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Nanoparticles are the building blocks for nanotechnology; they are better built, long lasting, cleaner, safer, and smarter products for use across industries, including communications, medicine, transportation, agriculture and other industries. Controlled size, shape, composition, crystallinity, and structure-dependent properties govern the unique properties of nanotechnology. Bio-Nanoparticles: Biosynthesis and Sustainable Biotechnological Implications explores both the basics of and advancements in nanoparticle biosynthesis. The text introduces the reader to a variety of microorganisms able to synthesize nanoparticles, provides an overview of the methodologies applied to biosynthesize nanoparticles for medical and commercial use, and gives an overview of regulations governing their use. Authored by leaders in the field, Bio-Nanoparticles: Biosynthesis and Sustainable Biotechnological Implications bridges the gap between biology and technology, and is an invaluable resource for students and researchers alike.

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CONTENTS

COVER

TITLE PAGE

LIST OF CONTRIBUTORS

INTRODUCTION

1 DIVERSITY OF MICROBES IN SYNTHESIS OF METAL NANOPARTICLES: PROGRESS AND LIMITATIONS

1.1. Introduction

1.2. Synthesis of Nanoparticles by Bacteria

1.3. Synthesis of Nanoparticles by Fungi

1.4. Synthesis of Nanoparticles by Algae

1.5. Applications of Metal Nanoparticles

1.6. Limitations of Synthesis of Biogenic Nanoparticles

Conclusion

Acknowledgements

References

2 ROLE OF FUNGI TOWARD SYNTHESIS OF NANO-OXIDES

2.1. Introduction

2.2. Fungus-Mediated Synthesis of Nanomaterials

2.3. Outlook

References

3 MICROBIAL MOLECULAR MECHANISMS IN BIOSYNTHESIS OF NANOPARTICLES

3.1. Introduction

3.2. Chemical Synthesis of Metal Nanoparticles

3.3. Green Synthesis

3.4. Biosynthesis of Nanoparticles

3.5. Mechanisms for Formation or Synthesis of Nanoparticles

3.6. Extracellular Synthesis of Nanoparticles

3.7. Conclusion

References

4 BIOFILMS IN BIO-NANOTECHNOLOGY: OPPORTUNITIES AND CHALLENGES

4.1. Introduction

4.2. Microbial Synthesis of Nanomaterials

4.3. Interaction of Microbial Biofilms with Nanomaterials

4.4. Future Perspectives

Acknowledgements

References

5 EXTREMOPHILES AND BIOSYNTHESIS OF NANOPARTICLES: CURRENT AND FUTURE PERSPECTIVES

5.1. Introduction

5.2. Synthesis of Nanoparticles

5.3. Mechanism of Nanoparticle Biosynthesis

5.4. Fermentative Production of Nanoparticles

5.5. Nanoparticle Recovery

5.6. Challenges and Future Perspectives

5.7. Conclusion

References

6 BIOSYNTHESIS OF SIZE-CONTROLLED METAL AND METAL OXIDE NANOPARTICLES BY BACTERIA

6.1. Introduction

6.2. Intracellular Synthesis of Metal Nanoparticles by Bacteria

6.3. Extracellular Synthesis of Metal Nanoparticles by Bacteria

6.4. Synthesis of Metal Oxide and Sulfide Nanoparticles by Bacteria

6.5. Conclusion

References

7 METHODS OF NANOPARTICLE BIOSYNTHESIS FOR MEDICAL AND COMMERCIAL APPLICATIONS

7.1. Introduction

7.2. Biosynthesis of Nanoparticles Using Bacteria

7.3. Biosynthesis of Nanoparticles Using Actinomycete

7.4. Biosynthesis of Nanoparticles Using Fungi

7.5. Biosynthesis of Nanoparticles Using Plants

7.6. Conclusions

References

8 MICROBIAL SYNTHESIS OF NANOPARTICLES: AN OVERVIEW

8.1. Introduction

8.2. Nanoparticles Synthesis Inspired by Microorganisms

8.3. Mechanisms of Nanoparticles Synthesis

8.4. Purification and Characterization of Nanoparticles

8.5. Conclusion

References

9 MICROBIAL DIVERSITY OF NANOPARTICLE BIOSYNTHESIS

9.1. Introduction

9.2. Microbial-Mediated Nanoparticles

9.3. Native and Engineered Microbes for Nanoparticle Synthesis

9.4. Commercial Aspects of Microbial Nanoparticle Synthesis

9.5. Conclusion

References

10 SUSTAINABLE SYNTHESIS OF PALLADIUM(0) NANOCATALYSTS AND THEIR POTENTIAL FOR ORGANOHALOGEN COMPOUNDS DETOXIFICATION

10.1. Introduction

10.2. Chemically Generated Palladium Nanocatalysts for Hydrodechlorination: Current Methods and Materials

10.3. Bio-Supported Synthesis of Palladium Nanocatalysts

10.4. Current Approaches for Synthesis of Palladium Catalysts in the Presence of Microorganisms

10.5. Bio-Palladium(0)-Nanocatalyst Mediated Transformation of Organohalogen Pollutants

10.6. Conclusions

Acknowledgements

References

11 ENVIRONMENTAL PROCESSING OF Zn CONTAINING WASTES AND GENERATION OF NANOSIZED VALUE-ADDED PRODUCTS

11.1. Introduction

11.2. Physical/Chemical/Hydrothermal Processing

11.3. Biohydrometallurgical Processing: International SCENARIO

11.4. Biohydrometallurgical Processing: Indian Scenario

11.5. Synthesis of Nanoparticles

11.6. Applications of Zinc-Based Value-Added Products/Nanomaterials

11.7. Conclusions and Future Directions

References

12 INTERACTION BETWEEN NANOPARTICLES AND PLANTS: INCREASING EVIDENCE OF PHYTOTOXICITY

12.1. Introduction

12.2. Plant–Nanoparticle Interactions

12.3. Effect of Nanoparticles On Plants

12.4. Mechanisms of Nanoparticle-Induced Phytotoxicity

12.5. Effect on Physiological Parameters

12.6. Genectic and Molecular Basis of NP Phytotoxicity

12.7. Conclusions and Future Perspectives

Acknowledgements

References

13 CYTOTOXICOLOGY OF NANOCOMPOSITES

13.1. Introduction

13.2. Cellular Toxicity

13.3. Nanoparticle Fabrication

13.4. Immunological Response

13.5. Factors to Consider to Reduce the Cytotoxic Effects of NP

13.6. Conclusions and Future Directions

Acknowledgements

References

14 NANOTECHNOLOGY: OVERVIEW OF REGULATIONS AND IMPLEMENTATIONS

14.1. Introduction

14.2. Scope of Nanotechnology

14.3. Safety Concerns Related to Nanotechnology

14.4. Barriers to the Desired Regulatory Framework

14.5. Biosynthesis of Microbial Bio-Nanoparticles: an Alternative Production Method

14.6. Conclusion

References

NAME INDEX

SUBJECT INDEX

END USER LICENSE AGREEMENT

List of Tables

Chapter 01

Table 1.1. List of different metallic nanoparticles synthesized by bacteria

Table 1.2. Synthesis of metal nanoparticles using different algae

Chapter 03

Table 3.1. Species used for the Synthesis of NPs

Chapter 04

Table 4.1. Summary of recent work on bacterial synthesis of metal(loid) nanomaterials

Chapter 05

Table 5.1. Major Types of Nanoparticles in Nanotechnology

Table 5.2. Standard Microorganisms Involved in the Biosynthesis of Nanoparticles

Table 5.3. Extremophiles in Biosynthesis of Nanoparticles

Table 5.4. Optimized Fermentation Media for Microbial Synthesis of Nanoparticles

Chapter 06

Table 6.1. Use of Bacteria in the Production of Metal Nanoparticles Intracellularly

Table 6.2. Use of Bacteria in the Production of Metal Nanoparticles Extracellularly

Table 6.3. Use of Bacteria in the Production of Metal Oxide and Sulfide Nanoparticles

Chapter 07

Table 7.1. List of various biological entities used in the biosynthesis of metal nanoparticles

Chapter 08

Table 8.1. Use of microorganisms for the synthesis of different nanoparticles

Chapter 09

Table 9.1. List of microorganisms capable of producing various nanoparticles

Chapter 10

Table 10.1. Half-lives of some probe compounds with Pd/nano-magnetite in different water matrices (

c

catalyst

=100 mg L

–1

;

c

Pd

=0.15 mg L

–1

;

c

0,pollutant

=30 mg L

–1

).

