Contents

Cover

Title page

Copyright page

Preface

Part I: Synthesis and Characterization

Chapter 1: Synthesis, Characterization and General Properties of Carbon Nanotubes
1. 1.1 Introduction
2. 1.2 The History of Carbon Nanotubes
3. 1.3 Graphene
4. 1.4 Graphite
5. 1.5 Fullerene
6. 1.6 Rehybridization
7. 1.7 Structure of Carbon Nanotubes (CNTs)
8. 1.8 Classification of CNTs
9. 1.9 Crystal Structures of Carbon Nanotubes
10. 1.10 Synthesis Methods
11. 1.11 The Purification Process of CNTs
12. 1.12 Mechanism of Growth CNTs
13. 1.13 Properties of Carbon Nanotubes
14. 1.14 Applications of Carbon Nanotubes
15. 1.15 Characterization of CNTs
16. 1.16 Composite of CNTs/Semiconductors
17. 1.17 Recent Updates on Synthesis of CNTs
18. References
Chapter 2: Synthesis and Characterization of Phosphorene: A Novel 2D Material
1. 2.1 Introduction
2. 2.2 Synthesis of Phosphorene
3. 2.3 Characterization of Phosphorene
4. 2.4 Environment Stability Issue of Phosphorene
5. 2.5 Summary and Future Prospective
6. References
Chapter 3: Graphene for Advanced Organic Photovoltaics
1. 3.1 Introduction
2. 3.2 History of Graphene
3. 3.3 Structure of Graphene
4. 3.4 Graphene Family Nanomaterials
5. 3.5 Properties of Graphene
6. 3.6 Graphene for Advanced Organic Photovoltaics
7. 3.7 Conclusion
8. References
Chapter 4: Synthesis of Carbon Nanotubes by Chemical Vapor Deposition
1. 4.1 Introduction
2. 4.2 Synthesis Methods
3. 4.3 The Parameters of CVD
4. 4.4 Deformations and Defects in Carbon Nanotubes
5. 4.5 Characterization of CNTs
6. 4.6 Conclusion
7. References

Part II: Environmental and Engineering Applications

Chapter 5: A Review of Pharmaceutical Wastewater Treatment with Nanostructured Titanium Dioxide
1. 5.1 Introduction
2. 5.2 Heterogeneous Photocatalysis
3. 5.3 Pharmaceuticals in the Environment
4. 5.4 Role of TiO₂ in Photocatalysis for Degradation, Mineralization, and Transformation Process of Pharmaceuticals
5. 5.5 Applications
6. 5.6 Conclusion
7. Acknowledgment
8. References
Chapter 6: Nanosilica Particles in Food: A Case of Synthetic Amorphous Silica
1. 6.1 Introduction
2. References
Chapter 7: Bio-Sensing Performance of Magnetite Nanocomposite for Biomedical Applications
1. 7.1 Introduction
2. 7.2 Potential Applications of Magnetic Nanoparticles
3. 7.3 Conclusion
4. References
Chapter 8: The Importance of Screening Information Data Set in Nanotechnology
1. 8.1 Introduction
2. 8.2 Review of the Literature
3. 8.3 Behavioral Patterns of Engineered Nanoparticles
4. 8.4 Conclusions and Recommendations
5. References
Chapter 9: Nanomaterials for Biohydrogen Production
1. 9.1 Introduction
2. 9.2 Major Biohydrogen Production Pathways
3. 9.3 Nanaparticle Effects on Biohydrogen Production
4. 9.4 Biohydrogen Producing Associated with Immobilized Enzymes (Cellulases and Hydrogenases)
5. 9.5 Outlook and Concluding Notes
6. Acknowledgment
7. References
Chapter 10: A Framework for Using Nanotechnology in Military Gear
1. 10.1 Introduction
2. 10.2 Literature Review
3. 10.3 Application of Nanotechnology in the Military
4. 10.4 Conclusions
5. References

