Plant mediated green synthesis of metallic nanoparticles

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Plant mediated green synthesis of metallic nanoparticles: challenges and opportunities

6

Umesh K. Parida1, Subash Das2, Padan K. Jena3, Niranjan Rout4 and Birendra K. Bindhani1 1

School of Biotechnology, KIIT University, Bhubaneswar, Odisha, India 2Formulation and Development Product Unit, Kemwell Biopharma Pvt Ltd, Bangalore, India 3Department of Botany, Ravenshaw University, Cuttack, Odisha, India 4Department of Onco-Pathology, A. H. Regional Cancer Centre, Cuttack, Odisha, India

6.1 INTRODUCTION Nanotechnology is one of the significant fields of present research including the synthesis, design, and exploitation of particle configurations ranging from about 1 to 100 nm (Florence and Konstantin 2010; Kumar, 2010). Nanotechnology is significant in different areas, such as cosmetics, environmental health, health care, food and feed, biomedical sciences, space industries, mechanics, energy science, reprography, optics, chemical industries, light emitters, electronics, nonlinear optical devices, optoelectronics, drug gene delivery, catalysis, single electron transistors, and photoelectrochemical applications (Figure 6.1) (Gao et al., 2004; Ferrari, 2005; McClelland et al., 2004; Sahoo et al., 2007; Kim et al., 2007; Zandparsa, 2014; Vaddiraju et al., 2010; Chellaram et al., 2014). There are two most important nanoparticles (gold and silver) that have been used in various fields due to their distinctive properties (i.e., size and shape, depending on optical, electrical, and magnetic properties). They basically act as biosensor materials, antimicrobial applications, cryogenic superconducting materials, composite fibers, electronic components, and cosmetic products (Ngo et al., 2011; Krystek, 2012; Bankura et al., 2012; Renato et al., 2015). Synthesis and stabilizing of silver and gold nanoparticles are generally done either by chemical or physical methods (Figure 6.2) (Hubenthal, 2011; Biswal et al., 2011; Srivastava and Kotov, 2011; Ngo et al., 2011). Generally gold and silver nanoparticles are chemically generated by reduction of gold and silver precursors using organic and inorganic reducing agents (Sinha et al., 2014; Ai-xia et al., 2012; Pal et al., 2013). Fabrication and Self-Assembly of Nanobiomaterials. DOI: http://dx.doi.org/10.1016/B978-0-323-41533-0.00006-4 © 2016 Elsevier Inc. All rights reserved.

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FIGURE 6.1 Applications of nanotechnology.

FIGURE 6.2 Synthesis of gold and silver nanoparticles by different methods.

Presently, researchers are more interested in adopting newly developed green synthesis methods due to their nontoxic features, as they are eco-friendly, nonexpensive, and have better particle sizes, morphology, quality, quantity, distribution, and purity (Chandran et al., 2006; Kumar and Yadav, 2009; Narayanan and Sakthivel, 2008).

6.2 Scopes

This review approaches the preparation of gold and silver nanoparticles by employing green synthesis techniques instead of chemical and physical methods. This study will provide valuable information for the preparation and characterization of silver and gold nanoparticles and its present and future prospects and prospective constraints of techniques in industry. In addition, we have particularly emphasized the role of silver and gold nanoparticles with other materials and their biomedical applications.

6.2 SCOPES Productions of different types of inorganic and metal-based nanoparticles with unique properties have tremendous applications in various environmental-related issues and human health safety, etc. Presently, all over the world, researchers have given emphasis to the synthesis of metallic nanoparticles (MNPs) by green chemistry methods because of its natural reducing, capping and stabilization with particular size and morphology. Generally, this chapter focuses on the synthesis of silver and gold nanoparticles by different types of biological methods without the use of any type of toxic or chemical materials, instead of employing any other methods. The extraction of certain organisms such as enzymes/proteins, amino acids, polysaccharides, and vitamins is found in bioreduction of metal ions with combinations of various types of biomolecules which are environmentally benign, yet chemically complex (Figure 6.3). The main advantages of green synthesis of

FIGURE 6.3 Synthesis of metallic nanoparticles using plant biomolecules.