Chapter 11

Table 11.1. Mining assets of HZL during 2010–11

Table 11.2. Smelting assets of HZL during 2010–11

Table 11.3. Synthesis of Nanoparticles by Different Microorganisms

Chapter 12

Table 12.1. Effect of Nanoparticles on Growth, Physiology, and Germination of Monocot Plants

Table 12.2. Effect of Nanoparticles on Growth, Physiology, and Germination of Dicot Plants

Table 12.3. ROS-Mediated Effect of Nanoparticles on Plants

Chapter 14

Table 14.1.  Nanomedicine Products on the market

Table 14.2.  FDA/s sub-center and their role in biologics evaluation (FDA, 2013b)

Table 14.3.  Global initiative and key legislations or activities to regulate nanomaterials. Adopted and modified from Grobe et al. (2008) and FAO/WHO (2010)

List of Illustrations

Chapter 01

Figure 1.1. Mechanisms of microbial fabrication of nanobiominerals, catalyzed by enzymatic reductive biotransformations of redox active metals, driven by a suitable electron donor such as hydrogen. In some cases, for example transformations of Fe(III) minerals and Se(IV), redox mediators such as AQDS (anthraquinone-2,6 disulfonate) are utilized to increase the kinetics of metal reduction and hence nanobiomineral formation.

Figure 1.2. Magnetosome bio-mineralization in magnetotactic bacteria (MTB). (I) MamI, MamL, MamB, and MamQ proteins initiate the membrane invagination and form a vesicular membrane around the magnetosome structure. (II) The protease-independent function of MamE recruits other proteins such as MamK, MamJ, and MamA to align magnetosomes in a chain. (III) Iron uptake occurs via MagA, a transmembrane protein, and initiation of magnetic crystal bio-mineralization occurs through MamM, MamN, and MamO proteins. (IV) Finally, MamR, MamS, MamT, MamP, MamC, MamD, MamF, MamG, the protease-dependent function of MamE, and Mms6, a membrane tightly bounded by GTP-ase, regulate crystal growth and determine morphology of the produced magnetic nanoparticles.

Figure 1.3. Possible mechanism of enzymatic reduction of the silver ions.

Figure 1.4. Biomineralization process for nanoparticle synthesis.

Figure 1.5. General mechanism for the intracellular synthesis of metal nanoparticles using algae.

Figure 1.6. General mechanism for the extracellular synthesis of metal nanoparticles using algae.

Chapter 02

Figure 2.1. Various approaches for the synthesis of nanoparticles.

Figure 2.2.  Transmission electron microscopy images of (a) zirconia; (b) silica; and (c) titania nanoparticles biosynthesized using the fungus

F. oxysporum.

Source: Images reprinted from Bansal, V.; Rautaray, D.; Ahmad, A.; Sastry, M., Biosynthesis of zirconia nanoparticles using the fungus Fusarium oxysporum.

Journal of Materials Chemistry

2004, 14(22), 3303–3305 and Bansal, V.; Rautaray, D.; Bharde, A.; Ahire, K.; Sanyal, A.; Ahmad, A.; Sastry, M., Fungus-mediated biosynthesis of silica and titania particles.

Journal of Materials Chemistry

2005, 15(26), 2583–2589. Reproduced by permission of The Royal Society of Chemistry.

Figure 2.3. Transmission electron microscopy images of magnetite nanoparticle synthesized using (a)

Fusarium oxysporum

and (b)

Verticillium

sp.

Figure 2.4. (a, b) Low- and (c, d) higher-magnification surface potential microscopy (SPM) images of BaTiO

3

nanoparticles synthesized using

Fusarium oxysporum

. SPM images from ferroelectric BaTiO

3

nanoparticles obtained in potential mode after application of +4 V (a, c) and –4 V (b, d) external DC bias voltages, where the reversal in image contrast on reversal of bias voltage is observed.

Figure 2.5. Transmission electron micrographs of (a) SiO

2

nanoparticles bioleached from rice husk after their biotransformation into quartz nanoparticles by

Fusarium oxysporum

and (b) single crystal quartz plates obtained after calcination of bioleached silica at 400 °C for 2 hours. Scanning electron micrographs and corresponding EDX patterns from rice husk (c, d) before and (e, f) after exposure to

Fusarium oxysporum

. Inset in (a) shows amorphous silica particles formed via rice husk bioleaching using cationic fungal proteins. Inset in (b) shows selected area electron diffraction pattern from the quartz plate shown in the main figure.

Chapter 03

Figure 3.1. Bottom-up -one-pot synthesis of SiNPs. Source: Redrawn from Yiling Zhong, Fei Peng, Feng Bao, Siyi Wang, Xiaoyuan Ji, Liu Yang, Yuanyuan Su, Shuit-Tong Lee, Yao He. Large-Scale Aqueous Synthesis of Fluorescent and Biocompatible Silicon Nanoparticles and Their Use as Highly Photostable Biological Probes.

Journal of the American Chemical Society

135(22): 8350–8356. Copyright © 2013, American Chemical Society.

Figure 3.2. Continuous nucleation–growth-capping mechanism.

Figure 3.3. Synthesis of gold nanoparticles from cucurbit[7]uril using potassium tetrachloroaurate (III) as a metal precursor. Source: Thathan Premkumar, Kurt E. Geckeler. Cucurbit[7]uril as a Tool in the Green Synthesis of Gold Nanoparticles.

Chemistry–An Asian Journal

5(12): 2468–2476. Copyright © 2010, John Wiley & Sons, Inc.

Figure 3.4. Processing of tellurite by the facultative phototroph

R. capsulatus

. Cys: cysteine; Grx: glutharedoxin; NAD(P)H

2

: Gor; NAD(P)H

2

: glutathione oxidoreductase; redox chain: respiratory electron transport chain; Qox: quinol oxidase; cbb

3

: cytochrome c oxidase. Source: Raymond J. Turner, Roberto Borghese and Davide Zannoni. Microbial processing of tellurium as a tool in biotechnology.

Biotechnology Advances

30(5): 954–963. Copyright © 2012, Elsevier.

Figure 3.5. The synthesis of silver nanoparticles using a bacterial cell wall. Source: Redrawn from Liesje Sintubin, Wim De Windt, Jan Dick, Jan Mast, David van der Ha, Willy Verstarete, Nico Boon. 2009. Lactic acid bacteria as reducing and capping agent for the fast and efficient production of silver nanoparticles. Applied Microbiology and Biotechnology 84(4): 741–7491. Copyright © 2009, Springer.

Figure 3.6. Representation of the microdroplet-generation model using a microfluidic device. .

Figure 3.7. Production of gold nanoparticles induced by a tripeptide consisting of leucine (Leu), α-aminoisobutyric acid (Aib), and tyrosine (Tyr) at the C-terminus of the peptide, which is able to reduce Au

3+

to Au

0

, capped by methylene oxide (OMe).

Figure 3.8. The synthesis of gold nanoparticles by

Stenotrophomonas maltophilia

through enzymatic reduction.

Figure 3.9. The interaction of metal ions with sulfhydryl groups on cysteine/imidazole rings on the histidine residues of metallothioneins.

Figure 3.10. The formation of t-Se nanoparticles using the bacterial strain of

Bacillus subtilis.

Figure 3.11. The formation of Se nanoparticles using a bacterial strain.

Figure 3.12. The two-step mechanism for the synthesis of silver nanoparticles.

Figure 3.13. The formation of silver and gold nanoparticles by L-DOPA-induced melanin derived from yeasts.

Figure 3.14. The synthesis of silver nanoparticles using xerophytes.

Figure 3.15. The synthesis of silver nanoparticles using mesophytes.

Figure 3.16. The synthesis of silver nanoparticles using hydrophytes.

Figure 3.17. The biocompatibility of AuNPs observed by

in vitro

cell culture assays.

Figure 3.18. The extracellular synthesis of silver nanoparticles using leaf extract.

