Biological Sources Used in Green Nanotechnology

Chapter 3

Biological Sources Used in Green Nanotechnology Mahmoud Nasrollahzadeh, S. Mohammad Sajadi, Zahra Issaabadi and Mohaddeseh Sajjadi

3.1 INTRODUCTION Nature provides great potential sources and insight to the synthesis of nanomaterials. Its biological systems are “biolaboratories” that produce nanomaterials using biomimetic approaches. These approaches use plants and microorganisms, such as bacteria, viruses, fungi, algae, yeasts, and waste materials. Nanostructures synthesized by these natural sources have advantages over those that are produced using physicochemical methods, i.e., they are greener, energy efficient, cost effective, and biocompatible due to the deposition of bioactive molecules on the surfaces of nanoparticles (NPs) during their production [1–4]. There are many studies available indicating the applications of metal nanoparticles (MNPs), all of which show promise. These include medical (especially treating cancer), environmental, industrial, and agricultural (especially biofertilizers) applications as well as uses in the cosmetics and electronics industries, as catalysts, and biolabeling filters. Table 3.1 summarizes some instances of MNP synthesis by microorganisms as well as providing their applications [4]. Biocompatibility properties demonstrate interesting applications in biomedicine and its related fields (Fig. 3.1) [5]. The biosynthesis of nanoparticles using living organisms is an excellent method of creating nanoscale formations, such as nanoparticles, wires, flowers, and tubes, acting as reducing and stabilizing agents. It is worth remembering that physicochemical methods can generate hazardous and highly toxicity environments, and so can be harmful to ecosystems. The biogenic synthesis of nanostructures offers many applications for curing various diseases due to the availability of a greater number of biological entities and eco-friendly procedures. In fact, biosynthesized nanoparticles with various morphologies and sizes can control many processes inside plants, such as oxidative stress, genotoxicity, and apoptosis-related changes, as well as being used to convert agricultural and food wastes into energy and useful by-products [6–8]. Interface Science and Technology, Vol. 28. https://doi.org/10.1016/B978-0-12-813586-0.00003-1 © 2019 Elsevier Ltd. All rights reserved.

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TABLE 3.1 Applications of Metal Nanoparticles in Various Fields Name of Microorganism

Nanoparticle/ Nanoformulation

A. alternata

Silver nanoparticles

Enhancement of the antifungal activity of fluconazole against P. glomerata

A. niger

Silver nanoparticles

Antibacterial activity

A. niger

Silver nanoparticles

Wound healing activity

Aspergillus sp.

Silver nanoparticles

Antimicrobial activity

F. acuminatum

Silver nanoparticles

Antibacterial activity

F. oxysporum

Silver nanoparticles

Textile fabrics

F. oxysporum

Cadmium sulfide nanoparticles

Live cell imaging and diagnostics

F. solani

Silver nanoparticles

Textile fabrics

L. lecanii

Silver nanoparticles

Textile fabrics

P. infestans

Silver nanoparticles

Antibacterial activity

R. oryzae

Gold nanoparticles

Water hygiene management

T. crassum

Silver nanoparticles

Antimicrobial activity

T. viride

Silver nanoparticles

Vegetable and fruit preservation

Alternaria alternate

Ag nanoparticle array membranes

Water quality monitoring

Plectonema boryanum

Carbon nanotubes

Electrochemical sensors: exposure to gases such as NO2, NH3, or O means the electrical resistance of CNTs changes dramatically—induced by charge transfer with the gas molecules or due to physical adsorption

Phoma glomerata

Carbon nanotubes with enzymes

Establish a fast electron transfer from the active site of an enzyme through a CNT to an electrode, in many cases enhancing the electrochemical activity of biomolecules

F. oxysporum

Carbon nanotubes

Sensors developed for glucose, ethanol, sulfides, and sequencespecific DNA analysis

Application

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TABLE 3.1 Applications of Metal Nanoparticles in Various Fields—Cont’d Name of Microorganism

Nanoparticle/ Nanoformulation

Volvariella volvacea

Magnetic nanoparticles coated with antibodies

Rapid detection of bacteria in complex matrices

Pseudomonas stuteri

Silver nanoparticles

Inhibition of hepatitis B virus replication

Aspergillus tubingensis

Silver nanoparticles

44% inhibition of syncitial virus infection

Neurospora oryzae

Silver nanoparticles

1–10 nm nanoparticles attach to virus restraining it from attaching to host cells (HIV-1)

Prosopis chilensis

Silver nanoparticles

Antibacterial to control vibriosis in Penaeus monodon

Citrullus colosynthis

Silver nanoparticles

Anticancer

Fucus vesiculosus

Gold nanoparticles

Antibacterial

Ulva fasciata

Silver nanoparticles

Antibacterial

Gelidiella acerosa

Silver nanoparticles

Antifungal

Bifurcaria bifurcata

CuO nanoparticles

Activity against Enterobacter aerogenes and Staphylococcus aureus

Acanthellia elargata

Gold nanoparticles

Agricultural, biomedical, and engineering sectors

Plectonema boryanum

Silver nanoparticles

Antifungal

Application

Reproduced with permission from Khandel P, Shahi SK. Microbes mediated synthesis of metal nanoparticles: current status and future prospects. Int J Nanomater Biostruct 2016;6(1):1–24.

Biomedia also acts as a capping agent in the biosynthesis of nanoparticles. In fact, nanoparticles can be functionalized and stabilized using surfactant-free capping agents from green sources in order to control their morphology and size, as well as to protect their surfaces and prevent aggregation. Synthetic surfactants show many limitations as they are difficult to remove, do not easily degrade, and are hazardous to the environment. Therefore there is an urgent need to develop and find environmentally friendly capping agents and synthetic routes both in laboratories and industry for the synthesis of NPs [9–11].

FIG. 3.1 Biological synthesis and applications of metal nanoparticles in biomedical and environmental fields. (Reproduced with permission from Singh P, Kim YJ, Zhang D, Yang DC. Biological synthesis of nanoparticles from plants and microorganisms. Trends Biotechnol 2016;34(7):588–99.)

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3.2 PLANTS Plants are photosynthetic systems that generate huge amounts of environmental biomass by converting sunlight into chemical energy. Therefore plants and plant derivatives are renewable and sustainable sources that can be used for the fabrication of nanoparticles. Plants, which are the main sources of natural antioxidants, are utilized to biosynthesize nanostructures in a rapid and inexpensive manner, producing highly stable nanoparticles. In fact, the application of these greener methods for the synthesis of nanoparticles benefits from the fact that it can occur at ambient temperatures and air pressures, resulting in huge energy savings [12–14]. The main advantages of a green approach to the synthesis of nanoparticles are illustrated in Scheme 3.1. In general, the application of plants for biosynthesizing nanoparticles has many advantages, such as being able to use water as an extracting solvent, their accessibility and biocompatibility, the simplicity of green methodologies, energy saving and cost-effectiveness, and their ability to produce stable nanoproducts while remaining environmental friendly. Therefore the application of plant sources for the biosynthesis of nanostructures with specific sizes, morphologies, and performances is the best method compared with other green sources [15–17]. The biosynthesis of metallic nanoparticles using intracellular and extracellular phytochemicals (Scheme 3.2) has received significant consideration due to its ability to produce nanoparticles with shapes and sizes comparable with those produced via other synthetic methods. Nowadays, to control the size and morphology of nanoparticles, researchers use individual plant phytochemicals during nanoparticle biosynthesis [18–20].

SCHEME 3.1 Advantages of a green approach to the synthesis of nanoparticles. (Reproduced with permission from Dauthal P, Mukhopadhyay M. Noble metal nanoparticles: plant-mediated synthesis, mechanistic aspects of synthesis, and applications. Ind Eng Chem Res 2016;55 (36):9557–77.)

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SCHEME 3.2 Plant-mediated approaches for the fabrication of nanoparticles. (Reproduced with permission from Dauthal P, Mukhopadhyay M. Noble metal nanoparticles: plant-mediated synthesis, mechanistic aspects of synthesis, and applications. Ind Eng Chem Res 2016;55(36):9557–77.)