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Ecofriendly

Non-toxic sis nthe using sy

Natural reducing agent

nt pla

Gree n

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Natural capping agent

Stabilizing agents

Not expensive

FIGURE 6.4 Advantages of plant-mediated green synthesis of gold and silver nanoparticles.

gold and silver nanoparticles are that it is nontoxic, biocompatible, stable, ecofriendly, etc. (Figure 6.4).

6.3 RECENT RESEARCH BACKGROUND OF GREEN SYNTHESIS OF SILVER AND GOLD NANOPARTICLES USING PLANT EXTRACTS MNPs, such as silver and gold, have been studied for more than 150 years. It is unlikely that MNPs will put together into high-performance logic circuits as a planar channel material within the next decade. Figure 6.5 illustrates the annual number of articles published in refereed journals containing different “green gold and silver nanoparticles” as key words. The recent dramatic growth of publications in gold and silver is remarkable with more than 1000 papers published in 2013 (B3 papers/day).

6.4 HISTORY OF MNPs (METALLIC NANOPARTICLES) 6.4.1 GNPs (GOLD NANOPARTICLES) Gold is one of the exceptional metallic elements and has a melting point of 1064  C and a boiling point of 2808  C. Several properties of gold, such as its

6.4 History of MNPs (Metallic Nanoparticles)

FIGURE 6.5 History: total annual number of publications and of scientific publications on gold and silver nanoparticles (www.scopus.com and www.sciencedirect.com).

exceptional conductive properties and its incapability to react with water or oxygen, have made it very helpful to mankind over time. During the fifth millennium BC, the extraction of gold started near Varna (Bulgaria) and it is believed that “soluble” gold become visible about the fifth or fourth centuries BC in Egypt and China. The marvelous statue of Touthankamon, which was constructed around that time, stands as proof. It was referred to with different names, such as soluble gold and drinkable gold, before the term “colloid” (from the French word, colle) was coined by Graham in 1861. Colloidal gold and its beautiful ruby-red color have fascinated people for many centuries, and can be traced back to ancient times (Graham, 1861; Hough et al., 2011; Marie-Christine and Didier, 2004). It was used extensively for cosmetic, decorative as well as for medicinal purposes (Kunckels, 1976; Savage, 1975). In the Middle Ages, “aurum potabile” or “drinkable gold” was used for the treatment of various types of diseases, such as heart problems, arthritis, dysentery, tumors, venereal diseases, and epilepsy and it was also used for the diagnosis of syphilis, a method which remained in use until the twentieth century (Kahn, 1928; Hauser, 1952; Anil et al., 2013).

6.4.2 AgNPs (SILVER NANOPARTICLES) In the time of the Roman Empire, AgNPs were used by glass founders, to create Lycurgus cup (fourth century AD), which is now in the British Museum. In the late twentieth century, the presence of MNP composition in 15 bronze-mounted insets of stained glass was found with an average diameter of 40 nm, 70% silver and 30% gold, respectively (Barber and Freestone, 1990; Lee and Meisel, 1982;

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Henglein, 1999; Nagy and Mestl, 1999). This is the remarkable explanation for the features of this bowl that allow it to alter its color from red in transmitted light to grayish green in reflected light. Silver nanoparticles (SNPs) were used as extremely isolated supports used for attractive signals in the Raman spectroscopy from organic molecules for scientific and practical interest before the 1980s (Frattini, 2005). It shows that SNPs reveal an exceptional arrangement of high electrical double-layer capacitance, welldeveloped surfaces, unique optical properties associated with the surface plasmon resonance (SPR), catalytic activity, etc. in the last three decades (Henglein, 1999). Therefore, these materials provided for the development of the latest inventions of electronics, optical and sensor devices. At present, the synthesis properties of SNPs are one of the most vigorously upward trends in colloid chemistry and the constant generous increase in scientific publications due to the renovation of technological processes in the last 20 years. Generally, silver is employed as a catalyst for the oxidation of methanol to formaldehyde and ethylene to ethylene oxide (Nagy and Mestl, 1999). The unique properties of colloidal silver are antibacterial activity, good conductivity, and catalytic and chemical stability (Frattini, 2005). For example, silver colloids are useful substrates for surface-enhanced spectroscopy, since it partly requires an electrically conducting surface (Tessier et al., 2000; Rosi and Mirkin, 2005).