Chapter 04

Figure 4.1. Illustration of the metal-reducing (MTR) pathway in

S. oneidensis

. The MTR pathway consists of a number of electron carrier proteins including CymA, MtrA, MtrC, and OmcA. The electrons obtained from bacterial metabolism are transferred across the periplasmic space to the outer membrane, where MtrC and OmcA can use the electrons to reduce metal(loid)s.

Figure 4.2. A representative depth-resolved profile of dissolved oxygen concentration in a

S. oneidensis

biofilm growing in air-saturated media.

Figure 4.3. The multiple-sites-targeted action of nanomaterials against bacteria. Certain nanomaterials can enter cell membranes and physically disrupt them. Some nanomaterials can generate ROS and oxidatively damage DNA, proteins, electron transport chains, and cell membranes. Certain nanomaterials can also release toxic ions that can enter cells and cause stress responses and damages.

Chapter 05

Figure 5.1. Bioreduction of metal ions on the surface of the cell wall due to the electrostatic interaction between the metal ions and positively charged groups in the enzymes of the cell wall. The enzymatic reduction of the metal ions soon follows, which are reduced by NADH-dependent reductase such as enzymes. The reductase gains electrons from NADH and oxidized NAD

+

. When the enzymes oxidize the metal ions simultaneously reduce, causing the formation of nanoparticles.

Figure 5.2. Mechanism of formation of ZnS nanoparticles in

Rhodobacter sphaeroides

. A series of reductions leads to the production of ZnS nanoparticles. Soluble sulfate enters the cell wall via diffusion and permease, and is then reduced to sulfite by ATP sulfurylase and phosphoadenosine phosphosulfate reductase. This sulfite is reduced to sulfide by sulfite reductase. The sulfide reacts with O-acetyl serine to synthesize cysteine via O-acetylserine thiolyase. Cysteine produces S

2–

by a cysteine desulfhydrase in the presence of zinc. S

2–

reacts with the soluble zinc salt and the ZnS nanoparticles are being synthesized and released from the cells into the solution.

Chapter 06

Figure 6.1. TEM micrographs of whole mounts of cyanobacteria

Plectonema boryanum

UTEX 485 cultured in the presence of Au(S

2

O

3

)

2

3–

or AuCl

4

solutions. (a) TEM micrographs of a thin section of cyanobacteria cells reacted with Au(S

2

O

3

)

2

3–

ions to form nanoparticles of gold and gold sulfide deposited on the sheaths and inside the cell. (b) Cubic nanoparticles of gold precipitated with smaller particles of gold sulfide also formed extracellularly in the Au(S

2

O

3

)

2

3–

containing solution. (c) Image of a thin-section of cyanobacteria cells reacted with AuCl

4

ions showing nanoparticles of gold deposited inside cells. (d) Octahedral gold platelets from cyanobacteria –AuCl

4

experiments at incubation.

Figure 6.2. TEM micrographs of

Lactobacillus

strains cultured in the presence of Au or Ag precursor ions to form Au, Ag, or Au–Ag alloy nanoparticles. (a) TEM micrographs of

Lactobacillus

strains cell with Au nanoparticles deposited on the cell surface. Several crystal morphologies are manifested. Arrows point to regions where the cell wall is being pushed with the edges of the crystals. (b) TEM micrographs of

Lactobacillus

strain with silver clusters or nanoparticles. The image illustrates the coalescence of clusters and the formation of large crystallites. (c) TEM of a bacterium with Au–Ag alloy crystallites. Smaller crystallites are also seen outside the bacteria.

Figure 6.3. TEM micrographs of

Magnetospirillum magnetotacticum

cultured in the presence of FeCl

3

solution to form Fe

3

O

4

magnetic nanoparticles. (a) TEM micrographs of

Magnetospirillum magnetotacticum

cell with Fe

3

O

4

nanoparticles intracellularly. The formed Fe

3

O

4

nanoparticles aligned in a chain parallel to the long axis of the bacteria. (b–e) TEM micrographs of Fe

3

O

4

magnetite colloids extracted from cells. Note the magnetic flux closure rings in (b). The tendency to form string-like aggregates can be clearly seen in (c–e).

Chapter 08

Figure 8.1. Isolated magnetosome particles form (a) straight chains in weak ambient magnetic fields but (b) bent chains or (c) flux-closure rings in zero fields adhered to each other by junctions of organic material (arrows). (d) Magnetic microstructure of a magnetosome chain. (d1) TEM bright-field image of a single bacterial cell of

M. magnetotacticum

; (d2) magnetic induction map recorded using off-axis electron holography from the magnetosome chain of the same cell. (e) Cryoelectron tomography image shows organization of the magnetosome chain and the cytoskeletal magnetosome filament (MF) in

M. gryphiswaldense

. (f) Tomographic reconstruction of a magnetic cell showing the cytoplasmic membrane, empty vesicles, growing and mature magnetite crystals, and the magnetosome filament.

Figure 8.2. Illustration of proposed mechanism for biogenesis of selenium nanospheres at different time intervals: (a) selenite reduction at 0 h; (b) formation of red elemental selenium in membrane fraction after 3–4 h of incubation; and (c) in soluble fraction after 12 h of incubation.

Figure 8.3. Synthesis of silver and gold nanoparticles from

Neurospora crassa

biomass after 24 h of incubation in aqueous solutions of AgNO

3

and HAuCl

4

: (a) silver nanoparticles; (b) gold nanoparticles; (c) fungal hypha with silver nanoparticles scanned under confocal microscopy (Abs/Em 420/515–530 nm); (d) hypha with gold nanoparticles scanned under confocal microscopy (Abs/Em 543/574–691 nm; scale bar: 10 μm); and (e) the role of extracellular proteins in the synthesis of silver nanoparticles from

Aspergillus flavus

.

Figure 8.4. Representative SEM images of

Yarrowia lipolytica

cells incubated with 1 mM HAuCl

4

: (a) control; (b) after 15 min; (c) after 3 h; (d) after 12 h; (e) after 24 h at magnification 5000× and (f) after 30 h at 10 000×. (b, c) Inset images at 30,000×. Scale bar: 5 μm (a–e) and 1 μm (f).

Figure 8.5. (a) Unfolding M1 peptides on the nanotube template showing the ZnS nanocrystal growth as a function of pH. (b) TEM image of ZnS nanocrystals on the M1 peptide nanotube template grown at pH 5.5. Inset image at high magnification; scale bar 70 nm. (c) Viral capsid-mediated reduction of gold ions to gold nanoparticles.

Figure 8.6. Photographs of aqueous solutions of gold nanospheres (upper panels) and gold nanorods (lower panels) as a function of increasing dimensions with respective transmission electron microscopy images of the nanoparticles (all scale bars 100 nm). (a–e) For nanospheres, the size varies in the range 4–40 nm. For nanorods, the aspect ratio (f–j) is 1.3–5 for short rods and (k) 20 for long rods.

Chapter 10

Figure 10.1. TEM image and TEM-EDX-spectrum of Pd/nano-magnetite (0.15 wt% Pd). Source: Hildebrand H, Mackenzie K & Kopinke F-D (2009). Highly Active Pd-on-Magnetite Nanocatalysts for Aqueous Phase Hydrodechlorination Reactions.

Environmental Science & Technology

43: 3254–3259. Copyright © the American Chemical Society, 2009.

Figure 10.2. Ferrimagnetic Pd/nano-magnetite particles are easily separated in everyday laboratory life by permanent magnets.

Figure 10.3. Polymer-coated catalysts particle.

Figure 10.4. Biosynthesized Pd(0) nanoparticles in the periplasm of a

Pseudomonas

sp.

Chapter 13

Figure 13.1.  ROS and RNS generation in macrophages, showing the generation of superoxide and hydrogen peroxide by NADPH phagocyte oxidase and superoxide dismutase, respectively. The inducible nitric oxide synthase (iNOS) generates nitric oxide from L-arginine. The reaction of nitric oxide with cysteine sulphydryls results in the formation of nitrosothiols. The combination of nitric oxide and superoxide generates peroxynitrite.

Figure 13.2.  Structure of glutathione and N-acetyl cysteine.

