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Biopolymer Grafting:
Applications
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ADVANCES IN POLYMERS AND FIBERS
Biopolymer Grafting:
Applications
Edited by
Vijay Kumar Thakur
Elsevier
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To my parents and teachers who helped me become what I am today.
Vijay Kumar Thakur
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Contents
List of Contributors........................................................................................................... xv
About the Editor ............................................................................................................. xvii
Preface.............................................................................................................................. xix
CHAPTER 1 Applications of Graft Copolymerization: A Revolutionary Approach ........ 1

Anupama Setia
1. Introduction................................................................................................1
1.1 Graft Copolymerization ..................................................................... 3
1.2 Concept of Molecular Brushes .......................................................... 3
1.3 Approaches for Graft Copolymerization ........................................... 4
1.4 Applications ..................................................................................... 20
1.5 Conclusion ....................................................................................... 32
References ..................................................................................................... 32
CHAPTER 2 Grafting of Hydroxyapatite for Biomedical Applications........................ 45
Pau Turon, Luís J. del Valle, Carlos Alemán, Jordi Puiggalí
1. Introduction..............................................................................................45
2. Control of Size and Morphology of Hydroxyapatite Crystals:
Ion Substitution of Hydroxyapatite .........................................................46
3. Hydroxyapatite Exfoliated Nanoplates by Surface Modification............49
4. Surface Modification of Hydroxyapatite to Improve Protein
Adsorption ...............................................................................................50
5. Antibacterial Coatings for Hydroxyapatite Particles ...............................51
6. Scaffolds and Membranes Based on Electrospun Nanofibers
Containing Hydroxyapatite......................................................................53
7. Polymer Grafting on Hydroxyapatite Surfaces .......................................56
8. Cross-Linked Structures Based on Hydroxyapatite Surfaces..................63
9. Conclusions..............................................................................................68
Acknowledgments ........................................................................................ 70
References .....................................................................................................70
CHAPTER 3 Grafting of Hydrophilic Monomers Onto Cellulosic Polymers for
Medical Applications .................................................................................. 81
Nursel Pekel Bayramgil
1. Introduction..............................................................................................81
2. Modifications of Cellulosic Polymers .....................................................83
2.1 Grafting ............................................................................................ 85
2.2 Commonly Used Monomers for Grafting Onto Cellulose .............. 87
vii
viii Contents
3. Basic Medical Applications of Hydrophilic Monomer Grafted

Cellulosic Polymers .................................................................................93
3.1 Drug Delivery .................................................................................. 93
3.2 Hemodialysis ................................................................................... 97
3.3 Platelet Adhesion ........................................................................... 102
3.4 Antimicrobial Activity ................................................................... 104
3.5 Others............................................................................................. 106
4. Conclusion .............................................................................................108
References ................................................................................................... 108
Further Reading ..........................................................................................114
CHAPTER 4 Surface Functionalization With Biopolymers via Plasma-Assisted
Surface Grafting and Plasma-Induced Graft Polymerizationd
Materials for Biomedical Applications .................................................... 115
Agnieszka Kyzioł, Karol Kyzioł
1. Introduction............................................................................................115
2. Fundamentals of Grafting Techniques ..................................................117
2.1 Grafting Polymerization................................................................. 119
2.2 ‘‘Grafting From”, ‘‘Grafting to”, and ‘‘Grafting Through”
Approaches .................................................................................... 120
3. Surface Modification of Biomaterials by Grafting Techniques ............123
3.1 Factors Influencing the Properties of Surfaces With Grafted
Biopolymers................................................................................... 124
3.2 Biocompatibility of Functionalized Surfaces ................................ 130
3.3 Surface Modifications Imparting Drug Delivery Functionality .... 134
4. Surface Functionalization of Biomaterials by Plasma-Induced
Grafting Polymerization ........................................................................137
5. Conclusions and Future Perspectives ....................................................143
References ................................................................................................... 145
CHAPTER 5 Synthesis and Application as Programmable Water Soluble Adhesive
of Polyacrylamide Grafted Gum Tragacanth (GT-g-PAM) ...................... 153
Pinki Pal, Jay Prakash Pandey, Gautam Sen
1. Introduction............................................................................................153
1.1 Classification of Polymers ........................................................... 155
1.2 Chemical Bonding in Polymers................................................... 155
1.3 Types of Primary Bonds.............................................................. 156
1.4 Secondary Bonding Forces.......................................................... 156
1.5 Synthetic Versus Natural Polymer .............................................. 157
1.6 Gum Tragacanth .......................................................................... 158
Contents ix
1.7Grafting: A Promising Technique for Modification.................... 159

1.8Methods of Graft Copolymerization............................................ 161
1.9Microwave Radiation: A Viable Case......................................... 168
1.10The Present Study: Microwave-Assisted Method of Graft
Copolymerization......................................................................... 169
1.11 Adhesive ...................................................................................... 169
1.12 Theories of Adhesion .................................................................. 169
2. Experimental ..........................................................................................173
2.1 Materials ........................................................................................ 173
2.2 Synthesis of GT-g-PAM by Microwave-Assisted Process ........... 173
2.3 Characterization ............................................................................. 175
2.4 Instrumental Analysis .................................................................... 176
2.5 Fourier Transform Infrared Spectrophotometry ............................ 177
2.6 Investigation of Adhesive Property of Graft Copolymer .............. 182
3. Results and Discussions ........................................................................186
3.1 Synthesis of GT-g-PAM by Microwave-Assisted Process ........... 186
3.2 Characterization ............................................................................. 190
3.3 Instrumental Analysis .................................................................... 191
3.4 Determination of Adhesive Strength ............................................. 193
4. Conclusion .............................................................................................198
Acknowledgments ...................................................................................... 198
References ...................................................................................................199
CHAPTER 6 Radiation Grafting of Biopolymers and Synthetic Polymers:
Synthesis and Biomedical Applications .................................................. 205
Victor H. Pino-Ramos, H. Iván Meléndez-Ortiz,
Alejandro Ramos-Ballesteros, Emilio Bucio
1. Introduction............................................................................................205
2. Biopolymers...........................................................................................206
2.1 Natural Biopolymers...................................................................... 206
2.2 Synthetic Biopolymers................................................................... 210
3. Properties of Biopolymers .....................................................................212
3.1 Density ........................................................................................... 213
3.2 Solubility........................................................................................ 213
3.3 Mechanical Properties.................................................................... 214
3.4 Thermal Properties......................................................................... 215
3.5 Biodegradability............................................................................. 217
3.6 Properties of Main Petroleum-Based Biopolymers ....................... 218
4. Grafting Methods Applied to Biopolymers...........................................221
4.1 Conventional Method by Chemical Means ................................... 222
x Contents
4.2 Microwave Method........................................................................ 222

4.3 High Energy Radiation Methods ................................................... 224
5. Radiation Grafting of Biopolymers .......................................................224
5.1 Radiation Grafting of Chitosan ..................................................... 226
5.2 Radiation Grafting of Cellulose..................................................... 228
5.3 Radiation Grafting of Alginate ...................................................... 231
5.4 Radiation Grafting of Gelatin ........................................................ 232
6. Biomedical Applications........................................................................232
6.1 Polymers in Biomedical Uses........................................................ 233
6.2 Application of Stimuli Responsive Polymers................................ 234
7. Potential Medical Devices .....................................................................237
7.1 Lysozyme Immobilization Onto PVC Urinary Catheters ............. 237
7.2 Functionalized Prodrug Onto Polypropylene Films for Drug
Delivery of Salicylic Acid ............................................................. 237
7.3 IPNs Grafted of N-isopropylacrylamide and Acrylic Acid
Onto Polyurethane Catheters for Medical Devices ....................... 238
8. Conclusions............................................................................................238
Acknowledgments....................................................................................... 239
References ...................................................................................................239
CHAPTER 7 Derivatized Chitosan: Fundamentals to Applications............................ 251
Deepali Rahangdale, Anupama Kumar
1. Introduction............................................................................................251
2. Modification of Chitosan .......................................................................254
2.1 Physical Modification .................................................................... 254
2.2 Chemical Modification .................................................................. 256
3. Density Functional Theory ....................................................................267
4. Molecular Imprinting Technique ...........................................................269
5. Applications ...........................................................................................270
5.1 Dye Removal ................................................................................. 270
5.2 Antibacterial Activity..................................................................... 271
5.3 Metal Ion Removal ........................................................................ 273
5.4 Wastewater Treatment ................................................................... 275
5.5 Biomedical Applications................................................................ 277
6. Conclusion .............................................................................................277
References ................................................................................................... 278
Contents xi
CHAPTER 8 Grafted Copolymerized Chitosan and Its Applications as a Green

Biopolymer ................................................................................................ 285
May-Yuan Wong, Bahman Amini Horri, Babak Salamatinia
1. Introduction..........................................................................................285
2. Polyethylene Glycol-g-Chitosan..........................................................287
2.1 Synthesis of Polyethylene Glycol-g-Chitosan via Schiff Base
Reaction Scheme ......................................................................... 288
2.2 Synthesis of Polyethylene Glycol-g-Chitosan via Genipin
Cross-Linking Reaction ............................................................... 289
2.3 Synthesis of Semiinterpenetrating Networks Polyethylene
Glycol-Chitosan via Glutaraldehyde Cross-Linking ................... 291
2.4 Synthesis of Polyethylene Glycol-Chitosan via Carbodiimide
Cross-Linking .............................................................................. 292
2.5 Synthesis of Polyethylene GlycoleChitosan Composite
via Blending................................................................................. 292
2.6 Synthesis of o-Substituted Polyethylene Glycol-o-Chitosan....... 293
2.7 Application of Polyethylene Glycol-g-Chitosan in
Immunotherapy ............................................................................ 294
2.8 Application of Polyethylene Glycol-g-Chitosan in In Vitro
Cancer Model .............................................................................. 295
2.9 Application of Polyethylene Glycol-g-Chitosan in Gene
Transfection Therapy ................................................................... 296
3. Poly(vinyl alcohol)-g-Chitosan ...........................................................298
3.1 Synthesis of Chitosan-g-Poly(vinyl alcohol) via Radiation
Technique..................................................................................... 299
4. Alkylated Chitosans.............................................................................299
4.1 Synthesis of N-Alkylated-Grafted Chitosan
(Hydroxymethylated-g-Chitosan) ................................................ 300
4.2 Synthesis of Disaccharide-Grafted Chitosan ............................... 300
4.3 Synthesis of Amylose-Grafted Chitosan ..................................... 301
5. Polyacrylamide-g-Chitosan..................................................................301
5.1 Synthesis of Polyacrylic Acid-g-Chitosan................................. 301
5.2 Synthesis of Polyacrylamide-g-Hydroxyethylcellulose-
g-Chitosan.................................................................................. 301
5.3 Synthesis of Polyacrylate-g-Chitosan Doped Metal Ions.......... 302
5.4 Application of Polyacrylamide-Grafted Chitosan and
Polyacrylic AcideGrafted Chitosan for Adsorption of Dyes ... 303
5.5 Application of Polyacrylate-Polyacrylamide-g-Chitosan,
PAMCS in Enhanced Oil Recovery .......................................... 304
xii Contents
5.6 Synthesis of Polyacrylamide-g-Chitosan Nanobeads via

