Table of Contents

Cover

Title Page

Preface

Part 1: Nanoscale Science

Chapter 1: Introduction
1. References
Chapter 2: Essential Approaches and Forces
1. 2.1 Top-Down Approach
2. 2.2 Bottom-Up Approach
3. 2.3 Aggregation of Nanoparticles
4. 2.4 Smoluchowski Aggregation Kinetics
5. 2.5 DLVO Theory
6. 2.6 Lennard–Jones Potential
7. 2.7 Hydrogen Bonding
8. 2.8 Hydrophobic Interactions
9. 2.9 Steric Forces
10. References
Chapter 3: Thermodynamics of Nanosystems
1. 3.1 Thermodynamics at Nanoscale
2. 3.2 Laws of Thermodynamics
3. 3.3 Concept of Entropy
4. 3.4 Gibbs Equation
5. 3.5 Thermodynamic Properties
6. References
Chapter 4: Phase Transitions and Stability at Nanoscale
1. 4.1 Generalized Observations
2. 4.2 Formation of Metastable Phases
3. 4.3 Stability of Small Objects
4. 4.4 Chemical Reactions in Nanosystems
5. References
Chapter 5: Interactions with Biomolecules and Applications to Biology
1. 5.1 Quantum Dot–Protein Interaction
2. 5.2 Nanoclay–Protein Interaction
3. 5.3 DNA–Nanoclay Interaction
4. 5.4 Size-Dependent Effect on Enzymatic Activity
5. 5.5 Applications to Biology
6. References

Part II: Bottom-Up Assembly of Inorganic Nanoparticles

Chapter 6: Metal Nanoparticles
1. 6.1 Gold Nanoparticles
2. 6.2 Silver Nanoparticles
3. 6.3 Palladium Nanoparticles
4. 6.4 Platinum Nanoparticles
5. 6.5 Samarium Nanoparticles
6. 6.6 Copper Nanoparticles
7. 6.7 Cobalt Nanoparticles
8. 6.8 Nickel Nanoparticles
9. 6.9 Bismuth Nanoparticles
10. 6.10 Aluminum Nanoparticles
11. 6.11 Lead Nanoparticles
12. References
Chapter 7: Metal Oxide Nanoparticles
1. 7.1 Alumina Nanoparticles
2. 7.2 Antimony Oxide
3. 7.3 Cobalt Oxide Nanoparticles
4. 7.4 Copper Oxide Nanoparticles
5. 7.5 Cerium Oxide Nanoparticles
6. 7.6 Indium Oxide Nanoparticles
7. 7.7 Iron Oxide Nanoparticles
8. 7.8 Lanthanum Oxide Nanoparticles
9. 7.9 Magnesium Oxide Nanoparticles
10. 7.10 Neodynium Oxide Nanoparticles
11. 7.11 Nickel Oxide Nanoparticles
12. 7.12 Samarium Oxide Nanoparticles
13. 7.13 Silica Nanoparticles
14. 7.14 Titanium Dioxide Nanoparticles
15. 7.15 Tin Oxide Nanoparticles
16. 7.16 Zinc Oxide Nanoparticles
17. 7.17 Zirconium Nanoparticles
18. References
Chapter 8: Metal Sulfide Nanoparticles
1. 8.1 Antimony Sulfide
2. 8.2 Bismuth Sulfide
3. 8.3 Cadmium Sulfide
4. 8.4 Copper sulfide
5. 8.5 Lead Sulfide
6. 8.6 Manganese Sulfide
7. 8.7 Nickel Sulfide
8. 8.8 Silver Sulfide
9. 8.9 Tin Sulfide
10. 8.10 Zinc Sulfide
11. References