Figure 13.3.  The cell cycle. In the S phase, DNA is synthesized and replication occurs. During the M phase or mitosis, nuclear chromosomes separate.

Figure 13.4  Diagram showing the zeta potential.

Chapter 14

Figure 14.1.  Nanomaterials in different forms as (a) rods; (b) poly-dispersal particles; and (c) layers.

Figure 14.2.  Nanomaterials and nanoparticles in context to other biological molecules.

Figure 14.3.  Projected benefits of nanotechnology in food- and biomedical-related sectors.

Guide

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BIO-NANOPARTICLES

Biosynthesis and Sustainable Biotechnological Implications

Edited by

Om V. Singh

 

 

 

 

 

 

Copyright © 2015 by Wiley-Blackwell. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New JerseyPublished simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data

Bio-nanoparticles : biosynthesis and sustainable biotechnological implications / edited by Om V. Singh.  p. ; cm. Includes bibliographical references and index.

 ISBN 978-1-118-67768-1 (cloth) I. Singh, Om V., editor. [DNLM: 1. Nanoparticles. 2. Bacteria–metabolism. 3. Biotechnology–methods. 4. Industrial Microbiology–methods. 5. Nanotechnology–methods. QT 36.5] QR88.3 579.3′17–dc23

    2015004421

The editor gratefully dedicates this book to Daisaku Ikeda, Uday V. Singh, and Indu Bala in appreciation of their encouragement.

LIST OF CONTRIBUTORS

Abhilash,

CSIR-National Metallurgical Laboratory (NML), Jamshedpur, Jharkand, India

Horacio Bach,

Department of Medicine, Division of Infectious Diseases, University of British Columbia, Vancouver, BC, Canada

Vipul Bansal,

NanoBiotechnology Research Laboratory (NBRL), School of Applied Sciences, RMIT University, Melbourne, VIC, Australia

Parameswaran Binod,

CSIR-National Institute for Interdisciplinary Science and Technology, Pappanamcode, Trivandrum, Kerala, India

Michael Bunge,

Institute of Applied Microbiology, Justus Liebig University of Giessen, Giessen, Germany

Bin Cao,

School of Civil and Environmental Engineering, Nanyang Technological University, Singapore; Singapore Centre on Environmental Life Sciences Engineering, Nanyang Technological University, Singapore

Thomas Colonna,

Center for Biotechnology Education, Zanvyl Krieger School of Arts and Sciences, The Johns Hopkins University, Rockville, MD, USA

Abhimanyu Dev,

Department of Pharmaceutical Sciences and Technology, Birla Institute of Technology, Mesra, Ranchi, Jharkand, India

Saurabh Dixit,

Center for Nanobiotechnology Research, Alabama State University, Montgomery, AL, USA

Anton Gudz,

Department of Chemistry, University of Connecticut, Storrs, CT, USA

Indarchand Gupta,

Department of Biotechnology, SGB Amravati University, Amravati, Maharashtra, India

Avinash Ingle,

Department of Biotechnology, SGB Amravati University, Amravati, Maharashtra, India

S.K. Khare,

Enzyme and Microbial Biochemistry Laboratory, Department of Chemistry, Indian Institute of Technology, Delhi, New Delhi, India

David A. Kriz,

Department of Chemistry, University of Connecticut, Storrs, CT, USA

Chung-Hao Kuo,

Department of Chemistry, University of Connecticut, Storrs, CT, USA

Katrin Mackenzie,

Department of Environmental Engineering, Helmholtz Centre for Environmental Research – UFZ, Leipzig, Germany

Irena Maliszewska,

Division of Medicinal Chemistry and Microbiology, Faculty of Chemistry, Wrocław University of Technology, Wrocław, Wybrzeże Wyspiańskiego, Poland

Shilpi Mishra,

Department of Biological Sciences, Alabama State University, Montgomery, AL, USA

Anee Mohanty,

School of Civil and Environmental Engineering, Nanyang Technological University, Singapore; Singapore Centre on Environmental Life Sciences Engineering, Nanyang Technological University, Singapore

Chun Kiat Ng,

Singapore Centre on Environmental Life Sciences Engineering, Nanyang Technological University, Singapore; Interdisciplinary Graduate School, Nanyang Technological University, Singapore

Ashok Pandey,

CSIR-National Institute for Interdisciplinary Science and Technology, Pappanamcode, Trivandrum, Kerala, India

B.D. Pandey,

CSIR-National Metallurgical Laboratory (NML), Jamshedpur, Jharkand, India

Mahendra Rai,

Department of Biotechnology, SGB Amravati University, Amravati, Maharashtra, India; Institute of Chemistry, Biological Chemistry Laboratory, Universidade Estadual de Campinas, Campinas, SP, Brazil

Rajesh Ramanathan,

NanoBiotechnology Research Laboratory (NBRL), School of Applied Sciences, RMIT University, Melbourne, VIC, Australia

Atmakuru Ramesh,

International Institute of Biotechnology and Toxicology (IIBAT), Padappai, Tamil Nadu, India

Raveendran Sindhu,

CSIR-National Institute for Interdisciplinary Science and Technology, Pappanamcode, Trivandrum, Kerala, India

Om V. Singh,

Division of Biological and Health Sciences, University of Pittsburgh, Bradford, PA, USA

Sneha Singh,

Department of Bio-Engineering, Birla Institute of Technology, Mesra, Ranchi, Jharkand, India

Rajeshwari Sinha,

Enzyme and Microbial Biochemistry Laboratory, Department of Chemistry, Indian Institute of Technology-Delhi, New Delhi, India

Shivani Soni,

Department of Biological Sciences, Alabama State University, Montgomery, AL, USA

Steven L. Suib,

Department of Chemistry, University of Connecticut, Storrs, CT, USA

Marimuthu Thiripura Sundari,

International Institute of Biotechnology and Toxicology (IIBAT), Padappai, Tamil Nadu, India

Perumal Elumalai Thirugnanam,

International Institute of Biotechnology and Toxicology (IIBAT), Padappai, Tamil Nadu, India

Ambarish Sharan Vidyarthi,

Institute of Engineering and Technology, Lucknow, Uttar Pradesh, India

Jetka Wanner,

Division of Biological and Health Sciences, University of Pittsburgh, Bradford, PA, USA

Alka Yadav,

Department of Biotechnology, SGB Amravati University, Amravati, Maharashtra, India

Jingyi Zhang,

INTRODUCTION

Nanoparticles are the building blocks of nanotechnology; they are defined as particles having more than one dimension measuring 100 nm or less. Nanostructured materials are being promoted as better built, longer lasting, cleaner, safer, and smarter products for use in communications, medicine, transportation, agriculture, and other industries. Applications such as molecular recognition, biomolecule-nanocrystal conjugates as fluorescence labels for biological cells, and DNA-mediated groupings of nanocrystals are widespread, intriguing researchers from both biological and engineering fields. The diversity of nanotechnology covers fields from biology to materials science and physics to chemistry.

The controlled size, shape, composition, crystallinity, and structure-dependent properties of nanoparticles govern the unique properties of nanotechnology. The controlled biosynthesis of nanoparticles is of high scientific and technological interest; the microorganisms grab target ions from their environment and turn them into the element metal through enzymatic mechanisms generated via intra- or extracellular activities.

Nanoparticles are known to enable cleaner and safer applications of various technologies. However, the current physiochemical methods for creating them (chemical vapor deposition, solgel technique, hydrothermal synthesis, precipitation, and micro-emulsion) are hazardous, environmentally unfriendly, cumbersome, and expensive, and require conditions of high temperature, pH, and/or pressure levels for synthesis. Due to current manufacturing practices, the United States Environmental Protection Agency (USEPA) issued a Significant New Use Rule (SNUR) in 2008 for 56 chemicals, including two nanoparticles (73 F.R. 65743): siloxane-modified silica nanoparticles, PMN No. P-05-673; and siloxane-modified alumina nanoparticles, PMN No. P-05-687.

The comparatively insignificant efforts toward safer and cleaner biosynthesis of nanoparticles may have green biotechnological implications. It would benefit human society to learn from microorganisms, as they have the potential to assist us in dealing with emerging diseases due to their tremendous metabolic strategies and ability to alter the physical and chemical forms of ionic molecules. The products of microbial metabolism (enzymes and proteins) are referred to as primary and secondary metabolic products, and they have proven their importance to biotechnology.