Plant-mediated methods for the green synthesis of nanostructures based on the prediction of the biosynthetic mechanism and can identify the phytoconstituents responsible for the formation of MNPs [21, 22]. The synthesis of bimetallic nanoparticles from plant sources, with their unique optical, electronic, biological, and chemical properties is of great importance and has attracted the attention of many researchers in recent years. Reducing agents, stabilizing agents, and solvent medium are the main components required for the biosynthesis of NPs. In fact, plant extracts act as both reducing and stabilizing agents. The bioreducing and stabilizing ability of an extract is likely linked to its phytochemical content, i.e., its phenolics, flavonoids, phenolic acid, terpenoids, vitamins, glycosides, polysaccharides, organic acids, and proteins. Phenolics are polyhydroxy water-soluble plant secondary metabolites consisting of cinnamoyl and benzoyl systems. The antioxidant potential of flavonoids and their free hydrogen, liberated during keto-enol conversion, are supposed factors involved in the fabrication of metallic nanoparticles, as heavily reported in the literature [23–25]. Therefore the flavonoid content of a plant extract is an indicator of the plant’s ability to synthesize MNPs [26–28]. Another category of phenolics, involved in the biosynthesis of nanostructures, are the phenolic acids that contain a phenolic ring and an organic carboxylic acid function. Biosynthesis of nanostructures using these phytochemicals is linked to the metal-chelating ability of the highly nucleophilic aromatic rings of phenolic acids, determining their antioxidant ability. The main phenolic acids used for the biosynthesis of nanostructures are gallic acid, caffeic acid, ellagic acid, and protocatechuic acid. These compounds are converted to quinones during the reduction process [29–31]. Also, lignans and tannins are other phenolic systems that have potential to be used for the bioreduction of metallic salts to biosynthesize nanostructures. Terpenoids are a large group of phytochemicals responsible for the aroma, taste, and color of various plants. Some terpenoids, such as linalool, eugenol, and methyl chavicol, can be used for the bioreduction of metal salts to produce NPs. Among the terpenoids, eugenol has the ability to convert to its anionic form, useful for the proton-releasing ability of its hydroxyl group. Through this transformation it can play a role in the reduction of metal ions [32–34].

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Another group of bioreducing phytochemicals that can probably be used to biosynthesize nanostructures via plants are proteins. In the case of the proteinmediated bioreduction process, nanoparticles can bind to proteins through their free amino or carboxylate groups. Amino acids, as the monomers of proteins, have an ability to reduce and bind to metal ions. This may represent a mechanism for bioreduction—binding metals on the surface of proteins with their bioreduction forming nanostructures using chelation and proton transformations [35–37]. Among the various groups of plant phytochemicals, alkaloids and organic acids are reported as acting as bioreducing agents for the fabrication of different metallic nanoparticles. They do this by releasing reactive hydrogen and ketoenol tautomerization [38–40]. Plant-mediated nanoparticles have a high polydispersity due to varying phytochemicals within plant extracts. In fact, pure phytochemicals can be utilized solely to synthesize nanoparticles to specifically determined and homogenized sizes, shapes, and morphologies [41–43]. Further details, as well as the precise mechanism of this process, are available in Chapter 6.

3.3 MICROORGANISMS Several microorganisms, such as bacteria, viruses, fungi, algae, and yeasts, are capable of synthesizing MNPs or other metallic nanostructures. Depending on the biological sources used, a variety of nanoparticles with different sizes has been reported. Table 3.2 summarizes the various microorganisms that mediate the synthesis of MNPs or other metallic nanostructures [4]. As shown in Table 3.2, different shapes of nanostructures have been created, with spherical particles being predominant.

3.3.1 Bacteria As mentioned in the previous sections, another alternative way of synthesizing safe and environmentally friendly metallic nanoparticles is by using living microorganisms such as bacteria, viruses, fungi, algae, and yeasts. The biosynthesis of metal and metal oxide nanoparticles, such as Au, Ag, Pb, Pt, Cu, Fe, and Cd, has been studied using prokaryote and eukaryote microorganisms. These green nanoparticles have a lot of applications in the agricultural, medicinal, textiles, electrical, and cosmetics industries, as well as for drug delivery and biochemical sensors [44–47]. In 1984, for the first time, Haefeli reported the synthesis of silver nanoparticles using Pseudomonas stutzeri AG259 [48]. Several bacterial genera, such as Streptomyces, Shewanella, Rhodopseudomonas, and Brevibacterium, are used to biosynthesize metal and metal oxide nanoparticles [49]. Since metal pervades the cytoplasm through the cell wall and is transferred back through the cell wall meshwork via extracellular liberation, bacterial cell

TABLE 3.2 The Synthesis of MNPs or Other Metallic Nanostructures by Different Microorganisms Nanoparticles Produced

Size Range (nm)

Shape

Method

Synthesis Location

Bacillus subtilis 168

Ag

10–20

Multishaped

Reduction

Extracellular

Stenotrophomonas malophilia

Ag, Au

12–20

Spherical

Reduction

Extracellular

Morganella sp.

Ag

20–50

Spherical

Reduction

Extracellular

Shewanella sp.

AsS

12.52–18.43

Spherical

Reduction

Extracellular

Rhodopseudomonas capsulate

Au

3–10

Quasispherical

Reduction

Intracellular

Morganella sp.

Ag

3–10

Spherical

Reduction

Intracellular

Pseudomona fluorescens

Ag

50–100

Spherical

Reduction

Extracellular

E. coli strain K12, Geobacillus sp. strain ID17

Ag

6–15

Spherical

Reduction

Intracellular, extracellular

Corynebacterium sp.

Zn

5–15

Spherical

Reduction

Extracellular

Pseudomonas stutzeri

Ag

>25

Quasispherical

Reduction

Extracellular

Lactococcus garvieae

Ag, Au, Pd

10–30

Spherical

Biosorption, reduction

Extracellular

Bacillus indicus

Ag

5–15

Spherical

Reduction

Extracellular

Microorganism (A) Bacteria

Actinobacter sp.

Fe

10–40

Spherical

Reduction

Extracellular

Marinobacter pelagius

Ag

15–30

Spherical

Reduction

Extracellular

Arthrobacter gangotriensis

Al, Au

12–20

Spherical

Reduction

Extracellular

Salmonella typhirium

Ag

<100

Spherical

Reduction

Extracellular

Pseudomonas aeruginosa

Au

15–30

Spherical rods

Reduction

Extracellular

Pseudomonas aeruginosa

Au

15–30

Spherical rods

Reduction

Extracellular

Desulfovibrio desulfuricans

Pd

10–50

Spherical

Reduction

Extracellular

Pseudomonas stutzeri

Ag, Cu

>200

Spherical

Reduction

Intracellular

Rhodococcus sp.

Au

5–15

Spherical

Reduction

Intracellular

Enterobacter cloacae

Ag

2–10

Spherical

Reduction

Extracellular

Bacillus licheniformis

Ag

>100

Spherical

Reduction

Extracellular

Bacillus cereus

Ag

5

Spherical

Reduction

Extracellular

Staphylococcus aureus

Ag

160–180

Spherical, rod shaped

Reduction

Extracellular

Delftia acidovorans

Au

12–15

Spherical

Reduction

Extracellular

Pyrobaculum islandicum

Au

12–30

Quasispherical

Reduction

Extracellular

Escherichia coli

Pd, Pt, Cds

2–5

Spherical

Reduction

Intracellular

Klebsiella pneumonia

Ag

20–40

Semipentagonal, hexagonal

Reduction

Extracellular

Thermomonospora sp.

Au

8

Spherical

Reduction

Extracellular

Brevibacterium casei

Ag

10–50

Spherical

Reduction

Extracellular Continued

TABLE 3.2 The Synthesis of MNPs or Other Metallic Nanostructures by Different Microorganisms—Cont’d Microorganism

Nanoparticles Produced

Size Range (nm)

Shape

Method

Synthesis Location

Bacillus thuringiensis

Ag, Au

10–20

Spherical

Reduction

Extracellular

Plectonema boryanum

Ag

3–8

Spherical

Reduction

Intracellular

Arthrobacter kerguelensis

Pd, CdS

13–28

Spherical

Reduction

Extracellular

Enterobacter cloacae

Ag

2–25

Spherical

Reduction

Extracellular

Cornebacterium sp.