Part III: Self-Assembly of Organic Nanoparticles

Chapter 9: Polymeric Nanoparticles
1. 9.1 Polyethylene Glycol (PEG)
2. 9.2 Polylactic Acid (PLA) Nanoparticles
3. 9.3 PNIPAM Nanoparticles
4. 9.4 Poly(D,L-lactide-co-glycolic acid) (PLGA) Nanoparticles
5. 9.5 Poly(methyl methacrylate) (PMMA) Nanoparticles
6. 9.6 Polyurethane Nanoparticles
7. 9.7 Polystyrene Nanoparticles
8. 9.8 Ethyl Cellulose Nanoparticles
9. 9.9 Polyacrylamide Nanoparticles
10. 9.10 Poly(vinylpyrrolidone) Nanoparticles
11. 9.11 Poly(ϵ-caprolactone) Nanoparticles
12. 9.12 Poly(vinyl alcohol) Nanoparticles
13. References
Chapter 10: Biopolymeric Nanoparticles
1. 10.1 Albumin Nanoparticles
2. 10.2 Alginate–BSA Nanoparticles
3. 10.3 BSA–Acacia Nanoparticles
4. 10.4 Chitosan Nanoparticles
5. 10.5 Tripolyphosphate–Chitosan Nanoparticles
6. 10.6 siRNA–Chitosan Nanoparticles
7. 10.7 DNA–Chitosan Nanoparticles
8. 10.8 Gelatin Nano- and Microparticles
9. 10.9 Heparin Nanoparticles
10. 10.10 Heparin–Chitosan Nanoparticles
11. 10.11 Heparin–Deoxycholic Acid Nanoparticles
12. 10.12 Heparin–Poly(β-benzyl-l-aspartate) Nanoparticles
13. 10.13 Hyaluronic Acid Nanoparticles
14. 10.14 Nucleic Acid Nanoparticles
15. 10.15 Pectin Nanoparticles
16. 10.16 Pectin–Cisplatin Nanoconjugate
17. 10.17 Silk Protein Nanoparticles
18. 10.18 Zein Nanoparticles
19. References
Index

End User License Agreement

List of Illustrations

Chapter 1: Introduction

Figure 1.1 Representative picture showing the size of nanostructures compared with biological objects.
Figure 1.2 Visualization of nano versus microscopic objects. Effect of size on surface area and melting is shown.
Figure 1.3 STM image of a single Lander molecule, which is seen to create a circular electronic wave modulation, 0.008 nm in amplitude, on the Cu (111) surface (scale bar: 3 nm).
Figure 1.4 Dependence of band gap and the DOS on the number of atoms present in a cluster (nanoparticles). It increases from right to left for metal clusters and bulk metals and decreases from left to right for insulating clusters and individual atoms/molecules. The parameter d is called the Kubo gap.
Figure 1.5 Various plant resources used for the synthesis of nanoparticles: (a) olibanum, (b) Euphorbiaceae plant extract, (c) lemon, (d) neem kernel, (e) Annona squamosa/cannon, (f) Crossandra infundibuliformis leaf, (g) banana peel, (h) Hibiscus rosa-sinensis, and (i) rice hull.

Chapter 2: Essential Approaches and Forces

Figure 2.1 Monolithic Gomateshwara statue at Shravanabelagola, which was built around 983 A.D. It is a 17 m monolith structure situated above a hill in Shravanabelagola in the Hassan district of Karnataka state, India. It is one of the largest freestanding statues in the world.
Figure 2.2 The Taj Mahal complex is believed to have been completed in its entirety in 1653. The full height of this monument is 171 m. This monument is located in Agra, India.
Figure 2.3 It is possible to approach the targeted nanostructure from top-down or bottom-up pathways.
Figure 2.4 Schematic representation of processes involving dispersion, aggregation, and sedimentation of nanoparticles.
Figure 2.5 Schematic representation of various competing forces that lead to homonucleation of nanoparticles.
Figure 2.6 Self-assembly of gelatin nanoparticles on silicon substrate. These particles were stabilized in a 45% ethanolic solution.
Figure 2.7 Aggregation of carbon nanoparticles with a monomer size of 30 nm in organic solvent. This aggregate has a fractal dimension of 1.76.
Figure 2.8 Increase in the surface potential of the particle causes increase in the coagulation energy barrier. The double-layer repulsion dominates.
Figure 2.9 Energy barrier increases with electrolyte concentration up to a certain limit. Beyond this concentration, a secondary minimum appears. This is called critical coagulation concentration.
Figure 2.10 Lennard–Jones potential showing hard-sphere repulsion and weak attraction components.
Figure 2.11 (a) MD simulation snapshots of zinc oxide nanoparticles in water. (b) Gray atom, Zn; red atom, O; white atom, H; red dashed lines, hydrogen bonds. The arrows in (b) indicate the connection of two nanoparticles through the network of hydrogen bonding.
Figure 2.12 (a) Hydrogen-bonded graphene oxide (horizontal gray lines) sheets in different conformations. Oxygen and hydrogen atoms are shown as red and white spheres, respectively. (b) Variation of the computed O⋯H bond energy between a pair of water molecules shown as a function of bond distance d. The optimum O bond distance is 2.55 Å, and the bond strength is 320 meV.
Figure 2.13 (a) Clathrate cage encapsulating a hydrophobe and (b) hydrophobic aggregation. Notice that the frozen water molecules trapped between the hydrophobic plates get displaced with time, leading to aggregation of the hydrophobes.
Figure 2.14 (a) A pair of nanoparticles (NP) coated with polymer chains shown at a distance δ of their closest approach. (b) A blown-up picture of their interface is shown here.