This book continues to bridge the technology gap and focuses on exploring microbial diversity and the respective mechanisms regulating the biosynthesis of metal nanoparticles. Chapter 1 (Rai et al.) presents a wide array of microorganisms that are employed as biological agents for the biosynthesis of nanoparticles of different shapes and sizes. The possible mechanisms and applications of synthesized metal nanoparticles is described, and details of the biochemical aspects of major events that occur during biosynthesis of metal nanoparticles are discussed. Inspired by the concept of microbial tolerance at high metal ion concentration, Ramanathan and Bansal explore the role of fungi in the synthesis of nano-oxide in Chapter 2, presenting the facts of biosynthesis of binary nano-oxide and mixed-metal nano-oxides using chemical precursors and natural precursors employing bioleaching and bio-milling approaches. In Chapter 3, Ramesh et al. elaborate on the microbial molecular mechanisms used in biosynthesis of nanoparticles. Ng et al. discuss unique approaches to microbial synthesis of nanomaterials in Chapter 4, with a special emphasis on molecular mechanisms and the emerging use of biofilms, the application of nanomaterials in biofilm control, and future prospects for microbial biofilms in biotechnology.

Extremophiles are the most mysterious category of life on planet Earth and perhaps also on other planets. Even though nature offers abundant opportunities to life forms that can consume or produce sufficient energy for their survival, normal survival may not be possible in environments that experience extreme conditions (e.g., temperature, pressure, pH, salinity, geological scale/barriers, radiation, chemical extremes, lack of nutrition, osmotic barriers, or polyextremity). Due to extraordinary properties, certain organisms (mostly bacteria, archaea, and a few eukaryotes) can thrive in such extreme habitats; they are called extremophiles. In Chapter 5, Zhang et al. discuss the role of extremophiles in the biosynthesis of nanoparticles. In view of the tremendous industrial potential of producing nanoparticles via extremophiles, this chapter also sheds light on specifics of fermentation media and the recovery of nanoparticles from the microbiological process using standard microorganisms. Discussions on limitations and challenges further outline the future of extremophile-mediated nanotechnology.

Most metallic nanoparticles are of size 0.1–1000 nm and have different shapes, including triangular, spherical, rod, and other irregular shapes. Because of their extremely small size and specific shape allowing them to bind with molecules of interest, nanoparticles have unusual characteristics that make them valuable. In Chapter 6, Kuo et al. elaborate on the biosynthesis of size-controlled metal and metal oxide nanoparticles by bacteria. Further, in Chapter 7, Mishra et al. discuss the methodologies applied to biosynthesize a variety of nanoparticles with medical and commercial significance. In Chapters 8 and 9, Singh et al. and Sindhu et al. provide overviews of microbial diversity in nanoparticle biosynthesis with insights into characterization and purification from biological medium.

The unique properties of nanoparticles have attracted attention from scientists to harness their great functionality. In Chapter 10, Bunge and Mackenzie compare the sustainable synthesis of palladium nanoparticles using chemical and biological methods, exploring their potential for detoxification of organohalogen compounds from contaminated waters. In Chapter 11, Abhilash and Pandey present a unique approach for the generation of nano-sized value-added products of commercial significance using environmental wastes. According to the authors, continuous depletion of high-grade resources necessitates the conversion of lower-grade ores into value-added products of commercial significance, and they claim to have developed a green process for the production of nanomaterials.

The increasing use of nanoparticles poses challenging issues of safety for the environment and human society. The stability of nanoparticles is one of the prime reasons for their broad potential; however, medical professionals, ecologists, and environmentalists are concerned about their safety. The release of nanoparticles has made it necessary to study nanotoxicity, which is being increasingly evidenced in microbial, human, and animal systems. In Chapter 12, Sinha and Khare present the facts about the involvement of plants in nanotechnology, along with comprehensive analyses of available information pertaining to the newly discovered domain of phytonanotoxicology. In Chapter 13, Bach discusses aspects of the toxicity of nanoparticles at a cellular level, the mechanisms of cytotoxicity, and the effects of the physicochemical characteristics of nanoparticles. The role of nanoparticles has also been defined in eliciting oxidative and nitrosative stress, including apoptosis and immunological responses.

The science of nanotechnology has great promise as a source of novel products with beneficial applications. It exploits the fact that quantum effects and higher surface-area-to-mass ratios give materials different properties on the nanoscale. However, like many new forms of technology, nanotechnology implemented with engineered nanoscale materials (ENMs) has its potential dangers. A legal regulatory framework is being sought to control the ENMs and deal with the risks they pose to human health and the ecosystem. Microbial nanoparticles produced using enzymes and proteins from biological sources present a potential solution to these problems. In Chapter 14, Singh and Colonna discuss the safety issues and the legal framework of regulatory policies in the United States and worldwide related to the nanotechnology field.

This book, Bio-nanoparticles: Biosynthesis and Sustainable Biotechnological Implications, is a collection of outstanding articles elucidating several broad-ranging areas of progress and challenges in the utilization of microorganisms as sustainable resources in nanotechnology. This book will contribute to research efforts in the scientific community and commercially significant work for corporate businesses. The expectations are to establish long-term safe and sustainable forms of nanotechnology through microbial implementation of nanoparticle biosynthesis with minimum impact on the ecosystem.

We hope readers will find these articles interesting and informative for their research pursuits. It has been my pleasure to put together this book with Wiley-Blackwell Press. I would like to thank all of the contributing authors for sharing their quality research and ideas with the scientific community through this book.

1DIVERSITY OF MICROBES IN SYNTHESIS OF METAL NANOPARTICLES: PROGRESS AND LIMITATIONS

Mahendra Rai

Department of Biotechnology, SGB Amravati University, Amravati Maharashtra, India; and Institute of Chemistry, Biological Chemistry Laboratory, Universidade Estadual de Campinas, Campinas, SP, Brazil

Irena Maliszewska

Division of Medicinal Chemistry and Microbiology, Faculty of Chemistry, Wroclaw University of Technology, Wroclaw, Wybrzeże Wyspiańskiego, Poland

Avinash Ingle, Indarchand Gupta, and Alka Yadav

Department of Biotechnology, SGB Amravati University, Amravati,Maharashtra, India

1.1. Introduction

Nanotechnology is a widely emerging field involving interdisciplinary subjects such as biology, physics, chemistry, and medicine (Bankar et al., 2010; Zhang, 2011; Rai and Ingle, 2012). Nanotechnology involves the synthesis of nanoparticles using the top-down and bottom-up approach (Kasthuri et al., 2008; Bankar et al., 2010; Nagajyothi and Lee, 2011). However, due to the growing environmental concern and the adverse effects of physical and chemical synthesis, most researchers are looking to the biological protocols for nanoparticle synthesis (Rai et al., 2008). The biological method of synthesis involves a wide diversity of biological entities that could be harnessed for the synthesis of metal nanoparticles (Sharma et al., 2009; Vaseeharan et al., 2010; Zhang et al., 2011a; Gupta et al., 2012; Rajesh et al., 2012). These biological agents emerge as an environmently friendly, clean, non-toxic agent for the synthesis of metal nanoparticles (Sastry et al., 2003; Bhattacharya and Gupta, 2005; Riddin et al., 2006; Duran et al., 2007; Ingle et al., 2008; Kumar and Yadav, 2009; Vaseeharan et al., 2010; Thakkar et al., 2011; Zhang et al., 2011b; Rajesh et al., 2012).

A wide array of microorganisms such as bacteria, fungi, yeast, algae, and actinomycetes are majorly employed as biological agents for the synthesis process (Kumar and Yadav, 2009; Satyavathi et al., 2010). The synthesis of metal nanoparticles employs both intracellular and extracellular methods (Sharma et al., 2009; Mallikarjuna et al., 2011). Some examples of these microbial agents include bacteria (Husseiny et al., 2007; Shahverdi et al., 2007, 2009), fungi (Kumar et al., 2007; Parikh et al., 2008; Gajbhiye et al., 2009), actinomycetes (Ahmad et al., 2003al Golinska et al., 2014), lichens (Shahi and Patra, 2003), and algae (Singaravelu et al., 2007; Chakraborty et al., 2009). These diverse groups of biological agents have many advantages over physical and chemical methods such as easy and simple scale-up, easy downstream processing, simpler biomass handling and recovery, and economic viability (Rai et al., 2009a; Thakkar et al., 2011; Renugadevi and Aswini, 2012). These different biological agents such as bacteria, fungi, yeast, algae, and acitnomycetes therefore demonstrate immense biodiversity in the synthesis of nanoparticles and lead to green nanotechnology (Vaseeharan et al., 2010; Singh et al., 2011, 2013; Thakkar et al., 2011).