6.5 PROPERTIES OF SILVER AND GOLD NANOPARTICLES Generally, nanoparticles are nanometer in scale in three dimensions. Nanoparticles are exhibited in different shapes, such as ellipsoidal, rod-shaped, spherical, triangular, cubical, shells, pentagonal, etc. Different complex nanostructures, such as nanowires, nanoclusters, nanoaggregates, and nanochains are created using nanoparticles which have a broad range of applications. Silver and gold nanoparticles are used to improve quantum efficiency in organic lightemitting diodes and electroluminescence (Park et al., 2004), platinum nanoparticles and palladium are used as proficient catalysts (Narayanan and El-Sayed, 2005), and glucose sensors are developed based on SNPs (Aslan et al., 2004; Riviere et al., 2005). Nanoparticles are minute and have a number of constituent atoms or molecules which vary from the properties inherent in their bulk counterparts. However, they cannot be treated as an isolated group of atoms or molecules due to them being constituents of a high number of atoms or molecules (Figure 6.6). Therefore, nanoparticles show various chemical, optical, electronic, and magnetic properties, which are extremely dissimilar from both the bulk and the constituent atoms or molecules (Eustis and El-Sayed, 2006; Daniel and Astruc, 2004). Furthermore, the optical properties of nanoparticles depend considerably on their

6.5 Properties of Silver and Gold Nanoparticles

FIGURE 6.6 Nanoparticles in comparison with other biological entities.

size and shape, as well as on the dielectric constant of the surrounding medium (Berciaud et al., 2005; Neeleshwar et al., 2005; Masumoto and Sonobe, 1997). SNPs appear blue and of triangular, pentagonal, and spherical shapes and they show green and red, respectively, in a dark-field microscope, which suggests that there is a strong correlation between the optical property and shape of the nanoparticles (Mock et al., 2002). Gold nanorods show more diverse optical properties than their spherical counterparts. The wavelength of the longitudinal plasmon mode increases with increasing aspect ratio of the nanorods due to the different transverse plasmon mode (Eustis and El-Sayed, 2005). In addition, GNPs are dissolved in diverse solvents, which show different wavelengths by plasmon absorption due to the effect of the surrounding media (Huang, 2002). Nanoparticles are very minute, ranging in size from 1 to 500 nm, which is much smaller than human cells, which are about 10 20 µm (Figure 6.6). However, the sizes of nanoparticles are similar to biomolecules in the cellular level. This leads to the development of nanosensors/nanodevices which can move into cells to probe proteins or DNA, either outside or inside of the cell. As a result, it produces hybrid nanoparticles: Nanoparticles labeled with molecules in the first step by the involvement of developing nanodevices/nanosensors which may target or investigate the specific cellular entities. By the application of a biological field, a plethora of hybrid nanoparticles labeled with peptides and proteins have been produced (Katz and Willner, 2004a,b; Niemeyer, 2001; Pellegrino et al., 2005). Furthermore, the specific role of gold hybrid nanoparticles has emerged in biomedical applications due to their stimulating chemical and optical properties along with their biocompatibility, dimensions, and ease of characterization. These properties are discussed in the following section.

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6.6 GREEN SYNTHESIS OF GOLD AND SILVER NANOPARTICLES Recently, researchers all over the world have successfully carried out green synthesis of silver and gold nanoparticles of desired size and morphology by green chemistry methods utilizing natural reducing, capping, and stabilizing agents. These biological methods for synthesis of silver and gold nanoparticles are widely used due to their nontoxic, inexpensive, eco-friendly features (Feng et al., 2000; Jha and Prasad, 2010; Mohanpuria Rana and Yadav, 2007). The extractions of certain organisms, such as enzymes/proteins, amino acids, polysaccharides, and vitamins are found in bioreduction of metal ions with combinations of various types of biomolecules which are environmentally benign, yet chemically complex. However, successful synthesis of silver and gold nanoparticles has already been reported by different researchers using microorganisms, biological systems, and extraction of plant products (Figure 6.7) (Hulkoti and Taranath, 2014; Otari et al., 2014; Begum et al., 2009; Shankar et al., 2005; Singh et al., 2010).