Chapter 4: Phase Transitions and Stability at Nanoscale

Figure 4.1 Representative melting profile of a quantum dot shown as a function of particle size. The solid line represents the predicted value.
Figure 4.2 Relation between equilibrium constant and the reciprocal of the size of CuO nanoparticles measured at the following temperatures: (a) 298 K, (b) 303 K, (c) 308 K, (d) 313 K, and (e) 323 K.
Figure 4.3 Relation between the Gibbs free energy and the reciprocal of the size of CuO nanoparticles measured at the following temperatures: (a) 298 K, (b) 303 K, (c) 308 K, (d) 313 K, and (e) 323 K.
Figure 4.4 Relation between molar enthalpy and the reciprocal of the size of CuO nanoparticles measured at the following temperatures: (a) 298 K, (b) 303 K, (c) 308 K, (d) 313 K, and (e) 323 K.
Figure 4.5 Relation between molar entropy and the reciprocal of the size of CuO nanoparticles measured at the following temperatures: (a) 298 K, (b) 303 K, (c) 308 K, (d) 313 K, and (e) 323 K.

Chapter 5: Interactions with Biomolecules and Applications to Biology

Figure 5.1 Logarithmic plot derived from the fluorescence data of various proteins [BSA (1.5 mM), β-Lg (5.5 mM), and HSA (1.5 mM)] as a function of concentration of QDs in moles per liter. The binding constant K and number of binding sites n were determined from the intercept and slope of least-square-fitted straight line to the data points as described by Eq. (5.1).
Figure 5.2 Dependence of binding constant K on H_index of protein molecule. Notice the sharp drop in K value with the increase in $c05-math-014$ . Solid line is the least-square fitting of the data to Eq. (5.8).
Figure 5.3 (a) Variation of scattering intensity of proteins (BSA, β-Lg, HSA) with and without QD recorded at room temperature. (b) Variation of zeta-potential of proteins (BSA, β-Lg, HSA) with and without QD recorded at room temperature.
Figure 5.4 (a) Representative CD spectra of proteins, BSA (1.5 mM) in the absence and presence of QDs. (b) Dependence of secondary structure (helicity) of proteins [BSA (1.5 mM), β-Lg (5.5 mM) and HSA (1.5 mM)] on the QD concentration. Note loss of secondary structure due to complexation of proteins with QD particles in region I.
Figure 5.5 FTIR spectra of proteins β-Lg (5.5 mM) in the absence and presence of QDs. Figure on the curve indicates micromolar concentration of QDs.
Figure 5.6 Plot of hydration of protein–QD complexes [BSA (1.5 mM), β-Lg (5.5 mM), and HSA (1.5 mM)] as a function of QD concentration. Note the loss of hydration by as much as 25% due to the binding in region I. The sharp drop in area demarcates the two regions (arrow).
Figure 5.7 Absorbance at λ = 280 nm of proteins, BSA (1.5 μM), HSA (1.5 μM), and β-Lg (5.5 μM) in the absence and presence of MMT and Laponite.
Figure 5.8 Variation of (a) hydrodynamic radius (R_h), (b) zeta-potential, and (c) pH of proteins (BSA (1.5 μM), HSA (1.5 μM), and β-Lg (5.5 μM)) with and without NCs recorded at room temperature.
Figure 5.9 Peak intensity of synchronous fluorescence spectra at Δλ = 60 nm (Tryptophan) and Δλ = 15 nm (Tyrosine) versus wavelength plot of various proteins in the absence and presence of various concentrations of (a) MMT and (b) Laponite.
Figure 5.10 Dependence of secondary structure (helicity) of proteins [BSA (1.5 μM), β-Lg (5.5 μM), and HSA (1.5 μM)] on the NC concentration. Note the drastic effect on secondary structure due to complexation of proteins with NC particles. In the case of β-Lg, we noticed a rise in helicity upon binding with both Laponite and MMT.
Figure 5.11 Schematic representation of the protein–nanoclay complexation and loss in protein helicity after interaction. As shown in this figure, measurement of helicity is for HSA with Laponite complex.
Figure 5.12 UV-vis spectra of (a) Laponite–DNA and (b) MMT-DNA solutions. Notice the change in the peak profile of characteristic DNA peak (260 nm) as a function of clay concentration.
Figure 5.13 Variation of absorption maxima at 260 nm as a function of clay concentration. Notice the saturation binding beyond 0.1% (w/v) clay concentration. The inset shows the low-concentration linear region.
Figure 5.14 Plot of relative viscosity as a function of clay concentration. Notice the two distinct binding regions separated by clay concentration 0.1% (w/v).
Figure 5.15 Variation of interfacial tension as a function of clay concentration. Notice the change in surface tension profile at 0.1% (w/v) clay concentration.
Figure 5.16 Representative helicity of DNA shown as a function of clay concentration. Notice that binding of MMT clay promoted helicity in the low clay concentration region (<0.1% (w/v)), whereas beyond this, there was no change in helicity value.
Figure 5.17 FTIR spectra of Laponite–DNA and MMT-DNA solutions.
Figure 5.18 Dependence of secondary structure (helicity) of lysozyme (5 mM) by 2.5 and 6.3 nm sized QD concentration (2.6–52.5 nM) at 298 K. Note the remarkable loss and gain of secondary structure due to complexation of proteins with 2.5- and 6.3-nm-sized QD particles, respectively.
Figure 5.19 Effect of 2.5- and 6.3-nm-sized QD concentration (2.6–52.5 nM) on the enzymatic activity of lysozyme (5 mM).
Figure 5.20 Schematic of lysozyme adsorption on CdSe QD.