Part III: Biological Applications

Chapter 11: Plasmonic Nanopores: A New Approach Toward Single Molecule Detection
1. 11.1 Introduction
2. 11.2 Sensing Principles of Plasmonic Nanopore
3. 11.3 Optical Properties
4. 11.4 Improving Performance
5. 11.5 Surface Patterning
6. 11.6 Applications – Next-Generation DNA Sequencing and Beyond
7. 11.7 Some Other Sensing Examples
8. 11.8 Future Perspectives
9. References
Chapter 12: Catalytically Active Enzyme Mimetic Nanomaterials and Their Role in Biosensing
1. 12.1 Introduction
2. 12.2 Different Types of Catalytically Active Enzyme Mimetic Nanomaterials
3. 12.3 Applications of Catalytically Active Nanomaterials in Biosensing
4. References
Index
End User License Agreement

List of Illustrations

Chapter 1

Figure 1.1 Honeycomb lattice structure of graphene, consisting of two triangular lattices a₁ and a₂, which are the lattice unit vectors, and δ₁, δ₂, δ₃, which are the nearest-neighbor vectors.
Figure 1.2 Honeycomb lattice structure of graphene, the Brillouin zone. The Dirac cones are located at the K and K^– points.
Figure 1.3 The structure of graphene in nature.
Figure 1.4 Distribution sigma δ (blue color) and pi π (bright color) bonds.
Figure 1.5 Graphene map chirality of (n, m) chiral vectors that give three structures armchair, zig-zag and chiral nanotubes
Figure 1.6 The X-ray diffraction patterns of SWNT (red color) and MWNT (green color).
Figure 1.7 The arc discharge system for the synthesis of A-MWNTs and B-SWNTs.
Figure 1.8 The laser ablation system for the synthesis of CNTs.
Figure 1.9 Schematic diagram for the flame reactor to the formation of carbon nanotubes.
Figure 1.10 Typical CVD apparatus for the production of carbon nanotubes.
Figure 1.11 A tip growth model of driving force carbon diffusion.
Figure 1.12 The base growth model of carbon diffusion.
Figure 1.13 Schematic diagram of M/CNTs showing the higher distribution of M on the surfaces of CNTs with the reaction in the fuel cell.
Figure 1.14 Schematic of the Stokes and anti-Stokes transition with a Raman shift.
Figure 1.15 Schematic diagram showing the types of transition of the electrons and the Rayleigh and Raman scattering.
Figure 1.16 Skim of typical Raman spectroscopy for (a) SWNT and (b) MWNT.
Figure 1.17 XPS of synthesized MWNTs. (a) C 1s spectra between 282 and 292 eV, (b) N–H spectra between 396 and 404 eV. Arrows show possible positions of carbon peaks as described in the text.
Figure 1.18 The evaluation of a single TGA curve.
Figure 1.19 Typical HIM image for synthesized CNTs.
Figure 1.20 Schematic of a proposed model for (a) TiO₂/MWNT and (b) TiO₂/SWNT mechanisms.
Figure 1.21 Schematic diagram for the mechanism of the reactions for the ternary composite (Pt-TiO₂/fCNTs).