Au, Ag

6–25

Spherical, hexagonal

Reduction

Extracellular

Ureibacillus thermosphaericus

Au

20

Spherical

Reduction

Extracellular

Clostridium thermoaceticum

Cds

12–15

Spherical

Reduction

Intracellular, extracellular

Enterococcus faecium

Ag, Pt

5–8

Spherical, triangular

Biosorption, reduction

Extracellular

Bacillus sphaericus JG-A12

Al, U, Pb, Cd

15–25

Spherical

Biosorption, reduction

Extracellular

Lactobacillus strains

Ag, Au

10–25

Spherical

Reduction

Intracellular

Spirulina platensis

Au–Ag

7–16

Spherical

Reduction

Extracellular

Oscillatoria willei

Ag

100–200

Spherical

Reduction

Extracellular

Phormidium tenue

Cd

3–8

Spherical

Reduction

Extracellular

(B) Cyanobacteria

(C) Actinomycetes Rhodococcus sp.

Au

5–10

Spherical, rod shaped

Reduction

Intracellular

Thermomonospora sp.

Au

12–20

Spherical

Reduction

Extracellular

Candida glabrata

CdS

110–130

Spherical

Reduction

Intracellular

Schizosaccharomyces pombe

CdS

200

Spherical

Reduction

Intracellular

Torulopsis sp.

PbS

2–5

Spherical

Reduction

Intracellular

MKY3

Ag

2–5

Spherical

Reduction

Extracellular

Yarrowia lipolytica

Ag

5–12

Spherical

Reduction

Extracellular

Pichta capsulate

Ag

50–100

Spherical

Reduction

Extracellular

Candida albicans

Ag

50–100

Spherical

Reduction

Extracellular

Rhodosporidium diobovatum

Ag, Pb

2–5

Spherical

Reduction

Extracellular

Trichoderma viride

CdS, Ag

10–15

Spherical

Reduction

Extracellular

Aspergillus flavus

Ag-Au, Ag

>120

Spherical

Reduction

Extracellular

Phyllanthus amarus

Ag

30

Spherical

Enzyme mediated

Extracellular

Penicillium brevicompactum

Ag, Au

10–22

Spherical

Reduction

Extracellular

Fusarium culmorum

Ag, Au, Pb, Cu

5–10

Spherical

Reduction

Extracellular

(D) Yeasts

(E) Fungi

Continued

TABLE 3.2 The Synthesis of MNPs or Other Metallic Nanostructures by Different Microorganisms—Cont’d Microorganism

Nanoparticles Produced

Size Range (nm)

Shape

Method

Synthesis Location

Cryphonectria sp.

Ag

<30

Spherical

Reduction

Intracellular

Cochliobolus lunatus

Ag

5–10

Spherical

Reduction

Intracellular

Rhizopus oryzae

Au

10

Nanocrystalline

Reduction

Cell surface

Pediococcus pentosaceus

Pt, Ag

30–60

Spherical

Biosorption, reduction

Extracellular

Rhizopus nigricans

Ag

7–20

Spherical

Reduction

Extracellular

Pleuratus sajor caju

Au, Ag

20–40

Spherical

Reduction

Extracellular

Pestalotia sp.

Ag

12–15

Spherical

Reduction

Extracellular

Fusarium semitectum

Au, Au-Ag

18–80

Multishaped

Reduction

Extracellular

Bipolaris nodulosa

Au, Ag

2–5

Spherical

Reduction

Intracellular

Helminthosporum solani

Pt, Zn, Cu

80–100

Spherical

Reduction

Extracellular

Tricholoma crassum

Au

8.62–9.12

Spherical

Reduction

Extracellular

Trichoderma aspercellum

Ag

13–18

Spherical

Reduction

Extracellular

Phoma infestans

Ag

40–60

Spherical

Reduction

Extracellular

Penicillium brevicompactum WA2315

Ag

58.35
17.88

Spherical

Reduction

Extracellular

Penicillium fellutanum

Ag

5–25

Spherical

Reduction

Extracellular

Yarrowiali polytica

Au

20–25

Spherical

Reduction

Extracellular

Volvariella volvacea

Ag

25–50

Spherical

Reduction

Extracellular

Penicillium citrinum

Ag

5–25

Spherical

Reduction

Extracellular

PPenicillium citrinum

Ag

5–25

Spherical

Reduction

Extracellular

Colletotrichum sp.

Ag

2–10

Spherical

Reduction

Extracellular

Fusarium solani

Ag

5–35

Spherical

Reduction

Extracellular

Agaricus bisporus

Ag

20–25

Spherical

Reduction

Extracellular

Phoma glomerata

Pb, Ag

60–80

Spherical

Reduction

Extracellular

Alternaria alternate

Ag, Cd

20–60

Spherical

Reduction

Extracellular

Aspergillus ochraceus

Ag

20

Spherical

Reduction

Extracellular

Cladosporium cladosproides

Ag

10–100

Hexagonal

Reduction

Extracellular

Coriolus versicolor

Ag, Au-Ag

10

Spherical

Enzyme mediated

Extracellular

Verticillium luteoalbum

Ag

12–22

Spherical

Reduction

Extracellular

Phanerochaete chrsosporium

Ag

80–100

Spherical

Reduction

Extracellular

Trichoderma harzianum

Cu, Ag

20–35

Spherical

Reduction

Extracellular

Verticillium luteoalbum

Au

12–15

Spherical

Reduction

Extracellular

Aspergillus clavatus

Ag, Au

10–35

Spherical, hexagonal

Reduction

Extracellular

Sclerotium rolfsii

Au

25

Triangular, decahedral, hexagonal

Reduction

Extracellular

Continued

TABLE 3.2 The Synthesis of MNPs or Other Metallic Nanostructures by Different Microorganisms—Cont’d Microorganism

Nanoparticles Produced

Size Range (nm)

Shape

Method

Synthesis Location

Rhizopus stolonifer

Au

1–5

Irregular

Reduction

Extracellular

Amylomyces rouxii KSU-09

Ag

5–27

Spherical, rod shaped

Enzyme mediated

Extracellular

Aspergillus clavitus

Ag

100–200

Spherical

Reduction

Extracellular

Phoma sorghina

Ag

120–160  30–40

Rod shaped

Reduction

Extracellular

Phaenerochaete chysosporium

Ag

50–200

Spherical, pyramidal

Reduction

Extracellular

Pestalotia sp.

Ag

10–40

Spherical

Reduction

Intracellular

Cochlibolus lunatus

Cu, Al

3–21

Quasispherical

Reduction

Extracellular

Aspergillus oryzae

Ag, Zn, Au

2.78–5.76

Spherical

Reduction

Extracellular

Neurospora oryzae

Ag

30–90

Spherical

Reduction

Intracellular, extracellular

Cylindrocladium floridam

Au

19.5

Spherical

Enzyme mediated

Extracellular

Thraustochytrium sp.

Ag, Zn

2–15

Spherical

Reduction

Extracellular

Aspergillus terreus

Ag, Au–Ag

1–20

Spherical

Reduction

Extracellular

Aureobasidium pullulans

Au

29
6

Spherical

Reduction

Intracellular

Fusarium oxysporum

Au, Ni

40.3
3.5

Spherical

Enzyme mediated

Extracellular

Hypocrea lixii

Cu

Average of 24.5

Spherical

Reduction

Extracellular

Rhizopus stolonifer

Au

1–5

Irregular

Reduction

Extracellular

M13 bacteriophage

CdS, ZnS

10–25

Spherical

Reduction

Extracellular

Bacteriophage

Ca

5–10

Spherical

Reduction

Extracellular

Tobacco mosaic virus (TMV)

Si, CdS, PbS

<30

Multishaped

Reduction

Extracellular

Sargassum wightii

Au

8–12

Spherical

Reduction

Extracellular

Fucus vesiculosus

Au

28–41

Spherical

Biosorption

Extracellular

Spirulina platensis

Au

7–16

Spherical

Reduction

Extracellular

Turbinaria conaides

Au, Ag

5–20

Spherical

Reduction

Extracellular

Acanthella elongate

Au

10–20

Spherical

Reduction

Extracellular

Cladosiphon okamuranus

Au

8.54–10.74

Spherical

Reduction

Extracellular

Kjellamaniella crassifolia

Au, Ag

30–35

Spherical

Reduction

Extracellular

Chlorella vulgaris

Au

9–20

Spherical

Reduction

Extracellular

Gelidiella acerosa

Ag

12–15

Spherical

Reduction

Extracellular

Ulva fasciata

Ag

8–10

Spherical

Reduction

Extracellular

Bifurcaria bifurcate

Cu

5–45

Spherical

Reduction

Extracellular

(F) Viruses

(F) Algae

Reproduced with permission from Khandel P, Shahi SK. Microbes mediated synthesis of metal nanoparticles: current status and future prospects. Int J Nanomater Biostruct 2016;6(1):1–24.