Chapter 6: Metal Nanoparticles

Figure 6.1 The Lycurgus Cup (a) looks green in reflected light and (b) red in transmitted light.
Figure 6.2 The Au:Sn ratio that controlled the Au nanoparticle size. The smaller ratio produced smaller particles.
Figure 6.3 Artabotrys odoratissimus (Nag Champa) plant.
Figure 6.4 Photographs and the UV-Vis absorption spectra depicting the color change during synthesis: (a) copper acetate solution, (b) addition of lactic acid, (c) addition of ammonia–water, and after addition of hydrazine hydrate: (d) 2 min, (e) 10 min, (f) 30 min, (g) 60 min.

Chapter 7: Metal Oxide Nanoparticles

Figure 7.1 Structure of hollow gamma-alumina nanoparticles prepared by annealing at (a) 400 °C, (b) 550 °C, (c) 700 °C, and (d) 950 °C.
Figure 7.2 SEM images of antimony trioxide: (a) nanoparticles; (b) nanowires; and (c) nanoribbons.
Figure 7.3 Schematic of the biosynthesis of antimony trioxide in the presence of yeast.
Figure 7.4 XRD data and FE-SEM images of the nanoparticles obtained from various cerium precursors used. (a) XRD data of ceria nanoparticles obtained from the precursors Ce(NO₃)₃·6H₂O and CeCl₃·7H₂O. FE-SEM images of ceria nanoparticles obtained from the precursors: (b) Ce(NO₃)₃·6H₂O, (c) CeCl₃·7H₂O, (d) Ce(CH₃CO₂)₃·xH₂O, and (e) Ce₂(SO₄)₃·8H₂O.
Figure 7.5 Scanning electron micrograph of Fe₃O₄ (a) and γ-Fe₂O₃ (b) NPs. Scale bar is 30 nm.
Figure 7.6 TEM images of intermediate and aerated iron oxide nanoparticles. The mean size of these nanoparticles was (a) and (d) 5 nm, (b) and (e) 11 nm, (c) and (f) 19 nm, respectively; insets show HRTEM images.
Figure 7.7 Schematic of the synthesis of lanthanum oxide and lanthanum hydroxide nanoparticles.
Figure 7.8 Synthesis scheme for neodymium oxide nanoparticles; (a) represents the general scheme; and (b) depicts salt precursor to Schiff base–ligand molar ratio (1 : 0.5 to 1 : 4) dependent morphologies.
Figure 7.9 Schematic representation of the formation Nd(OH)₃ nanoparticles.
Figure 7.10 (a) SEM and (b) TEM images of nickel oxide nanoparticles.
Figure 7.11 Various synthesis protocols for changing the morphology of silica nanoparticles.
Figure 7.12 Stöber method synthesis of silica nanoparticles where methanol:TEOS ratio was varied; SEM images depict the morphology before and after calcinations (Shimura and Ogawa, 2007). The methanol:TEOS synthesis ratios referred herein are as follows: (a) 300 (noncalcined), (b)750 (noncalcined), (c)1125 (noncalcined), (d) 1500 (noncalcined), (e) and (f)1500 (calcined), (g) 2250 (noncalcined),(h) and (i) 2250 (calcined), (j) 3000 (noncalcined), and (k) and (l) 3000 (calcined).
