al., 2001; Huang, Manolidis, Jun, & Hone, 2005; Huang, Matsunaga, Shimanoe, Yamazoe, & Kunitake, 2005; Safonova, Bezverkhy, Fabrichnyi, Rumyantseva, & Gaskov, 2002; Shukla, Seal, Ludwig, & Parish, 2004; Singh, Mehta, Joshi, Kruis, & Shivaprasad, 2007; Tan, Ho, Wong, Kawi, & Wee, 2008).
Different nanosized semiconductor oxides, such as TiO2, WO3, ZnO, V2O5, Fe2O3, CdO, CuO, Ga2O3, and CdSnO3, are employed to detect different gases, such as H2, CH3OH, LPG, H2S, and CO, with a range of different sizes that directly affect the sensitivity of the sensor (Benkstein & Semancik, 2006; Dario, Michael, Carlo, Paul, & Alessandro, 2008; Li et al., 2009; Liu et al., 2004; Rout, Govindaraj, & Rao, 2006; Waghulade, Patil, & Pasricha, 2007; Wang et al., 2008). The sensitivity, response time, and selectivity of gas sensors can be improved by metal additives, such as Pt or Pd, either by doping the material or using it as a support. These metal additives can substitute the host particles or become dispersed in the interstitial spaces (Mardare & Hones, 1999). This affects the electrical and optical properties of metal oxide NPs (Madhusudhana Reddy & Chandorkar, 1999). The metal can agglomerate at the surface of the semiconductor layer as nano- or micrometal aggregates (Ivanovskaya, Bogdanov, Faglia, & Sberveglieri, 2000). The gas sensing ability of semiconductor oxide nanoparticles assisted by metal additives emphasizes the configuration of metal-metal oxide NPs, depending on the type of metal additives a well as where the metal is incorporated in the metal oxide NP (Yamazoe, 1991). A number of research studies have been carried out to pinpoint the importance of metal additives. One example is SeO2 added to In2O3 and formed by the thermal evaporation method to produce a mixed film of SnO2 (Manno, Micocci, Serra, Di Giulio, & Tepore, 2000). In2O3 and WO3 was formed by the laser ablation method and mixed with Pt by the impregnation method to support a doped thin film (Starke & Coles, 2002), while In2O3 with Fe2O3 formed by the sol-gel and coprecursor method, respectively, formed a layer-by-layer surface (Ivanovskaya, Kotsikau, Faglia, & Nelli, 2003) to form an efficient gas sensor that does not depend on either of the morphologies. Increasing the Debye length for NPs, such as SnO2, brings about an improvement in the sensitivity of the sensor; for example, doping SnO2 with trivalent or pentavalent ions affects the Debye length by increasing or decreasing it accordingly (Xu, Tamaki, Miura, & Yamazoe, 1991). In gas sensors, the solid state surface interacts with the gas molecules either through physisorption or chemisorption; the former induces no charge transfer, while the latter process does. It has been demonstrated that at any semiconductor surface, the presence of adsorbed oxygen in the form of O− or O² − is found during chemisorption depending on energy considerations (Kohl, 1989; Liu, Huang, & Meng, 2007). The adsorbed species extracts an electron from the donor level of the NPs and creates an electron deficient or positive charge space near the surface. For a reducing gas Rg, the concentration of the adsorbed O2 species will decrease and an electron will be given back to the conduction band with a decrease in resistance for n-type semiconductors, while the reverse is true for oxidizing gases. P-type semiconductors interacting with Rg will decrease the adsorbed oxygen and produce holes, and thus decrease the conductivity due to the concentration of holes (Patrick, 2017).