6.7 MECHANISM OF GREEN SYNTHESIS OF GOLD AND SILVER NANOPARTICLES The mechanism of green synthesis of gold and silver nanoparticles is due to the presence of polyphenol in plant extracts which is responsible for reduction of nanoparticles. The molecular mechanism which gives the antioxidant properties of gold and silver nanoparticles endorses reduction of Au1 ions to Au atoms and Ag1 ions to Ag atoms (Figure 6.8). This reduction takes place by abstraction of hydrogen because of the OH groups in the polyphenol

FIGURE 6.7 Green synthesis of gold and silver nanoparticles.

6.8 Experimental Procedures Involved in the Synthesis of Gold

FIGURE 6.8 Mechanism of green synthesis of gold and silver nanoparticles.

molecules. The reducing agents and stabilizing effects for silver and gold nanoparticles are allowed due to the antioxidant activity of such molecular mechanisms. The synthesis of such silver and gold nanoparticles has been carried out using different biological systems (Płaza et al., 2014; Makarov et al., 2014; Baker et al., 2013; Nath and Banerjee, 2013).

6.8 EXPERIMENTAL PROCEDURES INVOLVED IN THE SYNTHESIS OF GOLD AND SILVER NANOPARTICLES USING PLANT EXTRACTS The synthesis of gold and silver nanoparticles has been started experimentally by many workers using different plant extracts (Salunke et al., 2014; Khan et al., 2014; Krishnaraj et al., 2014; Nagaraj et al., 2014; Mervat and Wael, 2014; Muthuvel et al., 2014; Parida et al., 2014a,b,c; Bindhani et al., 2013; Ganesh Kumar et al., 2011). A number of experiments were executed using different medicinal plants for synthesis of gold and silver nanoparticles. The gold (Au) nanoparticles show varying shapes and sizes in different ratios of metal salt as well as extraction in the reaction medium. Generally, nanoparticles are characterized by different techniques such as UV-vis spectroscopy, photoluminescence, transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) spectroscopy (Fayaz et al., 2011; Ponarulselvam et al., 2012; Das et al., 2011; Noruzi et al., 2012; Zahir and Rahuman, 2012; Hashemabadi et al., 2014).

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6.8.1 UV SPECTROMETRY ANALYSIS The UV-vis spectrometry has been used to observe the shape and size of the nanoparticles in aqueous suspensions. For SNPs, the absorption spectrum was produced at different time intervals, which reveals nanoparticles produced within 1 h of the silver ions when it contacts biomolecules. The changes of color were observed from colorless to brown just after the addition of the plant extract to the solution of silver nitrate within 1 h. The sharp absorbance of SNPs was observed between 400 and 500 nm, with increasing reaction time by UV-vis spectrum (Mittal et al., 2013). Similarly, the changes of color were observed on GNPs after reduction of gold ions to GNPs on contact with the plant extract. The SPR band at about 500 600 nm after 2 min of reactions was observed at different time intervals for the reaction with aqueous chloroauric acid solution in UV-vis spectra (MubarakAli et al., 2011).

6.8.2 FT-IR (FOURIER TRANSFORM INFRARED SPECTROSCOPY) FT-IR was used to observe the size distribution and characterization of gold and silver nanoparticles by green synthesis methods. It was observed that for changes in the COOH group for OH and the peak intensity also reduced for the C of the carboxylic group after the encapsulation of nanoparticles. H bonds can be formed between the amide groups. As the plant molecules became adsorbed onto the surface of the green-synthesized SNPs, the amide groups tended to form stronger bonds with the silver and gold atoms, breaking most of the H bonds between the N H groups and leading to narrowing and blue shifts in the amide bond. C N stretching of the amine group, and in the raw extract, the peak was broad and blends, but after encapsulation of nanoparticles, this peak was narrow and sharper. This implies that the COOH group in the compound was attached to the GNPs and there is a clear change in the spectra (Chidambaram et al., 2013; Schrofel et al., 2014).