Figure 7.13 Variation of surface area and density of silica nanoparticles as a function of size.
Figure 7.14 Picture of colony of (SIN strain) Bacillus mycoides isolate.
Figure 7.15 TEM (10 000× magnification) images of titania nanoparticles biosynthesized by Bacillus mycoides (a Gram-positive bacterium): (a) nanoparticles before and (b) after repeated washing in water. Inset (a) depicts the spherical morphology and (b) the particle size distribution histogram. Arrows point to individual particles.
Figure 7.16 Picture of Euphorbia prostrata plant (also known as False Daisy).
Figure 7.17 Schematic of the preparation of SnO₂ nanowires on substrates (stainless steel SS and copper).
Figure 7.18 Schematic of the formation of SnO₂ nanocrystals and their fractal clusters: (a) laser; (b) target; (c) plasma; (d) plume; (e) nucleation; (f) grain rotation; (g) coalescence; (h) growth; and (i) fractal.
Figure 7.19 Scanning electron micrographs of assembled ZnO nanostructures synthesized at: 60 °C (a and b), 70 °C (c and d), and 80 °C (e and f).
Figure 7.20 SEM images of ZnO nanoparticles prepared by using different amounts of (uncooked) rice (in g): 0 (a, b), 0.25 (c, d), 0.5 (e, f), 1 (g, h), 2 (i, j), 4 (k, l), and 8 (m, n).
Figure 7.21 Pictures of plants Hybanthus enneaspermus (a) and Abrus precatorius (b).
Figure 7.22 Synthesis flowchart of zirconia nanoparticles.

Chapter 8: Metal Sulfide Nanoparticles

Figure 8.1 Apparatus used by Sun and Tsuji (2015) to prepare antimony trisulfide nanoparticles.
Figure 8.2 (a) FTIR spectra of octylamine, mixture of octylamine and cadmium octanoate at 25 °C, mixture of octylamine and Cd(Oc)₂ at 100 °C, and Cd(Oc)₂. (b) Photo of elemental sulfur in ODE and octylamine solvents. (c) UV-vis spectra of sulfur dissolved in ODE and octylamine solvents.
Figure 8.3 TEM images of 6, 8, and 9 nm PbS nanocrystals.
Figure 8.4 Schematic of NiS hollow sphere synthesis. First, MMA in ethyl alcohol was cross-linked by γ-irradiation to form PMMA gel. Gel pieces were brought to swelling equilibrium in nickel salt precursor solution in the presence of isopropanol. The swollen gel was subjected to γ-irradiation to break the cross-links, which formed a distinct NiS mineralized shell around the MMA core. The core was vaporized by heating the sample at 125 °C for 3 h to receive NiS hollow spheres.
Figure 8.5 SEM (a, b) and TEM (c, d) images of SnS nanostructures prepared at 180 °C. The inset in c shows ED pattern taken from a single nanobelt while d shows the same taken from a nanobelt of the nano right angle.