Either the rate of chemical reaction affecting the electronic states or the electronic activation is responsible for the activation mechanism of metal additives (Pt or Ag on Pd) for semiconductor oxide nanoparticles (Yamazoe, Sakai, & Shimanoe, 2003). Energy band gaps of n-type In2O3 and p-type Ag2O have been studied to elucidate the electronic transitions within the electronic activation method. The higher work function of Ag2O (~ 5.3 eV) compared with In2O3 (~ 5.0 eV) results in the formation of a depletion layer at the interface of In2O3 (Jia et al., 2003; Tjeng et al., 1990; Tyagi, 1984). When a reducing gas, such as ethanol, is introduced, it reduces Ag2O to Ag, forming an In2O3-Ag interface, increasing the surface area at the same time and forming an accumulation layer due to the Fermi level being higher for Ag than In2O3, which increases the response of the gas sensor (Balasubramanian & Subrahmanyam, 1991). The response of In2O3 alone depends on the depletion layer formed due to the release of an electron to the adsorbed O2 species and the subsequent removal of O2 by ethanol, whereas at high temperatures the rate of reaction between the oxygen and ethanol increases. The drift problem can be reduced by using metal oxide nanowires in resistive sensors, improving the sensitivity by decorating with PdNPs.
2.1.2 Metal-Based NPs as OLEDs
The early 1990s saw a rapid advancement in organic light emitting diodes (OLEDs); however, their lifetime was limited by humidity, oxygen-prone organic materials, and a fast degradation under conditions of high operating currents (Jain, Willander, & Kumar, 2007). By introducing inorganic NPs that combined large surface area with light emitting inorganic semiconducting NPs, it was possible to overcome the limitations set by organic materials (Colvin, Schlamp, & Alivisatos, 1994; Murray, Norris, & Bawendi, 1993). It used glass coated with a transparent conducting oxide (TCO) as an electrode and substrate. The second cathode electrode must have a low work function. ITO, its alternative FTO, and Al- or Ga-doped ZnOx, have been researched as electrodes of choice (Bach et al., 1998; Minami, 2008; Raniero et al., 2006). The OLED-NP consists of a sandwiched active NP layer between the two electrodes; hence, holes from TCO and electrons from the other electrode recombine to emit light. Such a principle of work has been determined by employing quantum dots prepared by a solution-based process with precise control over size, doping, and composites. Attaching different ligands to the particle results in passivation, stabilization, and dispersion in different solvents. Hence, for LED-NP fabrication, QDs remain the first choice. Optimizing the band gap using Cd-free QDs is an area of much research and many promising results have been obtained (Alivisatos, 1996; Tan et al., 2007). The luminescence efficiency of QDs can be improved by modifying the surface with capping agents with the adsorption/emission wavelength shifted toward the blue. The blending of QDs with a hole and an electron conducting polymer sandwiched between the two electrodes demonstrated itself as an efficient LED (Colvin et al., 1994). This method was further modified by using hole-conducting and electron-conducting semiconductors and conducting polymers as host matrices (Dabbousi, Bawendi, Onitsuka, & Rubner, 1995; Li, Rizzo, Cingolani, & Gigli, 2006; Mattoussi et al., 1999). In order to obtain NPs of suitable size and properties, the surface of the QDs is chemically engineered to allow the NPs to be stable in physiological conditions. The surface of the QDs is also important to render the NPs biocompatible. QD-iron oxide has been used to detect and separate tumor cells.
2.1.3 Magnetic Metal-Based NPs
Magnetic NPs, if they are to be used in vivo for the purpose of delivering drugs and for real time monitoring, should be biocompatible to physiological pH, should have a surface chemistry to conjugate functional ligands to perform different functions, and should be nontoxic with the end product rapidly discharged from the body (Arruebo, Fernández-Pacheco, Ibarra, & Santamaría, 2007; Berry, 2005; Frullano & Meade, 2007; Riehemann et al., 2009). These NPs are directed by magnetic fields and can be used in combined therapy, for example, hyperthermia and cancer therapy (Ciofani, Riggio, Raffa, Menciassi, & Cuschieri, 2009). More specifically, iron oxide in the form of magnetite Fe3O4, g-Fe2O3, and MFe2O4, in which M can be Co, Zn, Ni, and iron-based alloys prepared by the coprecipitation method in an aqueous solution of salt in a basic medium, are important NPs for medical applications and therapeutics. Superparamagnetic iron oxide SPIONs have gained acceptance as contrast agents for magnetic resonance imaging (MRI) (Altavilla, 2011).
