Functionalized Carbon Nanotubes for Biomedical Applications
Description
The book highlights established research and technology on current and emerging trends and biomedical applications of functionalized carbon nanotubes by providing academic researchers and scientists in industry, as well as high-tech start-ups, with knowledge of the modern practices that will revolutionize using functionalized carbon nanotubes.
Nanotechnology suggests fascinating opportunities for a variety of applications in biomedical fields, including bioimaging and targeted delivery of biomacromolecules into cells. Numerous strategies have been recommended to functionalize carbon nanotubes with raised solubility for efficient use in biomedical applications. Functionalized carbon nanotubes have unique arrangements and extravagant mechanical, thermal, magnetic, optical, electrical, surface, and chemical properties, and the combination of these features gives them widespread biomedical applications. Functionalized carbon nanotubes are relatively flexible and interact with the cell membranes and penetrate different biological tissues owing to a "snaking" effect, therefore both the pharmacological and toxicological profiles of functionalized carbon nanotubes have gathered much attention in recent times.
This book covers a broad range of topics relating to carbon nanotubes, from synthesis and functionalization to applications in advanced biomedical devices and systems. As they possess unique and attractive physical, chemical, optical, and even magnetic properties for various applications, considerable effort has been made to employ functionalized carbon nanotubes as new materials for the development of novel biomedical tools, such as diagnostic sensors, imaging agents, and drug/gene delivery systems for both diagnostics and clinical treatment.
Audience
The book is intended for a very broad audience of researchers and scientists working in the fields of nanomaterials, nanomedicine, bioinspired nanomaterials, nanotechnology, and biomedical application of nanomaterials.
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Persons
Jeenat Aslam, PhD, is an associate professor in the Department of Chemistry, College of Science, Taibah University, Yanbu, Al-Madina, Saudi Arabia. She obtained her PhD in Surface Science/Chemistry at the Aligarh Muslim University, Aligarh, India. Her research is mainly focused on materials & corrosion, nanotechnology, and surface chemistry. Dr. Jeenat has published several research and review articles in peer-reviewed international journals and has edited 2 books and has contributed 20 book chapters.
Chaudhery Mustansar Hussain, PhD, is an adjunct professor and director of laboratories in the Department of Chemistry & Environmental Science at the New Jersey Institute of Technology (NJIT), Newark, New Jersey, United States. His research is focused on the applications of nanotechnology and advanced materials, environmental management, analytical chemistry, and other various industries. Dr. Hussain is the author of numerous papers in peer-reviewed journals as well as a prolific author and editor of around a hundred books.
Ruby Aslam, PhD, is a research associate in the Department of Applied Chemistry, Aligarh Muslim University, India. She graduated with an M.Sc. in Chemistry at Aligarh Muslim University and presented her M.Phil. dissertation and PhD-thesis in Applied Chemistry, also at Aligarh Muslim University. She has published widely on corrosion inhibition and corrosion protective coatings.
Content
Preface xv
Part 1: Overview of Functionalized Carbon Nanotubes 1
1 Functionalized Carbon Nanotubes: An Introduction 3
Sheerin Masroor
1.1 Introduction 4
1.2 Carbon Nanotube's Classification 6