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walls play an important role. The presence of polyanions in cell wall composition (of peptidoglycans) causes interactions between metals and chemically reactive groups. The cell wall contains a large number of metal-binding sites, which can be altered through chemical reactions (for specific groups, such as carboxyl groups and amines), and made to convert positive charges to negative charges—the most important step in the metal-binding process [50]. Biosynthesis of NPs using bacteria can be categorized according to the place where they are formed, i.e., intracellular and extracellular synthesis (Fig. 3.2). Despite many studies in this field, the exact mechanisms associated with the preparation of NPs using bacteria are not fully understood. However, reports propose that nanoparticles are generally formed in two stages: (1) trapping metal ions on the surface or inside microbial cells and (2) reducing metal ions in the presence of enzymes acting as reducing agents. Of the two, it is extracellular synthesis that has attracted a lot attention due to its advantages over intracellular approaches, such as easy downstream processing, rapid scaling up of processing, easy recovery, and purification [45–51]. The use of microbes for the optimal production of stabilized nanoparticles, having desired sizes and shapes, is of great importance since such processes do not require stabilizing agents, chemicals, photoreduction in reverse micelles, chemical radiation, and thermal decomposition in organic solvents [52, 53].

Intracellular

+

Metal ions

+

NP

–

+ +

–

Negatively charged cell wall

Diffuse from cell wall

Metal nanoparticle (NP)

NP

Extracellular

NADH-dependent enzymes

Metal ions

Reduction

Metal nanoparticle (NP)

FIG. 3.2 Intracellular and extracellular syntheses of nanoparticles using bacteria. (Reproduced with permission from Das RK, Pachapur VL, Lonappan L, Naghdi M, Pulicharla R, Maiti S, Cledon M, Dalila LMA, Sarma SJ, Brar SK. Biological synthesis of metallic nanoparticles: plants, animals and microbial aspects. Nanotechnol Environ Eng 2017;2:18.)

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3.3.2 Viruses Furthermore, some other organic processes, based on biological substances, can be used as templates for the mediated synthesis of metal nanostructures. Viruses are unicellular organisms that utilize the replication machinery of host cells and suspend most endogenous cellular activities. Within the structure of viruses are different compounds, such as nucleic acid and either DNA or RNA. The synthesis of nanocrystals using bacteria and fungi has limitations, such as surfactantassembled pathways, DNA recognizing linkers, and the use of protein cages. However, these restrictions can be addressed using engineered viruses via the production of self-assembled/support semiconductor surfaces that possess highly oriented quantum dot (QD) structures with monodisperse shapes and sizes along the lengths of nanoparticles [51, 54]. Fig. 3.3 shows the synthesis of nanoparticles from various sources [55]. Among these biological templates, viruses are good candidates for the synthesis of metal oxide NPs via the oxidative hydrolysis method. Also, viruses can be used to synthesize nanowires with functional components. These nanowires have different applications, such as supercapacitors, battery electrodes, and photovoltaic devices [56]. In some cases virus templates, due to their outer surface functional groups, are used for the cocrystallization of nanoparticles through other physicochemical methods. In addition to metal nanostructures, some viruses have enough potential to be used as biological templates for the synthesis of quantum dot

FIG. 3.3 Schematic of the synthesis of nanoparticles from various sources. (Reproduced with permission from Ingale AG, Chaudhari AN. Biogenic synthesis of nanoparticles and potential applications: an eco-friendly approach. J Nanomed Nanotechol 2013;4(165):1–7.)

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nanotubes. In this case, peptides of the PVIII fusion protein in the crystalline capsid of the M13 bacteriophage virus, are used to biosynthesize CdS nanowires on a viral capsid template [57].

3.3.3 Fungi Fungi are one of the most important microorganisms for the synthesis of MNPs. They have attracted significant attention due to their monodisperse nanoparticles which have well-defined sizes and shapes. In addition, their cells contain large numbers of enzymes and proteins that are important sources for MNP synthesis. Synthesis of nanoparticles using fungi has several advantages over synthesis using bacteria, such as providing synthesized nanoparticles with nanoscale dimensions and providing more tolerable monodispersity. These microorganisms offer potential for the extracellular synthesis of nanoparticles with improved commercial viability [58, 59]. Fungi as nonphototrophic, eukaryotic microorganisms consist of a rigid cell wall—something that simplifies their nutritional requirements as chemoorganotrophs (Fig. 3.4) [60–62]. High-throughput sequencing methods have revealed the presence of about 5.1 million species of fungi on Earth, of which about 70,000 have been documented. The high-metal ion tolerance and bioaccumulation properties of fungi led to their use in mycofabrication. However, further benefits of the use of fungi over other biological methods are mainly associated to their natural abundance and their simple isolation and extraction. Myconanotechnology (myco ¼ fungi; nanotechnology ¼ the creation and exploitation of materials in the size range of 1–100 nm) is a novel term that is suggested here for the first time [63]. Mycosynthesis is a simple, environmentally friendly and cost-effective method for product recovery offering easy biomass handling [64, 65]. Myconanotechnology, as a combination of nanotechnology and mycology, benefits from the application of a wide range of diverse fungi, such

Cell membrane Glycoprotein Cross-linked glucan, hitin and glycoprotein

Enzyme

FIG. 3.4 Representation of a fungal cell wall. (Reproduced with permission from Yadav A, Kon K, Kratosova G, Duran N, Ingle AP, Rai M. Fungi as an efficient mycosystem for the synthesis of metal nanoparticles: progress and key aspects of research. Biotechnol Lett 2015;37:2099–120.)

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as Fusarium oxysporum, Fusarium acuminatum, Aspergillus fumigatus, Aspergillus niger, Aspergillus clavatus, Penicillium brevicompactum, Penicillium fellutanum, Cladosporium cladosporioides, and Fusarium semitectum. This method has already been exploited for the biosynthesis of metal and metal oxide NPs extracellularly [66–70]. As shown in Fig. 3.5, fungi can synthesize metallic nanoparticles either intracellularly or extracellularly. Intracellular synthesis of gold NPs consists of two steps. In the first step, gold metal ions are attached to fungal cell surfaces via electrostatic interactions that result from opposite charges on the metal ion surface and fungal cell surface. In the next step, the enzymes in the fungal cell wall, through positively charged groups, reduce the gold metal ions and produce gold NPs. In extracellular synthesis, the presence of nitrate reductase enzymes in the cytoplasm reduces the silver metal ions to silver NPs (B) [4]. The presence of glycoprotein and polysaccharide content in fungal cell walls produces a high wall binding capacity, intracellular metal uptake capability, a high metal tolerance, and the ability to bioaccumulate metals [71, 72]. In fact, fungi metabolites are responsible for reducing toxic metal ions to nontoxic metallic solid nanoparticles through the catalytic effects of extracellular enzymes [73]. Some reports suggested the action of hydroxyquinoline and quinones as fungi metabolites in the electron transport process within mitochondria or chloroplasts.

FIG. 3.5 Mechanisms for the intracellular (A) and extracellular (B) synthesis of gold (Au) and silver (Ag) NPs using fungi. (Reproduced with permission from Kashyap, P.L., Kumar, S., Srivastava, A.K., Sharma, A.K., 2013. Myconanotechnology in agriculture: a perspective. World J. Microbiol. Biotechnol. 29, 191–207.)

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3.3.4 Algae Another green source that can be used for the biosynthesis of nanostructures with different sizes and shapes, is algae, offering an important source of carbohydrates, proteins, and lipids. Processes associated with algae are often considered time consuming. Algae are eukaryotic aquatic oxygenic photoautotrophs [71]. Depending on the type of algae, the biosynthetic process includes the preparation of algal extract in water or in an organic solvent by heating or boiling it for a specific duration, the preparation of molar solutions of ionic metallic compounds, and the incubation of algal solutions and molar solutions of ionic metallic compounds. This is followed by either continuous stirring or no stirring at all for a specific duration under controlled conditions [74, 75]. The exact number of algae that can synthesize nanoparticles while controlling their sizes and shapes is not clear. The synthesis process of nanoparticles can be either intracellular or extracellular. The enzymes and functional groups in the cell walls of algae are responsible for reducing metal ions and producing metal nanoparticles (Fig. 3.6) [76].