Atom Transfer Radical Polymerization Approach .................... 305
5.7 Synthesis of Polyacrylamide-g-Chitosan Nanorug via
“Grafting-Through” Approach................................................... 306
5.8 Synthesis of Polyacrylamide-g- Polystyrene-g-Chitosan
Hybrid Molecular Brush Prepared via Grafting-to Approach... 309
5.9 Synthesis of Hydrophobically Modified Chitosan-g-Magnetic
Nanoparticles ............................................................................. 310
5.10 Synthesis of Fe3O4-Magnetic Nanoparticle-M Chitosan
Nanoparticles ............................................................................. 310
6. Cyclodextrin-Linked Chitosans ...........................................................312
6.1 Cyclodextrins-Chitosan With Adamantane ................................. 312
6.2 Chitosan-Grafted Polyethylene Glycol Methacrylate Mixed
With a-CD Composite................................................................. 313
7. Protein-Grafted Chitosan .....................................................................314
7.1 CollageneChondroitin-SulfateeChitosan ................................... 314
7.2 Polylysine-Grafted-Chitosan........................................................ 315
7.3 Polyethylene Glycol-poly(L-alanine-co-L-phenyl alanine)-
Grafted Chitosan .......................................................................... 315
8. Catechol-g-Chitosan ............................................................................316
9. Acid-Grafted Chitosan.........................................................................317
9.1 Azidobenzoic-g-Chitosan Hydrogel ............................................ 317
9.2 Polylactic Acid-g-Chitosan.......................................................... 318
9.3 Polymaleic Acid-g-Chitosan........................................................ 319
9.4 Polylactic AcideGrafted Chitosans............................................. 319
10. Others...................................................................................................322
10.1 Chitosan-Graphene Oxide: The Making of Antimicrobial
Film............................................................................................ 322
10.2 Chondroitin Sulfate-S: The Making of a Biosorbent of
Caustic DyeeContaining Wastewater ....................................... 322
10.3 Chitosan-Glycerol Phosphate Hydrogel .................................... 323
10.4 ChitosaneAlginate Hydrogel .................................................... 324
10.5 Polyethylene OxideeChitosan Blend........................................ 325
10.6 Carboxymethylated Chitosan..................................................... 326
11. Summary..............................................................................................327
12. Conclusion ...........................................................................................329
References ................................................................................................... 330
Contents xiii
CHAPTER 9 Grafting Onto Biopolymers: Application in Targeted Drug Delivery ... 335
Saundray R. Soni, Animesh Ghosh
1. Introduction............................................................................................335
2. Biopolymers...........................................................................................341
2.1 Classification of Biopolymers........................................................ 341
3. Biopolymers Grafting ............................................................................352
3.1 Grafting Strategy............................................................................ 352
3.2 Grafting Techniques ...................................................................... 353
4. Applications as Stimuli Responsive Targeted Drug Delivery
System....................................................................................................359
4.1 Temperature Responsive Polymers: Applications in Targeted
Drug Delivery System ................................................................... 360
4.2 pH Responsive Polymers: Applications in Targeted Drug
Delivery System............................................................................. 363
5. Applications as Receptor Targeted Drug Delivery System...................367
5.1 Targeting via Folate Receptors...................................................... 367
5.2 Targeting via RGD Peptide Toward Integrin Receptors ............... 371
6. Application of Grafted Biopolymers in Controlled Drug
Delivery System.....................................................................................372
7. Concluding Remarks .............................................................................375
Acknowledgments....................................................................................... 375
References ...................................................................................................379
CHAPTER 10 Fibroin Grafting Onto Wool Fibers: Recent Advances and
Applications ............................................................................................. 391
Franco Ferrero, Anna Garetto, Raffaella Mossotti, Claudio Tonin
1. Introduction.......................................................................................... 391
2. Grafting of Epoxy Resins Onto Wool................................................. 393
3. Grafting of Epoxy Resins Onto Silk ................................................... 397
4. Materials .............................................................................................. 400
4.1 Wool .............................................................................................400
4.2 Fibroin...........................................................................................400
4.3 Epoxy Resins ................................................................................402
5. Experimental Methods......................................................................... 403
5.1 Laboratory Equipment ..................................................................403
5.2 Morphology Analyses...................................................................403
5.3 Spectrophotometric and Thermal Analyses..................................404
5.4 Determination of Amino Groups by the Ninhydrin Assay ..........404
5.5 Epoxy Equivalent Determination .................................................405
xiv Contents
5.6 Amino Acid Composition by High-Performance Liquid

Chromatography ...........................................................................405
6. Results and Discussion ........................................................................ 406
6.1 Grafting of Epoxides on Wool .....................................................406
6.2 Fibroin Grafting on Epoxidated Wool..........................................417
7. Conclusions.......................................................................................... 426
References ................................................................................................. 427
CHAPTER 11 Grafting Modification of Wood for High Performance........................ 431
Yongfeng Li, Xiaoying Dong
1. Introduction.......................................................................................... 431
2. Materials and Methods ........................................................................ 434
2.1 Materials .......................................................................................434
2.2 Methods ........................................................................................435
3. Grafting Modification of Wood by Polymer ....................................... 438
3.1 Synthesis of the Target Functional Monomer ..............................438
3.2 Grafting Modification of Wood by Copolymerization of
Glycidyl Methacrylate and the Synthesized Monomer ................440
4. Grafting Modification of Wood by OrganiceInorganic Hybrid
Polymer Derived From the Doping Method ....................................... 448
5. Grafting Modification of Wood by OrganiceInorganic Hybrid
Polymer Derived From the SoleGel Method ..................................... 459
6. Conclusions.......................................................................................... 468
Acknowledgments ..................................................................................... 469
References ................................................................................................. 469
Further Reading ........................................................................................ 471
CHAPTER 12 Processing and Characterization of Grafted Bio-composites:
A Review .................................................................................................. 473
Anbukarasi Kathiresan, Sivakumar Kalaiselvam
1. Introduction.......................................................................................... 473
2. Graft Polymerization Process .............................................................. 474
2.1 Grafting of Biopolymer ................................................................476
2.2 Grafting of Bio-fiber .....................................................................487
3. Conclusion ........................................................................................... 506
References ................................................................................................. 506
Index ............................................................................................................................... 513

List of Contributors
Carlos Alemán
Universitat Politècnica de Catalunya, Barcelona, Spain
Bahman Amini Horri
University of Surrey, Surrey, United Kingdom
Emilio Bucio
Universidad Nacional Autónoma de México, Ciudad Universitaria, CDMX, Mexico
Luís J. del Valle
Xiaoying Dong
Shandong Provincial University Key Laboratory of Silviculture; Shandong Institute of
Wood Science; Forestry College, Shandong Agricultural University, Taian, China
Franco Ferrero
Politecnico di Torino, Torino, Italy
Anna Garetto
CNR e ISMAC, Institute for Macromolecular Studies, Biella, Italy
Animesh Ghosh
Birla Institute of Technology, Mesra, Ranchi, India
Sivakumar Kalaiselvam
Anna University, Chennai, India
Anbukarasi Kathiresan
Thanthai Periyar Government Institute of Technology, Vellore, India; Anna University,
Chennai, India
Anupama Kumar
Visvesvaraya National Institute of Technology, Nagpur, India
Agnieszka Kyzioł
Jagiellonian University, Kraków, Poland
Karol Kyzioł
AGH University of Science and Technology, Kraków, Poland
Yongfeng Li
Shandong Provincial University Key Laboratory of Silviculture; Shandong Institute of
Wood Science; Forestry College, Shandong Agricultural University, Taian, China
H. Iván Meléndez-Ortiz
CONACyTeCentro de Investigación en Química Aplicada, Saltillo, Mexico
Raffaella Mossotti
Pinki Pal
xv
xvi List of Contributors
Jay Prakash Pandey

Nursel Pekel Bayramgil
Hacettepe University, Ankara, Turkey
Victor H. Pino-Ramos
Jordi Puiggalí
Deepali Rahangdale
Visvesvaraya National Institute of Technology, Nagpur, India
Alejandro Ramos-Ballesteros
Babak Salamatinia
Monash University Malaysia, Subang Jaya, Malaysia
Gautam Sen
Anupama Setia
Jan Nayak Chaudhary Devi Lal Memorial College of Pharmacy, Sirsa, India
Saundray R. Soni
Claudio Tonin
Pau Turon
B. Braun Surgical, Barcelona, Spain
May-Yuan Wong
Monash University Malaysia, Subang Jaya, Malaysia
About the Editor
Vijay Kumar Thakur, PhD; MSc
Faculty in Manufacturing
Enhanced Composites and Structures Center
School of Aerospace, Transport, and Manufacturing
Cranfield University, Cranfield, Bedfordshire MK43 0AL
Prior to commencing in the School of Aerospace, Transport, and Manufacturing

at Cranfield University, Dr. Vijay Kumar Thakur was working as a Staff
Scientist in the School of Mechanical and Materials Engineering at
Washington State University in the United States (2013e16). Some of his
other prior significant appointments include being a Research Scientist in
Temasek Laboratories at Nanyang Technological University, Singapore
(2009e12), and a Visiting Research Fellow in the Department of Chemical
and Materials Engineering at LHUeTaiwan. He did his postdoctoral study in
Materials Science and Engineering at Iowa State University and received a
PhD in Polymer Chemistry (2009).
In his academic career, he has published more than 100 SCI journal research
articles in the field of chemical sciences/materials science and holds one US
patent. He has also published 33 books and 35 book chapters on the advanced
state-of-the-art of polymer science/materials science/nanotechnology with
numerous publishers. His research interests include the synthesis and
processing of biobased polymers and composites, nanostructured materials,
hydrogels, polymer micro/nanocomposites, nanoelectronic materials, novel
high dielectric constant materials, engineering nanomaterials, electrochromic
materials, green synthesis of nanomaterials, and surface functionalization
of polymers/nanomaterials. Application aspects range from automotive to
aerospace, energy storage, water purification, and biomedical fields.
Vijay is an editorial board member of several international journals, as well