6.8.3 XRD (X-RAY DIFFRACTION) The XRD pattern of the AgNPs and AuNPs synthesized via plant extract was compared and interpreted using standard data. The major peaks at 2θ values correspond to the reflections from the (111), (200), (220), and (311) planes, respectively, and confirm the crystalline phase of the AgNPs and AuNPs. The polycrystalline nature of extract-synthesized AgNPs and AuNPs can be inferred from the fact that the XRD data suggest smaller crystallite sizes than the particle sizes observed in TEM images (Nair et al., 2010).

6.8.4 TEM (TRANSMISSION ELECTRON MICROSCOPY) TEM analysis confirms the approximate shape, nanogram, and diameter (,100 nm) after the bioreduction of green synthesis of gold and silver nanoparticles after 24 h. The shapes of some nanoparticles were roughly circular with smooth edges and

6.9 Biomedical Applications of Gold and Silver MNPs

anisotropic structures with irregular contours. The TEM images of most of the SNPs are in close physical contact, being separated by a quite uniform interparticle distance. In the same way, synthesized GNP size and morphology were determined. The shapes of the particles produced were hexagonal, spherical, triangular, and some were nanotriangles which were formed by being monodispersed with a large surface area. The formation of spherical nanoparticles was due to the capping agents of biomolecules rather than the formation of triangular or hexagonal nanostructures. TEM images with high magnification showed predominantly hexagonal, triangular, and circular biologically synthesized GNPs. TEM images also confirmed a large quantity of circular GNPs with thin smooth ends on the exterior part of the nanoparticles (Philip et al., 2011; Mondal et al., 2011).

6.9 BIOMEDICAL APPLICATIONS OF GOLD AND SILVER MNPs MNPs have several promising applications in the biological field (Figure 6.9) (Ge et al., 2014). MNPs are particularly promising in biological applications because of their unique properties including: their optic, conductivity and catalytic properties and their biocompatibility, high surface-to-volume ratio and density (Majdalawieh et al., 2014; Poulose et al., 2014; Boote et al., 2014). Compared to colloidal MNPs traditionally used for biological applications, NPs have the advantages of ease of synthesis, colloidal stability, and the ability to be easily conjugated with biological molecules. In addition, the optical properties of MNPs allow them to be visualized using several methods, and there is little evidence of MNP corrosion. MNPs, which include gold and silver, have recognized importance in chemistry, physics, and biology because of their unique optical, electrical, and photothermal properties. Lastly, MNPs are inert, which enhances

FIGURE 6.9 Applications of gold and silver nanoparticles.

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their biocompatibility, which is vital in most biological applications (Ong et al., 2013; Yu et al., 2013; Sweet et al., 2012).

6.9.1 GENE DELIVERY Gene delivery techniques which is generally begin a gene of curiosity in order to articulate its encoded protein in a appropriate host or host cell (Hui and Danke, 2014; Ravindran et al., 2013; Zain et al., 2014; Kozielski et al., 2013; Farkhani et al., 2014). There are various types of gene delivery, however there are three important types: nucleic acid transfection, nucleic acid electroporation, and viral vectors (retroviruses and adenoviruses). In the case of viral vectors gene delivery, it is highly efficient (80 90%) but may possibly introduce viral vector nucleic acid sequences into the host genome and causing undesirable effects, for example, the unsuitable appearance of deleterious genes. Therefore, such methods are comparatively more secure in medical applications after improvements in their efficiency (Martin-Ortigosa et al., 2014; Karuppaiya et al., 2013; Torney et al., 2007). Different types of nanoparticles have been used in basic research, particularly in cultured cells to increase the transfection efficiencies. As a result, complex nanoparticles and nucleic acid are supplemented first in cell culture media and then onto the cell surface by the application of magnetic force (Figure 6.10). On the other hand, biomedical applications are very limited in both in vivo and in vitro conditions due to the high toxicity of these nanoparticles to the cells (You-yu et al., 2014). Therefore, nanoparticles are coated with compounds, such as natural polymers (proteins and carbohydrates) (Nair et al., 2010), synthetic organic polymers (polyethylene glycol), polyvinyl alcohol, poly-L-lactic acid,

FIGURE 6.10 MNPs gene delivery system. Plasmids are bound to MNPs, which then move from the media to the cell surface by applying a magnetic force.

