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Nanotechnology and Nanomaterials in the Treatment of Life-threatening Diseases

Nanotechnology and Nanomaterials in the Treatment of Life-threatening Diseases

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Nanotechnology and Nanomaterials in the Treatment of Life-threatening Diseases

Length:
756 pages
7 hours
Released:
Dec 5, 2013
ISBN:
9780323264501
Format:
Book

Description

Nanotechnology and Nanomaterials in the Treatment of Life-threatening Diseases takes a scientific approach to nanotechnology and nanomaterials applications in medicine, while also explaining the core biological principles for an audience of biomedical engineers, materials scientists, pharmacologists, and medical diagnostic technicians. The book is structured by major disease groups, offering a practical, application-based focus for scientists, engineers, and clinicians alike. The spectrum of medical applications is explored, from diagnostics and imaging to drug delivery, monitoring, therapies, and disease prevention. It also focuses specifically on the synthesis of nanomaterials and their potential health risks (particularly toxicity).

Nanomedicine — the application of nanomaterials and devices for addressing medical problems — has demonstrated great potential for enabling improved diagnosis, treatment, and  monitoring of many serious illnesses, including cancer, cardiovascular and neurological disorders, HIV/AIDS, and diabetes, as well as many types of inflammatory and infectious diseases.

  • Gain an understanding of how nanotechnologies and nanomaterials can be deployed in the fight against the major life-threatening diseases: cancer, neurological disorders (including Alzheimer's and Parkinson's), cardiovascular diseases, and HIV/AIDS
  • Discover the latest developments in nanomedicine, from therapies and drug delivery to diagnostics and disease prevention
  • The authors cover the health risks of nanomaterials as well as their benefits, considering toxicity and potential carcinogens
Released:
Dec 5, 2013
ISBN:
9780323264501
Format:
Book

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Nanotechnology and Nanomaterials in the Treatment of Life-threatening Diseases - Narenda Kumar

1

Introduction

Abstract

The chapter on Introduction is designed to introduce the basic concepts of nanoscience/nanotechnology. The general synthetic routes to prepare nanomaterials, particularly useful for medical applications, are described together with their characterization, unique properties arising out of the small size, and potential applications including those for health care. One section of the chapter is devoted to building blocks of human body at molecular and cellular levels in order to develop an understanding about the diagnostic/therapeutic effectiveness of nanomaterials at cellular levels. Other sections, on the other hand, give a brief description about the emerging applications of different types of nanomaterials, in different roles (i.e., drug delivery, therapeutics, imaging contrast agents, etc.), together with toxicity and regulatory issues.

Keywords

Nanoscience; Top-down; Bottom-up; Unique properties; Novel applications; Molecular and cellular levels; Diagnostic and therapeutic effectiveness; Imaging contrast agents; Toxicity

1.1 Nanoscience and nanotechnology

The three big scientific revolutions that happened in the 20th century and are continuously changing over everyday life are information technology, biotechnology, and science of nanomaterial at micro- and nanoscale. As a consequence of such changes, a series of technologies have emerged as ways to improve human wellbeing, particularly in terms of their comfort as well as health care.

Nanoscience is the study of the properties of, and phenomenon in, materials having typical sizes in the range of 1–100 nm. The prefix Nano is a Greek word which means dwarf. Nanometer refers to the length scale of one billionth of a meter (10−9 m). It is the most important development during the last couple of decades. Many definitions have been suggested to define nanotechnology [1]. However, the one suggested by NASA is taken to be more acceptable, i.e. Nanotechnology is the technology that creates functional materials, devices and systems through control of matter on a nanometer length scale (1–100 nm) and exploitation of novel phenomena and properties (physical, chemical, and biological) at nanometer scale or said in a simple way, at atomic and molecular level. Figure 1.1 gives an idea about the size and shape of materials at atomic, molecular, nano-, micro-, and macro scale together with existing building blocks of life and synthetic structures falling in nanometer size [2].

Figure 1.1 Size comparison between man-made and biologically available nanomaterials [2a]. Reproduced with permission from ASPBS.