as a member of scientific bodies around the globe. Some of his significant
appointments include Associate Editor for Materials Express (SCI);
Advisory Editor for SpringerPlus (SCI); Editor for Energies (SCI); Editor
xvii
xviii About the Editor
for Cogent Chemistry (SCI); Associate Editor for Current Smart Materials;
Associate Editor for Current Applied Polymer Science; Regional Editor
for Recent Patents on Materials Science (Scopus); and Regional Editor for
Current Biochemical Engineering (CAS). He also serves on the Editorial
Advisory Board of Polymers for Advanced Technologies (SCI) and is on
the Editorial Board of Journal of Macromolecular Science, Part A: Pure
and Applied Chemistry (SCI), International Journal of Industrial
Chemistry (SCI), Biointerface Research in Applied Chemistry (SCI), and
Advances in Natural Sciences: Nanoscience and Nanotechnology (SCI).
Preface
There is growing interest in biopolymer-based materials all over the universe, especially if the
materials are based on renewable raw materials. The use of renewable resources is becoming
more and more important in present civilizations. It is intensively connected to natural
bioresources, agricultural production, and new developments in biobased materials. In fact,
sustainable development has become a key idea. Sustainable development over the next
century requires the use of natural polymer-based materials from renewable resources as
alternatives to the Earth’s limited petroleum resources. The 21st century offers enormous
challenges but also exciting opportunities at economic and environmental levels.
Among various materials, natural biopolymers are the most abundant polymer found in nature;
they are found in plants and trees, along with other biomass. Though this research in general has
become prevalent, studies pertinent to biobased materials are limited compared to synthetic
polymers. The prime reason for this is the inherent disadvantages of these materials such as
hydrophilic nature and poor resistance to chemicals/weathering conditions. Improvements in
the surface modification of biopolymers through graft copolymerization are enormously
important because they will widen the scope of their applications. The development of new
graft copolymer materials from biopolymers with excellent mechanical and barrier properties
has been an important research challenge for industries for promising applications of their
products. Hence advances in graft copolymerization of biopolymers with excellent
mechanical and barrier properties have been an important research challenge. Biopolymer
Grafting: Applications is organized in such a manner to provide the most relevant and
realistic information on natural polymer-based graft copolymers for different applications
including automotive, toxic ion removals, biomedical, defense, etc. The book bridges the
knowledge gap between the scientific principles and industrial applications of polymer grafting.
This volume of the book series Advances in Polymer and Fibers is solely focused on the
“applications” of biopolymer-based graft copolymers. Some of the important topics include,
but are not limited to: graft copolymerization: a revolutionary approach; grafting of
hydroxyapatite for biomedical applications; grafting of hydrophilic monomers onto cellulosic
polymers for medical applications; surface functionalization with biopolymers via plasma-
assisted surface grafting and plasma-induced graft polymerization; synthesis and application
as programmable water-soluble adhesive of polyacrylamide grafted gum; radiation grafting of
biopolymers and synthetic polymers: synthesis and biomedical applications; processing and
characterization of grafted biocomposites; derivatized chitosan: fundamentals to applications;
grafted copolymerized chitosan and its applications as a green biopolymer; grafting onto
biopolymers: application in targeted drug delivery; chitosan grafted copolymers for drug
delivery applications; fibroin grafting onto wool fibers: recent advances and applications; and
grafting modification of wood for high performance.
xix
xx Preface
Several critical issues and suggestions for future work are comprehensively discussed in this
volume with the hope that the book will provide a deep insight into the state-of-the-art of
“Biopolymer Grafting: Applications” of the biopolymer-based graft copolymers. I would like
to thank Elsevier and Jennifer Pierce for the invaluable help in the organization of the editing
process. Finally, I would like to thank my parents and spouse for their continuous
encouragement and support.
Vijay Kumar Thakur, PhD

Cranfield University, United Kingdom
Applications of Graft Copolymerization:
Chapter
1
A Revolutionary Approach
Anupama Setia
Jan Nayak Chaudhary Devi Lal Memorial College of Pharmacy, Sirsa, India
1. INTRODUCTION
Natural polysaccharides are polymeric carbohydrates that are abundant in
nature including animals, plants, and marine sources. They contain repeti-
tive units that are joined together by glycoside linkages with various
branches (Gao and Yan, 2004; Lapasin and Pricl, 1995). Polysaccharides
have been proven to be widely used in the food (Sahoo et al., 2013), phar-
macy (Pillai et al., 2009), and industry (Meshram et al., 2009; Yu et al.,
2011) sectors, as well as many more diversified fields. They are preferred
over synthetic polymers due to their availability, nontoxicity, and low
cost, though they possess certain disadvantages of being thermosensitive,
prone to microbial contamination, lowering of viscosity during storage,
and sensitive to highly stressful conditions (Gupta et al., 2004). To overcome
these drawbacks, various modification approaches have come to attention,
e.g., etherification (Edgar et al., 2001), cross-linking (Bastos et al., 2009),
derivatization of functional groups (Battaerd and Treglar, 1967; Fares
et al., 2003; Haag et al., 2004; Jenkins and Hudson, 2001; Kaith and Kalia,
2008a,b; Moreira et al., 1997; Reis et al., 2007; Shi et al., 2007), and graft
copolymerization using chemical, radiation, photochemical, plasma-
induced, and enzymatic methods (Bastos et al., 2009; Kalia et al., 2011;
Rana et al., 2015; Roy et al., 2009). Graft copolymerization is found to be
the most assuring overture among the aforementioned approaches, as deriv-
atization of gum has only limited attributes (Fares et al., 2003); especially,
the increase in molecular weight cannot be achieved due to lesser attach-
ments of the functional groups. Also the introduction of new functional
groups changes the charge on the molecule, molecular chain’s aggregation
state, hydrophilicehydrophobic capability (Cunha and Gandini, 2010),
capacity to form complexes (Moreira et al., 1997), ability to respond to
the stimulus, and rheological behavior of gums (Lapasin and Pricl, 1995),
Biopolymer Grafting: Applications. http://dx.doi.org/10.1016/B978-0-12-810462-0.00001-6

Copyright © 2018 Elsevier Inc. All rights reserved. 1
2 CHAPTER 1 Applications of Graft Copolymerization: A Revolutionary Approach
due to which application domain of the gums was found to be increased but
up to an extent.
Graft copolymerization has multifaceted potential, which has been exploited
by the scientists to introduce targeted properties in the copolymer devel-
oped. Apart from the alteration in melting point, permeability, elasticity,
solubility, chemical reactivity, and glass transition temperature due to graft
copolymerization, there has been no change in the biodegradable nature of
the polymer, making this tool much more advantageous (Fares et al., 2003;
Haag et al., 2004; Shi et al., 2007). Depending upon the monomer grafted on
the polysaccharide, the properties of the upcoming product (Kalia and Sabaa,
2013) are selected.
Grafting has been recognized as the authentic method, which can make
changes in the structure of the polymer by reacting with the synthetic mono-
mer and hence lead to the formation of a new biomaterial that is much more
sophisticated when compared with its native polysaccharide, which suffers
from the severe enzymatic attack and also from uncontrolled swelling and
erosion (Jenkins and Hudson, 2001).
A graft copolymer is nothing but a combination of a polymer (trunk
polymer) and a synthetic monomer reacted together to make a macromole-
cule where a main chain, also called the backbone of the polymer, has the
monomer attached continuously as the side chain, leading to the formation
of the copolymer. The functional groups of both the constituents attach
themselves by covalent bonding. Although graft copolymerization is very
advantageous and an effective method of altering the properties of the
polymer, it also suffers from one drawback, i.e., formation of concurrent
homopolymer, which is the major constraint in grafting, resulting in lower
yield (Battaerd and Treglar, 1967).
Various methods of grafting are available and are further described in detail;
among them, redox initiator-induced grafting is the one of the conventional
methods, which has been replaced by microwave-irradiated grafting due to
numerous disadvantages like lengthy continuance of reaction, unwanted
homopolymer formation, degradation of the polymer, use of catalyst, and
also due to the advantages of microwave-irradiated grafting (Rana et al.,
2015).
Microwave irradiation significantly reduces the reaction time for almost all
the grafting reactions as well as the use of the toxic solvents, leading to high
yields, clean product formations, and product selectivity. The applications
of grafting have been exploited by miscellaneous systems as per change
in the properties of the graft copolymer for corresponding active ingredient,
1. Introduction 3
flocculating agents (Barikani and Mohammadi, 2007), and targeted (Sun

et al., 1999), controlled, and sustained drug delivery carriers, (Soppimath
et al., 2001) adsorption of toxic heavy metals and dyes (Crini, 2005),
water-saving materials, sand-binding materials, daily chemicals, thickening
agents, electrical biomaterials, macromolecular surfactants, and water treat-
ment processes (Wang and Wang, 2013).
1.1 Graft Copolymerization

When two different monomers club repetitively in a sequence, the polymer
is called a copolymer. The pattern in which the copolymer and the monomer
will be attached is decided by the comparative responsiveness of the mono-
mer and the polymer. The copolymer can further be classified as block
copolymer, random copolymer, alternate copolymer, and the graft copol-
ymer. When monomer units are present in an ordered form, it is called an
alternate copolymer, whereas when it is attached randomly, it is called a
random copolymer. Block copolymer is a combination of two or more seg-
ments of different polymers, which are linearly joined end-to-end (Battaerd
and Treglar, 1967; Zohuriaan-Mehr, 2005). Graft copolymer is composed of
a natural polymer and a synthetic polymer in which the natural polymer acts
as a backbone of the grafted copolymer, and a synthetic monomer acts as the
side chain, which is attached to the preformed polymer at various sites. The
synthetic polymer could be monomer or a vinyl monomer or it can be a
binary mixture. The grafting reactions in which only monomers are involved
can be completed within one step; however, graft copolymerization
involving vinyl monomers or the mixtures involves a series of reactions
by sequentially or simultaneously adding the monomers to the grafting
reaction. Graft copolymerization involves the presence of vinyl group on
the preformed polymer chain as an essential requirement of the reaction to
occur. The medium in which graft copolymerization can be done could be
homogeneous, i.e., single phase, or could be heterogeneous (biphasic); it
totally depends upon the solubility of the polymers and monomers involved
(Rana et al., 2015).
1.2 Concept of Molecular Brushes

Molecular brushes are recognized as a macromolecular structure that con-
sists of a main polymeric backbone with side chains attached by covalent
or noncovalent bonding, which looks like a bottle brush. The side chains
of this macromolecule make it unique, and it looks like the microvillus
on the intestinal surface. The multibranched side chains have specific and
special features compared to the linear polymers of similar molecular
weights. The hypothetical structure of the molecular brushes has been
shown in Fig. 1.1. The concept of molecular brushes has wider applications
and can be synthesized by the different approaches of graft copolymeriza-
tion, as discussed in detail in the next section (Sheiko et al., 2008; Zhang
and Müller, 2005).
1.3 Approaches for Graft Copolymerization

There are three basic approaches that are responsible for the formation of
the graft copolymer. They are “grafting on”, “grafting from”, and “grafting
through”.
1.3.1 Grafting On
The grafting on approach involves the coupling reaction between the poly-
mer chain containing randomly distributed active functional groups X on
the backbone (Fig. 1.2) with the functional groups (Y) at the chain ends
of the other reactive polymer. The coupling or the covalent reaction
n FIGURE 1.1 Hypothetical diagram of molecular brushes.
n FIGURE 1.2 Schematic presentation of grafting on approach of graft copolymerization.