3.3.5 Yeasts Similar to other microorganisms, yeasts have also been extensively studied for the extracellular synthesis of the metal NPs [77, 78]. Research completed to date shows that all yeasts have the ability to collect heavy metals. Yeasts can produce nanoscale materials in three ways [79]: l l l

Enzymatic oxidation Enzymatic reduction Cell wall biosorption

Yeasts are commonly acknowledged as “semiconductor crystals” or “quantum semiconductor crystals.” Therefore they are mostly used to produce semiconductor nanoparticles, particularly cadmium sulfides (CdS) [80].

3.4 MECHANISMS FOR THE BIOSYNTHESIS OF METAL NANOPARTICLES BY MICROORGANISMS Recently, the application of microbes as a green approach to biosynthesis has been associated with many benefits like decreasing the toxicity of metal ions by the aggregation of nonsoluble complexes with such metal ions to produce ecofriendly colloidal particles. In addition, a distinct morphology of nanoparticles can be easily obtained via the optimization of the conditions used to culture biological organisms. The main biomolecules involved in the synthesis of nanoparticles via the bioreduction process are polysaccharides, peptides, and pigments. The stabilizing and capping of nanoparticles is completed using amino groups, cysteine

FIG. 3.6 Mechanism for the biosynthesis of NPs using algae. (Reproduced with permission from Sharma D, Kanchi S, Bisetty K. Biogenic synthesis of nanoparticles: a review. Arab J Chem 2015. doi:10.1016/j.arabjc.2015.11.002.)

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residues, and sulfated polysaccharides of proteins. The low toxicity of green synthesized nanoparticles is an important parameter that has been highly studied using bacteria, viruses, fungi, algae, yeasts, enzymes, biomolecules, and components of plants, such as flowers, fruits, leaves, seeds, oils, etc., as bioreducing, stabilizing, and capping agents. However, some organisms produce inorganic materials either intracellularly or extracellularly. Intracellular synthesis methods involve a specific ion transportation system in microbial cells. On the other hand, in intracellular direction, metal ions first bind to the microbe’s cell surface through electrostatic interaction forces. They are then reduced by enzymes present in the microbe’s cell wall, finally forming metal nanoparticles. The extracellular method uses nitrate reductase enzymes in the cytoplasm to reduce the metal ions into highly stable zerovalent NPs [81, 82]. The intracellular synthesis method of nanostructures employs an ion transportation system in which the negatively charged cell wall of a microorganism plays an important role in the reaction of positive charged metallic ions through electrostatic interaction [83]. Nitrate reductase enzymes can rapidly and efficiently reduce and thermodynamically stabilize some nanoparticles with desired sizes, shapes, and morphologies [84–86].

3.5 THE EFFECT OF DIFFERENT PARAMETERS ON THE BIOLOGICAL SYNTHESIS OF MNPS USING MICROORGANISMS Nanotechnology can provide the tools for investigating and transforming biological systems to a green approach for nanomaterial synthesis, while preventing toxicity. Thus, there has been an increased tendency to reexplore microorganisms for the synthesis of functional nanostructures, which based on the dissimilar properties of microorganisms for the rapid and ecofriendly biosynthesis of metal nanoparticles either as intracellularly or extracellularly. The sizes, shapes, and morphologies of biosynthesized nanoparticles produced by microorganisms, such as bacteria, viruses, fungi, yeasts, and actinomycetes, can be controlled by manipulating pH, temperature, concentration of substrate, and length of exposure to substrate (Fig. 3.7) [87–89]. Generally, the variety in morphology and shape of bacteria, such as bacillus, coccus, fusiform bacilli, and spirillum, as either rod-shaped or star-shaped, as well as pH, are two important parameters linked to the biosynthesis of nanostructures with specific shapes, sizes, morphologies, and even activities. The biosynthesis of nanostructures using bacteria, beside the stationary phase, is a time-consuming method compared with the other methods, e.g., Escherichia coli (bacteria) 18 min, Saccharomyces cerevisiae (yeast) 100 min, and Chlorella vulgaris 3.35 days. During the stationary phase in the synthesis of nanostructures using bacteria, stronger bioreducing metabolites are synthesized that can rapidly reduce metal ions to efficiently produce nanoparticles [90–92].

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Biological synthesis Metal salt concentration

Microorganism or plant extract

Optimization

Production of heterogeneous NPs with low yield Processing parameters: 1. Incubation period 2. Mixing ratio 3. Temperature 4. pH 5. Aeration

Stable production of homogenous and capped NPs with high yield Metal salts Metal nanoparticles (NPs)

Modify processing parameters

Square

Spherical Triangular Hexagonal

Rod

Controlled shape and morphology of NPs

Trends in Biotechnology

FIG. 3.7 Parameters considered when producing monodisperse, stable, and high-yield biological NPs. It is widely accepted that extracts of microorganisms and plants can be used to synthesize MNPs. However, controlling parameters, such as salt concentration, mixing ratio of biological extract and metal salt, pH value, temperature, incubation time, and aeration, still requires optimization for producing homogenous nanoparticles of a similar size and shape. Biological synthesis can also provide an additional capping layer on synthesized nanoparticles with the attachment of several biologically active groups, which can enhance the efficacy of biological NPs. (Reproduced with permission from Singh P, Kim YJ, Zhang D, Yang DC. Biological synthesis of nanoparticles from plants and microorganisms. Trends Biotechnol 2016;34(7):588–99.)

3.5.1 pH The synthesis of nanoparticles at various pH values, along with the influence of pH on size and shape of NPs, has been reported in the literature. According to the research, large-sized nanoparticles are formed in the pH range 7–10. Research results show that the optimum metal accumulation by microbial cells usually happens in the pH range 2–6 [80, 93, 94]. Gericke et al. synthesized gold NPs using Verticillium luteoalbum at different values of pH (3, 5, 7, and 9). The synthesized particles had sizes of <10.0 nm with spherical

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FIG. 3.8 TEM images showing the effect of pH on nanoparticle formation in Verticillium luteoalbum. (Reproduced with permission from Gericke M, Pinches A. Biological synthesis of metal nanoparticles. Hydrometallurgy 2006;83:132–40.)

morphologies at pH 3. Gold NPs, synthesized at pH 5, were small and spherical. Larger particles with well-defined shapes, including hexagons, triangles, rods, and spheres, were also formed at this pH level. However, aggregation of particles was observed at pH 7 and 9. Researchers reported that a change in pH from 7 to 9 resulted in an increase in particle size and the production of nanoparticles with irregular, undefined shapes (Fig. 3.8) [80].

3.5.2 Temperature Temperature is one of the main physical factors of NP synthesis. The optimum temperatures for cell growth and metal accumulation vary. The rate of formation of NPs was found to be associated to incubation temperature, such that an increased temperature allowed particles to grow at a faster rate [80, 95, 96]. In this regard, Gericke et al. presented the biogenic synthesis of gold NPs using V. luteoalbum at different temperatures [80]. They showed that low temperatures led to the production of spherical NPs with an average diameter of less than 10nm and also the formation of NPs after 1 h exposure to a gold solution. In addition, with increasing incubation periods up to 24h, the number of smaller particles decreased, whereas the number of larger particles with well-defined shapes, increased. At 50°C, the size and morphology of the NPs produced after 1-h and 24-h exposures to gold were the same (Fig. 3.9) [80].

3.5.3 Concentration of Metal Ions It is clear that the concentration of metal ions plays a significant role in the synthesis of MNPs [80, 94, 97]. For example, in the biosynthesis of Au NPs using a Verticillium biomass in the presence of different concentrations of gold, the results showed that particles synthesized after exposing the biomass to 250 and 500 mg/L gold were similar in size and shape (small and spherical). However, 2500 mg/L gold produced very large particles with irregular shapes (Fig. 3.10) [80].

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FIG. 3.9 TEM images of thin sections illustrating the effect of temperature on nanoparticle production in Verticillium luteoalbum cells after exposure to Au3+ ions for 1 and 24 h. (Reproduced with permission from Gericke M, Pinches A. Biological synthesis of metal nanoparticles. Hydrometallurgy 2006;83:132–40.)

FIG. 3.10 Representative TEM images showing the effect of different AuCl4- concentrations on the formation of gold nanoparticles in Verticillium luteoalbum after incubation for 24 h. (Reproduced with permission from Gericke M, Pinches A. Biological synthesis of metal nanoparticles. Hydrometallurgy 2006;83:132–40.)