When matter is divided into such a small dimension as nanometric, its physical, chemical, and biological properties change drastically. Accordingly the relationship between Nanoscience and nanotechnology has been largely symbiotic, with scientific discoveries leading to new technologies that in turn usher in new fundamental insights. This ability to precisely control atoms and build molecules at extremely small length scales holds the promise for important breakthroughs in healthcare, manufacturing, agriculture, energy, information technology, national securities, etc. This is why some are calling it a Nanoscience and nanotechnology revolution.

One of the fascinating features of nanotechnology is that on the nanometer scale all the natural sciences meet and intertwine. Physics meets life sciences as well as chemistry, engineering, materials sciences, and computational approaches, which communicate together and are closely linked. This inherent interdisciplinary feature, not seen in any other science and technology discipline, poses a challenge and offers enormous potential for fruitful cross-fertilizations in a specific area. Undoubtedly, the growth in this area has been tremendous and unprecedented for contribution of a number of factors. Important among them are unique and novel physical, chemical, and biological properties with application in diverse fields together with the availability of a variety of new tools such as scanning probe microscopy, spectroscopy, etc. That we can see, measure, and manipulate materials in the nanometric scale regime below.

1.1.1 Historical

It is rather difficult to fix a date for the discovery of Nanoscience, as the existence of nanomaterials and nanotechnology in both living and nonliving things can be traced back to when science began. For instance, cells in animals and plants are the glaring examples of the multifunctional nano-machine together with naturally occurring or man-made colloidal particles which fall very much in line with nanomaterials.

In ancient times, nanoparticles were used by the Damascans to create swords with exceptionally sharp edges and by Romans to craft iridescent glassware. For example, the Lycurgus Cups, Figure 1.2, known since AD 400 are made of a glass that changes color when light is shown upon them. These contain silver-gold alloyed nanoparticles distributed in such a way so as to look green in reflected light and brilliant-red in transmitted light. Which type of light is passed through these historic structures is the result of hundreds of years of trial-and-error experimentation by craftsmen passing their skills and know-how down through generations. Without realizing that what they have achieved is known now as nanotechnology is an emerging discipline of science and technology. Modern nanotechnologists can however learn from the wisdom of those forgotten antics.

Figure 1.2 The Lycurgus Cup made from glass appears red in transmitted light and green in reflected light. The glass contains 70 nm particles as seen in the transmission electron micrograph. The cup itself is dated to 4th century AD, but the metallic holder is a later addition [2b]. © Trustees of the British Museum.

The idea of atom-by-atom construction was first put forth in a scientific manner by the Nobel Prize winning physicist Richard Feynman in 1959 [3] in his famous lecture called There is Plenty of Room at the Bottom. In his speech he predicted that an entire encyclopedia would one day fit on the head of a pin and a library with all the world books would fit in three square yards. He also predicted that microscopic computers, atomic rearrangements, and Nanomedicines could float in veins.

Unfortunately, scientists and engineers did not take too much notice of these predictions at that time. Though a few years later in 1963, Sandomirskii theoretical predication [4] showed that the band gap energy of semiconductors can vary with thickness and there were experimental verifications by Stasenko [5] in 1968, called quantum size effect in a related event of nanotechnology. As a matter of fact, the term Nanotechnology was first used and defined in 1974 by Norio Taniguchi of the Tokyo Science University in Japan. According to his definition Nanotechnology mainly consists of processing, separation, consolidation, and deformation of materials by one atom or one molecule. Ekimov’s [6] reported the finding of three-dimensional quantum confinements of nanoparticles in 1981 however, the actual publication of a book entitled Engine of creation by Eric Drexler in 1986 [7] is considered to be the beginning of the present-day nanotechnology revolution. This book indeed became very popular and excelled in the treatment of the promises and potential of nanotechnology. Drexler envisioned a molecular nanotechnology discipline that would allow manufacturers to fabricate products from the bottom-up with increased molecular control. This technology would allow every molecule to be inserted into its specific place, so that the manufacturing systems using this process would be clean, efficient, and highly productive. The brief showed higher throughputs than modern manufacturing techniques that use macroscopic manipulators to fabricate devices. Around the same time the development of scanning probe microscopy by IBM Scientists allowed them fulfill Feynman’s vision of atom-by-atom construction of molecules.

Furthermore, the discovery of Fullerene by Smalley in 1986 [8] and carbon nanotubes by Iijima [9] in 1991, both allotropes of carbon in nanosize form, were other cornerstones to give a boost to the research on nanotechnology.