Chapter 2

Figure 2.1 Crystal structure of phosphorene; top view of single-layer phosphorene; the puckered structure of three-layer phosphorene. The x and z axis are along the zigzag and armchair directions, respectively [30]. Reproduced with permission Copyright 2015, Nature Publishing Group.
Figure 2.2 Mechanical exfoliation method to produce phosphorene from bulk BP by tape exfoliation.
Figure 2.3 (a) Schmatic representation for plasma etching of phosphorene. (b, c) AFM image of multilayered pristine phosphorene after and before Ar+ plasma thinning, respectively. Reprinted (adapted) with permission from [75]. Copyright 2015, American Chemical Society.
Figure 2.4 Schematic description of the liquid exfoliation method. (a) Sonication-assisted exfoliation, (b) ion intercalation, and (c) ion exchange.
Figure 2.5 Photograph of the few-layer phosphorene dispersions in the solvents DMF and DMSO.
Figure 2.6 Structural view of phosphorene. (a) Side view and (b) top view of monolayer phosphorene. Reproduced with permission from [92]. Copyright 2015, Royal Society of Chemistry. (c) ADF-STEM image viewed along the [101] direction. (d) ADF-STEM image captured at an edge of a BP flake along the [100] direction showing multiple layers stacked together. (e) Magnified image of the region highlighted in (d). (c–f) Reproduced with permission from [93]. Copyright 2015, AIP Publishing.
Figure 2.7 (a) and (b) SEM image of phosphorene nanoflakes. Reproduced with permission from [95]. Copyright 2015, IOP Publishing. (c) TEM and HRTEM image (in inset) of phosphorene flake. (d) Electron diffraction. Reproduced with permission from [96].
Figure 2.8 (a) and (b) AFM image of an exfoliated few-layered phosphorene crystal with a sectional profile displaying 0.85 nm. Reproduced with permission from [14]. Copyright 2014, American Chemical Society.
Figure 2.9 (a) Thickness dependence of the intensity ratio between the Agl and Si peaks [48]. Copyright 2014, IOP publishing. (b) Temperature dependence of A_g1, B_2g, and A_g2 Raman peak positions. (c) Polarization-resolved Raman spectra of a BP layered thin film with 532-nm linearly polarized laser excitation incident in the z direction. The D direction is along the 45° angle relative to the x- and y-directions, as shown in the bottom panel. Reproduced with permission from [98] Copyright 2014, Nature Publishing Group. (d) Raman spectra of phosphorene under uniaxial strain along the ZZ direction. Reproduced with permission from [99]. Copyright 2014, AIP publishing.
Figure 2.10 PL spectra of 2L, 3L, 4L, and 5L phosphorene flakes. Reproduced with permission from [112]. Copyright, American Chemical Society.
Figure 2.11 Schematic representation of the PL process in phosphorene.
Figure 2.12 UV-vs-NIR spectroscopy of black phosphorus and its liquid-exfoliated few-layer flakes. (a) Optical absorbance of bulk phosphorus and exfoliated few layer BP. (b) Absorbance of phosporene suspensions with varying fraction. (c) Representative direct Tauc plots used to determine the high-energy band-to-band transition. (d) Representative direct Tauc plots of the low-energy optical transition. Reproduced with permission from [118]. Copyright 2014, AIP publishing.
Figure 2.13 Time dependent degradation of unprotected and protected phosphorene.

Chapter 3

Figure 3.1 Basic structure of graphene.

Chapter 4

Figure 4.1 The structure of graphene in nature.
Figure 4.2 The classification of carbon nanotubes by the number of graphene layers: (a) SWNT, (b) DWNT, (c) FWNT, (d) MWNT.
Figure 4.3 Methods for synthesis CNTs by Arc discharge, laser ablation, flame, and, chemical vapor deposition.
Figure 4.4 Different natural sources to synthesize CNTs.
Figure 4.5 Raman spectra of purified carbon nanotubes grown at different temperature.
Figure 4.6 Different deformation in the skeleton of carbon nanotubes.
Figure 4.7 Deformation modes in a nanotube: (a) axial deformation, (b) radial deformation, and (c) twisting deformation.
Figure 4.8 Post-synthesis defect on the outer surfaces of CNTs.
Figure 4.9 Small vacancy defects in the graphene system. Mono-vacancy (a) before and (b) after reconstruction and the H-termination of the remaining dangling bond. Di-vacancy (c) before and (d) after reconstruction.
Figure 4.10 Typical Raman spectroscopy for (a) SWNT and (b) MWNT.