3.5.4 Exposure Time to Substrate The preparation of NPs over various time intervals was also investigated [98, 99]. Studies show that increasing the incubation time produces nanoparticles with different sizes and shapes. It has also been found that increasing time of incubation increases the amount of nanoparticles. In 2010, Gade et al. found

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that nanoparticles could be prepared after an incubation of 1 h in a metalcontaining solution [98]. They further found that by increasing the incubation time to 24 h, larger sized nanoparticles were synthesized due to clump formation or the segregation of smaller sized nanoparticles.

3.5.5 Type of Enzyme Used Another important factor for the biosynthesis of nanoparticles is the type of enzyme used [100–102]. The use of enzymes in the biosynthesis of nanoparticles has several advantages, such as the in vitro synthesis of nanoparticles using fungal mycelia and eliminating optimization and harvesting processes during their intracellular synthesis. For example, in 2010, Ahmed et al. reported the biosynthesis of Ag NPs. Their results indicated that a Fusarium oxysporum strain was able to produce Ag NPs due to the presence of a specific reductase enzyme (NADH-dependent reductase), while another strain of Fusarium moniliforme could not produce nanoparticles due to the lack of a specific reductase enzyme.

REFERENCES [1] Kuppusamy P, Yusoff MM, Maniam GP, Govindan N. Biosynthesis of metallic nanoparticles using plant derivatives and their new avenues in pharmacological applications—an updated report. Saudi Pharm J 2016;24(4):473–84. [2] Ahmed S, Ahmad M, Swami BL, Ikram S. A review on plants extract mediated synthesis of silver nanoparticles for antimicrobial applications: a green expertise. J Adv Res 2016;7(1): 17–28. [3] Narayanan KB, Sakthivel N. Biological synthesis of metal nanoparticles by microbes. Adv Colloid Interface Sci 2010;56(1-2):1–13. [4] Khandel P, Shahi SK. Microbes mediated synthesis of metal nanoparticles: current status and future prospects. Int J Nanomater Biostruct 2016;6(1):1–24. [5] Singh P, Kim YJ, Zhang D, Yang DC. Biological synthesis of nanoparticles from plants and microorganisms. Trends Biotechnol 2016;34(7):588–99. [6] Mittal AK, Chisti Y, Banerjee UC. Synthesis of metallic nanoparticles using plant extracts. Biotechnol Adv 2013;31(2):346–56. [7] Li Y, Duan X, Qian Y, Yang L, Liao H. Nanocrystalline silver particles: synthesis, agglomeration, and sputtering induced by electron beam. J Colloid Interface Sci 1999;209(2):347–9. [8] Tsai SC, Song YL, Tsai CS, Yang CC, Chiu WY, Lin HM. Ultrasonic spray pyrolysis for nanoparticles synthesis. J Mater Sci 2004;39(11):3647–57. [9] Nasrollahzadeh M, Issaabadi Z, Sajadi SM. Green synthesis of a Cu/MgO nanocomposite by Cassytha filiformis L. extract and investigation of its catalytic activity in the reduction of methylene blue, congo red and nitro compounds in aqueous media. RSC Adv 2018;8(7): 3723–35. [10] Pritchard J, Kesavan L, Piccinini M, He Q, Tiruvalam R, Dimitratos N, Lopez-Sanchez JA, Carley AF, Edwards JK, Kiely CJ, Hutchings GJ. Direct synthesis of hydrogen peroxide and benzyl alcohol oxidation using Au-Pd catalysts prepared by sol immobilization. Langmuir 2010;26(21):16568–77.

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3 107

[11] Yang F, Cheng K, Wu T, Zhang Y, Yin J, Wang G, Cao D. Au-Pd nanoparticles supported on carbon fiber cloth as the electrocatalyst for H2O2 electroreduction in acid medium. J Power Sources 2013;233:252–8. [12] Gangula A, Podila R, Karanam L, Janardhana C, Rao AM. Catalytic reduction of 4-nitrophenol using biogenic gold and silver nanoparticles derived from Breynia rhamnoides. Langmuir 2011;27(4):15268–74. [13] Devi TB, Ahmaruzzaman M, Begum SA. A rapid, facile and green synthesis of Ag@AgCl nanoparticles for the effective reduction of 2,4-dinitrophenyl hydrazine. New J Chem 2016;40:1497–506. [14] Dauthal P, Mukhopadhyay M. Noble metal nanoparticles: plant-mediated synthesis, mechanistic aspects of synthesis, and applications. Ind Eng Chem Res 2016;55(36):9557–77. [15] Rai M, Yadav A, Gade A. CRC 675-current trends in phytosynthesis of metal nanoparticles. Crit Rev Biotechnol 2008;28(4):277–84. [16] Narayanan KB, Sakthivel N. Green synthesis of biogenic metal nanoparticles by terrestrial and aquatic phototrophic and heterotrophic eukaryotes and biocompatible agents. Adv Colloid Interface Sci 2011;169(2):59–79. [17] Girling CA, Peterson PJ. Gold in plants. Gold Bull 1980;13:151–7. [18] Iravani S. Green synthesis of metal nanoparticles using plants. Green Chem 2011;13: 2638–50. [19] Jha AK, Prasad K, Prasad K, Kulkarni AR. Plant system: nature’s nanofactory. Colloids Surf B 2009;73(2):219–23. [20] Chen JC, Lin ZH, Ma XX. Evidence of the production of silver nanoparticles via pretreatment of Phoma sp.3.2883 with silver nitrate. Lett Appl Microbiol 2003;37(2):105–8. [21] Gurunathan S, Lee KJ, Kalishwaralal K, Sheikpranbabu S, Vaidyanathan R, Eom SH. Antiangiogenic properties of silver nanoparticles. Biomaterials 2009;30:6341–50. [22] Huang H, Yang X. Synthesis of polysaccharide-stabilized gold and silver nanoparticles: a green method. Carbohydr Res 2004;339:2627–31. [23] Jacob SJP, Finub JS, Narayanan A. Synthesis of silver nanoparticles using Piper longum leaf extracts and its cytotoxic activity against Hep-2 cell line. Colloid Surf B 2012;91:212–4. [24] Jain D, Daima HK, Kachhwaha S, Kothari SL. Synthesis of plant-mediated silver nanoparticles using papaya fruit extract and evaluation of their antimicrobial activities. Dig J Nanomater Biostruct 2009;4:557–63. [25] Jayaseelan C, Rahuman AA, Rajakumar G, Kirthi AV, Santhoshkumar T, Marimuthu S, Bagavan A, Kamaraj C, Zahir AA, Elango G. Synthesis of pediculocidal and larvicidal silver nanoparticles by leaf extract from heartleaf moonseed plant, Tinospora cordifolia Miers. Parasitol Res 2011;109:185–94. [26] Jha AK, Prasad K, Kumar V, Prasad K. Biosynthesis of silver nanoparticles using Eclipta leaf. Biotechnol Prog 2009;25:1475–9. [27] Joerger R, Klaus T, Granqvist CG. Biologically produced silver–carbon composite materials for optically functional thin-film coatings. Adv Mater 2000;12:407–9. [28] Kasthuri J, Kathiravan K, Rajendiran N. Phyllanthin-assisted biosynthesis of silver and gold nanoparticles: a novel biological approach. J Nanopart Res 2009;11:1075–85. [29] Kora AJ, Sashidhar RB, Arunachalam J. Aqueous extract of gum olibanum (Boswellia serrata): a reductant and stabilizer for the biosynthesis of antibacterial silver nanoparticles. Process Biochem 2012;47(10):1516–20. [30] Kouvaris P, Delimitis A, Zaspalis V, Papadopoulos D, Tsipas SA, Michailidis N. Green synthesis and characterization of silver nanoparticles produced using Arbutus unedo leaf extract. Mater Lett 2012;76:18–20.