1.1.2 Synthesis of nanoparticles [10]

Several hundreds of nanomaterials belonging to maybe inorganic, organic, or polymeric or composite categories have now been obtained by the following general approaches, i.e.

(a) A top-down approach.

(b) A bottom-up approach.

The main objectives for applying a particular technique were as follows: (I) the synthetic method should be reproducible, (II) the method should produce monodispersed nanoparticles, (III) the surface of the nanoparticle should be defect free, and (IV) the method should be economical, scalable, and environment friendly.

1.1.2.1 Top-down methods

The top-down approach involves the breaking down of the bulk material into nanosized structure and particle. These approaches are inherently an extension of those that have been used for producing micron-sized products. They involve the slicing or successive cutting of a bulk material to get nanosized particles or to produce their desired structure with appropriate properties. This technique is quite useful to produce nanosized particles on a large scale by using mechanical force. However, the biggest problems associated with this are their imperfection of surface structure, polydispersions, surface dislocation, formation of aggregates, and clustering together with difficulty in controlling morphology of the particles.

1.1.2.2 Bottom-up methods

While nanomaterials have been generated by top-down or in other words physical methods such as arc discharged, laser aviation, chemical vapor deposition, etc., the bottom-up or in other words, the chemical approach is found to be more useful. It involves more effective build-up of a material from the bottom: atom by atom, molecule by molecule, or cluster by cluster. Though the bottom-up approach has often been referred to in nanotechnology, it is not a new concept. All the living beings in the nature only undergo growth by this approach and it has been in industrial use for the production of a variety of chemicals. Examples include the production of soap etc. The major advantages of the bottom-up approach lie in the production of nanostructures with less defects, more homogeneous chemical composition, better control of size and shape, etc.

Some of the common methods belonging to bottom-up approaches are: (I) precipitation/wet chemical/soft chemical methods, (II) reduction of metal salt/solution method, (III) hydrothermal/Solvothermal, (IV) hot thermolysis/colloidal synthesis, (V) flame synthesis, (VI) photochemical synthesis, (VII) sol-gel methods, (VIII) self-assembly, IX) biometic, etc.

Chemical method: details and procedure

(a) Precipitation/wet chemical method/soft chemical method

Precipitation is the most common technique to grow the desire sized NPs. Traditionally, both aqueous and organic solvents are used.

(b) Reduction of metal salt/solution method

Generally, metal nanoparticles are generated by this method. A number of reducing agents like NaBH4 are used, for example, for the synthesis of Au NPs [11]. In a typical reaction, the solution of chloroauric acid, H [AuCl4], is rapidly stirred while a reducing agent (NaBH4) is added. This causes Au³+ ions to be reduced to neutral gold atoms. As more and more of these gold atoms form, the solution becomes supersaturated, and gold gradually starts to precipitate in the form of sub-nanometer particles. The rest of the gold atoms stick to the existing particles, and, if the solution is stirred vigorously enough, the particles will be fairly uniform in size. To prevent the particles from aggregating, some sort of stabilizing agent that sticks to the nanoparticle surface is usually added.

(c) Hydrothermal/solvothermal

This is another solution-based method to prepare a wide range of nanomaterials having diverse shapes and sizes. Hydrothermal synthesis can be defined as a method of synthesis of single crystals that depends on the solubility of minerals in hot water under high pressure [12]. The crystal growth is performed in an apparatus consisting of a steel pressure vessel called an autoclave, Figure 1.3, in which a nutrient is supplied along with water. A gradient of temperature is maintained at the opposite ends of the growth chamber, so that the hotter end dissolves the nutrient and the cooler end causes seeds to take additional growth.

Figure 1.3 Schematic diagram of the solvothermal synthesis setup: (1) stainless steel autoclave, (2) precursor solution, (3) Teflon liner, (4) stainless steel lid, and (5) spring.