1.3 Structural and Morphological Analysis of Carbon Nanotubes 7
1.4 Synthetic Techniques of Carbon Nanotubes 8
1.5 Functionalization of Carbon Nanotubes 9
1.6 Commercial Scale Use of Functionalized Carbon Nanotubes 12
1.7 Conclusion and Future Prospects 14
References 15
2 Functionalized Carbon Nanotubes: Synthesis and Characterization 21
Neelam Sharma, Shubhra Pareek, Rahul Shrivastava and Debasis Behera
2.1 Introduction 22
2.2 Synthesis Methods 24
2.2.1 Arc Discharge 24
2.2.2 Laser Ablation 25
2.2.3 Chemical Vapor Deposition 26
2.3 Characterization 27
2.3.1 Raman Spectroscopy 27
2.3.2 Fourier Transform Infrared Spectroscopy (FT-IR) 28
2.3.3 Thermogravimetric Analysis (TGA) 29
2.3.4 Scanning Electron Microscopy (SEM) 29
2.3.5 Transmission Electron Microscopy (TEM) 30
2.3.6 X-Ray Diffraction (XRD) 31
2.3.7 X-Ray Photoelectron Spectroscopy (XPS) 32
2.4 Functionalized Routes of CNTs 33
2.4.1 Surface Oxidation 33
2.4.2 Doping Heteroatoms 33
2.4.3 Alkali Activation 33
2.4.4 Sulfonation 34
2.4.5 Halogenation 34
2.4.6 Grafting 34
2.4.6.1 Grafting via Oxygen-Containing Groups 35
2.4.6.2 Grafting via Diazonium Compounds 36
2.4.6.3 Other Grafting Methods 37
2.4.7 Non-Covalent Functionalization of CNTs 37
2.4.8 Deposition on Functionalized CNTs 37
2.4.9 Physiochemical Approaches 38
2.4.10 Electrochemical Deposition 38
2.4.11 Electroless Deposition 39
2.5 Conclusion 39
References 40
3 Carbon Nanotubes: Types of Functionalization 49
Manilal Murmu, Debanjan Dey, Naresh Chandra Murmu and Priyabrata Banerjee
3.1 Introduction 50
3.2 Carbon Nanotubes 50
3.3 Functionalization of Carbon Nanotubes 52
3.3.1 Covalent Functionalization 52
3.3.2 Non-Covalent Functionalization of Carbon Nanotubes 58
3.3.2.1 Reversibility in Non-Covalent Functionalization 63
3.3.2.2 Solvent Variation in Non-Covalent Functionalization 64
3.3.3.3 pH of the System in Non-Covalent Functionalization 64
3.3.3.4 Temperature Responsive System in Non-Covalent Functionalization 65
3.4 Conclusion and Future Outlook 65
Acknowledgements 65
Web Links 66
References 66
4 Functionalization Carbon Nanotubes Innovate on Medical Technology 75
Afroz Aslam, Jeenat Aslam, Hilal Ahmad Parray and Chaudhery Mustansar Hussain
4.1 Introduction 75
4.2 Functionalization CNTs for Biomedical Applications 78
4.3 Potential Applications of CNTs in Cancer Therapy 79
4.3.1 Anti-Tumor Immunotherapy 80
4.3.2 Anti-Tumor Hyperthermia Therapy 80
4.3.3 Anti-Tumor Chemotherapy 81
4.3.4 Other Cancer Treatment Strategies 82
4.4 Treatment of Central Nervous System Disorders 82
4.5 Treatment of Infectious Diseases 84
4.6 CNTs-Based Transdermal Drug Delivery 85
4.7 f-CNTs for Vaccination 86
4.8 Application of f-CNTs in Tissue Engineering 86
4.9 Conclusion 88
Important Websites 89
References 89
Part 2: Functionalized Carbon Nanotubes: Current and Emerging Biomedical Applications 95
5 Functionalized Carbon Nanotubes: Applications in Biosensing 97
N. Palaniappan, Nidhi Vashistha and Ruby Aslam
5.1 Introduction 97
5.2 CNTs-Based Biosensors 99
5.2.1 Electrochemical Biosensors 100
5.2.1.1 Electrochemical Enzyme Sensors 100
5.2.1.2 Electrochemical Immunosensors 101
5.2.1.3 Electrochemical DNA Sensors 102
5.2.1.4 Non-Biomolecule Based Electrochemical Sensors 104
5.2.2 Optical CNT Sensors 105
5.2.3 Field-Effect CNTs Sensors 106
5.2.4 CNT Human Strain Sensor 107
5.3 Conclusion 108
References 108
6 Applications of Functionalized Carbon Nanotubes in Drug Delivery Systems 117
N. Palaniappan, Malgorzata Kujawska and Kader Poturcu
6.1 Introduction 118
6.2 Nanoparticles-Doped Carbon Nanotubes 121
6.3 Brain-Targeted Delivery 123
6.4 The Organic Molecules Functionalized CNTs as Drug Delivery Vehicles 125
6.5 Functionalized CNTs with Nanoparticles for Drug Active Molecular Mechanism 126