108 An Introduction to Green Nanotechnology [31] Krishnaraj C, Jagan EG, Rajasekar S, Selvakumar P, Kalaichelvan PT, Mohan N. Synthesis of silver nanoparticles using Acalypha indica leaf extracts and its antibacterial activity against water borne pathogens. Colloids Surf B: Biointerfaces 2010;76(1):50–6. [32] Logeswari P, Silambarasan S, Abraham J. Synthesis of silver nanoparticles using plants extract and analysis of their antimicrobial property. J Saudi Chem Soc 2012;4(3):311–7. [33] Maensiri S, Laokul P, Klinkaewnarong J, Phokha S, Promarak V, Seraphin S. Indium oxide (In2O3) nanoparticles using Aloe vera plant extract: Synthesis and optical properties. J Optoelectron Adv Mater 2008;10(3):161–5. [34] Manikanth SB, Kalishwaralal K, Sriram M, Pandian SRK, Youn HS, Eom SH, Gurunathan S. Anti-oxidant effect of gold nanoparticles restrains hyperglycemic conditions in diabetic mice. J Nanobiotechnol 2010;8(1):16. [35] Monda S, Roy N, Laskar RA, Sk I, Basu S, Mandal D, Begum NA. Biogenic synthesis of Ag, Au and bimetallic Au/Ag alloy nanoparticles using aqueous extract of mahogany (Swietenia mahogani JACQ.) leaves. Colloid Surfaces B: Biointerfaces 2011;82(2):497–504. [36] Moulton MC, Braydich-Stolle LK, Nadagouda MN, Kunzelman S, Hussaina SM, Varma RS. Synthesis, characterization and biocompatibility of “green” synthesized silver nanoparticles using tea polyphenols. Nanoscale 2010;2:763–70. [37] MubarakAli D, Thajuddin N, Jeganathan K, Gunasekaran M. Plant extract mediated synthesis of silver and gold nanoparticles and its antibacterial activity against clinically isolated pathogens. Colloid Surfaces B: Biointerfaces 2011;85(2):360–5. [38] Nishino T, Fukuda A, Nagumo T, Fujihara M, Kaji E. Inhibition of the generation of thrombin and factor Xa by a fucoidan from the brown seaweed Ecklonia kurome. Thromb Res 1999;96(1):37–49. [39] Pankhurst QA, Connolly J, Jones SK, Dobson J. Applications of magnetic nanoparticles in biomedicine. J Phys D: Appl Phys 2003;36:R167–81. [40] Parial D, Pal R. Biosynthesis of monodisperse gold nanoparticles by green alga Rhizoclonium and associated biochemical changes. J Appl Phycol 2015;27(2):975–84. [41] Perez GR, Zavala SM, Perez GS, Perez GC. Antidiabetic effect of compounds isolated from plants. Phytomedicine 1998;5(1):55–75. [42] Fayaz A, Balaji K, Girilal M, Yadav R, Kalaichelvan PT, Venketesan R. Biogenic synthesis of silver nanoparticles and their synergistic effect with antibiotics: a study against grampositive and gram-negative bacteria. Nanomedicine 2010;6(1):103–9. [43] Polavarapu L, Xu QH. A single-step synthesis of gold nanochains using an amino acid as a capping agent and characterization of their optical properties. Nanotechnol 2008;19(7): 075601. [44] Basavaraja S, Balaji SD, Lagashetty A, Rajasab AH, Venkataraman A. Extracellular biosynthesis of silver nanoparticles using the fungus Fusarium semitectum. Mater Res Bull 2007; 43(5):1164–70. [45] Mishra A, Tripathy SK, Wahab R, Jeong SH, Hwang II, Yang YB, Kim YS, Shin HS, Yun SI. Microbial synthesis of gold nanoparticles using the fungus Penicillium brevicompactum and their cytotoxic effects against mouse mayo blast cancer C2C12 cells. App Microbiol Biotechnol 2011;92(3):617–30. [46] Mala JGS, Rose C. Facile production of ZnS quantum dot nanoparticles by Saccharomyces cerevisiae MTCC 2918. J Biotechnol 2014;170:73–8. [47] Johnston CW, Wyatt MA, Li X, Ibrahim A, Shuster J, Southam G, Magarvey NA. Gold biomineralization by a metallophore from a gold-associated microbe. Nat Chem Biol 2013;9:241–3.

Biological Sources Used in Green Nanotechnology Chapter

3 109

[48] Thostenson DT, Li C, Chou TW. Nanocomposites in context. Compos Sci Technol 2005;65(3):491–516. [49] Li X, Xu H, Chen ZS, Chen G. Biosynthesis of nanoparticles by microorganisms and their applications. J nanomater 2011;2011:16. [50] Das RK, Pachapur VL, Lonappan L, Naghdi M, Pulicharla R, Maiti S, Cledon M, Dalila LMA, Sarma SJ, Brar SK. Biological synthesis of metallic nanoparticles: plants, animals and microbial aspects. Nanotechnol Environ Eng 2017;2:18. [51] Velusamy P, Kumar JV, Jeyanthi V, Das J, Pachaiappan R. Bio-inspired green nanoparticles: synthesis, mechanism, and antibacterial application. Toxicol Res 2016;32(2):95–102. [52] Philip D. Biosynthesis of Au, Ag and Au-Ag nanoparticles using edible mushroom extract. Spectrochim Acta A: Mol Biomol Spectrosc 2009;73(2):374–81. [53] Sastry M, Ahmad A, Khan MI, Kumar R. Biosynthesis of metal nanoparticles using fungi and actinomycete. Curr Sci 2003;85(2):162–70. [54] Thakkar KN, Mhatre SS, Parikh RY. Biological synthesis of metallic nanoparticles. Nanomedicine 2010;6(2):257–62. [55] Ingale AG, Chaudhari AN. Biogenic synthesis of nanoparticles and potential applications: an eco-friendly approach. J Nanomed Nanotechol 2013;4(165):1–7. [56] Nam KT, Kim DW, Yoo PJ, Chiang CY, Meethong N, Hammond PT, Chiang YM, Belcher AM. Virus-enabled synthesis and assembly of nanowires for lithium ion battery electrodes. Science 2006;312:885–8. [57] Gusseme b SL, Baert L, Thibo E, Hennebel T, Vermeulen G, Uyttendaele M, Verstraete W, Boon N. Biogenic silver for disinfection of water contaminated with viruses. Appl Environ Microbiol 2010;76(4):1082–7. [58] Mukherjee P, Senapati S, Mandal D, Ahmad A, Khan MI, Kumar R, Sastry M. Extracellular synthesis of gold nanoparticles by the fungus Fusarium oxysporum. Chem Biol Chem 2002;3(5):461–3. [59] Ahmad A, Mukherjee P, Senapati S, Mandal D, Khan MI, Kumar R, Sastry M. Extracellular biosynthesis of silver nanoparticles using the fungus Fusarium oxysporum. Colloid Surfaces B: Biointerfaces 2003;28(4):313–8. [60] Vahabi K, Mansoori GA, Karimi S. Biosynthesis of silver nanoparticles by fungus Trichoderma reesei (a route for large-scale production of AgNPs). Insciences J 2011;1(1):65–79. [61] Chakraborty N, Banerjee A, Lahiri S, Panda A, Ghosh AN, Pal R. Biorecovery of gold using cyanobacteria and an eukaryotic alga with special reference to nanogold formation—a novel phenomenon. J Appl Phycol 2009;21:145–52. [62] Yadav A, Kon K, Kratosova G, Duran N, Ingle AP, Rai M. Fungi as an efficient mycosystem for the synthesis of metal nanoparticles: progress and key aspects of research. Biotechnol Lett 2015;37:2099–120. [63] Rai M, Yadav A, Bridge P, Gade AK, editors. Myconanotechnology: a new and emerging science. In: Applied mycology. 14th ed. New York: CAB International; 2009. p. 258–67. [64] Mukherjee P, Ahmad A, Mandal D, Senapati S, Sainkar SR, Khan MI, Parishcha R, Ajaykumar PV, Alam M, Kumar R, Sastry M. Fungus-mediated synthesis of silver nanoparticles and their immobilization in the mycelial matrix: a novel biological approach to nanoparticle synthesis. Nano Lett 2001;1(10):515–9. [65] Gajbhiye M, Kesharwani J, Ingle A, Gade A, Rai M. Fungus-mediated synthesis of silver nanoparticles and their activity against pathogenic fungi in combination with fluconazole. Nanomedicine 2009;5(4):382–6.