6.9 Biomedical Applications of Gold and Silver MNPs

silica (Nitin et al., 2004; Ito et al., 2005; de Temino et al., 2005; Donald and Watkin, 2006; Mertz et al., 2005; Mikhaylova et al., 2004; Qiu and Winnik, 2000; Yiu et al., 2001; Ameur et al., 2000; Arsianti et al., 2011; Williams et al., 2006). However, surface modification of nanoparticles is very important before any biomedical applications. The development of new nonviral methods to facilitate high transfection efficiency is strongly desirable. In recent years, MNPs have been used in alternative approaches to gene transfection (Cai et al., 2007; Noh et al., 2007; Swami et al., 2007; Prow et al., 2006; Rosi et al., 2006). Cationic gold and silica nanoparticles have been used for efficient transfection of 293T and COS-1 cells. Prow et al. (2006) and Thomas and Klibanov (2003) used GNPs, semiconductor nanocrystals, and magnetic nanoparticles that were modified with biotin-labeled transcriptionally active PCR products for gene transfection. Sandhu et al. (2002) reported gene transfection using GNPs modified with N,N,N-trimethyl (11-mercaptoundecyl) ammonium chloride and alkylthiol with several chain lengths. It is reported in the preparation of GNPs coated with 2-aminoethanethiol and their application in gene transfection (Kneuer et al., 2000; Niidome et al., 2004).

6.9.2 DRUG DELIVERY There are two types of drug delivery: conventional and targeted drug delivery. Targeted drug delivery is more suitable than conventional drug delivery as drugs are targeted mainly at the particular affected area and drugs are delivered locally so minimizing any side effects. Most important is that the efficiency improvements in development of anticancer agents where side effects caused by conventional drugs are minimized. A great deal of work has been carried out by different scientists through the synthesis of both gold and silver nanoparticles for targeted drug delivery (Figure 6.11) (Anandhakumar et al., 2012; Yan and Chen, 2014; Anil et al., 2013). MNPs are suitable for therapy and bioimaging of affected cancerous cells. MNPs are important for an effective drug delivery system or drug therapy due to its distinctive chemical and physical properties with strong binding attraction for

FIGURE 6.11 MNPs targeted drug delivery.

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carboxylic acid aptamers, proteins, thiols, and disulfides. Therefore, they have been used widely for cancer therapy in the field of biosciences. The three main pathways of MNPs for cellular uptake are phagocytosis, fluid phase endocytosis, and receptor-mediated endocytosis (Anil et al., 2013; Lori et al., 2012; Ghosh et al., 2008). MNP toxicity depends on the surface coating, synthesis method, size, shape, surface charge, and functionalized molecules, but generally MNP cytotoxicity is at an acceptable level when nanoparticles are measured to be nontoxic agents. Both drug release and transport are very important for an efficient drug delivery system. Loading of drugs on nanocarriers was done either by covalent conjugation or noncovalent interaction through the help of pro-drug, which is treated by the cell. MNPs include functional flexibility because of their monolayers so they provide an efficient system (Ajnai et al., 2014).

6.9.3 X-RAY IMAGING MNPs are simply produced into a variety of shapes and sizes with flexible functionalities (Jadzinsky et al., 2007; Dykmana and Khlebtsov, 2012; Tiwari et al., 2011). However, disparity improvement with a reduction in the shape and size of the nanoparticles was studied by X-ray imaging (Jackson et al., 2011). Different practical biosensing applications of MNPs include for cancers (Sokolov et al., 2003; Lee et al., 2008) as a biocompatible imaging agent (Shukla et al., 2005). MNPs are successfully accumulated in organs when they are injected intravenously. An application of Au probably helps to demonstrate the early diagnosis and medical treatment of vascular diseases. The MNPs provide unlimited imaging time along with high contrast and they are very much applicable for biomedical applications such as assessment of atherosclerotic plaques/stenoses, determination of vascularity, noninvasive imaging of blood flows in coronary and cerebral arteries, enhancement of mammography/renal angiography/virtual colonoscopy, and delineation of stroke/arteriovenous malformations/aneurysms. The noninvasive detection of small tumors (e.g., ,1 cm) needs enhanced contrast for superior prognosis which was enabled by existing accessible techniques (Hwu et al., 2004). The invasiveness is closely related to tumor vascularity (Hainfeld et al., 2006), as a result, noninvasive staging is possible to make vascularity indices (Figure 6.12). MNPs can be capable of also differentiating greatly vascularized vulnerable plaques from stable plaques.