1. Introduction 5
responsible for grafting can be made possible by alterations employing

different chemical approaches, e.g., living system, free radical, anionic,
and atom transfer radical polymerization techniques. The grafting on process
basically employs the anionic polymerization technique for the reaction to
occur (Hadjichristidis et al., 2004).
1.3.2 Grafting From

Chemical modification of the macromolecular backbone is done to generate
active sites on it that would have the capability of initializing the monomer
polymerization reactions (Fig. 1.3). The number of chains of the monomer
grafted can be easily controlled by controlling the generation of the active
sites. Further generation of the active sites can be controlled by varying
the type of initiator and reactions. Numbers of reaction mechanisms have
been already discussed in the literature in detail, i.e., free radical, anionic,
and cationic graft copolymerization and also atom transfer radical graft
copolymerization technique. The graft copolymers thus synthesized have
different chain lengths, which may be due to the steric ion hindrance effects
(Boerner and Matyjaszewski, 2002; Gao and Matyjaszewski, 2007; Inceoglu
et al., 2004; Inoue and Matyjaszewski, 2004; Inoue et al., 2004; Kobayashi
and Mullen, 2015; Lutz et al., 2004; Neugebauer et al., 2006; Okrasa et al.,
2004; Paik et al., 1998; Percec and Asgarzadeh, 2001; Shinoda et al., 2001,
2003; Tsarevsky et al., 2007; Van Camp et al., 2007).
1.3.3 Grafting Through Method

Another approach or mechanism of grafting is via the grafting through
method, in which the participating monomer is mainly the vinyl functional
groups that get copolymerized with the polymer (Fig. 1.4). It may or may
not use the initiator for the reaction to proceed as the function groups are pre-
made only. The monomer involved in this approach is usually of lower
n FIGURE 1.3 Schematic presentation of grafting from approach of graft copolymerization.

molecular weight, and the polymer involved is acrylate functionalized

polymer (macromonomer). Based on the reactivity of the functional group
present on the terminal portion of the monomer, the homogeneous or hetero-
geneous nature of the graft copolymer is decided. The ratio of concentration
of monomers and polymers also have significant effect on the outcome of the
product and the ratio of both changes as the reaction proceeds due to branch-
ing of the monomers onto the polymer backbone. The grafting through
process can proceed by using any of the polymerization techniques given
in the grafting on and from methods, and due to its flexible nature, it is
the most extensively studied and used (Battaerd and Treglar, 1967; Boerner
and Matyjaszewski, 2002; Gao and Matyjaszewski, 2007; Hadjichristidis
et al., 2004; Inceoglu et al., 2004; Inoue and Matyjaszewski, 2004;
Inoue et al., 2004; Kobayashi and Mullen, 2015; Lutz et al., 2004;
Neugebauer et al., 2006; Okrasa et al., 2004; Paik et al., 1998; Percec and
Asgarzadeh, 2001; Shinoda et al., 2001, 2003; Tsarevsky et al., 2007; Van
Camp et al., 2007).
1.3.4 Grafting by Chemical Method

Graft copolymers are usually prepared by the following steps using conven-
tional chemical methods:
n generation of the free radicals
n free radicals as macroinitiators
n graft polymerization of macroinitiators with the vinyl or acrylic
monomer
Free radicals can be generated by the use of chemicals as initiators, which
create the active sites on the backbone of the polymer. A number of initiator
systems such as ceric ammonium nitrate (CAN) ammonium persulfate,
potassium persulfate used in free radical polymerization, thiocarbonation po-
tassium bromate, potassium diperiodatocuprate (III), azobisisobutyronitrile
n FIGURE 1.4 Schematic presentation of grafting through approach of graft copolymerization.

1. Introduction 7
(AIBN), and ferrous ammonium sulfate in other polymerization techniques

have already been developed to initiate graft copolymerization process or
generate free radicals. Table 1.1 describes the different types of initiators
used to initiate the various grafting reactions along with monomers and poly-
saccharides. This type of technique leads to the formation of graft copolymers
that have many applications in industrial production. The properties of the
copolymer formed are mainly affected by the length, molecular structure,
and number of side chains (Chiang, 1996; Cho and Lee, 2002; Hsu and
Pan, 2007; Misra and Dogra, 1980; Prabaharan and Mano, 2007; Zhang
et al., 2003).
Researchers and scientists have even reported various types of redox initi-
ators, e.g., metal carbonyls, Lewis acid, strong bases, etc., for chemically
induced grafting. Investigation of new redox systems and initiators is still
under research to develop the new polymers with the desired functional
properties. New redox systems are still under research to incorporate desir-
able properties into the backbone and hence to develop a polymer with more
specific functional properties (Ikhuoria et al., 2010; Vlcek et al., 2006;
Zahran and Mahmoud, 2003).
1.3.5 Grafting by Living Systems

1.3.5.1 Enzymatic Grafting
By the time enzymes have been discovered, they are acting as a versatile
means of catalyzing the reactions of various types due to their specificity
for the reactants, high efficiency, and quick rate of reactions. They have a
high potential in the area of polymer synthesis and modification approaches
due to several advantages, e.g., limiting the hazards due to the use of chem-
icals as initiators or catalysts in various modification approaches. Similar
property of specificity is observed in enzymes, which have significant appli-
cation in the field of modification of the polysaccharide structure to get the
highly efficient and specific copolymers (Kaur et al., 1998; Kumar et al.,
1999; Tizzotti et al., 2010; Yamada et al., 2000).
Chao et al. (2004) used the enzymatic method to introduce carboxyl groups
onto chitosan as a means to confer the ability to adsorb cationic dyes on
beads. The presence of new functional groups on the surface of beads
resulted in the increase of the surface polarity and the density of sorption
sites, thereby improving the sorption selectivity for the dye (Chao et al.,
2004).
A hydrophilic compound chlorogenic acid was grafted onto chitosan in the
presence of enzyme tyrosinase to attain the water solubility of chitosan
under basic conditions. Tyrosinase converts phenolic substrate into
Table 1.1 List of Different Types of Initiators Used for Grafting

Initiator Polymer Monomer References
Benzoyl peroxide Cellulose acetate Acrylic acid and acrylamide Abdelwahab et al. (2015)
Azobisizobutyronitrile Sodium alginate N,N dimethyl acrylamide Akin and Isiklan (2016)
Potassium per sulfate Acryloyl chloride Amino acid-based Alfaifi et al. (2014)
monomer
Potassium bromate/ Palm tree cellulose Acrylic acid Al-Hoqbani et al. (2014)
Thiourea dioxide
Potassium Poly(vinyl alcohol) Styrene Bai et al. (2009)
diperiodatocuprate (III)
Cerium(IV) ammonium Starch Acrylamide Bulut (2015)
nitrate
Cerium(IV) ammonium Chitosan Polyacrylamide Bulut (2016)
nitrate
Stannous octoate Starch Poly-1-lactic acid Egri et al. (2016)
Cerium(IV) ammonium Chitosan Acrylic Acid Huacai et al. (2006)
nitrate
Cerium(IV) ammonium Starch Acrylonitrile Ikhuoria et al. (2010)
nitrate
Cerium(IV) ammonium Locust bean Acrylamide Kaity and Ghosh (2016)
nitrate
Cerium(IV) ammonium Locust bean Acrylamide Kaity et al. (2013)
nitrate
Cerium(IV) ammonium Hydroxyl ethyl starch N,N-dimethyl acrylamide Kolya and Tripathy (2013)
nitrate and Acryl amide
Ammonium nitrate (CAN) Amylopectin Acrylamide and N,N- Kolya and Tripathy (2014)
dimethylacrylamide
Cerium(IV) ammonium Xanthan gum Acrylamide Kumar et al. (2009)
nitrate
Cerium(IV) ammonium Cellulose Glycidyl methacrylate Kumar et al. (2013)
nitrate
Cerium(IV) ammonium Starch Methyl methacrylate Kumar et al. (2015)
nitrate
Horseradish peroxidase/ Starch Dimethyldiallylammonium Lv et al. (2014)
H2O2 chloride
Cerium(IV) ammonium Soya peptone Acrylamide Mahto et al. (2014)
nitrate
Ammonium persulfate Gum kondogogu Acrylamide Malik and Ahuja (2011)
Ammonium persulfate Carboxymethyl tamarind Acrylonitrile Meenkashi et al. (2014)
kernel
Benzoyl peroxide 5-fluorouracil Methacrylic acid Minhas et al. (2013)
Cerium(IV) ammonium Agar Acrylamide Mishra et al. (2011a,b)
nitrate
1. Introduction 9
Table 1.1 List of Different Types of Initiators Used for Grafting continued
Cerium(IV) ammonium Starch Acrylamide Mishra et al. (2011a,b)

nitrate
2,2-azobis[2-(2-imadazolin- Carboxymethylated guar N-vinylformamide Mishra et al. (2015)
2-yl) propane] gum
dihydrochloride
Potassium persulfate Dextrin Acrylamide Pal et al. (2010)
Ammonium Xanthan gum Aniline Pandey and Ramontja
peroxydisulfate (2016)
Potassium Guar gum N,N’-dimethylacrylamide Pandey et al. (2014a,b)
peroxymonosulfate
Potassium Gellan gum N,N-dimethylacrylamide Pandey et al. (2014b)
peroxymonosulfate
Chromic acid Potato starch Methacrylic acid Pathania and Sharma
(2012)
Ammonium persulfate Salep 3-(methacryloylamino) Pourjavadi et al. (2013)
(aps) propyl]
trimethylammonium
chloride
Cerium(IV) ammonium Inulin Acrylamide Rahul et al. (2014)
nitrate
Cerium(IV) ammonium Agar Acrylamide Rani et al. (2012a,b)
nitrate
Cerium(IV) ammonium Gum ghatti Acrylamide Rani et al. (2012a,b)
nitrate
Cerium(IV) ammonium Sodium alginate Methyl methacrylate Rani et al. (2013)
nitrate
Cerium(IV) ammonium Agave angustifolia Methyl methacrylate Rosli et al. (2015)
nitrate
Potassium persulfate Carboxymethyl cellulose 2-(dimethylamino) ethyl Salama et al. (2015)
methacrylate
Stannous 2-ethyl Starch Lactic Acid Salimi et al. (2014)
hexanoate
Ammonium persulfate Aegle marmelos gum Acrylamide Setia and Kumar (2014)
Potassium persulfate Chitosan Acrylic acid, acrylamide, Sharma et al. (2014)
and acrylonitrile
K2S2O8/Ascorbic acid Chitosan Methymethacrylate Singh et al. (2006a,b,c)
Ferrous ammonium sulfate- Cellulose Methylacrylate Thakur et al. (2013)
potassium persulfate
Cerium(IV) ammonium Gellan Acrylamide Vijan et al. (2012)
nitrate
Cerium(IV) ammonium Bamboo cellulose Methyl methaacrylate Wan et al. (2011)
nitrate
Continued
Table 1.1 List of Different Types of Initiators Used for Grafting continued
Potassium persulfate Starch Phenyl methacrylate Worzakowska and