2.1.4 Metal-Based NPs as Sunscreens
The use of nano-sized ZnO and TiO2 NPs in cosmetics and sunscreens due to their uniform coverage has been indispensable in our lives. However, the health implications due penetration by topical use owing to the very small size of the NPs, has been completely ignored. When TiO2 absorbs light, the electron in the valence band can be promoted to the conduction band because of the small energy band gap as compared with the energy absorbed. This results in the migration of the electron to the surface of the particle, forming superoxide and hydroxyl radicals with O2 that damage DNA. This may be avoided by chemically attaching an anionic polymer to the surface of TiO2 (William & Raifailovich, 2011).
2.1.5 Metal-Based NPs in Virology and Bacteriology
In virology, metal NPs and their oxides (Au, Ag, ZnO, SPIONs, TiO2) have been used for combating HIV, hepatitis, and herpes simplex virus infection (Yadavalli & Shukla, 2017). Therapeutics for HIV, for example, have been closely followed by SPIONs and other metal NPs as drug delivery devices that use TAT protein for targeting receptor cells to block glycoprotein for the virus and prevent infection proliferation (Dodd et al., 2001; Lewin et al., 2000; Rao, Reddy, Horning, & Labhasetwar, 2008; Tkachenko et al., 2004). Similarly, a novel treatment to treat HIV can be accomplished through the use of SPIONs as MRI contrast agents loaded with antiretroviral drugs and guided to the specific location by a magnetic field (Gorantla et al., 2006). The treatment of cells infected with HIV using SPIONs, along with magnetic field heating to > 45°C, has been reported (Williams et al., 2013). An antiretroviral drug encapsulated into a SPION nano-carrier with a bilayer coating and guided by a magnetic field was investigated by Jayant et al. to treat neuroAIDs (Jayant et al., 2015). SPIONs can also deliver drugs across the blood-brain barrier (Fiandra et al., 2015). In order to protect the magnetic core from leaching, oxidation and reactions with acids or bases and functionalization with different stabilizers, such as disodium tartrate or polymers, is crucial. Because of their biocompatible nature and unique surface chemistry, SiO2 NPs have been used to detect hepatitis virus. They have also been used as fluorescent dyes functionalized with lanthanide chelates, such as Eu or Tb, to develop highly sensitive and time responsive immune-linked fluorescent assays (Xia, Xu, Zhao, & Li, 2009; Xu & Li, 2007; Yang, Zhang, Qu, Yang, & Xu, 2004). These NPs were tagged with antibodies to detect antigen hepatitis virus and showed more sensitivity than gold-standard AuNPs. Magnetic silica NPs have been used to detect hepatitis B virus and have been employed to kill hepatitis C virus by labeling with DNAzymes (Bae, Tan, & Hong, 2012). TiO2 has been used to inhibit avian influenza virus (H9N2) with a high inhibitory activity when the NPs are activated by UV light (Jiang, Cui, Yang, Cai, & Wu, 2009). Cu² +/TiO2 NPs, however, exhibit higher antiviral activity as compared with their counterpart (Haixin et al., 2010). Additionally, when TiO2 was tagged with DNA to target viral DNA (H3N2), it successfully inhibited the reproduction of the virus (Levina et al., 2014). Similar studies have shown the same with viruses H1N1 and H5N1 (Levina et al., 2015). NPs based on calcium compounds induce inactivation of the influenza virus (Knuschke et al., 2013; Thammakarn et al., 2014; Zhou, Moguche, Chiu, Murali-Krishna, & Baneyx, 2014). ZnO NPs with a tetrapod structure have been engaged to counteract HSV virus at different levels of treating and blocking by electrostatically attaching negatively charged NPs, thus acting simultaneously as virus trappers and blockers for viral activity (Antoine et al., 2012; Mishra et al., 2011; Yadavalli & Shukla, 2017).