Chapter 5

Figure 5.1 The photocatalytic degradation of acyclovir under visible light irradiation using (a) pure TiO₂, g-C₃N₄, and g-C₃N₄/TiO₂; (b) the photocatalysts prepared at 1.0 g NH₄F and treated for 72 h with different hydrothermal temperatures; (c) the photocatalysts prepared at hydrothermal temperature of 150^oC treated for 72 h with different NH₄F concentrations; (d) the photocatalysts prepared at 1.0 g NH₄F and hydrothermal temperature of 150^oC treated at different times (reproduced with permission from [40]).
Figure 5.2 Proposed visible-light-driven photocatalytic degradation pathway of acyclovir in water by g-C₃N₄/TiO₂ hybrid photocatalyst (reproduced with permission from [40]).
Figure 5.3 Schematic representation of the reactor used for photocatalytic ozonation process (reproduced with permission from [41]).
Figure 5.4 TEM images of (a) MMT and (b-c) TiO₂/MMT samples (reproduced with permission from [41]).
Figure 5.5 FE-SEM images of (A) MWCNT and (B) MWCNTs/TiO₂ nano-composites, along with corresponding EDX micrographs (reproduced with permission from [44]).
Figure 5.6 Scanning electronic micrographs (SEM) of (a) PAC and (b) TiO₂/AC (reproduced with permission from [46]).

Chapter 7

Figure 7.1 Crystal structure of hematite rhombohedral, R3c.
Figure 7.2 Crystal structure of magnetite cubic, Fd3m.
Figure 7.3 Crystal structure of maghemite cubic, P4₃32/Tetragonal, P4₁2₁2.
Figure 7.4 Plot of M vs. H for paramagnetism.
Figure 7.5 Plot of M vs. H for diamagnetism.
Figure 7.6 Magnetic arrangement ferromagnetic material.
Figure 7.7 Parallel alignment in ferromagnetism.
Figure 7.8 Magnetic ordering in the antiferromagnetic material.
Figure 7.9 Particle size hugely affects the magnetic properties (DM = diamagnetic, PM = paramagnetic, SPM = superparamagnetic, FM = ferromagnetic) [20].
Figure 7.10 Illustrations of high performance abilities of magnetic nanoparticles in several fields of application.
Figure 7.11 Magnetic separation [39, 40].
Figure 7.12 (a, b, c) The fluorescence reflectance imaging of a nude mouse before and (d, e, f) 3h after the injection of GadoSiPEG2C (K: kidneys; B: bladder) [48].
Figure 7.13 (Left) T in-vivo T1 MRimages of a mouse before and injection after 90 min (right) of the sample solution into the tail vein of the mouse; it also shows a clear contrast improvement in the kidneys (illustrated by an arrow) [55].
Figure 7.14 Equivalent anatomical image structures from the same rat at two adjacent slice locations, during magnetic nanoparticles present in microbubble injection. After injection, when the time lapse, the images display that the T₂ signal in liver decreases at rest and then increases [57].
Figure 7.15 The graphical illustration of magnetic nanoparticle-targeted drug delivery mechanism [60].
Figure 7.16 Specific tissue delivery of magnetic nanoparticles via active targeting, which is facilitated by “leaky” vasculature. Nanoparticle internalization by (A) formation of an endosome and receptor-mediated endocytosis. (B) Endosomal acidification by proton pumps that results in elevated swelling, osmotic pressure, and (C) rupture of the endosome allowing the release of the nanoparticle and conjugated therapeutic agents reprinted from [61].
Figure 7.17 Mechanism of cell death induced by magnetic hyperthermia with nanoparticles of γ-Mn_xFe₂–xO₃ [63].
Figure 7.18 The gene delivery principle by the usage of magnetic particles. The cells are to be transfected and positioned between the nucleic acids and hemagnetic field gradient which are then attached to the particles. The applied field is the reason for the particles to progress towards the target cells; here, the cell entry is achieved, e.g., by endocytosis [64].

Chapter 9

Figure 9.1 Major biohydrogen production methods.
Figure 9.2 Schematic representation of a typical two-chamber MEC reactor and its operation.
Figure 9.3 Different aspects and types of immobilization systems used in the production of biohydrogen from biomass sources.