Grochowicz (2015)
Cerium nitrate amine Starch Acrylic amide and the Xu et al. (2013)
methyl methacrylate
Cerium(IV) ammonium Alginate Poly(N- Xu et al. (2014)
nitrate isopropylacrylamide)
Cerium(IV) ammonium Chitin 2-hydroxy ethyl Yalinca et al. (2016)
nitrate methacrylate and 4-
vinylpyridine.
Azobisisobutyronitrile Lignin Acrylonitrile and N,N- Youe et al. (2016)
dimethyl formamide
O-quinone, which can undergo reaction with the amino group of chitosan to
form graft copolymer (Kumar et al., 1999).
Chitosan gets converted to its modified form in the presence of chlorogenic
acid (a natural product) as well as acidic medium. Enzymatic modification
can yield chitosan derivatives with unique pH-sensitive water solubility and
adhesive properties. The feasibility of using tyrosinase as a catalyst for
grafting hexyl oxy phenol and also Bombyx mori silk fibroin onto the chito-
san was investigated (Chen et al., 2000).
In order to confer the functional properties of chitosan, horseradish perox-
idase was also used as a catalyst in the grafting reaction. Using this
enzyme, grafting of the phenolic substrate dodecyl gallate onto the chito-
san was possible (Vachoud et al., 2001). Quinones are another category
that is being used to modify the chitosan, e.g., menadione, which is a
derivative of napthaquinone, contains similar physiological properties as
that of vitamin K, which is responsible for the reaction with chitosan and
introducing the increased surface hydrophobicity and the spectral features
of the modified chitosan (Muzzarelli and Muzzarelli, 2002). Another
example of modification of polysaccharide is by using the enzyme immo-
bilization technique. J. Darta and T. Jesionowski in 2014 developed an
adsorption immobilization technique to graft amino lipase onto a silica sur-
face using glutaraldehyde as an intermediate. The outcome of the research
was that the properties of the substrate were modified and now the product
can be utilized in a better way. Also, the amount of the enzyme that was
received after the reaction was much more than the amount introduced
initially (Jesionowski et al., 2014).
1. Introduction 11
Horseradish peroxidase in the presence of H2O2 initiated the graft copoly-

merization of starch and diallylammonium chloride (DMDAAC). The graft
copolymerization resulted in stronger hydrophobic areas and greater cationic
property. The grafted cationic starch had improvised sludge dewatering
properties when compared with ungrafted cationic starch, which may be
due to the increase in cationic degree as well as stronger hydrophobic areas
that reduced the resistance of filtration and capillary suction time to a signif-
icant effect and led to the formation of the porous structure in the sludge;
sludge water content was found to reduce up to 50.6% from 97.85%. The
research suggested the potential application in the development of highly
efficient sludge dewatering agents (Won et al., 2004). Biological properties
of these enzymatically altered polysaccharides are still an area of high inter-
est for researchers and have a real hope for revolutionary outcomes (Fujioka
et al., 2004).
1.3.5.2 Plasma-Initiated Grafting

Modification of the polysaccharides via plasma initiation approach is
receiving much attention due to day-by-day exploitation of the polysaccha-
rides. Plasma conditions attained through slow discharge offer about the
same possibilities as with ionizing radiation. The main processes involved
in plasma are dissociation, electron-induced excitation, and ionization, which
are responsible for graft modification. Subsequently, the electrons that were
accelerated from the plasma have adequate energy to induce cleavage of
the chemical bonds in the polymeric structure, which forms macromolecular
radicals to initiate the graft copolymerization (Bhattacharyaa and Misra, 2004;
Kaith et al., 2011; Zhang and Yao, 2016). Plasma-initiated polymerization of
grafting can be carried out by using polymerizing gases and precursors like
fluorocarbons, hydrocarbons, and silicone-containing monomers. Carrier gas
plays important roles in these plasmaesurface interactions, and usually inert
gas like helium or argon is used as carrier gases. For example, intelligent,
perceptive, and smart polymers play an important role in drug delivery since
they may dominate not only where a drug has to delivered, but also when and
with which interval it has to release (Soppimath et al., 2002).
The grafting of monomers containing vinyl functional groups, e.g., acrylic
acid and acrylamide, was performed on polyethylene, poly (ethylene
terephthalate), and polypropylene films. The films of polysaccharides are
exposed to the plasma only for 90 s and allow the further postpolymeriza-
tion to occur at room temperature. Finally, the grafted films of polyethylene,
which had modified properties of adsorption and desorption of the metal,
were synthesized (Bastos et al., 2009).
Two treatment types of plasma with polymers had been attempted by the
researchers in order to get the monofunctional surfaces on the polymer:
n plasma treatment via oxygen
n plasma treatment via charged particle bombardment leading to frag-
mentation of the polymer
However, plasma treated with these two approaches resulted with the lower
stability products having several functional groups, which are not desired
effects; hence these approaches were not carried further. Perhaps among
the successful techniques, one is decreasing the applied energy to the
maximum extent using low powered plasma and also reducing the density
of the particles damaged while under treatment by the plasma. One example
of plasma-initiated grafting is polypropylene, due to its simpler chemical
structure. Also, hydroxyl, carboxyl, and epoxy groups were selected as
the functional groups that are introduced by direct plasma treatment or by
grafting methods. Plasma grafting can be evaluated by electron spectros-
copy for chemical analysis and infrared spectroscopy methods, which
revealed that plasma-initiated grafting leads to homogeneous distribution
of participating functionalities and also a better retention of the precursor
structure (Kale and Desai, 2011).
1.3.6 Cationic Graft Copolymerization

Cationic grafting is another approach to attempt graft copolymerization by
living system. Living cationic polymerization involves various steps, i.e., initi-
ation of the chain reaction, followed by chain propagation, and finally leading
to chain termination and further continued with transfer of the chain. It allows
the synthesis of very well-defined polymers with lower molecular weight and
also of polymers with unusual architecture, such as star polymers and block
copolymers, making living cationic polymerization a tool of commercial
and academic interest. Common monomers that can be graft copolymerized
by the cationic method could be vinyl ethers, alpha-methyl vinyl ethers,
isobutene, styrene, methyl styrene, and N-vinyl carbazole, plus many more.
The basic characteristic required for a monomer is the nucleophilic nature,
and it should also have the potential to neutralize the carbocation charge on
the substituents (Matyjaszewski and Muller, 2009).
Cationic polymerization is nothing but a type of chain growth polymeriza-
tion involving a monomer that gets reactive due to the transfer of charge
from cationic initiator, which further acts as initiator for other monomers
and finally leads to formation of the monomer. Olefins, electron donating
groups, and heterocycles can specifically act as monomers in cationic graft
copolymerization. They have high sensitivity to the solvents in which the
1. Introduction 13
reaction proceeds and are the key component in the grafting, which
propagates the reaction according to its reactivity with the monomers
(Huang et al., 2007a,b). Living cationic polymerization is a type of living
polymerization technique that involves cationic propagating species. A
chemical equilibrium exists between the ionic species, which are propa-
gating actively, and the covalent species, which are dormant. Use of solvents
requires purification of the monomer as well as of the solvent. Cationic
polymerization has many applications, e.g., the production of polyisobuty-
lene, which is a constituent of inner tubes and poly(N-vinylcarbazole).
Polymeric grafted silica nanoparticles had been synthesized and initiated
by the cationic ring opening method of grafting, utilizing 2-methyl-1,2-
oxazoline and involving a solvent-free dry system. To prevent the environ-
ment pollution and also to simplify the process, the whole grafting process
had been scaled up and investigated about the outcomes (Ueda et al.,
2008). Cationic graft copolymerization of a cationic starch (sludge dewater-
ing agent) and dimethyl diallyl ammonium chloride (DMDAAC) using
horseradish peroxidase/H2O2 as an initiator was performed. Stronger hydro-
phobic regions and cationic groups producing a porous structure within the
sludge were observed after grafting, which are good characteristics of a
dewatering agent. Hence it may have significant potential in the develop-
ment of high-performance sludge dewatering agents (Oberstar and
Westman, 1977; Singh et al., 2006a,b,c).
1.3.7 Grafting by Radiation

Graft polymerization persuaded by radiation has the potential to introduce
numerous varieties of functions without the loss of the physical character-
istics of existing shape and configuration. It is excellent as a creation
technology of the high-functional materials. Description of the general
scheme of grafting by radiation is shown in Fig. 1.5.
Grafting by radiation involve two basic techniques:
n individual Radiation Technique
o preradiation
o peroxidation
n mutual Radiation technique
1.3.7.1 Individual Radiation Technique

In this technique, polymers are irradiated individually and after generation
of the free radical then exposed to the monomer.
Preradiation: free radicals are generated by irradiation of the backbone of
polymers in the state of vacuum or in the presence of the inert atmosphere.
n FIGURE 1.5 General scheme of grafting by radiation.
Peroxidation: irradiated polymer substrate was further treated with monomer

in the presence of some liquid or in a solution of a suitable solvent. During
treatment of monomer with the preradiated polymer substrate, high radiation
leading to the formation of peroxides or diperoxides depends on the type of
the polymer backbone or the type of reaction.
1.3.7.2 Mutual Radiation Technique

In this technique, polymers and monomers are irradiated simultaneously to
form the graft copolymer or to generate the free radicals and subsequent
formation of the graft copolymer (Burlant and Hoffmann, 1960; Kaur
et al., 1998; Wojnarovits et al., 2010; Zhou et al., 2015).
1.3.7.3 Advantages of Radiation Technique Over the

Chemical or Conventional Methods
n It is the most convenient method of graft copolymerization.
n Number and length of graft copolymer can be easily controlled.
n It maintains the purity of the product as it is free from product.
n Depending on the penetrating power of the radiation, interaction at
different depths of the backbone can be achieved.
n It helps in maintaining the molecular weight of the copolymer.
1.3.7.4 Types of Radiation-Induced Grafting