6.5.1 Future of Scope of Functionalized Carbon Nanotube Drug Delivery Application 126
6.6 Conclusion 127
References 127
7 Functionalized Carbon Nanotubes for Gene Therapy 139
Tejas Agnihotri, Tanuja Shinde, Manoj Gitte, Pankaj Kumar Paradia, Rakesh Kumar Tekade and Aakanchha Jain
7.1 Introduction 140
7.2 Functionalized CNTs and Gene Therapy 141
7.3 Cellular Uptake of CNT 146
7.4 Functionalized Carbon Nanotubes and Cancer 147
7.5 Miscellaneous Diseases and Gene Delivery Through Functionalized CNT 150
7.6 Toxicology and Environmental Aspects of Functionalized CNT 158
7.6.1 Cellular Toxicity 159
7.6.2 Liver Toxicity 159
7.6.3 Central Nervous System Toxicity 160
7.6.4 Cardiovascular Toxicity 161
7.7 Regulatory Concerns Over Functionalized Carbon Nanotubes 162
7.8 Conclusion and Future Prospects 164
Important Website 165
References 165
8 Applications of Functionalized Carbon Nanotubes in Cancer Therapy and Diagnosis 171
Irshad Ahmad, Talat Parween, Lina Khandare, Aafaq Tantray and Weqar Ahmad Siddiqi
8.1 Introduction 172
8.2 Characteristic Properties of CNTs and Their Performance 175
8.2.1 Physicochemical Properties of CNTs 176
8.3 The Techniques of CNTs Functionalization 177
8.4 Application of Carbon Nanotubes in Cancer Therapy and Diagnostic 180
8.4.1 The Use of Carbon Nanotubes in Cancer Treatment 180
8.4.2 Intracellular Targeting Using Carbon Nanotubes 180
8.4.2.1 Nucleus Targeting 181
8.4.2.2 Cytoplasm Targeting 181
8.4.2.3 Mitochondria Targeting 181
8.4.3 CNTs for Immunotherapy 182
8.4.4 Cancer Stem Cell Inhibition 183
8.5 Carbon Nanotubes in Cancer Diagnosis 183
8.5.1 CNTs in Cancer Imaging 184
8.5.1.1 Raman Imaging 184
8.5.1.2 Nuclear Magnetic Resonance Imaging 184
8.5.1.3 Ultrasonography 184
8.5.1.4 Photoacoustic Imaging 185
8.5.1.5 Near-Infrared Fluorescence Imaging 185
8.6 Future Prospects 186
8.7 Conclusion 186
Important Websites 187
References 188
9 Functionalized Carbon Nanotubes for Biomedical Imaging: The Recent Advances 197
Alina Abbas, Saman Zehra, Ruby Aslam, Mohammad Mobin and Shahidul Islam bhat
9.1 Introduction 198
9.2 CNT-Based Imaging Methods 199
9.2.1 Fluorescence Imaging 200
9.2.2 Raman Imaging 204
9.2.3 Photoacoustic Imaging 207
9.2.4 Magnetic Resonance Imaging 209
9.2.5 Nuclear Imaging 212
9.3 Prospects and Challenges 212
9.4 Conclusion 214
References 214
10 Functionalized Carbon Nanotubes for Artificial Bone Tissue Engineering 225
Sougata Ghosh and Ebrahim Mostafavi
10.1 Introduction 226
10.2 CNT-Based Scaffolds and Implants 230
10.2.1 Hydroxyapatite 231
10.2.2 Polymers 234
10.2.2.1 Poly(e-Caprolactone) 235
10.2.2.2 Polymethyl-Methacrylate 237
10.2.2.3 Poly(Lactide-Co-Glycolide) 238
10.2.2.4 Poly-L-Lactic Acid 240
10.2.2.5 Polyvinyl Alcohol 241
10.2.2.6 Others 242
10.2.3 Biopolymers 242
10.2.3.1 Chitosan 244
10.2.3.2 Collagen 244
10.2.3.3 Others 247
10.3 Intellectual Property Rights and Commercialization Aspects 248
10.4 Conclusion and Future Perspectives 251
References 252
11 Application of Functionalized Carbon Nanotubes in Biomimetic/Bioinspired Systems 257
Mohammad Mobin, Ruby Aslam, Saman Zehra, Jeenat Aslam and Shahidul Islam bhat
11.1 Introduction 258
11.2 Naturally Occurring Materials 259
11.2.1 Nacre and Bone 259
11.2.2 Petal Effect and Gecko Feet 259
11.2.3 Lotus Effect 260
11.2.4 Structural Colors, Antireflection, and Light Collection 261
11.3 Bioinspired Functionalized CNTs Material 261
11.4 Challenges and Solutions in Using CNTs 272
11.5 Conclusion and Perspectives 272
References 274
12 Functionalized Carbon Nanotubes: Applications in Tissue Engineering 281
Ajahar Khan, Khalid A. Alamry and Raed H. Althomali
12.1 Introduction 282
12.2 Structural, Physical, and Chemical Properties 284
12.3 Interactions and Biodegradation of CNTs with Biomolecule 287