Chapter 10

Figure 10.1 Estimated percentage of risk via exposure routes.
Figure 10.2 The hierarchy of controls for risk reduction and control when working with ENMs [33].
Figure 10.3 Safety and ethics issues to be addressed when new technology is developed to enhance the soldier’s performance. Adapted from [20, 21, 22].

Chapter 11

Figure 11.1 Schematic diagram showing working principle of nanopore.
Figure 11.2 Schematic showing working principle of plasmonic nanopore.
Figure 11.3 Electron microscopy images of plasmonic nanopores. (a) A square nanopore array in a 120 nm gold film on an 80 nm supporting silicon nitride membrane fabricated by electron beam lithography. (b) A long range ordered nanohole array in 50 nm silver prepared by colloidal self-assembly. (c) Nanopores in gold (20 nm) – silicon nitride (50 nm) – gold (20 nm) triple layers. (d) Nanoholes in multilayers of ultrathin aluminum and aluminum nitride films (with schematic). (e) A “double nanohole” in 100 nm gold fabricated by ion beam milling. (f) A nanopore in a single suspended 20 nm gold film imaged by transmission electron microscopy (inset showing diffraction pattern). (Reference: Dahlin, A.B., Analyst, 2015, 140, 4748–4759) [121].
Figure 11.4 Using nanohole arrays as a conventional surface plasmon resonance sensor by excitation in the Kretschmann configuration (SPR). The response to polyelectrolyte multilayers is compared with a gold film without nanoholes and with excitation in transmission (EOT) (Ref. Couture et al., [64]).
Figure 11.5 Schematic illustration of the optical sequencing method. Each base is converted into an extended sequence that is hybridized to a fluorophore–quencher beacon, where each base is represented by a different fluorophore color. The DNA/beacon complex is then threaded through a nanopore and the color barcode is detected optically. Each released beacon is automatically closed, quenching its own fluorescence while diffusing away from the vicinity of the pore (Ref. Glioba et al., Analyst, 2015, 140, 4733–4747) [122].
Figure 11.6 Optical detection of the four 2-bit combinations representing the four different nucleotides. (a) Illustration of the four samples labeled with two fluorophores correspond to the four bases. (b) The color ratio (R) distribution of 1774 events revealing two peaks corresponding to the two fluorophores. (c) Representative intensity-corrected fluorescence traces of unzipping events. Corresponding bit called, base called, and certainty score indicated above the event. The intensities in the two channels were corrected automatically by a computer code after each bit is called using a fixed threshold R value (Ref. Glioba et al., Analyst, 2015, 140, 4733–4747) [122].
Figure 11.7 Single- and dual-color barcode detection using low PL nanopore. (a, d) Illustration of the ssDNA template consisting 16-mer binding sequences hybridized to molecular fluorophore-quencher labeled beacons. Each DNA strand is labeled with either five green (“F1”) fluorophores (a) or specific sequence of green and red (“F1” and “F2”, respectively) fluorophores (d) as well as a quencher oligo. The strands are threaded through a low PL, 3 nm nanopores. The marked beacons are stripped off one at a time creating a distinct fluorescent burst (b, e). The electrical and optical signals are measured simultaneously, showing five clear photon bursts per event in the green channel (c) or green and red channels (f) according to the sample. (Ref. Glioba et al., Analyst, 2015, 140, 4733–4747) [122].
Figure 11.8 Detection of cancer markers in exosomes using plasmonic nanopores. The top shows the detection concept. Exosomes are captured by antibodies and the shift in the transmission maximum is measured. The resulting matrix for two cancer markers, 20 patients and 10 healthy controls, is shown below (Ref: Dahlin, A. B., Analyst, 2015, 140, 4748–4759) [121].

Chapter 12

Figure 12.1 SNP detection of complementary (CDNA) and mismatched (M-DNA) duplex DNA based on enzyme mimetic.
Figure 12.2 Schematic diagram showing oxidation color reaction of TMB by H₂O₂ catalyzed by GQDs.
Figure 12.3 Schematic representation of (a) preparation of GFH and (b) cancer cell detection by using target-directed GFH.
Figure 12.4 Schematic illustration of peroxidase-mimicking catalytic color reaction for sensitive sensing of dopamine.
Figure 12.5 Colorimetric detection of glucose by using GOx and GO-COOH-catalyzed reactions.
Figure 12.6 Fe₃O₄ MNPs as nanozymes for immunoassay.