Photochemical Radiations: initiation of the free radicals is done using
photochemical radiations. Free radicals are formed when chromophore of
macromolecule absorbs light and it gets into excited state and forms an
1. Introduction 15
intermediate, which further gets dissociated into free radicals. Various types of
photoinitiators available are uranyl nitrate, hydrogen peroxide, benzoin ethyl
ether, and some ketone Benzoin derivatives, Benzil ketals, Acetophenone de-
rivatives, Hydroxyl alkylphenones, and Acylcro ximino ketones (Khan, 2004;
Kubota and Shigehisa, 1995; Shukla and Athalye, 1994). Copolymers of cel-
lulose had also been grafted on methacrylic acid, acrylic acid, and their deriv-
atives (Irwan et al., 2004; Kubota et al., 2001) using photochemical irradiation.
Gamma Radiations: High energy gamma radiations are very effective to
generate a free radical site on the backbone of the polymer especially for
flouropolymers as they are more stable. Gamma radiations are mainly
used commercially for graft copolymerization. The major disadvantage of
the gamma radiations is it causes unpredictable changes to the backbone
of the polymer. Gamma radiations had been used by Teena sehgal and sunita
rattan in graft copolymerization of the Isotactic polypropylene films on N-
vinyl-2-pyrrolidine using cobalt 60 as the source of gamma radiations.
The grafted films were characterized using fourier transform infrared spec-
troscopy (FTIR), atomic-force microscopy and SEM studies. The optimized
batch was evaluated for swelling studies and pH sensitivity and concluded
that the graft copolymer had better swelling behavior and pH sensitivity
and can be used in the controlled drug delivery system (Sehgal and Rattan,
2010). An attempt was made by Singh et al. to prepare gamma radiation-
induced graft copolymerization of poly vinyl pyrrolidine on sterculia gum
and also further formulation of biocompatible, mucoadhesive hydrogels us-
ing this graft copolymer. Effect of gamma radiation on swelling behavior
and other parameters related to the swelling behavior, e.g., polymer fraction
in the swollen state (f), molecular weight of the polymer chain between two
neighboring cross-links (Mc), cross-link density (r), and mesh size (x),
were studied. Characterization of the hydrogels was done using FTIR,
SEM, X ray diffraction, TGA, and swelling studies. It was found that with
the increase in the dose of the radiation the cross-link density and gel
strength was found to increase, whereas swelling and mesh size were found
to decrease with increasing dose of gamma radiations. It was conferred that
the optimized batch of the hydrogels had mucoadhesive nature and have the
potential to deliver the drug in a controlled manner in the gastrointestinal
tract (GIT) due to its mucoadhesive nature (Singh et al., 2014a,b,c). A binary
mixture of methacrylic acid and 4-vinyl pyridine was grafted on a poly vinyl
fluoride film using preradiation technique with gamma radiations. Maximum
percentage grafting of 77.50% was obtained by irradiating the film by swift
heavy ions, silicon, and carbon. Characterization of the copolymer was done
with FTIR, TGA, swelling ratio, and ion and metal uptake studies (Kaur
et al., 2013). Graft copolymerization of the rayon fiber was done on the
acrylic acid using mutual radiation technique, i.e., by using Ce(4þ)-HNO3 as

redox initiator (chemical method) and gamma radiations (mutual radiation).
Results obtained with both the chemical method as well as the radiation
method were compared. The copolymer obtained by both the methods
were characterized for FTIR, TGA, SEM, swelling behavior, thermal
behavior, dye intake capacity, etc. After comparing the results of both the
methods, it was revealed that the graft made by the radiation method was bet-
ter than one grafted by the chemical method (Kaur et al., 2010). Gamma
radiation-induced graft copolymerization of methyl methacrylate onto jute
fibers was carried out by the preirradiation method in an aqueous medium
using octyl phenoxy poly ethoxy ethanol as an emulsifier. Graft copolymer-
ization of poly (vinyl alcohol) and polymer blend of zein (a natural protein)
was carried with acrylic acid on exposure to gamma radiation. The study also
evaluated the effect of gamma radiation on the compatibility of a polymer
blend. The copolymer was structurally and morphologically evaluated by
FTIR and SEM. The polymer blend had a multilayered structure before
grafting, which was further converted into matrix when irradiated with
gamma radiation (Senna et al., 2010). Gamma radiations have been utilized
for synthesis of hydrogels of psyllium and acrylic acid, which found appli-
cations in sustained delivery of copper sulfate, used as a fungicide in agricul-
tural fields (Kumar and Kaith, 2010).
UV radiations: UV radiations have also been used for induction of the free
radical sites on polymer backbone for graft copolymerization. Graft copoly-
merization using UV radiation is usually possible using photo initiators, e.g.,
benzophenone. UV radiations do not produce copolymers with uniform
grafting and also with low grafting efficiency, which may be attributed
due to the low penetration ability of UV radiations. These disadvantages
of UV radiations limit their use in grafting (Bardajee et al., 2011a,b). Poly-
ether sulfone ultrafiltration membrane using vinyl sulfonic acid as functional
monomer was graft copolymerized on N,N0 -methylenbisacrylamide using
UV photo radiation. The gravimetric method and ATR-FTIR spectroscopy
were used to evaluate the effect of the polymerization conditions on the de-
gree of grafting (Bernstein et al., 2012). Bardajee et al. in 2011 synthesized
highly swellable nanoporous hydrogels by grafting acrylic acid on a salep
backbone using UV photo radiation. Formulation of the hydrogel was
conferred by FTIR and TGA, and morphology was confirmed with SEM.
It was revealed from the results that nanoporous hydrogels has potential
application in colonic drug delivery, as it can successfully deliver the drug
in the colon without losing the drug in the stomach (Bardajee et al., 2011a,b).
Microwave Radiations: microwave radiations have been revealed as an
effectual source for graft copolymerization. It is the most favorable source
1. Introduction 17
for generation of free radicals with or without use of initiator. It has resulted
in greater control over the grafting efficiency as microwave radiations can
easily be controlled by controlling exposure time and strength of the radia-
tion by controlling power. Microwave radiations can quickly transfer the
energy into the major proportion of the reacting mixture or the suspension,
which lead to rapid exposure of the reactants in the reaction vessel. With
polysaccharides, mainly three types of microwave-grafting reactions have
been attempted by scientists: (1) homogeneous solutions with aqueous
media in which all the reactants are completely soluble and no observed
phase separation occurs. Aqueous phase is used as a solvent usually, as
most of the polysaccharides have been found to be soluble in water. It is
the polar nature of the water that absorbs microwaves and convert them to
heat energy significantly. (2) The second type of of microwave-grafting
reaction is heterogeneous suspension, in which all components of the reac-
tion mixture are not fully miscible rather suspended in the mixture. (3) In the
third type of microwave grafting, mixture reactants are in the solid phase.
Polymers, monomers, and initiators are combined together on a solid support
that is nonreactive with all the components of the reaction mixture (Rani
et al., 2012a,b).
The major and most important advantages of microwave-irradiated graft
copolymerization are reduction in time of reaction, least consumption of
the toxic chemicals during grafting, commendable grafting efficiency,
and the formation of selective and clean products. The reasons due to
which these advantages are observed could be that electromagnetic
radiations of 300 MHz to 300 GHz frequency are generated during
microwave irradiation, which is directly and immediately exposed to
bulk mixture. The exposure of these electromagnetic reactions selectively
excites the polar bonds present in the reactants, leading to the breakage or
cleavage of them, which in turn produces the free radicals on the
backbone of the polymer. However, the bonds in the CeC sequence
remain unaltered due to their nonpolar nature, which confirms the product
selective nature of the microwave radiations (Chapiro, 1962; Deshayes
et al., 1999; Singh et al., 2006a,b,c, 2012). Formulation methodology
of the grafting of polymers using microwave has been illustrated in
Fig. 1.6.
Microwave-irradiated grafting is mainly of three types:
n Microwave-initiated grafting: in this type of microwave, radiations are
responsible for initiation of the reaction, and no initiator is required for
formation of free radicals. It is not even an ecofriendly approach of
grafting; rather, it results in too much control and higher
n FIGURE 1.6 Formulation methodology of grafting of polymers using microwave.
reproducibility of percentage grafting in the grafted copolymer (Singh

et al., 2012).
n Microwave-assisted grafting: in this type of grafting, along with micro-
wave irradiations, radicals are produced in the presence of external
redox initiators, which play a vital role in the conversion of microwave
energy into heat energy, which in turn is responsible for free radical
generation and also for successful occurrence of the graft copolymeri-
zation. The initiators or catalysts that are mainly used are persulfate
and ceric salts. The major advantage of the initiator is that the initial
radical is very efficient and quick under the effect of microwave, and
the grafting efficiency is also found to be improvised to a certain
extent (Singh et al., 2012).
n Microwave grafting using solid media: as discussed above, this type of
grafting occurs with use of solid media in presence of microwave radi-
ations done by impregnating reactants over the solid supports. Reac-
tants are preadsorbed on the microwave supporting transparent
materials, e.g., silica and aluminum, or it can be clay or may be
absorbed on the inorganic support following the doping by the cata-
lyst. These types of reactions are attracting interest of the researchers
as it involves usage of domestic microwave ovens, which make the
grafting a highly affordable, safe, efficient, and clean technology that
1. Introduction 19
is very simple to utilized. The graft copolymerization of acrylamide on

chitosan, xanthan gum, guar gum, Artemisia seeds, locust been gum,
carboxymethylstarch, etc. has already been performed with successful
results of high grafting efficiency. Grafting of acrylamide on chitosan
has been compared by both the methods, i.e., conventional as well as
microwave assisted, and grafting efficiency by microwave irradiation
was found to be eight times more than the conventional heating (Rani
et al., 2012a,b). The general scheme of graft copolymerization using
free radical mechanism has been shown in Fig. 1.7.
Grafting of polyacrylic acid on Artemisia seeds (Zhang et al., 2007), chito-
san (Huacai et al., 2006), polyacrylonitrile on tamarind seeds (meenakshi),
cassia siamea (Singh and Tripathi, 2006), hydroxyl methyl acrylate onto
wool fibers (Daneault et al., 1988; Xu et al., 1996), methyl methacrylate
onto flax fibers (Kaith and Kalia, 2008a,b), and Xyloglucan obtained from
Tamarind seed mucilage (Goyal et al., 2008; Mishra and Malhotra, 2012;
n FIGURE 1.7 General scheme of graft copolymerization using free radical mechanism.
Mishra et al., 2012; Pal et al., 2008; Wan et al., 2011), has already been
reported in literature.
1.4 Applications
1.4.1 Drug Delivery System
The design of drug delivery systems has intensively exploited the use of
polysaccharides. The use of polysaccharides in the field of drug delivery
has certain limitations in spite of being biodegradable, biocompatible,
nontoxic behavior with low cost, ready availability, and high regulatory
acceptance attribute and easily metabolized by the microflora present in
the colon into their respective monomers. Polysaccharides have extensive
applications in various fields as binding, disintegrating, thickening, floccu-
lating, and stabilizing agents in oral dosage form and also in transdermal
form. Apart from these advantages and applications, polysaccharides have
certain limitations also as described in Section 1, which has created a way
of modification of the polysaccharides by using various methods, e.g.,
carboxymethylation, side chain grafting, cyanoethylation, chemical cross-
linking, and graft copolymerization using various sources with and without
initiators and many other processes. Graft copolymers are more advanta-
geous compared to the raw polysaccharide as they can be easily tailored
to the requirements for particular applications, e.g., controlled drug delivery
systems. In this section, we have focused on the applications of modified
polysaccharides or graft copolymers using the graft copolymerization
approach with the help of microwave irradiation.
1.4.2 Controlled Drug Delivery