12.4 Bio-Security of CNT-Based Scaffolds Toward In Vivo Analyses 288
12.5 CNTs Towards the Bone Compatibility 293
12.6 Applications of Functionalized CNTs in Tissue Engineering 294
12.6.1 Functionalized CNTs for Cardiac Tissue Engineering 294
12.6.2 Functionalized CNTs for Neuronal Tissue Regeneration 297
12.6.3 Functionalized CNT for Cartilage Tissue Engineering 298
12.6.4 CNT for Bone Tissue Regeneration 300
12.7 Future Perspectives and Challenges 303
12.8 Conclusion 304
Important Websites 305
References 305
13 Functionalized Carbon Nanotubes for Cell Tracking 319
Sagar Salave, Dhwani Rana, Jyotsna Vitore and Aakanchha Jain
Abbreviations 319
13.1 Introduction 320
13.2 Carbon Nanotubes 321
13.2.1 Cellular Interaction of CNTs 325
13.3 Cellular Tracking via CNT 325
13.3.1 Effect of the Surface Coating of CNTs in Single-Particle Tracking 328
13.4 3D Tracking Using CNTs 328
13.4.1 Detection of Single Protein Molecules Through CNTs 329
13.4.2 Stem Cell Labeling and Tracking Through CNTs 330
13.4.3 Labelling and Tracking of Human Pancreatic Cells Through CNTs 330
13.4.4 CNT as Macrophage Carrying Microdevices 331
13.4.4.1 Intracellular Fluctuations and CNT 331
13.4.5 Limitations of CNTs 332
13.5 Concluding Remarks and Future Perspective 332
Important Links 333
Acknowledgment 333
References 333
14 Functionalized Carbon Nanotubes for Treatment of Various Diseases 339
Ajahar Khan, Khalid A. Alamry and Raed H. Althomali
14.1 Introduction 340
14.2 CNTs: Basic Structure, and Synthesis Methods 342
14.2.1 Structure and Synthesis of CNTs 342
14.2.2 Arc Discharge Technique 342
14.2.3 Laser Ablation Technique 342
14.2.4 Catalytic Chemical Vapor Deposition Technique 343
14.3 Functionalization of CNTs 343
14.3.1 Covalent Functionalization 344
14.3.2 Non-Covalent Functionalization 344
14.4 Toxicity/Bio-Safety Profile of Carbon Nanotubes 346
14.5 Investigating the Promising Biomedical Effects of Functionalized CNTs 349
14.5.1 Functionalized CNTs-Based Remediation of Infectious Diseases 350
14.5.2 Functionalized CNTs for the Treatment of Central Nervous System Disorders (CNS) 350
14.5.3 Functionalized CNTs for Gene Delivery 351
14.5.4 Implication of Functionalized CNTs in Cancer Diagnosis and Treatment 354
14.5.5 Functionalized CNTs for Drug Targeting and Release 357
14.6 Future Prospective 362
14.7 Conclusion 363
Important Websites 364
References 365
15 Role of Functionalized Carbon Nanotubes in Antimicrobial Activity: A Review 377
Monika Aggarwal, Samina Husain and Basant Kumar
15.1 Introduction 378
15.2 Introduction to CNTs 378
15.2.1 Classification of CNTs 379
15.2.2 Structure of CNTs 381
15.3 Overview on CNTs Functionalization 382
15.3.1 Types of Functionalization 384
15.4 Anti-Microbial Activity of f-CNTs: Interaction and Action 387
15.5 Antifungal Activity of f-CNTs 388
15.6 Antibacterial Activity of f-CNTs 390
15.6.1 For SWNTs 390
15.6.2 For MWCNTs 392
15.7 Commercial Application of Antimicrobial Activity of f-CNTs 400
15.8 Overview on Antimicrobial Activity of f-CNTs 401
15.9 Future Scope 405
15.10 Conclusion 405
Acknowledgement 406
References 406
Index 413
1
Functionalized Carbon Nanotubes: An Introduction
Sheerin Masroor*
Department of Chemistry, A. N. College, Patliputra University, Patna, Bihar, India
Abstract