List of Tables

Chapter 1

Table 1.1 Binding energy for different functional groups.
Table 2.1 Comparative summary of electronic and mechanical properties of monolayer phosphorene with graphene and MoS₂. The value in the bracket corresponding to the zigzag direction in contrast to the value in armchair direction.

Chapter 6

Table 6.1 Physical and chemical properties of E551 [13].

Chapter 7

Table 7.1 Some of the important magnetic parameters which includes (room temperature saturation magnetization, first degree anisotropy constants, Curie temperatures, and superparamagnetic transition sizes of ferrites.
Table 7.2 Summary of different types of magnetic behavior.
Table 7.3 Comparison between methods for the synthesis of magnetic nanoparticles.
Table 7.4 MRI parameters: components which have impact on the signal from an individual location [56].

Chapter 8

Table 8.1 Forms of silver and approximate size and charge (adapted from [16]).
Table 8.2 Comparative analysis of engineered nanoparticles and asbestos.
Table 8.3 Products containing nanosilver with subcategories and routes of exposure (adapted from [16] and [20]).
Table 8.4 Reported cases of over-the-counter colloidal medicine (adopted from [16]).
Table 8.5 Predicted silver in the environment in Europe (adopted from [16]).

Chapter 9

Table 9.1 Applications of nanoparticles on dark fermentative hydrogen production.

Chapter 10

Table 10.1 Functions of nano-engineered body gear (Thilagavathi et al., 2008 and Gupta, 2011).

Nanomaterials: Biomedical, Environmental, and Engineering Applications

Edited by

Suvardhan Kanchi

Shakeel Ahmed

Myalowenkosi I. Sabela

Chaudhery Mustansar Hussain

This edition first published 2018 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA
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Library of Congress Cataloging-in-Publication Data

ISBN 978-1-119-37026-0

Preface

Nanostructure science and technology is a broad and interdisciplinary area of research and development that has been growing explosively in the past decades. Nanomaterials can be obtained either naturally or incidentally or can be manufactured. They are crystalline or amorphous of organic or inorganic materials having sizes in the range of 1-100 nm, which exist in unbound state or as an aggregate or agglomerate. Nanomaterials are classified as nanostructured and nanophase/nanoparticle materials. Their properties are significantly different and they can be significantly improved relative to those of their coarser-grained counterparts. Most benefits of nanomaterials depend on the fact that it is possible to tailor the essential structures of materials at the nanoscale to achieve specific properties. Hence, the evolution of nanotechnology represents an ever improving process in the design, discovery, creation, and novel utilization of artificial nanoscale materials. Research on variety of chemical, mechanical, and physical properties is beginning to yield a glimmer of understanding on how this interplay manifests itself in the properties of these new materials.

To meet the major challenges in environmental sustainability, these nanomaterials in various hierarchical fashions are stimulating various important practical applications in the environmental sector. Their applications involve addressing the existing environmental problems, preventive measures for future problems resulting from the interactions of energy and materials with the environment.

In comparison to their larger counterparts, nanomaterials also have unique physico-chemical and biological properties. Therefore, nanomaterials properties, such as size, shape, chemical composition, surface structure and charge, aggregation and agglomeration, and solubility, have been investigated for advancement of diagnostic biosensors, drug delivery, and biomedical imaging.

The contents of the book includes mainly the fundamentals of nanoparticles, state-of-the-art in synthesis and characterization of nanomaterials and their influence of nanomaterials on the analytical systems (macro to micro & lab-on-a-chip) for biomedical and environmental applications. The evolution in the nanotechnology world clearly signifies a need for broader understanding and, therefore, we hope this book with contribute to this effort.