The major challenge in the area of drug delivery is to at least maintain the
concentration of the drug between minimum effective concentration and
maximum safe concentration of a drug in the intended tissue or organ or,
in other words, to maintain the concentration of the drug within the thera-
peutic index. Controlled drug delivery is characterized by releasing the drug
in the specified period of time in predetermined rate. Biodegradable poly-
mers have already been used for controlled release, but major problems
associated with the polysaccharides (discussed earlier) paved the way for
grafted copolymers in this area due to environmental friendly qualities of
polymers and stable and site-specific properties due to synthetic polymers
present in them (Brown et al., 1974; Evans et al., 1988; Friend, 1991;
Meldrum et al., 1972; Wilson and Washington, 1989).
Controlled release application of acrylamide grafted moth bean starch and
sago starch was evaluated by Singh and Nath in 2012 and 2013, respectively,
1. Introduction 21
using lamivudine as the model drug. Acute toxicity and drug compatibility
studies of the copolymer were investigated. Kinetic studies of the formula-
tion of both the copolymers exhibited highest correlation (R) value and
selected Higuchi model for the release mechanism study suggested that
the formulation exhibited a combination of diffusion and erosion-based
release process. Significant differences in the various pharmacokinetic
parameters (Tmax, Cmax, AUC, Vd, t1/2 and MDT) of the optimized formu-
lation were found compared to the marketed conventional tablet Lamivir,
and in vivo pharmacokinetic studies of sago starch-g-polyacrylamide were
also performed on rabbits and conferred the IVIVC correlation as a
controlled release tablets of graft copolymers (Singh and Nath, 2012,
2013). Similarly, sustained release tablets of polyacrylamide grafted Aegle
marmelos gum and xanthan gum were also attempted recently by Setia
et al. and Kumar et al. Sustained release tablets of model water-insoluble
drug diclofenac sodium were formulated using the grafted xanthan gum
and aegle marmelos gum (AMG) as a rate-controlling polymer. Xanthan
gum was able to sustain the drug release over a period of 12 h, the release
kinetics followed the Higuchi model, and the mechanism was governed
by Fickian diffusion, whereas AMG matrix tablets were successful in con-
trolling the release of the drug up to 24 h, exhibiting zero order kinetics
with n value greater than 1, suggesting that the mechanism for drug release
as super case II transport, i.e., rate of release of the drug completely domi-
nated by swelling and erosion of the copolymer. Microwave-assisted graft
copolymerization using ceric ammonium nitrate and ammonium per sulfate
as initiators was successful and the method was concluded to be an easy and
efficient time saver that was easy to reproduce. The single pot synthesis
method to develop the graft copolymers can be further exploited and used
for formulation of the sustained-release drug delivery system (Kumar
et al., 2009; Setia and Kumar, 2014).
Controlled release tablets of graft copolymer of psyllium and methacrylic
acid, which were synthesized using the microwave-assisted method with sil-
ver sulfate as an initiator, were also prepared by R. Kumar and K. Sharma
(2013). The swelling studies, in vitro controlled drug release in different pH
solutions, and the biodegradability studies were performed. It was found that
swelling of Psy-g-PMA was higher than that of the corresponding psyllium,
and drug release in the acidic pH (pH ¼ 4) was 85.67% in the first 3 h,
whereas it was only 82.04% up to 11 h in basic medium. It was also
concluded that the tablets can be used to control the release in GIT based
on pH environments. Also, the graft copolymer due to high superabsorbent
capacity can be used in diapers and feminine sanitary pads. On the same lieu,
Sen and Pal in 2009 and Sen et al. in 2010 investigated the controlled release
behavior of 5-amino salicylic acid from matrix tablets prepared by

microwave-initiated synthesized polyacrylamide grafted guar gum and
carboxymethyl starch. The controlled release matrix tablets prepared were
simple, ecofriendly, worthy for commercial production, and had greater
control and higher reproducibility of percentage grafting in the finally
optimized batch. The percentage grafting was directly proportional to the
time of exposure to microwave irradiation. The matrix tablets formulated
were further characterized by USP drug dissolution apparatus (paddle
method) in different pH solutions, and it was conferred that percentage
grafting was found to increase the release of drug was more sustained and
also release rate was much lesser at low pH, i.e., acidic environment with
the matrix tablets of both the grafted polymers. Finally, it was concluded
that the acrylamide grafted guar gum and carboxymethyl starch have the po-
tential to act as a controlled release carrier and can be used for pH triggered
release for colon targeted drug delivery (Sen et al., 2009, 2010). In 2015,
methacrylamide-grafted gellan gum copolymer was synthesized and investi-
gated for controlled release behavior by formulating matrix tablets of
diclofenac sodium (Nandi et al., 2015), and it was concluded that tablets
prepared from copolymer were able to sustain the drug up to 8 h.
Apart from the controlled release tablets the graft copolymer has also been used
in the formulation of hydrogels (Mohd-Amin et al., 2014), which can be used as
oral controlled release drug delivery carriers. The bacterial cellulose-g-poly
(acrylic acid coacrylamide) {(BC-g-poly(AA-co-AM))} hydrogels and stercu-
lia gum were successfully synthesized using a microwave-irradiation tech-
nique with BC dissolved in an aqueous NaOH/urea solvent system. The
hydrogels demonstrated a pH-responsive swelling behavior, with decreased
swelling in acidic media, which increased with an increase in pH of the media,
reaching maximum swelling at pH 7. Also, the hydrogels showed lesser release
in simulated gastric fluid (SGF) than in simulated intestinal fluid (SIF), sug-
gesting that hydrogels may be suitable drug carriers for oral controlled release
of drug delivery in the lower gastrointestinal tract.
Novel and site-specific curcumin microparticles and nanoparticles were also
prepared via graft copolymerization technique. Primarily amphiphilic copol-
ymer poly (D,L-lactide)-graft-pullulan (PL) in a monomode microwave reactor
was synthesized (Xiao-Jiao et al., 2014). The effects of microwave power, the
ratio of catalyst/lactide, the ratio of the lactide/hydroxyl group of pollen (lac-
tide/OHeP), and solvent on the synthesis were further investigated. Three
samples (designated as PL 8, 9, and 6), characterized by FTIR and NMR,
were applied to form nanoparticles and microparticles investigated by
dynamic light scattering, fluorescence spectroscopy, and transmission electron
microscopy. PL9 and PL6 were used for loading model drug curcumin. The
1. Introduction 23
results indicated that microwave-assisted synthesis shortened the copolymeri-

zation of PL, with higher yield and lactide conversion, from 24 h to 5 min and
showed some specific microwave effects compared with conventional oil heat-
ing. PL with a relatively higher substitution degree gave nanoparticles with
smaller sizes and critical aggregation concentrations. The solubility of curcu-
min in water was increased up to 1.97 mg/mL as the forms of nanoparticles,
which were previously negligible (Mohanty and Sahoo, 2010). Further inves-
tigations, e.g., thermostimuli drug release and liver target, are still under
progress.
Drug troche of Rosin-(2-acryloyloxy) ethyl ester (RAEE) and RAEE graft
copolymerized on chitosan (CTS) with fenoprofen calcium (FC) as an
investigating drug were prepared. SEM images of the CTS and of Cts-g-
PRAEE showed the significant difference in the morphological characters.
The graft copolymer of chitosan was able to sustain the release of the FC
determined by dialysis method in the intestinal juice compared to chitosan
alone. This confirmed the controlled release behavior of the FC from the of
Cts-g-PRAEE copolymer (Wengui et al., 2008).
1.4.3 Enhanced Drug Delivery

Many dosage forms are designed to release the drug immediately or at least
as quickly as possible after administration. This is useful if a faster onset of
action is required for therapeutic reasons. For example, a tablet containing a
painkiller should disintegrate quickly in the gastrointestinal tract to allow a
fast uptake into the body. However, onset of action is very fast in intrave-
nous injections and infusions, and the pharmacological effect may be seen
within seconds after administration. The reason for this instant pharmaco-
logical effect could be first that the drug is already in solution, so the
drug need not be released from the dosage form. Secondly, the drug is being
directly administered inside the body, so there is no loss of time, which is
usually taken by the drug due to drug permeation through the skin or before
the drug reaches the target organs. But in oral solutions the drug is also
already released, and the solution will have to first mix with the gastrointes-
tinal fluids. When powders and granules are taken as oral dosage form, they
need to be dissolved first before the drug is released by dissolution. How-
ever, when tablets are concerned, it is necessary for the tablet to get disinte-
grated, then followed by mixing and dissolution, and then showing the
pharmacological effect after getting permeated if the drug is lipophilic. In
order for capsules to release their drug content the major necessity is for
the capsule shell material (e.g., gelatin or hydroxyl propyl methylcellulose
(HPMC)) first to disintegrate. After that the drug can either dissolve from
the usually solid powders or granules, in the case of hard gelatin or
HPMC capsules, or it can be dispersed from the usually liquid, lipophilic