Chapter 9: Polymeric Nanoparticles

Figure 9.1 Synthesis by emulsification–evaporation technique.
Figure 9.2 Synthesis by solvent displacement technique. **Surfactant is optional. ***In interfacial deposition method, a fifth compound may be needed for preparation of nanocapsules.
Figure 9.3 Synthesis by emulsion solvent diffusion (ESD) technique.
Figure 9.4 Synthesis by salting-out technique.
Figure 9.5 Stereoisomeric forms of lactic acid.
Figure 9.6 Single-pot synthesis of PEG–PLA NPs using precursor HEMA-PEG_m.
Figure 9.7 TEM images and particle size distribution of PLA nanoparticles prepared using plant extracts. PLA-1 through PLA-5 refers to NPs prepared with the plant extracts Syzygium cumini, Bauhinia variegata, Cedrus deodara, Lonicera japonica, and Elaeocarpus sphaericus, respectively. Corresponding TEM images are designated (a–e).
Figure 9.8 Synthesis scheme of PBAE polymer.
Figure 9.9 Molecular structure of PLGA copolymer.
Figure 9.10 SEM images of PS nanoparticles and their typical size: (a) PS-LUT (96 nm), (b) PS-LUT-co-acrylic acid (81 nm), (c) PS-LUT-co-2-aminoethyl methacrylate (89 nm), and (d) PS-SDS (170 nm). LUT refers to Lutensol AT-50.
Figure 9.11 Fluorescence image of ethyl cellulose containing hydrophobic (1) and hydrophilic (2) QDs under UV light illumination (λ_ex = 365 nm).
Figure 9.12 Ethyl cellulose microparticles.
Figure 9.13 TEM images of PVA HNPs synthesized from low molecular weight (13–23 kDa) (a, b), medium molecular weight (89 kDa) (c), and high molecular weight (190 kDa) (d) PVA samples (5 g/l). Scale bars are 1 µm (a) and 200 nm (b−d).

Chapter 10: Biopolymeric Nanoparticles

Figure 10.1 Molecular structure of human serum albumin.
Figure 10.2 Chemical structure of chitosan.
Figure 10.3 Chemical structure of N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride.
Figure 10.4 Ionic gelation method for synthesis of chitosan nanoparticles.
Figure 10.5 Formation of TPP–chitosan NPs.
Figure 10.6 Formation of TPP–chitosan coacervates.
Figure 10.7 SEM image of chitosan-coated nanoparticles with docetaxel cargo.
Figure 10.8 Dependence of zeta-potential of gelatin A and B molecules measured at room temperature.
Figure 10.9 Particle size distribution of nano- and microparticles with mean diameter = 50, 260, and 500 nm dispersed in water.
Figure 10.10 AFM image of 300 Bloom gelatin nanoparticle. Scale bar: 200 nm.
Figure 10.11 Transmission electron micrography of gelatin nanoparticles. Scale bar: 500 nm.
Figure 10.12 Depiction of Huggins plot for gelatin nano- (50 nm) and microparticles (500 nm) dispersed in water. The same for gelatin chain is shown for comparison. Note the significant increase in the k_H value as the size is reduced from micro- to nano-domain.
Figure 10.13 Protocol for synthesis of gelatin nano- and microparticles at room temperature of 20 °C.
Figure 10.14 Representative SEM images of gelatin nanoparticles.
Figure 10.15 Molecular structures of heparin.
Figure 10.16 Molecular structure of pectin.
Figure 10.17 Molecular structure of zein.

List of Tables

Chapter 1: Introduction

Table 1.1 List of biopolymers used for surface functionalization of nanoparticles for specific in vivo targeting applications
Table 1.2 List of some representative biosynthetic methods for preparation of metal nanoparticles (NPs)
Table 1.3 Some representative differential properties of bulk and nanoscale antimony oxide (AO) materials

Chapter 5: Interactions with Biomolecules and Applications to Biology

Table 5.1 The binding constant K, number of occupied binding sites n, fluorescence quenching constant K_q, and fluorescence lifetime τ₀ of various protein–QD samples
Table 5.2 The binding constant K, number of occupied binding sites n, fluorescence quenching constant K_q, and fluorescence lifetime τ₀ of various protein–NC samples (see Das, et al. 2016a for details)
Table 5.3 Representative list of nanomaterial–biomolecule/cell interaction works reported in the literature

Chapter 6: Metal Nanoparticles

Table 6.1 Various methods of synthesis of Au NPs
Table 6.2 Various methods used for synthesis of silver nanoparticles
Table 6.3 Various synthesis methods for preparation of Pd nanoparticles
Table 6.4 Various synthesis methods for preparation of Pt nanoparticles
Table 6.5 Various synthesis methods for preparation of Sm nanoparticles
Table 6.6 Various synthesis methods for preparation of Cu nanoparticles
Table 6.7 Various synthesis methods for preparation of Co nanoparticles and their derivatives
Table 6.8 Various synthesis methods for preparation of Ni nanoparticles and their derivatives
Table 6.9 Various synthesis methods for preparation of Bi nanoparticles and their derivatives
Table 6.10 Various synthesis methods for preparation of Al nanoparticles and their derivatives
Table 6.11 Various synthesis methods for preparation of Pb nanoparticles and their derivatives
Table 6.12 Consolidated summary of bioreduction methods to produce metal nanoparticles