6.9.4 BIOSENSOR APPLICATIONS Nobel nanoparticles are important in the field of nanotechnology, which plays a major role in the improvement of innovative biosensing techniques to accomplish the requirement for further precise and extremely sensitive biomolecular diagnostics. A wide variety of biosensors can be developed through the distinctive physiological properties of metals at the nanoscale level which are as follows: (i) other

6.9 Biomedical Applications of Gold and Silver MNPs

FIGURE 6.12 X-ray computed tomography volume-rendered images. (a) Mouse without GNPs. (b) Mouse with nontargeted GNPs. (c) Mouse with targeted GNPs.

nanotechnology-based tools that benefit scientific research on basic biology and (ii) nanobiosensors for point-of-care disease diagnosis and nanoprobes for in vivo sensing/imaging, cell tracking, and monitoring disease pathogenesis or therapy monitoring (Jain, 2007, 2008; Zhao et al., 2011; Conde et al., 2012; Baptista et al., 2011). In fact, nanotechnology-based applications for improved biosensors are the most common due to its high surface areas, physiochemical malleability, and simplicity (Azzazy and Mansour, 2009). It can be measured within the range 1 100 nm in diameter, a variety of shapes and is composed of one or more inorganic compounds. Among the most widely studied nanomaterials, gold is one of the noble nanoparticles developed through innumerous methods for therapeutics, imaging, drug delivery, and molecular diagnostics (Figure 6.13). The most exclusive physiological properties at the nanoscale is localized surface plasmon resonance, which has been explored for the improvement of novel biosensors (Conde et al., 2012; Baptista et al., 2008, 2011).

6.9.5 ENZYME IMMOBILIZATION The immobilization process has been used in aqueous media for enhancing enzyme activity and stability (Fernandez-Lafuente, 2009) and also in nonaqueous media (de Temino et al., 2005; Wang et al., 2007; Iyer and Ananthanarayan, 2008). In biotechnological processes, the enzyme immobilization paying attention for their low cost of industrial applications, high operational stability, durability and easy separation of products (Mateo et al., 2007). A number of extensive varieties of immobilization techniques can be used for covalent attachment (Hamerska-Dudra et al., 2006; Lopez-Callego et al., 2007) and adsorption on solid supports (Alonso et al., 2005; Kondo et al., 1993). It may lead to the leaching of the enzyme with conformational changes

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FIGURE 6.13 Biosensor applications of MNPs.

(Kim et al., 2006; Zhao et al., 2010). Infrequently, at the cost of the partial inactivation, covalent attachment leads to better enzyme stability because of the conformational changes induced by the covalent bonding of the enzyme residues to the matrix (Ma et al., 2009). However, it leads to structural changes and affects the entire molecule when it induces immobilization on a solid surface. The physicochemical properties may induce diverse conformational states in an immobilized enzyme (Lundqvist et al., 2004; Kelly et al., 2005). The enzyme immobilization can easily be performed by selecting support matrix and designing the carrier. Recently, broad applications of nanostructured materials have been considered in matrices for enzyme immobilization. The most common nanoparticles, such as gold and silver, are extremely attractive to be used as host matrices. Silver (Ag) and gold (Au) nanoparticles are used for enzyme immobilization owing to their stable surface, good electronic properties, and large surface areas. Both silver and gold can act as conduction centers to facilitate transfer of electrons. Immobilization of the redox enzymes collectively with colloidal gold/silver is thought to either make possible conducting channels between the prosthetic groups and the gold/silver surface or help the protein to assume a favorable orientation (Hayat, 1989). For the reason that the gold and silver surfaces permit absorption of protein molecules, silver and gold nanoparticles have been used as a matrix for enzyme immobilization where the activity of enzymes is retained (Wu et al., 2008). Au and Ag nanoparticle enzymatic immobilization is completed on solid supports by using them either as whole cells or