NPs have wide applications for biomedical technology. NPs such as ZnO, CuO, TiO2, and Fe2O3 (Ismail, Sulaiman, Abdulrahman, & Marzoog, 2015; Jesline, John, Narayanan, Vani, & Murugan, 2015; Ren et al., 2009) have been widely used for their bactericidal and bacteriostatic properties due to the unique large surface-to-volume ratio. This allows a large number of ligands in the form of receptors, such as proteins and phospholipids, to bind to the surface of the pathogenic microbes by contributing to a cascade of events, including the disruption of the membrane or protein denaturation, induction of oxidative stress by ROS affecting the DNA, or by blocking the source of food (Cowan, 1999). The green synthesis of NPs by using plants, for example, renders them nontoxic, which is an important implication for in vivo targeted dosage administration through NPs as a drug delivery device, as well as being environmentally friendly and cheaper (Happy, Soumya, Venkat Kumar, & Rajeshkumar, 2018). Plants, fungi, and algae host a number of phytochemicals that act as both reductants and stabilizers against targeted multidrug-resistant bacterial genes that cause fatal bacterial infections and diseases (Agarwal, Venkat Kumar, & Rajeshkumar, 2017). These NPs are coated with important therapeutic biomolecules, such as amides, aldehydes, polysaccharides, organic acids, and quinone, that allow conjugation between the green NPs and the membrane of the bacteria (Yadav, Kumar, Budhwar, Yadav, & Yadav, 2016). NPs synthesized by greener methods demonstrate better antibacterial activity than those synthesized by physical or chemical methods (Shet, Ghose, Patil, Hombalimath, & College, 2015). ZnO has gained popularity due to its unique features, including being biocompatible with faster electron transfer rates and its activity against a broad spectrum of gram positive and gram negative bacteria having a peptidoglycan layer; nevertheless, (Huang, Wu, & Aronstam, 2010) functionalization of ZnO with maltodextrin increases the internalization of NPs into the bacteria by many fold.
2.1.6 Metal-Based NPs as Supercapacitors
The liquid-liquid extraction method was used to codisperse MnO2 NPs formed by reduction in n-butanol and MWCNT in the water/butanol phase by using Lauryl gallate (LG) as a dispersant (Wallar, Zhang, Shi, & Zhitomirsky, 2016). The LG works on the same principal as gallic acid and catecholates incorporating a larger group galloyl and a longer hydrophobic end that helps in steric dispersion. MnO2-MWCNT electrode material was used as a positive electrode for fabrication of asymmetric supercapacitors with carbon-carbon black as the negative electrode. In order to avoid agglomeration of NPs from solution due to the formation of oxo-bridges and hydroxides, it is imperative to mix the NPs with other materials, such as MWCNT, that also improve its conductivity. Hence, in the study, MnO2 NPs were codispersed with MWCNT by extracting it in n-butanol in the presence of LG as a dispersant. The LG interacts through its OH groups to MnO2, while the R group in LG, which comprises the hydrophobic part, is involved with the sidewalls of CNT, and codispersion is possible. The active mass for the electrode is impregnated on Ni-foam as a current collector and results in excellent supercapacitor performance of 8.0 F cm− 2 at a scan rate of 2 mV s− 1 with a high loading of active mass (Wallar et al., 2016).
More information about metal-based nanoparticles in Pharmaceutical Analysis can be obtained in Chapter 5, "Chemical Nanosensors in Pharmaceutical Analysis and Chapter 6,
Noble Metal Nanoparticles in Electrochemical Analysis of Drugs."