Chapter 7: Metal Oxide Nanoparticles

Table 7.1 Representative methods for the preparation of Al₂O₃ nanoparticles reported in the literature
Table 7.2 Representative methods for the preparation of Sb₂O₃ nanoparticles reported in the literature
Table 7.3 Representative methods for the synthesis of cobalt oxide nanoparticles
Table 7.4 Representative methods for the synthesis of copper nanoparticles and their derivatives
Table 7.5 Representative methods for the synthesis of cerium oxide nanoparticles
Table 7.6 Representative methods for the synthesis of indium oxide nanoparticles
Table 7.7 Some representative methods for the preparation of iron oxide nanoparticles and their derivatives reported in the literature
Table 7.8 Some representative methods for the preparation of magnesium oxide nanoparticles and their derivatives reported in the literature
Table 7.9 Some representative methods for the preparation of neodymium nanoparticles and their derivatives reported in the literature
Table 7.10 Some representative methods for the preparation of nickel oxide nanoparticles and their derivatives reported in the literature
Table 7.11 Some representative methods for the preparation of samarium nanoparticles and their derivatives reported in the literature
Table 7.12 Some representative methods for the preparation of silica nanoparticles and their derivatives reported in the literature
Table 7.13 Representative methods for the preparation of TiO₂ nanoparticles reported in the literature
Table 7.14 Representative list of methods for the synthesis of tin oxide nanoparticles reported in the literature
Table 7.15 Representative methods for the synthesis of ZnO nanoparticles reported in the literature
Table 7.16 Representative list of methods for the synthesis of zirconia nanoparticles reported in the literature

Chapter 8: Metal Sulfide Nanoparticles

Table 8.1 Some representative synthesis methods and the average size of CdS nanoparticles synthesized
Table 8.2 Some representative synthesis methods and the average size of MnS nanoparticles
Table 8.3 Some representative synthesis methods and the average size of nickel sulfide nanoparticles
Table 8.4 Some representative synthesis methods and the average size of silver sulfide nanoparticles
Table 8.5 Some representative synthesis methods and the average size of tin sulfide nanoparticles synthesized
Table 8.6 Some representative synthesis methods and the average size of zinc sulfide nanoparticles synthesized

Chapter 9: Polymeric Nanoparticles

Table 9.1 Reviews on polymeric nanoparticles
Table 9.2 Various methods for synthesis of PLA Nanoparticles
Table 9.3 Various methods for synthesis of PLGA NPs
Table 9.4 Various methods for synthesis of PMMA Nanoparticles
Table 9.5 Various methods for synthesis of PU NPs
Table 9.6 Various methods for synthesis of PS NPs
Table 9.7 Various methods for synthesis of EC NPs
Table 9.8 Various methods for synthesis of PA NPs
Table 9.9 Various methods for synthesis of PCL NPs
Table 9.10 Various methods for synthesis of PVP NPs

Chapter 10: Biopolymeric Nanoparticles

Table 10.1 Representative list of applications of albumin and albumin-derived nanoparticles
Table 10.2 Representative list of preparations and applications of chitosan and their derivatives reported in the literature
Table 10.3 Composition of gelatin (per 100 amino acid)
Table 10.4 Physical properties of gelatin chain and its nano- and microparticles measured at 20 °C (pH = 5.5)
Table 10.5 Representative list of applications of gelatin nanoparticles (GNP) and their derivatives reported in the literature in the past 10 years
Table 10.6 Applications of heparin and heparin-conjugated nanoparticles
Table 10.7 Applications of hyaluronic acid (HA) nanoparticles
Table 10.8 Various methods for condensation of DNA/RNA and preparation of their nanoparticles and derivatives
Table 10.9 Applications of pectin nanoparticles and their nanoconjugates
Table 10.10 Applications of zein and its conjugated nanoparticles (NPs)