The present review also deals with the diversity of microbes involved in the synthesis of metal nanoparticles. The possible mechanisms and different applications for the synthesis of metal nanoparticles are also discussed.

1.2. Synthesis of Nanoparticles by Bacteria

Although it is known that bacteria have the ability to produce various inorganic nanoparticles (e.g., metal, calcium, gypsum, silicon), research in this area is usually focused on the formation of metals and metals sulfide/oxide (Fig. 1.1).

Figure 1.1. Mechanisms of microbial fabrication of nanobiominerals, catalyzed by enzymatic reductive biotransformations of redox active metals, driven by a suitable electron donor such as hydrogen. In some cases, for example transformations of Fe(III) minerals and Se(IV), redox mediators such as AQDS (anthraquinone-2,6 disulfonate) are utilized to increase the kinetics of metal reduction and hence nanobiomineral formation.

Source: Lloyd, J.R., Byrne, J.M., Coker, V.S. 2011. Biotechnological synthesis of functional nanomaterials. Current Opinion in Biotechnology 22: 509–515. Copyright © 2011, Elsevier.

Different bacteria from different habitats and nutritional modes have been studied for the synthesis of metallic nanocrystals, as summarized in Table 1.1. Some of the earliest reports on the reduction and accumulation of inorganic particles in bacteria can be traced back to the 1960s, where zinc sulfide was described in sulfate-reducing bacteria (Temple and Le-Roux, 1964). Later studies in this area date back to the 1980s, when Beveridge and Murray (1980) described how the incubation of gold chloride with Bacillus subtilis resulted in the production of octahedral gold nanoparticles with a dimension of 5–25 nm within the bacterial cell. It is believed that organophosphate compounds secreted by the bacterium play an important role in the formation of these nanostructures (Southam and Beveridge, 1996). Another example of bacterial reduction and precipitation of gold was described by Kashefi and co-workers (2001). These authors demonstrated that iron-reducing anaerobic bacteria Shewanella algae can reduce gold ions in the presence of H2 gas, which results in the formation of 10–20 nm gold nanoparticles. It was further hypothesized that specific hydrogenase might be involved in the reduction of gold ions when hydrogen was used as an electron donor.

Table 1.1. List of different metallic nanoparticles synthesized by bacteria

Metallic material

Bacteria (reference)

Au

0

Bacillus subtilis

(Beveridge and Murray, 1980);

Shewanella algae

(Kashefi et al., 2001);

Rhodopseudomonas capsulate

(Kashefi et al., 2001; He et al., 2007, 2008);

Pseudomonas aeruginosa

(Karthikeyan and Beveridge, 2002);

Lactobacilli

strains (Nair and Pradeep, 2002);

Thermomonospora

sp. (Ahmad et al., 2003

b

);

Rhodococcus

sp. (Ahmad et al., 2003

a

);

Ralstonia metallidurans

(Reith et al., 2006);

Actinobacter

sp. (Bharde et al., 2007);

Streptomyces viridogens

strain HM10 (Balagurunathan et al., 2011);

Streptomyces griseus

(Derakhshan et al., 2012);

Streptomyces hygroscopicus

(Sadhasivam et al., 2012);

Streptomyces

sp. ERI-3 (Zonooz et al., 2012)

Ag

0

Pseudomonas stutzeri

A259 (Klaus et al., 1996; Joerger et al., 2000);

Corynebacterium

sp. SH09 (Zhang et al., 2005);

Enterobacteriaceae

(

Klebsiella pneumoniae

,

E. coli

and

Enterobacter cloacae

) (Shahverdi et al., 2007);

Morganella spp.

(Parikh et al., 2008);

Bacillus licheniformis

(Kalishwaralal et al., 2008);

Lactobacillus fermentum

(De-Gusseme et al., 2010);

Morganella psychrotolerans

(Ramanathan et al., 2011);

Escherichia coli

AUCAS 112 (Kathiresan et al., 2010);

Idiomarina

sp. PR58-8 (Seshadri et al., 2012)

Fe

3

S

4

M. magnetotacticum

(Mann et al., 1984; Philipse and Maas, 2002);

Magnetospiryllum

(Farina et al., 1990); Sulfate-reducing bacteria (Mann et al., 1990);

M

.

gryphiswaldense

(Lang et al., 2006);

Acinetobacter

sp. (Bharde et al., 2008)

Fe

3

O

4

, Fe

2

O

3

Magnetotactic bacteria (Blakemore, 1975; Mann et al., 1984);

Geobacter metallireducens

(Vali et al., 2004);

Actinobacter

sp. (Bharde et al., 2005)

Pt

0

Shewanella algae

(Konishi et al., 2007)

Pd

0

Desulfovibrio desulfuricans

(Yong et al., 2002

a

,

b

)

Cu

0

Serratia

sp. (Hasan et al., 2008);

E. coli

(Singh et al., 2010)

Co

3

O

4

Marine cobalt-resistant bacterial strain (Kumar et al., 2008)

CdS

Clostridium thermoaceticum

(Cunningham and Lundie, 1993);

R. palustris

(Bai et al., 2009)

ZnS

Sulfate-reducing bacteria (Labrenz et al., 2000)

Se

0

Thauera selenatis

(DeMoll-Decker and Macy, 1993; Bledsoe et al., 1999; Sabaty et al., 2001);

Rhizobium selenitireducens

strain B1 (Hunter and Kuykendall, 2007; Hunter et al., 2007);

E. coli

(Avazeri et al., 1997);

Clostridium pasteurianum

(Yanke et al., 1995);

Bacillus selenitireducens

(Afkar et al., 2003);

Pseudomonas stutzeri

(Lortie et al., 1992);

Wolinella succinogenes

(Tomei et al., 1992);

Enterobacter cloacae

(Losi and Frankenberger, 1997);

Pseudomonas aeruginosa

(Yadav et al., 2008);

Pseudomonas alkaphila

(Zhang et al., 2011

a

)

Te

0

Sulfurospirillum barnesii

,

B. selenireducens

(Baesman et al., 2007)

Ti

0

Lactobacillus

sp. (Prasad et al., 2007),

Bacillus

sp. (Prakash et al., 2009)

UO

2

Micrococcus lactilyticus

(Woolfolk and Whiteley, 1962);

Alteromonas putrefaciens

(Myers and Nealson, 1988);

G. metallireducens

GS-15 (Lovley et al., 1991);

S. oneidensis

MR-1 (Marshall et al., 2006);

Desulfosporosinus

sp. (O’Loughlinej et al., 2003)

Karthikeyan and Beveridge (2002) observed microbial reduction of gold ions by Pseudomonas aeruginosa, resulting in intracellular accumulation of gold nanoparticles with a particle diameter of 20 nm. In another study, it was shown that bacterium Rhodopseudomonas capsulate was capable of reducing gold ions into gold nanoparticles (He et al., 2007). When the biomass of R. capsulate was incubated with gold ions at neutral pH, gold nanoparticles of 10–20 nm size were formed. Further, when the same reaction was carried out under acidic pH conditions, triangular gold particles with an edge length of c. 500 nm were obtained as well as the spherical gold nanoparticles (He et al., 2008).