The solvothermal method is very much similar to the hydrothermal route (where the synthesis is conducted in a stainless steel autoclave), the only difference being that the precursor solution is usually not aqueous. Using the solvothermal route one gains the benefits of both the sol-gel [13] and hydrothermal routes [12]. Thus solvothermal synthesis allows for the precise control over the size, shape distribution, and crystallinity of metal oxide nanoparticles or nanostructures. These characteristics can be altered by changing certain experimental parameters, including reaction temperature, reaction time, solvent type, surfactant type, and precursor type. In a typical synthesis, titanium(IV) alkoxide, 10 g, was dissolved in a 70 cm³ portion of an alcohol in a test tube, which was then set in a 200 cm³ autoclave. The autoclave was thoroughly purged with nitrogen, heated to the desired temperature (523–573 K) at a rate of 2.5 K min−1, and kept at that temperature for 2 h. After the autoclave treatment, the resulting powders were washed repeatedly with acetone and dried in air.

(d) Reverse micelle method [14]

Reverse micelles are water-in-oil droplets stabilized by a surfactant. The surfactant most often used is sodium salt of bis(2-ethylhexyl) sulfosuccinate, usually called Na (AOT). These droplets are displayed randomly and subjected to Brownian motion. They exchange their water content and re-form two distinct micelles. Furthermore, the size of the water-in-oil droplets increases linearly, i.e. the micellar concentration decreases, with increasing water content, defined as w = [H2O]/[AOT]. The most widely used approach is shown in Figure 1.4. This involves the preparation of two separate microemulsions, incorporating the different reactants. Upon mixing, nucleation occurs on the micelle edges as the water inside them becomes supersaturated with reactants. Growth then occurs around this nucleation point, with the arrival of more reactants fed via intermicellar exchange.

Figure 1.4 Illustration of the reverse micelle preparation route for hierarchical structuring of TiO2 [14].

The reverse micelle permits the synthesis of a very wide range of nanomaterials such as II–VI semiconductors, metals, etc., with good control of size and shape.These are formed by adding a small amount of water to a surfactant in a hydrocarbon solvent, e.g. precipitation of CdS by adding sulfide to a solution of a cadmium salt. The size is determined by the size of the droplet (controlled by the water/surfactant ratio).

(e) Sol-gel process [15]

The sol-gel process, as the name implies, involves the evolution of inorganic networks through the formation of a colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid phase (gel). The precursors for synthesizing these colloids usually consist of a metal or metalloid element surrounded by various reactive ligands. The starting material is processed to form a dispersible oxide and forms a sol in contact with water or dilute acid. Removal of the liquid from the sol yields the gel, and the sol/gel transition controls the particle size and shape. Calcination of the gel produces the oxide.

Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based precursors such as Si (OEt)4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the sol-gel chemistry based on the hydrolysis and condensation of metal alkoxides M(OR)z can be described as follows:

The sol-gel method of synthesizing nanomaterials is very popular among chemists and is widely employed to prepare oxide materials. The sol-gel process can be characterized by a series of distinct steps, Figure 1.5.

Figure 1.5 Schematic representation of the sol-gel process of synthesis of nanomaterials [15]

Step 1 Formation of different stable solutions of the alkoxide or solvated metal precursor (the sol).

Step 2 Gelation resulting from the formation of an oxide- or alcohol-bridged network (the gel) by a polycondensation or polyesterification reaction that results in a dramatic increase in the viscosity of the solution.

Step 3 Aging of the gel (syneresis), during which the polycondensation reactions continue until the gel transforms into a solid mass, accompanied by contraction of the gel network and expulsion of solvent from gel pores. Ostwald ripening (also referred to as coarsening, is the phenomenon by which smaller particles are consumed by larger particles during the growth process) and phase transformations may occur concurrently with syneresis. The aging process of gels can exceed 7 days and is critical for the prevention of cracks in gels that have been cast.

Step 4 Drying of the gel, when water and other volatile liquids are removed from the gel network. This process is complicated due to fundamental changes in the structure of the gel. The drying process has itself been broken down into four distinct steps: (i) the constant rate period, (ii) the critical point, (iii) the falling rate period, (iv) the second falling rate period.

If isolated by thermal evaporation, the resulting monolith is termed a xerogel. If the solvent (such as water) is extracted under supercritical or near-supercritical conditions, the product is an aerogel.

Step 5 Dehydration, during which surface-bound M-OH groups are removed, thereby stabilizing the gel against rehydration. This is normally achieved by calcining the monolith at higher temperature.