Carbon nanotubes written in short form as, CNTs are the tubes which are made from carbon having diameters in nanometers (nm) or 10-9 meters. They can be considered as one of the best carbon allotropes like graphene, graphite, fullerene, diamond and amorphous carbon. Many experimental processes have been obtained to synthesize nanotubes in different sizeable quantities, such as chemical vapor deposition, arc discharge, and laser ablation methods. The blooming of technology related to nanomaterials is mostly happened in drug delivery, biomedical imaging, biosensing and designing of useful nanocomposites. While some more methods relating and realizing applications are continuing to evolve. Carbon nanotubes may be of two types single-wall carbon nanotubes (SWCNTs) having diameters in the range of a nanometers only or multi-wall carbon nanotubes (MWCNTs) possesses nest like structure of single-wall carbon nanotubes. These tubes can be allowed to functionalize via two general reactions such as esterification and amidation of nanotubes with carboxylic acids ends in it. General property like solubility of these tubes helps to know the properties of them by applying solution-based processes. A number of literatures relating functionalization of the carbon nanotubes in the modification of applications in nanocomposites and biological techniques can be seen there.
Keywords: Carbon nanotubes, allotropes, nanocomposites, drug, esterification
1.1 Introduction
Carbon (C) is having atomic number six (6), which is non-metallic in nature and having (four electrons or tetravalency available to form covalent chemical bonds and makes about 0.025 percent of Earth's crust [1, 2]. There are three naturally occurring isotopes of carbon discovered so far, symbolized as 12C and 13C and 14C. Out of all three first two are stable while third one is radionuclide whose half-life is about 5,730 years [3].
Also, the carbon is considered as 15th most existed element in the crust of Earth, and the fourth most abundant element in the universe in terms of mass after hydrogen (H2), helium (He), and oxygen (O2). Carbon is abundant element found and its unique diversity to form multiple organic compounds or collection of monomers (polymers) at the temperatures commonly encountered on Earth surface enables this element to serve as a the most common element of all known life. In addition, it is also considered as the second most abundant element found in the human body by mass of approximately 18.5% after oxygen [4].
It's a unique property of carbon atoms that they can bind together in multiple forms generating different number of carbon allotropes. Some of the well-defined allotropes of carbon include graphite, amorphous carbon, fullerenes and diamond. In turn the physical property of carbon mainly depends upon its allotropic form, like graphite is black in color and opaque, while diamond is transparent in nature. Graphite is known for its softness while the diamond is hardest material. In terms of electrical conductivity graphite always acts as good electrical conductor while diamond has diminished electrical conductivity. Recently carbon nanotubes have been also studied for best thermal conductivities along with graphite, graphene and diamond at standard temperature and pressure (STP) or under normal conditions. It can be considered as most of the carbon allotropes are solid at STP or under normal conditions, while graphite is being effectively stable thermodynamically at STP. They all are resistant chemically and generally require very high temperature and oxygen to make reaction.
The carbon in atomic form is very short-lived in nature and hence it is stabilized in different multi-atomic structures with vast molecular arrangements which are generally called as allotropes. One allotrope of carbon which is fullerene is commonly synthesized nowadays successfully and uniquely harvesting it in research in the form of carbon nanotubes, carbon nanobuds, bucky balls, and nanofibers [5-10].
Diverse variety of the exotic allotropes has also been discovered so far, such as glassy carbon, lonsdaleite, carbon nanofoam, and linear acetylenic carbon (carbyne) [11-14].