The ability of bacterium Ralstonia metallidurans to precipitate colloidal gold nanoparticles from aqueous gold chloride solution has recently been reported, but the exact mechanism of this process is not yet clear (Reith et al., 2006). In a series of reports, Sastry’s group screened different bacterial strains for the biosynthesis of gold and silver nanoparticles with control over morphologies and size distribution. It was shown that alkalothermophylic actinomycete, Thermomonospora sp., synthesized spherical gold nanoparticles of size 8 nm with a narrow size distribution (Ahmad et al., 2003b). In other case, an alkalotolerent actinomycete, Rhodococcus sp., was reported for the formation of nearly monodisperse 10 nm gold nanoparticles (Ahmad et al., 2003a). Further study demonstrated that the size and shape of gold nanoparticles could be controlled by adjusting the reaction parameters. Gold nanoparticles with variable size and shape were obtained using a strain of actinomycetes, Actinobacter sp. (Bharde et al., 2007). When this strain reacted with gold ions in the absence of molecular oxygen, gold nanoparticles of triangular and hexagonal shapes were produced along with some spherical particles. It was consequently concluded that protease enzyme secreted by Actinobacter sp. was responsible for the reduction of gold ions. Moreover, it was described how molecular oxygen slows down the reduction of gold ions in an unknown manner, possibly by inhibiting the action of protease secreted by this strain. Other bacterial systems able to reduce gold ions to make nanoparticles include: Streptomyces viridogens strain HM10 (Balagurunathan et al., 2011), Streptomyces griseus (Derakhshan et al., 2012), Streptomyces hygroscopicus (Sadhasivam et al., 2012), and Streptomyces sp. ERI-3 (Zonooz et al., 2012). The reduction appears to be initiated via electron transfer from NADH-dependent enzymes as an electron carrier.

Some bacteria have been reported for the formation of more than one metal nanoparticle and bimetallic alloy. Nair and Pradeep (2002) synthesized nanoparticles of gold, silver, and their alloys using different Lactobacillus strains, lactic acid-producing bacteria, and the active bacterial component of buttermilk. It is well known that ionic silver is highly toxic to most microbial cells. Nonetheless, several bacterial strains have been reported to be silver resistant. Pseudomonas stutzeri A259, isolated from a silver mine in Utah (USA), was the first bacterial strain with reductive potential to form silver crystals (Klaus et al., 1996; Joerger et al., 2000). This bacterium produced a small number of crystalline α-form silver sulfide acanthite (Ag2S), crystallite particles with the composition of silver and sulfur at a ratio of 2:1. The resistance mechanism of P. stutzeri towards silver ions is poorly understood however; several groups postulated that efflux cellular pumps might be involved in the formation of silver nanoparticles (Silver, 2003; Ramanathan et al., 2011). Parikh and co-workers (2008) used Morganella sp., a silver-resistant bacterium for the synthesis of silver nanoparticles, and established a direct correlation between the silver-resistance machinery of this bacteria and silver nanoparticles biosynthesis. Three silver-resistant homologue genes (silE, silP, and silS) were recognized in Morganella sp. The presence of these genes suggested that this organism has a unique mechanism for protection against the toxicity of silver ions that involves the formation of silver nanoparticles. Similarly, the intracellular production of silver nanoparticles by the highly silver-tolerant marine bacterium, Idiomarina sp. PR58-8, was described by Seshadri et al. (2012). The strain of Escherichia coli AUCAS 112 isolated from mangrove sediments is also capable of reducing the silver ions at a faster rate (Kathiresan et al., 2010).

Zhang and co-workers (2005) demonstrated that dried cells of Corynebacterium sp. SH09 produced silver nanoparticles at 60 °C in 72 h on the cell wall in the size range of 10–15 nm with diamine silver complex [Ag(NH3)2]+. The culture supernatants of Enterobacteriaceae (Klebsiella pneumoniae, E. coli, and Enterobacter cloacae) also formed silver nanoparticles by reducing Ag+ to Ag0. With the addition of piperitone, silver ions reduction was partially inhibited, which suggested the involvement of nitro-reductase in this process (Shahverdi et al., 2007). Similarly, the formation of silver nanoparticles by Bacillus licheniformis (Kalishwaralal et al., 2008), Lactobacillus fermentum (De-Gusseme et al., 2010), and psychro-tolerant bacteria Morganella psychrotolerans (Ramanathan et al., 2011) was described.

Attempts to synthesize metallic nanoparticles such as iron, platinum, palladium, copper, selenium, and uranium have only been made recently. Most of the work in this area has been oriented towards synthesis of magnetite nanoparticles. For instance, a simple and green approach for the synthesis of iron sulfide has been shown in bacteria such as Magnetospiryllum (Farina et al., 1990), M. magnetotacticum (Mann et al., 1984; Philipse and Maas, 2002), sulfate-reducing bacteria (Mann et al., 1990), M. gryphiswaldense (Lang and Schüler, 2006), and Acinetobacter sp. (Bharde et al., 2008). Nanoparticles formed by these strains showed predominant morphologies of octahedral prism, cubo-octahedral, and hexagonal prism in the size range 2–120 nm. The results obtained indicated that bacterial sulfate reductases are responsible for the process. The possibility of using bacteria for the formation of iron oxide nanoparticles has also been studied. Magnetotactic bacteria (Blakemore, 1975; Mann et al., 1984), iron-reducing bacteria Geobacter metallireducens (Vali et al., 2004), and Actinobacter sp. (Bharde et al., 2005) were able to form magnetite (Fe3O3) or maghemite (γ-Fe2O3).

The process of magnetic nanoparticles mineralization can be divided into four steps: (1) vesicle formation and iron transport from outside of the bacterial membrane into the cell; (2) magnetosomes alignment in a chain; (3) initiation of crystallization; and (4) crystal maturation (Fig. 1.2; Faramarzi and Sadighi, 2013).

Figure 1.2. Magnetosome bio-mineralization in magnetotactic bacteria (MTB). (I) MamI, MamL, MamB, and MamQ proteins initiate the membrane invagination and form a vesicular membrane around the magnetosome structure. (II) The protease-independent function of MamE recruits other proteins such as MamK, MamJ, and MamA to align magnetosomes in a chain. (III) Iron uptake occurs via MagA, a transmembrane protein, and initiation of magnetic crystal bio-mineralization occurs through MamM, MamN, and MamO proteins. (IV) Finally, MamR, MamS, MamT, MamP, MamC, MamD, MamF, MamG, the protease-dependent function of MamE, and Mms6, a membrane tightly bounded by GTP-ase, regulate crystal growth and determine morphology of the produced magnetic nanoparticles.

Source: Faramarzi, M.A., Sadighi, A. 2013. Insights into biogenic and chemical production of inorganic nanomaterials and nanostructures. Advances in Colloid and Interface Science 189–190: 1–20. Copyright © 2013, Elsevier.

Platinum and palladium nanoparticles have also been explored as they are interesting materials with a wide range of applications. Konishi et al. (2007) demonstrated platinum nanoparticle synthesis by the resting cells of Shewanella algae in the presence of N2–CO2 gas mixture. S. algae were able to reduce PtCl6–2 ions to platinum nanoparticles during 60 minutes of reaction time at neutral pH and 25 °C. It should be noted that the underlying biochemical process as to how these organisms are able to synthesize platinum nanoparticles is still unclear and remains an open challenge. The first report for the synthesis of palladium nanoparticles appeared in early 2000 using a sulfate-reducing bacterium Desulfovibrio desulfuricans (Yong et al., 2002a,b). The formation of palladium nanoparticles of approximately 50 nm in size in the presence of molecular hydrogen or formate as an electron donor when reacted with aqueous palladium ions at pH 2–7 was demonstrated.

Gram-negative rod, such as Serratia sp. (Hasan et al., 2008) isolated from insect gut and Escherichia coli (Singh et al., 2010) when challenged with aqueous copper precursors, were able to synthesize a mixture of copper and copper oxide quasi-spherical nanoparticles of size range 10–40 nm. It was postulated that two proteins/peptides of molecular weight 25 kDa and 52 kDa might be involved in the reduction and stabilization of these nanoparticles. Kumar et al. (2008) reported the extracellular synthesis of ferromagnetic Co3O4 nanoparticles by a marine cobalt-resistant bacterium isolated from the Arabian Sea.

Different bacterial strains have also been explored for the synthesis of semiconductors (so-called quantum dots), such as CdS and ZnS. Production of CdS nanocrystals was observed in the case of Clostridium thermoaceticum (Cunningham and Lundi, 1993), K. pneumoniae (Smith et al., 1998), E. coli (Sweeney et al., 2004), and R. palustris (Bai et al., 2009). It is believed that bacterial cysteine desulfhydrase is responsible for the formation of CdS nanoparticles. Labrenz et al. (2000) has demonstrated that sphalerite crystals (ZnS) are produced within natural biofilms, which are dominated by the sulfate-reducing bacteria.