Step 6 Densification and decomposition of the gels at high temperatures (T > 800 °C). The pores of the gel network are collapsed, and the remaining organic species are volatilized.

(f) Biomimetic approaches [16]

Bionics or biomimicry seeks to apply biological methods and systems, found in nature, to the study and design of engineering systems and modern technology. Biomineralization is one example of the systems studied. Bionanotechnology is the use of biomolecules for applications in nanotechnology, including the use of virus. Nano-cellulose is a potential bulk-scale application.

(g) Self-assembly [17]

Self-assembly, Figure 1.6, means setting up an environment such that atoms assemble or grow automatically on prepared surfaces. In this approach, an environment is created in which structures assemble automatically. Examples include chemical vapor deposition and the patterned growth of nanotubes. Nature, of course, uses self-assembly mechanisms, such as the self-assembly of cell membranes. Our ability to create nanostructures improves as we gain understanding of biological self-assembly, develop new molecular structures, and construct new tools.

Figure 1.6 Polystyrene spheres self-assembling [17].

1.1.2.3 Wet chemical synthesis of important nanomaterials for medical applications

1.1.2.3.1 FeCo NPs [18]

Synthesis of core-shell metal alloy nanoparticles is a simple two-step process wherein the first step involves the room temperature synthesis of nanocomposites of mixed metal oxide (Fe-Co) in the copolymer matrix of aniline formaldehyde and the second step involves the pyrolysis of as prepared nanocomposite under inert atmosphere.

In a typical synthesis, copolymer of aniline and formaldehyde is prepared by adding 10 ml (0.10 mol) of aniline to 50 ml of distilled water. To this 12 ml (0.12 mol) of conc. HCl is added which results in the formation of water-soluble aniline hydrochloride. To this mixture 10 ml (0.10 mol) of formaldehyde is added. The reaction proceeds through the formation of p-aminobenzyl alcohol, followed by the subsequent condensation between the amino and the hydroxyl groups. As this is an exothermic reaction, it is accompanied by the evolution of large amount of heat, so the solution is kept aside for cooling down to room temperature. Simultaneously, salt solution is prepared by dissolving the metal halide (Fe and Co halides) in 50 ml distilled water. This salt solution is then added to the precooled copolymer solution with constant stirring. This entire mixture is added to 200 ml of 10% sodium hydroxide solution with stirring. It is further stirred for 10 min and then allowed to stand for approximately 45 min to 1 h. This is then filtered under vacuum and washed with distilled water till the filtrate is free of alkali (pH 7–8). This composite is then dried at room temperature to get the nanocomposite of the mixed metal oxide(s) in the powder form.

Further, metal oxide nanocomposite powder is taken in a small quartz holder and placed in quartz reactor tube. Initially, high purity N2 (99.99%) is passed in the reactor tube for 5 min to flush off ambient air. The reactor tube containing nanocomposites is then placed in a tubular furnace and the temperature is raised at the rate of 10 °C/min. The nanocomposite is heat-treated at 900 °C for 1 h under continuous flow of N2 gas. Finally, the furnace was cooled to room temperature to obtain the desired product. The final product is core-shell graphite-coated FeCo alloy nanoparticles.

1.1.2.3.2 Iron oxide NPs [19]

Superparamagnetic iron oxide nanoparticles (SPIONs), Figure 1.7, were synthesized from Fe³+/Fe²+ salts in the presence of different coating bio-materials such as glycine, gelatine, gum arabic, and mixture of gelatine and gum arabic using NaOH as a precipitating agent. In a typical synthesis, a source of iron is prepared by dissolving 0.02 mole FeCl3 and 0.01 mole Fe2SO4 in 250 ml water. An appropriate amount of coating material is added to the source of iron solution.

Figure 1.7 Scheme for the synthesis of superparamagnetic iron oxide (SPION) wet [19]. Reproduced with permission from ASPBS.

The co-precipitation of SPION was carried out in a reaction with magnetic stirring, by slowly adding 5 M NaOH until obtaining pH 9–10 at room temperature. The resulting solution was kept for 1 h to complete the reaction. Then the precipitate was magnetically separated from the supernatant and washed several times with distilled water, until obtaining pH 7. During each washing step, samples were separated from the supernatant using a permanent magnet. Thoroughly washed magnetic particles were dried at room temperature, yielding a fine powder.