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Preface

Nanoscience has grown into an all-pervasive discipline now. We find it in all spheres of life, a word that is ubiquitous. Needless to say, nanotechnology happens to be an enabling provision that deals with nanosized materials, and it has encompassed enormous expectations. It is these expectations that accrue sky high and have remarkable bearing in the development of novel materials, devices, and systems. There are several dimensions to nanoscience research, out of which the “nanomaterial level design and synthesis” is the most developed at present, both in terms of scientific understanding and their commercial exploitations. At the end of the twentieth century, nanoparticles and their superstructures were studied for their size-dependent physiochemical properties. Now, they have entered a commercial exploration domain. Nonetheless, we are far away from achieving a complete nanocycle: synthesis, characterization, application, and then, their disposal. Needless to say, the word nano has become a household name these days. This field witnessed an explosion of novel and potentially useful application platforms in the past three decades. The ability to design nanoparticles of customized shape and size has given rise to remarkable interest in developing new protocols for applications in industries such as pharmaceuticals, biomedical, semiconductor, to name a few. At the same time, the flip side of these glorious nanoparticles is that many of them have the disadvantage of being potentially toxic.

This book is designed as a common foundation for application scientists and involved researchers desiring to acquire firsthand knowledge about the intricacies of science such as thermodynamics, phase transitions, biomolecular interactions at the nanoscale. Intelligent design and customized assembly of nanostructures, which constitute the first cycle of any nanoscience activity, are deliberated in this book with adequate depth. Any experimental exploration in the area of nanoscience necessitates the controlled and reproducible preparation of a desired nanostructure. This particular aspect has been somewhat addressed in a limited domain in many research articles and in several books. However, to the best of our knowledge, there is no book that discusses the preparation protocols of metallic, metal oxides, quantum dots, polymeric, and biopolymeric nanoparticles in a single volume, which has been emphasized exclusively herein. This book is written with the objective of presenting the design protocols in a rationalized and pedagogical manner for the benefit of the researcher.

The intelligent reorganization of cluster atoms or molecules at nanoscale can create many smart and novel materials with properties quite different from those in their bulk state and not always predictable from our existing knowledge base. Remarkably, within the near-limitless heterogeneity and diversity of these nanomaterials, some are quite toxic to biosystems; some are relatively benign, while others may confer considerable health benefits. Intelligent design of nanomaterials with customized synthesis is essential to reap the benefits associated with this new technology while minimizing their adverse impacts. Therefore, a robust understanding of thermodynamics, phase transitions, and biomolecular interactions at nanoscale is called for. We believe these issues must be discussed along with preparation protocols under a single umbrella. Therefore, we have attempted to present these aspects in a lucid and seamless manner in this book.

For a young and new researcher, starting an academic career in nanoscience is not trivial as it involves a deeper understanding of physics, physical chemistry, material science, polymer science, and, sometimes, bipophysics. A matured nanoscientist is one who understands the basics of nanoscience and is able to synthesize, characterize, use, and, finally, dispose of the nanomaterial concerned. Thus, one is expected to walk the complete nanocycle. Therefore, the journey begins with the understanding of science at the nanoscale; it must subsequently cover the path of intelligent and customized design of the desired nanoparticles and/or their derivatives. Considering the fact that today's nanoscientist can be a physicist with no biology background, or a chemist with no physics, or a biologist with no material science background, it is difficult, if not impossible, for him/her to customize the desired nanoparticles.

It should not be forgotten that the details of design protocols of most of the types of nanoparticles are well documented in the literature spread over more than 100 journals, many of which may not be easily accessible. In addition, the protocols are often presented in a very circular and confusing manner, making the procedures difficult to follow, and to reproduce the results. We have realized this while training our Master's and Ph.D. students. They are at a loss when it comes to taking the first-step toward the long journey in the arena of nanoscience. In this volume, it has been ensured that the potential reader is a novice with no specialized background in physics, chemistry, biology, and/or material science. The presentation has been maintained at a very elementary level, and the figures and tables are used liberally to ensure lucid presentation of the text. It is envisaged that the potential reader will benefit from reading this book. Further, this book is expected to serve as a ready reckoner for an experienced nanoscientist.

This book is dedicated to the memory of Prof. Amarnath Maitra, a visionary who pioneered nanoscience research in India in the 1980s. The senior author had the privilege to walk the initial miles in nanoscience research under his wonderful mentorship and guidance. We are grateful to our numerous young and ever-enthusiastic students who drive the nanoscience program in our laboratory on a day-to-day basis and come up with exciting formulations, and they are never tired of showing us their colorful nanodispersions, which they have just synthesized, with amazing enthusiasm. It is this spirit that drives this wonderful branch of science.

Himadri B. Bohidar and Kamla Rawat

10 November 2016
New Delhi

Design of Nanostructures

Self-Assembly of Nanomaterials

Preface

Part I
Nanoscale Science