Selenium and tellurium respiration studies have fascinated scientists as these ions are rarely in contact with microbes in their natural environment. Some studies have suggested that SeO32− reduction may involve the periplasmic nitrite reductase in Thauera selenatis (DeMoll-Decker and Macy, 1993; Bledsoe et al., 1999; Sabaty et al., 2001) and Rhizobium selenitireducens strain B1 (Hunter and Kuykendall, 2007; Hunter et al., 2007), nitrate reductase in E. coli (Avazeri et al., 1997), hydrogenase I in Clostridium pasteurianum (Yanke et al., 1995), and arsenate reductase in Bacillus selenitireducens (Afkar et al., 2003) or some of the non-enzymatic reactions (Tomei et al., 1992). Most research on the biogenesis of selenium nanoparticles are based on anaerobic systems. However, there are also a few reports in the literature on the aerobic formation of these nanostructures by bacteria such as: Pseudomonas stutzeri (Lortie et al., 1992), Enterobacter cloacae (Losi and Frankenberger, 1997), Pseudomonas aeruginosa (Yadav et al., 2008), Bacillus sp. (Prakash et al., 2009), and Pseudomonas alkaphila (Zhang et al., 2011a). Another metalloid semiconductor, tellurium (which belongs to the chalcogen family), has been reduced from tellurite to elemental tellurium by two anaerobic bacteria, Sulfurospirillum barnesii and B. selenireducens. Interestingly, the two different species yielded a different morphology of tellurium nanoparticles. S. barnesii formed extremely small nanospheres of diameter less than 50 nm that coalesced to form large aggregates, while B. selenitireducens initially formed nanorods of approximately 10 nm in diameter by 200 nm length, which clustered together forming large rosettes (c. 1000 nm) made from individual shards of 100 nm width by 1000 nm length (Baesman et al., 2007). Titanium nanoparticles of spherical aggregates of 40–60 nm were also produced extracellularly using the culture filtrate of Lactobacillus sp. at room temperature (Prasad et al., 2007).

Another interesting metal, especially in its nanoparticulate form, is uranium. In the same way as for gold, uranium is soluble in the oxidized form, U(VI); the reduced form of uranium, U(IV), is insoluble however. Among the first reports of U(IV) synthesis, Woolfolk and Whiteley (1962) found that the cell-free extracts of Micrococcus lactilyticus reduced U(VI) to UIV). Alteromonas putrefaciens grown in the presence of hydrogen as an electron donor and U(VI) as an electron acceptor also reduced U(VI) to U(IV) (Myers and Nealson, 1988). In line with these observations, Lovley et al. (1991) demonstrated that G. metallireducens GS-15, when grown anaerobically in the presence of acetate and U(VI) as electron donor and electron acceptor, reduced soluble uranium U(VI) to insoluble U(IV) oxidizing acetate to CO2. Marshall and co-workers (2006) found out that c-type cytochrome (MtrC) on the outer membrane and extracellular of dissimilatory metal-reducing bacterium S. oneidensis MR-1 was involved in the reduction of U(VI) predominantly with extracellular polymeric substance as UO2-EPS in cell suspension and intracellularly in periplasm. Desulfosporosinus sp., a gram-positive sulfate-reducing bacterium isolated from sediments when incubated with mobile hexavalent uranium U(VI) reduced to tetravalent uranium U(IV) which precipitated uraninite. These uraninite (UO2) crystals coated on the cell surface of Desulfosporosinus sp. were within the size range 1.7 ± 0.6 nm (O’Loughlinej et al., 2003).

1.3. Synthesis of Nanoparticles by Fungi

Fungi have also been used for the synthesis of different kinds of metal nanoparticles (Basavaraja et al., 2008; Bawaskar et al., 2010; Raheman et al., 2011). Rai et al. (2009b) proposed the term “myconanotechnology” to describe research carried out on nanoparticles synthesized by fungi, the integrated discipline of mycology and nanotechnology. Many fungal species have so far been exploited for the synthesis of metal nanoparticles, including endophytic fungi.

Ahmad et al. (2003c) exploited Fusarium oxysporum for the synthesis of silver nanoparticles. They reported that when exposed to the fungus F. oxysporum, aqueous silver ions were reduced in solution thereby leading to the formation of an extremely stable silver hydrosol. The silver nanoparticles were in the range of 5–15 nm in dimensions and stabilized in solution by proteins secreted by the fungus. Exposure of F. oxysporum to an aqueous solution of K2ZrF6, resulting in the protein-mediated extracellular hydrolysis of zirconium hexafluoride anions at room temperature, leading to the formation of crystalline zirconia nanoparticles, was reported by Bansal et al. (2004). They concluded that as F. oxysporum is a plant pathogen which is not exposed to such ions during its life cycle, it secretes proteins capable of hydrolyzing ZrF62.

Bansal et al. (2005) reported the synthesis of silica and titania nanoparticles by F. oxysporum when the fungal cell filtrate was challenged with their respective salts, that is, K2SiF6 and K2TiF6. The resulting nanoparticles formed were in the range of 5–15 nm and had an average size of 9.8 ± 0.2 nm. Duran et al. (2005) studied the production of metal nanoparticles by several strains of F. oxysporum. They found that when aqueous silver ions were exposed to the cell filtrate of F. oxysporum, they reduced to the formation of silver nanoparticles. The resulting silver nanoparticles were in the range of 20–50 nm. They hypothesized that the reduction of the metal ions occurs by a nitrate-dependent reductase enzyme and a shuttle quinone extracellular process. F. oxysporum f. sp. lycopersici, causing wilt in tomato, was exploited for intracellular and extracellular production of platinum nanoparticles (Riddin et al., 2006). Bharde et al. (2006) reported the synthesis of magnetite nanoparticles from F. oxysporum. F. acuminatum isolated from infected ginger was successfully exploited for the mycosynthesis of silver nanoparticles by Ingle et al. (2008). Ingle and coworkers (2008) also proposed the hypothetical mechanism for the synthesis of silver nanoparticles. According to them, NADH-dependent nitrate reductase played an important role in the synthesis of nanoparticles (Fig. 1.3).

Figure 1.3. Possible mechanism of enzymatic reduction of the silver ions.

Source: Ingle, A., Gade, A., Pierrat, S., Sonnichsen, C., Rai, M.K. Mycosynthesis of silver nanoparticles using the fungus Fusarium acuminatum and its activity against some human pathogenic bacteria. Current Nanoscience 4: 141–144. Copyright © 2008, Bentham Science Publishers.

They reported the formation of polydispersed, spherical nanoparticles in the range of 4–50 nm with average diameter of 13 nm. Ingle et al. (2009) used F. solani isolated from infected onion for the synthesis of silver nanoparticles; again, polydispersed, spherical nanoparticles were synthesized in the size range of 5–35 nm.

Soil-born fungus Aspergillus fumigatus is also reported to produce the silver nanoparticles extracellularly when the cell extract was challenged with aqueous silver ions (Bhainsa and D’Souza, 2006). Gade et al. (2008) reported the biosynthesis of silver nanoparticles from A. niger isolated from soil, and also suggested the mechanism for the action of silver nanoparticles on E. coli. Similarly, Jaidev and Narsimha (2010) reported the synthesis of silver nanoparticles using A. niger. Vigneshwaran et al. (2007) reported the potential of A. flavus for the intracellular production of silver nanoparticles; when treated with aqueous silver ions, the silver nanoparticles were synthesized in the cell wall. Moharrer and co-workers (2012) reported the extracellular synthesis of silver nanoparticles using A. flavus which was isolated from soil of Ahar copper mines. Extracellular biosynthesis of silver nanoparticles was studied using the fungus Cladosporium cladosporioides (Balaji et al., 2009). The transmission electron microscope (TEM) image showed polydispersed and spherical particles with size ranges of 10–100 nm.

Mukherjee et al. (2001) were the first to report the use of fungal systems for the synthesis of silver and gold nanoparticles. They observed for Verticillium