2.2 Carbon-Based Nanomaterials
Because of their versatile properties, such as extraordinary surface-to-volume ratio, electrical conductivity, biocompatibility, mechanical strength, and chemical stability, carbon- based materials, such as multiwalled carbon nanotubes, single-walled carbon nanotubes, single-walled carbon nanohorns, fullerenes, graphene, and chemically modified graphene (Erol et al., 2017; Kim, Jang, & Cha, 2017; Teradal & Jelinek, 2017; Zhang & Lieber, 2016), have been extensively used for sensing applications in environmental, biomedical, and energy applications for their enhanced sensitivity and low limit of detection (LOD) (Jariwala, Sangwan, Lauhon, Marks, & Hersam, 2013; Marmisollé & Azzaroni, 2016). The functionalization of carbon based nanomaterials for enhancement of their features is very appealing. Hence, impurities, surface functional groups, and active sites at the surface or edge plane are responsible for boosting the sensing and electrocatalytic activity of such materials (Fig. 2).
Fig. 2 Carbon nanomaterials, such as the fullerene C60, CNT, graphene, and nanodiamond, for advanced technological applications ( Zhai, Srikanth, Kong, & Zhou, 2017).
2.2.1 Carbon-Based Nanomaterials as Gas Sensors
Field effect transistors (FETs) based on CNT quantum wires have been synthesized by the CVD method. They behave as semiconductors in which doped molecules cause an appreciable change in the electrical properties of the CNTs near the surface. These CNTs have been used to sense gases (Tans et al., 1997; Tans, Verschueren, & Dekker, 1998). Hence, an oxidizing gas (NO2) or a reducing gas (NH3) can either decrease or increase the conduction of SWCNTs in FETs (Kong et al., 2000). The presence of oxygen modifies the electrical conductivity of CNTs (Collins, Bradley, Ishigami, & Zettl, 2000), while the conductivity of SWNTs may change from p-type to n-type in the presence of minute quantities of H2O in an ambient atmosphere (Fujiwara et al., 2001; Zahab, Spina, Poncharal, & Marlière, 2000). These important greenhouse gases have been studied, lending importance to environmental considerations. The modification of the CNT sidewalls can totally change the behavior of the conductivity to an insulating one; hence, a noncovalent modification to keep the electronic structure of the CNTs intact is preferred (Fujiwara et al., 2001), for example, coating the SWCNTs with Pd to sense hydrogen, thus making the interaction highly specific for the target molecule, which pristine SWCNT could not detect directly (Kong, Chapline, & Dai, 2001). Furthermore, SWCNTs with PEI (polyethylenimine) can change the SWCNT-FET from a p-type to an n-type upon functionalization to detect oxygen (Shim, Javey, Shi Kam, & Dai, 2001).
Other sensing techniques employing different principles than a FET with CNTs have also been used. Examples of sensors that have been employed to detect different gases include using a thermoelectric chemical response to sense changes in thermoelectric power (Adu, Sumanasekera, Pradhan, Romero, & Eklund, 2001; Sumanasekera et al., 2002), using a change in dielectric constant (Chopra, McGuire, Gothard, Rao, & Pham, 2003), and using a change in resonance frequency by developing sensors based on surface acoustic waves (Penza, Antolini, & Antisari, 2004). SWCNTs have also been used as mechanical sensors based on the shift of strain from the matrix to the D-Raman band of SWCNTs to measure the stress field of a polymer matrix embedded as a glass fiber (Zhao, Frogley Mark, & Wagner, 2003). Different researchers have used enzymes, such as glucose oxidase or horseradish peroxidase, immobilized on SWCNTs to enhance the catalytic signals to sense analytes (Azamian, Davis, Coleman, Bagshaw, & Green, 2002; Sotiropoulou, Gavalas, Vamvakaki, & Chaniotakis, 2003; Zhao et al., 2003). Most of the sensing devices that are based on nanowires other than CNTs, such as SnO2, Mo, Pd, and In2O3 nanowires, work on the principle of a FET that measures changes in the conductance over the gate and bias potential to detect gases (Li et al., 2003; Walter et al., 2002; Walter, Ng, Zach, Penner, & Favier, 2002; Wang, Jiang, & Xia, 2003).