1.1.2.3.3 Silver NPs [20]

A novel method is reported here for the synthesis of optically clear and stable colloidal solutions of silver nanoparticles. According to size they show different colors, Figure 1.8, depending on their plasmonic absorption frequencies.

Figure 1.8 Scheme for the synthesis of colloidal silver nanoparticles.

The materials have been synthesized at room temperature by chemical reduction of silver ions (silver nitrate) coordinated with dendrigraft polymer, polyethyleneimine (PEI), using formaldehyde in aqueous medium. In a typical synthesis, 0.85 g of AgNO3 (Merck Ltd., India) was dissolved in 100 ml of aqueous solution of 0.85 wt.% PEI (Fluka, Mw 600,000–1,000,000) and homogenized by stirring for 2 min. Followed by this, 1 ml of 35% solution of formaldehyde (Merck Ltd., India) was added and mixed well. A light yellow color appeared after 2 min, indicating the nucleation and growth of Ag nanoparticles. Extensive experiments were carried out by varying the AgNO3/PEI ratio to optimize the synthetic condition for specific particle sizes and associated property variations.

1.1.2.3.4 Doped ZnS NPs [21]

ZnS nanophosphors doped with halides (F−, Cl−, Br−, or I−), Cu+-halides, Cu+-Al³+, Cu+-Al³+-Mn²+, or Mn²+ have been prepared by the colloidal precipitation method at room temperature. In a typical synthesis, aqueous ZnSO4 solution is taken and to it, aqueous copper (II) acetate solution is added. Then Na2SO3 is added to the Zn²+-Cu²+ precursor (pH ∼ 4) and the SO2 gas generated in the solution during this process reduces Cu²+ to Cu+. This is followed by the addition of a precursor solution of Mn²+/Al³+/halides and PVP solution. Finally, Na2S solution is added leading to the precipitation of doped ZnS nanoparticles.

1.1.2.3.5 Au NPs [11]

One of the most simple and reproducible methods to synthesize Au nanorods is the seed-mediated growth method. It consists of a two-step process, i.e. nucleation and then successive growth of the NPs. By introducing some modifications in the preparative conditions (e.g. careful control of the solution’s temperature, stirring, ratio of seed to metal salt, etc.), it is possible to obtain a defined aspect ratio of the Au NRs. In the first step, a growth solution is prepared by the mild reduction of Au ions (HAuCl4 0.0010 M) with L-ascorbic acid (0.0778 M) in the presence of AgNO3 (0.0400 M) which promotes anisotropy and (Hexadecyltrimethylammonium Bromide) CTAB (0.20 M) and (Benzyldimethylhexadecylammonium Chloride) BDAC (0.15 M) as surfactants. The seed solution is prepared afterwards by rapid reduction of the Au precursor with a strong reducing agent (NaBH4 0.010 M) in the presence of CTAB (0.20 M) as a surfactant.

In another typical preparation, an aqueous solution of Au was first mixed with mercaptosuccinic acid (MSA) in methanol to give a transparent solution. Under vigorous stirring a freshly prepared aqueous sodium borohydride solution was then added at a certain rate. The solution turned dark brown immediately but remained transparent (which indicates that the nanoparticles do not form) until enough reductant was added. The pH of the solution increased gradually with the addition of reactant. A flocculent dark-brown precipitate would be generated by further addition of the reductant, and finally the pH of the solution was brought to 8.6. We can see that just as in the common synthesis in aqueous solution, the pH must be adjusted. After being stirred for a specific duration, the solvent was removed by decantation after the centrifugation. The precipitate were washed, suspended in ethanol, and dried by rotary evaporation.

1.1.3 Characterization of nanomaterials: physicochemical approaches [15,22]

Common characterization techniques of nanomaterials are given in Table 1.1

Table 1.1

Common Characterization Techniques of Nanomaterials

1.1.3.1 X-ray diffraction

Waves of wavelength comparable to the crystal lattice spacing are strongly scattered (diffracted). Analysis of the diffraction pattern, Figure 1.9, allows obtaining information such as lattice parameter, crystal structure, sample orientation, and particle size.

Figure 1.9 XRD Pattern of a w-ZnS nanowire [22a].