6.9 Biomedical Applications of Gold and Silver MNPs

isolated enzymes, which include lysozyme (Vertegel et al., 2004), glucose oxidase (Lan et al., 2008; Sun et al., 2006), aminopeptidase (Wu et al., 2008), as well as alcohol dehydrogenase (Keighron and Keating, 2010).

6.9.6 CHEMOTHERAPY These days, the number of deaths due to cancer have increased all over the world. Chemotherapy is one of the most important treatments for various types of cancers. Toxicity on healthy proliferating cells and acquisition of multidrug resistance are the main obstacles to effective treatment of cancer (Gottesman et al., 2002). Hence, careful increases in the concentrations of anticancer drugs inside tumor tissues is one of the major challenges for minimizing the side effects (Maeda, 2001; Oishi et al., 2007; Szakacs et al., 2006). Recently, nanotechnology has become the only alternative by which such problems can rapidly be solved by the applications of nanotherapeutics (Vlerken and Amiji, 2006; Han et al., 2007), especially for drug delivery of siRNA, gene and tumor targeting therapy, bioimaging, and biosensing (Han et al., 2007; Qi et al., 2012; Pan et al., 2007; Huang et al., 2011; Nowicka et al., 2013). Among the different types of MNPs, GNPs play an important role in drug delivery vehicles because of their unique size, shapes, surface-dependent properties (Cheng et al., 2006; Ghosh et al., 2008), noncytotoxicity (De et al., 2008), and the drug delivery applications of AuNPs (Huang et al., 2007; Kattumuri et al., 2007). Therefore, nanoparticles have important roles in drug delivery for the treatment of targeted cancer cells (Shan and Tenhu, 2007; Paciotti et al., 2004) and effective therapy (Katz and Willner, 2004a,b) (Figure 6.14).

FIGURE 6.14 Designing of nanoparticles for chemotherapy.

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6.9.7 ANTIMICROBIAL ACTIVITIES MNPs have also been used against numerous species of bacteria, including the universal kitchen microbe (i.e., Escherichia coli) because of its high antimicrobial properties. There are several mechanisms on MNPs which arrest the respiration, metabolic pathway by an interaction with the outer membrane of the bacteria leading to death of bacteria. Presently, all over the world, such inorganic nanomaterials have been used as antimicrobial drugs in different medical and pharmaceutical industries. Among all types of nanoparticles, SNPs shows especially good bactericidal action against Gram-negative and Gram-positive bacteria including multiresistant strains (Shrivastava et al., 2007; Zeng et al., 2007). SNPs have the ability to kill about 650 microorganisms that cause diseases, because of its nontoxic nature and safe inorganic antibacterial agent. SNP ions have either bacteriostatic (growth inhibition) or even a bactericidal (antibacterial) impact and are also considered “oligodynamic.” As a result, antimicrobial activity is endorsed in the presence of electronic effects, which lead to changes in the local electronic structure of the surface because of the smaller size. Such effects are measured due to the improvement of reactivity of SNPs on the surface. It was observed that when Ag (silver) forms an ionic stage may powerfully interact with thiol groups of vital enzymes and inactivate them. It has been suggested that once the silver ions react with bacteria they loses the ability for DNA replication (Morones and Elechigerra, 2005) (Figure 6.15).

FIGURE 6.15 Antimicrobial activity of silver nanoparticles.

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6.10 CONCLUSIONS This chapter focused on the development of environmentally friendly green synthesis methodologies to produce biologically benign gold and silver nanoparticles labeled with biologically relevant molecules. Furthermore, the gold and silver nanoparticles were used in both in vitro stability and in vivo bio-distribution. This study opens an innovative opportunity to advance research in the design and development of novel techniques to make gold and silver nanoparticles with desired properties to suit antimicrobial activities, cancer diagnosis, and therapy applications.

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