2.2.2 Carbon-Based Nanomaterials as Electrochemical Sensors and in Fluorescence Quenching
Functionalized CNTs can be tuned for the delivery of therapeutic agents, such as proteins, peptides, and drugs, and are best suited for pharmaceutical and medical applications (Maduraiveeran, Sasidharan, & Ganesan, 2018). For example, Nb-coated CNTs have been found to electrochemically sense dopamine. CNT-Nb sensors showed higher sensitivity than ones based on pristine CNTs. The ascorbic acid in a rat brain has been measured by using aligned CNT fiber (CNF) as a simple high-performance biosensor (Yang et al., 2016).
Graphene consists of a hexagonal geometry with a 2D carbon network, which displays excellent sensitivity and selectivity, durability, a potential window of wide range, good mechanical strength, and outstanding electronic properties (Yu, Zhang, Zhang, & Su, 2017). Many biomedical applications of graphene and its different forms (GO, rGO, GNR), as well as novel graphene-like materials, have been explored (Wang et al., 2017; Zhang & Chen, 2017; Zhu, Du, & Lin, 2017). For example, rGO has been used to detect acetaminophen in body fluids and pharmaceutical formulations. The defects due to O2 vacancies create superb properties, leading to a rapid response with high sensitivity (Adhikari, Govindhan, & Chen, 2015). Graphene, along with metal NPs, such as AuNP/rGO, have been employed to form a nanocomposite for NADH sensing, displaying the excellent electrocatalytic activity of NADH at pH 7 (Govindhan, Amiri, & Chen, 2015). 3D porous graphene is used as a support for immobilizing enzymes to sense various biomolecules functionalized with different metal NPs, such as Fe3O4, Co3O4, and NiO, to explore peroxidase activity (Maduraiveeran et al., 2018; Wang, Zhang, Huang, Zhang, & Dong, 2017).
Electrochemical sensors are compact simple sensing devices and depend on the redox potential for detection. Thus, selectivity toward HMs can be accomplished on bare electrodes; however, the sensitivity is improved by using different recognition layers, especially an electrode modified with NPs. Several techniques have been used, such as voltammetry, amperometry, and potentiometry, among which anodic stripping voltammetry (ASV) has a high rate of success for HM detection (Gao, Wei, Yang, Yin, & Wang, 2005; Tarley, Santos, Baêta, Pereira, & Kubota, 2009; Wang, Lu, Hocevar, Farias, & Ogorevc, 2000). An electrode modified with NPs can overcome the required large overpotential, a high stripping potential required for analytes, and the interference of other metals and supporting electrolyte ions. Due to high surface area and a faster electron transfer rate, low S/N ratio studies on NP-modified electrodes have sped up (Aragay & Merkoçi, 2012; de la Escosura-Muñiz, Ambrosi, & Merkoçi, 2008). Electrodes modified with NPs, such as graphene, CNTs, and CNFs, have been extensively explored for sensing HMs (Chen et al., 2012; Wanekaya, 2011).
CNT-modified electrodes have been constructed to detect Cd² + and Pb² + in HCl solution by SWASV, as CNTs are an excellent sorbent of metal ions (Bui, Li, Han, Pham, & Seong, 2012; Musameh, Hickey, & Kyratzis, 2011). The functionalization of hydrophobic CNTs with functional groups to make them hydrophilic changes their affinity to HMs. GCEs modified with CNT/thiacalixarene to detect trace levels of Pb² + ions have been studied (Wang, Wang, Shi, Peng, & Ding, 2012). Thiacalixarene made it possible to selectively detect Pb² + ions while the CNTs improved the electron transfer kinetics. Similarly, cysteine-modified CNTs on GCE were studied to detect Pb² + and Cu² + ions (Morton, Havens, Mugweru, & Wanekaya Adam, 2009).