We will only mention that lattice parameters are obtained from the Bragg formula: 2dsinθ = , where d is the lattice spacing. In a typical setup, a collimated beam of X-rays is incident on the sample. The intensity of the diffracted X-rays is measured as a function of the diffraction angle 2θ, Figure 1.14. The intensities of the spots provide information about the atomic basis. The sharpness and shape of the spots relates to the perfection of the crystal. The two basic procedures involve either a single crystal or a powder. With single crystals, a lot of information about the structure can be obtained. On the other hand, single crystals might not be readily available and orientation of the crystal is not straightforward. One disadvantage of XRD is the low intensity of the diffracted beam for low-Z materials.

Figure 1.10 UV-Vis absorption spectra of ZnO nanoparticles, nanoflowers, and nanorods morphology. Inset shows the corresponding Tauc’s plot [22e].

Figure 1.11 Raman spectra of CNTs [22c].

Figure 1.12 Transmission electron microscope.

Figure 1.13 Schematic of a scanning-tunneling microscope [22d].

Figure 1.14 AFM. (a) Schematic AFM and (b) tip of AFM [23a].

Figure 1.15 Synthesized graphene balls (a) AFM image (the shaded bar is a measure of height); (b) a cross-section along the line indicated in (a) [23b]. Reproduced with permission from ASPBS.

1.1.3.2 Optical spectroscopy

Optical spectroscopy uses the interaction of light with matter as a function of wavelength or energy in order to obtain information about the material. For example, absorption or emission (photoluminescence or PL) experiments with visible and UV light tend to reveal the electronic structure. Vibrational properties of the lattice (i.e. phonons) are usually in the IR and studied using either IR absorption or Raman spectroscopy. Raman is an example of an inelastic process whereby the energy of the incoming light is changed. The others are elastic processes whereby the intensity is changed. Typical penetration depth is of the order of 50 nm. Optical spectroscopy is attractive for materials characterization because it is fast, nondestructive, and of high resolution.

(a) UV-Vis spectroscopy

This technique involves the absorption of near-UV or visible light, Figure 1.10. One measures both intensity and wavelength. It is usually applied to molecules and inorganic ions in solution. Broad features make it not ideal for sample identification. However, one can determine the analyte’s concentration from absorbance at one wavelength and using the Beer-Lambert law:

where a = absorbance, b = path length, and c = concentration. A schematic of the technique is shown in Figure 1.15, together with a sample data.

(b) Raman spectroscopy

The Raman process describes the excitation of vibrational modes (phonons) in the sample using light, whose frequency is then reduced due to energy conservation. Such a scattering process is weak; experimentally, a laser is needed for good signal.

Raman spectroscopy has been used to characterize, Figure 1.11, the chirality of nanocarbon materials, i.e. carbon nanotubes, fullerene and graphenes [22].

1.1.3.3 TEM and SEM

Electron beams can be used to produce images. The basic operation in a transmission electron microscope (TEM) is for electrons to be generated from an electron gun, which are then scattered by the sample, focused using electrostatic lenses, and finally form images, Figure 1.12.

A typical accelerating voltage is 100 kV for which the electrons have mean free paths of the order of a few tens of nm for light elements and a few hundreds of nm for heavy elements. These would be the ideal nm thicknesses since much thinner films would lead to too little scattering and much thicker ones would lead to too much scattering of the same electron resulting in a blurred image of low resolution.

The imaging mode can be controlled by the use of an aperture. If most of the unscattered electrons are allowed through, the resulting image is called a bright-field image. If specific scattered beams are selected, the image is known as a dark-field image. In addition to forming images, a TEM can be used for chemical analysis and melting-point determination.

If the TEM is operated in scanning mode, it is known as a scanning electron microscope or SEM. Electrons scattered from the sample are collected on a CRT to form the image. The resolution is of a few nm and magnification is from ∼10 to 500,000 times.

1.1.3.4 Scanning-tunneling microscope

The scanning-tunneling microscope (or STM), Figure 1.13, is one of the most powerful microscopes available. It provides atomic-scale resolution of surfaces and is also being developed to move atoms on surfaces. STM relies on the fact that electrons near surfaces have wave functions which decay into the vacuum outside the surface

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