110 An Introduction to Green Nanotechnology [66] Ingle A, Gade A, Pierrat S, Sonnichsen C, Rai M. Mycosynthesis of silver nanoparticles using the fungus Fusarium acuminatum and its activity against some human pathogenic bacteria. Curr Nanosci 2008;4(2):141–4. [67] Bhainsa KC, D’souza SF. Extracellular biosynthesis of silver nanoparticles using the fungus Aspergillus fumigatus. Colloid Surf B: Biointerfaces 2006;47(2):160–4. [68] Gade AK, Bonde P, Ingle AP, Marcato PD, Duran N, Rai MK. Exploitation of Aspergillus niger for synthesis of silver nanoparticles. J Biobased Mater Biol 2007;2(3):243–7. [69] Saravanan M, Nanda A. Extracellular synthesis of silver bionanoparticles from Aspergillus clavatus and its antimicrobial activity against MRSA and MRSE. Colloid Surf B: Biointerfaces 2010;77(2):214–8. [70] Kathiresan K, Manivannan S, Nabeel MA, Dhivya B. Studies on silver nanoparticles synthesized by a marine fungus, Penicillium fellutanum isolated from coastal mangrove sediment. Colloid Surf B: Biointerfaces 2009;71(1):133–7. [71] Balaji DS, Basavaraja S, Deshpande R, Mahesh DB, Prabhakar BK, Venkataraman A. Extracellular biosynthesis of functionalized silver nanoparticles by strains of Cladosporium cladosporioides fungus. Colloid Surf B: Biointerfaces 2009;68(1):88–92. [72] Ahmad A, Senapati S, Khan MI, Kumar R, Sastry M. Extra-/intracellular biosynthesis of gold nanoparticles by an alkalotolerant fungus, Trichothecium sp. J Biomed Nanotechnol 2005;1(1):47–53. [73] Mukherjee P, Roy M, Mandal BP, Dey GK, Mukherjee PK, Ghatak J, Tyagi AK, Kale SP. Green synthesis of highly stabilized nanocrystalline silver particles by a non-pathogenic and agriculturally important fungus T. asperellum. Nanotechnology 2008;19(7):075103–10. [74] Castro L, Bla´zquez ML, Mun˜oz JA, Gonza´lez F, Ballester A. Biological synthesis of metallic nanoparticles using algae. IET Nanobiotechnol 2013;7(3):109–16. [75] Singaravelu G, Arockiamary JS, Kumar VG, Govindaraju K. A novel extracellular synthesis of monodisperse gold nanoparticles using marine alga, Sargassum wightii Greville. Colloids Surf B: Biointerfaces 2007;57(1):97–101. [76] Sharma D, Kanchi S, Bisetty K. Biogenic synthesis of nanoparticles: a review. Arab J Chem 2015. https://doi.org/10.1016/j.arabjc.2015.11.002. [77] Seshadri S, Saranya K, Kowshik M. Green synthesis of lead sulfide nanoparticles by the lead resistant marine yeast, Rhodosporidium diobovatum. Biotechnol Prog 2011;27:1464–9. [78] Mourato A, Gadanho M, Lino AR, Tenreiro R. Biosynthesis of crystalline silver and gold nanoparticles by extremophilic yeasts. Bioinorg Chem Appl 2011;2011:8. [79] Dameron CT, Reese RN, Mehra RK, Kortan AR, Carroll PJ, Steigerwald ML, Brus LE, Winge DR. Biosynthesis of cadmium sulphide quantum semiconductor crystallites. Lett Nat 1989;338:596–7. [80] Gericke M, Pinches A. Biological synthesis of metal nanoparticles. Hydrometallurgy 2006;83:132–40. [81] Bharde A, Rautray D, Bansal V, Ahmad A, Sarkar I, Yusuf SM, Sanyal M, Sastry M. Extracellular biosynthesis of magnetite using fungi. Small 2006;2(1):135–41. [82] Farrukh A, Akram A, Ghaffar A, Hanif AS, Hamid A, Duran H, Yameen B. Design of polymer-brush-grafted magnetic nanoparticles for highly efficient water remediation. ACS Appl Mater Interfaces 2010;5(9):3784–93. [83] Hosseini-Abari A, Emtiazi G, Lee SH, Kim BG, Kim JH. Biosynthesis of silver nanoparticles by Bacillus stratosphericus spores and the role of dipicolinic acid in this process. App Biochem Biotechnol 2014;174(1):270–82. [84] Bansal V, Poddar P, Ahmad A, Sastry M. Room-temperature biosynthesis of ferroelectric barium titanate nanoparticles. J Am Chem Soc 2006;128(36):11958–63.

Biological Sources Used in Green Nanotechnology Chapter

3 111

[85] Velmurugan P, Shim J, You Y, Choi S, Kamala-Kannan S, Lee KJ, Kim HJ, Oh BT. Removal of zinc by live, dead, and dried biomass of Fusarium spp. isolated from the abandoned-metal mine in south korea and its perspective of producing nanocrystals. J Hazard Mater 2010;182(1–3):317–24. [86] Birla SS, Tiwari VV, Gade AK, Ingle AP, Yadav AP, Rai MK. Fabrication of silver nanoparticles by Phoma glomerata and its combined effect against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus. Lett Appl Microbiol 2009;27(2):173–9. [87] Zhang X, Yan S, Tyagi RD, Surampalli RY. Synthesis of nanoparticles by microorganisms and their application in enhancing microbiological reaction rates. Chemosphere 2011;82(4):489–94. [88] Engel E, Michiardi A, Navarro M, Lacroix D, Planell JA. Nanotechnology in regenerative medicine: the materials side. Trends Biotechnol 2008;31(1):39–47. [89] Mahdieh M, Zolanvari A, Azimee AS, Mahdieh M. Green biosynthesis of silver nanoparticles by Spirulina platensis. Sci Iran 2012;19:926–9. [90] Kumar A, Mandal S, Selvakannan PR, Pasricha R, Mandal AB, Sastry M. Investigation into the interaction between surface-bound alkylamines and gold nanoparticles. Langmuir 2003;19(15):6277–82. [91] Ankamwar B, Damle C, Ahmad A, Sastry M. Biosynthesis of gold and silver nanoparticles using Emblica officinalis fruit extract. J Nanosci Nanotechnol 2005;5(10):1665–71. [92] Chithrani BD, Ghazani AA, Chan WC. Determining the size and shape dependence of gold nanoparticle uptake into mammalian cells. Nano Lett 2006;6(4):662–8. [93] Sanghi R, Verma P. Biomimetic synthesis and characterisation of protein capped silver nanoparticles. Bioresour Technol 2009;100:501–4. [94] Davis MW, Ogden WC. Free resources and advanced alignment for cross-language text retrieval. In: TREC 1997; 1997. p. 385–95. [95] Punjabi K, Choudhary P, Samant L, Mukherjee S, Vaidya S, Choudhary A. Biosynthesis of nanoparticles: a review. Int J Pharm Sci Rev Res 2015;30(1):219–26. [96] Dhillon GS, Brar SK, Kour S, Verma M. Green approach for nanoparticle biosynthesis by fungi: current trends and applications. Crit Rev Biotechnol 2012;32:49–73. [97] Shankar SS, Ahmad A, Pasricha R, Sastry M. Bioreduction of chloroaurate ions by geranium leaves and its endophytic fungus yields gold nanoparticles of different shapes. J Mater Chem 2003;13(7):1822–6. [98] Gade A, Gaikwad S, Tiwari V, Yadav A, Ingle A, Rai M. Biofabrication of silver nanoparticles by Opuntia ficus-indica: in vitro antibacterial activity and study of the mechanism involved in the synthesis. Curr Nanosci 2010;6:370–5. [99] Darroudi M, Ahmad MB, Zamiri R, Zak AK, Abdullah AH, Ibrahim NA. Time-dependent effect in green synthesis of silver nanoparticles. Int J Nanomedicine 2011;6:677–81. [100] Bansal A, Yang H, Li C, Cho K, Benicewicz BC, Kumar SK, Schadler LS. Quantitative equivalence between polymer nanocomposites and thin polymer films. Nat Mater 2005;4(9):693–8. [101] Shakibaie M, Forootanfar H, Mollazadeh-Moghaddam K, Bagherzadeh Z, Nafissi-Varcheh N, Shahverdi AR, Faramarzi MA. Green synthesis of gold nanoparticles by the marine microalga Tetraselmis suecica. Biotechnol Appl Biochem 2010;57(2):71–5. [102] Kashyap PL, Kumar S, Srivastava AK, Sharma AK. Myconanotechnology in agriculture: a perspective. World J Microbiol Biotechnol 2013;29:191–207.