2.2.3 Carbon Nanomaterials as High-Performance Energy Storage Devices
The use of nonrenewable and unsustainable fossil fuel has caused a global concern that demands replacing it with renewable and clean energy sources, which include lithium ion batteries (LIBs), supercapacitors (SCs), and hydrogen storage. Furthermore, toxic gas emission, GHG, metal ions and other organic species from industry and the agriculture sector have caused severe environmental pollution that has led to ecological unbalance (Holdren, 2007; Winter & Brodd, 2004).
With the advancement of technology, and in order to respond to the ever increasing challenge of replacing traditional energy storage and conversion devices, supercapacitors have emerged as promising high-performance energy sources owing to their high energy and power density. Because a surface phenomenon is employed in SCs, carbon electrodes with large surface areas have been used. Limited capacitance because of low accessibility of the electrolyte due to pore size, together with the poor conductivity of activated carbon, translates to limited energy density and power density for capacitors (Frackowiak & Béguin, 2001). Hence, the search for new materials in the domain of nanomaterials has been hotly pursued. Thus, CNTs and graphene have been extensively investigated as active electrodes for SCs due to high SA, mesoporosity and electrolyte accessibility, and good conductivity (Dai, Chang Dong, Baek, & Lu, 2012; Geim & Novoselov, 2007; Zhang, Zhou, & Zhao, 2010). Because of the rich chemistry of CNTs and graphene, numerous strategies could be adopted to functionalize the structures to develop high-performance SCs. Supercapacitors with a high specific capacitance of 180 F g− 1 have been developed by using random SWNTs in KOH electrolyte with energy and power density of 10 W h kg− 1 and 20 kW kg− 1 (An et al., 2001), while entangled MWCNTs in H2SO4 have resulted in a specific capacitance of 102 F g− 1 with very small energy and power densities of 1 W h kg− 1 and > 8 kW kg− 1 (Niu, Sichel, Hoch, Moy, & Tennent, 1997), which resulted from a significant decrease in SA. Vertically aligned CNTs (VACNTs) with well-defined tube spacing have demonstrated superior performance compared with randomly entangled MWCNTs for charging/discharging processes (Futaba et al., 2006). Furthermore, to access the inner cavities of VACNTs, plasma etching can be used to open the end tips at the top of the VACNTs for access to electrolyte that would otherwise be inaccessible (Lu, Qu, Henry, & Dai, 2009). These VACNTs have improved energy density and power density of 148 W h kg− 1 and 315 kW kg− 1, respectively (Chen et al., 2010; Dai et al., 2003; Qu & Dai, 2007). High specific capacitances of 365 and 440 F g− 1 in H2SO4 and ionic liquid have been demonstrated by VACNTs prepared by CVD (Chen et al., 2004; Zhang, Cao, Yang, & Gu, 2008). Further improvements can be accomplished by functionalizing VACNTs with conductive polymer or metal oxide nanoparticle, such as MnO2, TiO2, or RuO2, which introduce pseudocapacitance to store charge (Hou, Cheng, Hobson, & Liu, 2010; Hu et al., 2012; Huang, Lou, & Chen, 2012; Kim, Tadai, & Mitani, 2005; Wang, Wen, & Li, 2006). The high contact resistance between the CNT active electrode and the current collector, the inefficiency of electrolyte interaction, and the difficulty of scaling up VACNT production for commercialization, has resulted in lower performance than expected (Van Noorden, 2011). However, GO formed from exfoliation of graphite powder by solution oxidation and edge functionalized graphene (EFG) prepared using a ball mill have allowed for mass production of graphene for commercial use of SCs (Jeon et al., 2012, 2013; Park & Ruoff,
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