Two natural occurring crystalline forms of pure carbon are graphite and diamond. Here in diamond, the atoms of carbon show sp3 hybridization wherein the four bonds are directly attached towards the corners of regular tetrahedron, making diamond so strong and rigid due to three-dimensional network. While in graphite we can easily see carbons hybridization in sp2 form, in which all atoms are joined uniformly to three carbons with an angle of 120°. In 1985 a new form of carbon, Buckminster fullerene symbolized as (C60) was discovered by Korto et al. [15]. In addition, with graphite, diamond and fullerene (C60), quasi-one-dimensional nanotube was also invented in another form of carbon which was first reported in 1991 by Ijima. He reported in his finding that the soot was made by an arc-discharge method to synthesize multiwalled carbon nano-tube-MWCNTs [16].
One of the allotropes of carbon is which may be tubular or rod like structure in shape fully made of graphite. The provided tubes may have at least two to many layers ranged for diameter from 3 to 30 nm in size. Later in about two years, the single-walled carbon nanotubes (SWCNTs) came into existence [17]. In and around same period of time, Dresselhaus and his co-workers synthesized single-walled carbon nanotubes by following the previous track of producing multi walled carbon nanotubes (MWCNTs) with the addition of some transition metal particles to the electrodes of carbon [18]. The expected shapes of single-walled carbon nanotubes and multiple walled carbon nanotubes can be depicted from the Figure 1.1 (a and b). Here we can easily see that wall of SWCNT are generally narrower than the MWCNT, which is having a diameter in the range of 1-2 nm, and took curved shape instead to be straight.
Figure 1.1 Structure of carbon nanotube (a). Single walled carbon nanotubes (b). Multiple walled carbon nanotubes.
Figure 1.2 Important applications of functionalized CNTs.
The utmost properties of carbon nanotubes such as electrical, electrochemical, mechanical and chemical properties are extensively studied by huge amount of research that has been going on throughout since last few decades. Various reactions had been going on to find best possible results to harvest them at best possible. Nowadays the researchers have been focusing on changing/improving the quality of nanotubes those who are engaged in catalytic reactions [19]. Some important utilization of functionalized CNTs is pictorially present here in Figure 1.2.
1.2 Carbon Nanotube's Classification
Broadly classified in the given ways such as [20-23]: the form of graphene sheets, especially benzene (Cyclohexa-1,3,5-triene) type hexagonal rings of carbon atoms. These graphene sheets look cylinders which may be borrowed from a honeycomb lattice, showing a single atomic layer of crystalline graphite. While the multiwalled carbon nanotubes are heap of graphene sheets which can be rolled up into cylinders in the concentric form. Nanotube can be considered as single molecule made up of millions of atoms and whose length can be in the range of micrometers with diameters of about 0.7 nanometers [26]. The single walled carbon nanotubes mainly contain ten (10) atoms which are present over the circumference whose thickness is only one atom thick of the whole tube. Generally, the carbon nanotubes have massive length-to-diameter ratio of approx. value of about 1000, which conclude them as one-dimensional structures [27]. The structure of multi walled carbon nanotube, mainly contains large and numerous single walled tubes which are stacked over and above each other. If the diameter of nanostructures formed have a diameter of about 15 nanometers, then it can be called as multi walled carbon nanotubes otherwise the structures are better known as carbon nanofibers, which are strands of layered-graphite sheets [28].
- Single-walled carbon nanotubes (SWCNTs).
- Multiple-walled carbon nanotubes (MWCNTs).
- Single-walled carbon nanotubes (SWCNTs).
- They are only made from single layer of graphene.
- The synthetic route requires catalyst, which requires an appropriate control over growth and reaction conditions.
- Can exist in bundle structures.
- If synthesized the product may be found with the yield percentage of 30-50% by general method but if synthesized via arc discharged synthetic method, yield may be achieved up to 80%.
- As they are simple in nature, they are easy to characterize on synthesis.
- Multiple-walled carbon nanotubes (MWCNTs).
- They are made from multiple layers of graphene.
- Synthetic route doesn't need catalyst and bulk synthesis is easy.
- The purity is high by the synthetic route of Chemical vapor deposition (CVD) method with a yield of about 35-90%.
- Here the unintentional defect is less especially when it is synthesized by arc-discharged method.
- It has a convoluted structure which can't be easily...