content of a soft gelatin capsule. Immediate-release dosage forms discussed
here have an onset of action in the order of minutes to hours. Challenge for
the enhancement of drug delivery is to enhance the release of drug from
water-insoluble drugs. Extensive efforts have been undertaken for the
development of products containing a combination of natural as well as syn-
thetic and to derive an array of significantly efficient analog candidates of
grafted copolymer, which can enhance the release of the drug, especially
drugs that are water insoluble (Dahan and Hoffman, 2006).
Microwave-assisted grafting was used as a tool for enhancement of the drug
delivery by developing hydrogels of grafted sterculia gum, 2-
hydroxyethylmethacrylate. The release of the drug from the hydrogel matrix
occurred through non-Fickian diffusion mechanism. Rate of release of the
drug from the hydrogel matrix was higher at the initial stage compared to
the later stage, where release of the drug occurred in a sustained manner.
When the values of the diffusion coefficients were compared, it was
much more for the initial stage compared to the later stages. It suggested
that after a certain concentration has been attained, the release of the drug
from the hydrogel matrix occurred in a controlled manner. It was further
accomplished that hydrogels developed from the modification of sterculia
gum have the potential to act as controlled drug delivery devices and can
also be used for targeted drug delivery by altering some other monomers
(Singh and Vashishtha, 2008).
Kumar et al. examined graft copolymerization, employing conventional as
well as microwave-assisted methods on xanthan gum. The results revealed
that grafting efficiency was higher with microwave-assisted grafting
compared to the conventional method; also, grafting efficiency was directly
proportional to microwave exposure time and power. The copolymer thus
synthesized using the microwave-assisted method was further investigated
for kinetic release studies. The researchers in their succeeded study
compared the release rate of the grafted and ungrafted xanthan gum matrix
tablets of diclofenac sodium. The release rate of the grafted matrix tablets
was faster when compared with the ungrafted xanthan gum tablets, and
as the % grafting was increasing the release rate and erosion were also
increasing, whereas swelling of the Xanthan-g-polyacrylamide was
decreasing. The kinetic modeling study exhibited that release of the drug
from matrix tablets fit best into zero order kinetics (Kumar et al., 2009).
Release and kinetic modeling studies were also performed by Malik et al. in
2012 to investigate the release behavior of the diclofenac sodium (model
drug) from the matrix tablets of grafted and ungrafted gum kondagogu
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wife, M. Pichon and his American wife, Mr. and Mrs. Madison, and
some other persons whose names were not mentioned. When
dinner was announced, the President offered his hand to Mrs.
Madison and took her to table, placing her on his right. Mme. Yrujo
took her seat on his left.
“Mrs. Merry was placed by Mr. Madison below the Spanish
minister, who sat next to Mrs. Madison. With respect to me,” continued
the British minister in his account of the affair,[267] “I was proceeding
to place myself, though without invitation, next to the wife of the
Spanish minister, when a member of the House of Representatives
passed quickly by me and took the seat, without Mr. Jefferson’s using
any means to prevent it, or taking any care that I might be otherwise
placed....
“I will beg leave to intrude a moment longer on your Lordship’s
time,” continued Merry’s report, “by adding to this narrative that
among the persons (none of those who were of this country were the
principal officers of the government except Mr. Madison) whom the
President selected for a dinner which was understood to be given to
me, was M. Pichon the French chargé d’affaires. I use the word
selected, because it could not be considered as a diplomatic dinner,
since he omitted to invite to it the Danish chargé d’affaires, who, with
the Spanish minister, form the whole body.”
Merry’s report was brief; but Yrujo, who also made an official
report to his Government, after mentioning the neglect shown to
Merry before dinner, added a remark that explained the situation
more exactly:[268]—
“I observed immediately the impression that such a proceeding of
the President must have on Mr. and Mrs. Merry; and their resentment
could not but be increased at seeing the manifest, and in my opinion
studied, preference given by the President throughout to me and my
wife over him and Mrs. Merry.”
There the matter might have rested, had not Madison carried the
new “canons” beyond the point of endurance. December 6, four days
after the dinner at the White House, the British minister was to dine
with the Secretary of State. Pichon and Yrujo were again present,
and all the Cabinet with their wives. Yrujo’s report described the
scene that followed.
“I should observe,” said he, “that until then my wife and I had
enjoyed in the houses of Cabinet ministers the precedence of which
we had been deprived in the President’s house; but on this day the
Secretary of State too altered his custom, without informing us
beforehand of his resolution, and took to table the wife of the
Secretary of the Treasury. This unexpected conduct produced at first
some confusion, during which the wife of the British minister was left
without any one giving her his hand, until her husband advanced, with
visible indignation, and himself took her to table.”
Even Pichon, though pleased to see the British minister humbled,
felt his diplomatic pride a little scandalized at this proceeding. He
admitted that it was an innovation, and added,—
“There is no doubt that Mr. Madison in this instance wished to
establish in his house the same formality as at the President’s, in
order to make Mr. Merry feel more keenly the scandal he had made;
but this incident increased it.”
The scandal which Merry had made consisted in saying that he
believed his treatment at the White House was a premeditated insult
against his country. Madison’s course took away any remaining
doubt on the subject in his mind. Merry became bitter. He wrote
home informally:[269]—
“On this occasion, also, the pas and the preference in every
respect was taken by, and given to, the wives of the Secretaries of the
Departments (a set of beings as little without the manners as without
the appearance of gentlewomen), the foreign ministers and their wives
being left to take care of themselves. In short the latter are now placed
here in a situation so degrading to the countries they represent, and
so personally disagreeable to themselves, as to have become almost
intolerable. The case yesterday was so marked and so irritating that I
determined to hand Mrs. Merry myself to the table, and to place
ourselves wherever we might conveniently find seats.”
Merry then received an official explanation that Jefferson

invariably gave precedence to the wives of his Cabinet ministers,
and that he made no exceptions in favor of foreigners in his rule of
pêle-mêle.[270] Merry notified Lord Hawkesbury to that effect. He did
not fail to point out the signs which indicated to him that these
proceedings were but part of a general plan intended to press on the
British government. In truth, the whole issue lay in the question
whether that intent influenced Jefferson’s behavior.
A sort of civil war ensued in the little society of Washington, in
which the women took prominent part, and Mrs. Merry gave back
with interest the insults she considered herself to have received. The
first serious evil was an alliance between Merry and Yrujo, the two
men whom Jefferson had most interest in keeping apart. Pichon
wrote home a lively account of the hostilities that followed.[271]
“M. Yrujo, who is vanity itself, blew the flame more vigorously than
ever.... He concerted reprisals with Mr. Merry, and it was agreed that
whenever they should entertain the secretaries and their wives, they
should take none of them to table, but should give their hands to their
own wives. This resolution was carried out at a dinner given some
days afterward by M. Yrujo. Mr. and Mrs. Merry were next invited by
the Secretary of the Navy. Mrs. Merry refused; yet this minister, a very
well-bred man (homme fort poli), had so arranged things as to give
her his hand. Apparently what had taken place at Mr. Madison’s was
thought harsh (dur), and it was wished to bring Mr. and Mrs. Merry
back to a reconciliation. The Cabinet took up the question, as reported
in the newspaper of which I sent you an extract, and it was resolved
that hereafter the President should give his hand to the lady who
might happen to be nearest him, and that there should be no
precedence. Mr. Merry was invited to a tea by the Secretary of War
and by the Secretary of the Treasury. To avoid all discussion he wholly
refused the first, and after accepting the second he did not come.
Finally, New Year’s Day gave another occasion for scandal. On this
day, as on the Fourth of July, it is the custom to call upon the
President; and even the ladies go there. This year neither Mme. Yrujo
nor Mrs. Merry went, and the Marquis took care to answer every one
who inquired after his wife’s health, that she was perfectly well. Since
then Washington society is turned upside down; all the women are to
the last degree exasperated against Mrs. Merry; the Federal
newspapers have taken up the matter, and increased the irritation by
sarcasms on the Administration and by making a burlesque of the
facts which the Government has not thought proper to correct. The
arrival of M. Bonaparte with his wife in the midst of all this explosion
has furnished Mr. Merry with new griefs. The President asked M. and
Mme. Bonaparte to dinner, and gave his hand to Madame. There was,
however, this difference between the two cases,—the President had
invited on this day, besides myself and Mme. Pichon, only the two
Messrs. Smith and their wives, who are of Mme. Bonaparte’s family.
But when Mr. Merry heard of it, he remarked that Mme. Bonaparte had
on this occasion taken precedence of the wife of the Secretary of the
Navy.... I am aware,” continued the delighted Pichon, “that with tact on
the part of Mr. Jefferson he might have avoided all these scandals.”
The British minister wrote to Lord Hawkesbury a brief account of
his reception, closing with the remark:[272]—
“Under these circumstances, my Lord, I have thought it advisable
to avoid all occasions where I and my wife might be exposed to a
repetition of the same want of distinction toward us until I shall have
received authority from you to acquiesce in it, by a signification of his
Majesty’s pleasure to that effect.”
Accordingly, when the President invited the two ministers to dine
at the White House without their wives, they replied that they could
not accept the invitation until after receiving instructions from their
Governments. Jefferson regarded this concerted answer as an
insult.[273] He too lost his temper so far as to indulge in sharp
comments, and thought the matter important enough to call for
explanation. In a private letter to Monroe, dated Jan. 8, 1804, he
wrote:[274]—
“Mr. Merry is with us, and we believe him to be personally as
desirable a character as could have been sent us; but he is unluckily
associated with one of an opposite character in every point. She has
already disturbed our harmony extremely. He began by claiming the
first visit from the national ministers. He corrected himself in this; but a
pretension to take precedence at dinner, etc., over all others is
persevered in. We have told him that the principle of society as well as
of government with us is the equality of the individuals composing it;
that no man here would come to a dinner where he was to be marked
with inferiority to any other; that we might as well attempt to force our
principle of equality at St. James’s as he his principle of precedence
here. I had been in the habit when I invited female company (having
no lady in my family) to ask one of the ladies of the four Secretaries to
come and take care of my company, and as she was to do the honors
of the table I handed her to dinner myself. That Mr. Merry might not
construe this as giving them a precedence over Mrs. Merry I have
discontinued it, and here as in private houses the pêle-mêle practice
is adhered to. They have got Yrujo to take a zealous part in the claim
of precedence. It has excited generally emotions of great contempt
and indignation (in which the members of the Legislature participate
sensibly) that the agents of foreign nations should assume to dictate
to us what shall be the laws of our society. The consequence will be
that Mr. and Mrs. Merry will put themselves into Coventry, and that he
will lose the best half of his usefulness to his nation,—that derived
from a perfectly familiar and private intercourse with the Secretaries
and myself. The latter, be assured, is a virago, and in the short course
of a few weeks has established a degree of dislike among all classes
which one would have thought impossible in so short a time.... With
respect to Merry, he appears so reasonable and good a man that I
should be sorry to lose him as long as there remains a possibility of
reclaiming him to the exercise of his own dispositions. If his wife
perseveres she must eat her soup at home, and we shall endeavor to
draw him into society as if she did not exist.”
Of all American hospitality none was so justly famous as that of
Virginia. In this State there was probably not a white man, or even a
negro slave, but would have resented the charge that he was
capable of asking a stranger, a foreigner, a woman, under his roof,
with the knowledge that he was about to inflict what the guest would
feel as a humiliation. Still less would he have selected his guest’s
only enemy, and urged him to be present for the purpose of
witnessing the slight. Reasons of state sometimes gave occasion for
such practices, but under the most favorable conditions the tactics
were unsafe. Napoleon in the height of his power insulted queens,
browbeat ambassadors, trampled on his ministers, and made his
wife and servants tremble; but although these manners could at his
slightest hint be imitated by a million soldiers, until Europe, from
Cadiz to Moscow, cowered under his multiplied brutality, the insults
and outrages recoiled upon him in the end. Jefferson could not afford
to adopt Napoleonic habits. His soldiers were three thousand in
number, and his own training had not been that of a successful
general; he had seven frigates, and was eager to lay them up in a
single dry-dock. Peace was his passion.
To complicate this civil war in the little society of Washington,
Jerome Bonaparte appeared there, and brought with him his young
wife, Elizabeth Patterson, of Baltimore. Jerome married this beautiful
girl against the remonstrances of Pichon; but after the marriage took
place, not only Pichon, but also Yrujo and Jefferson, showed proper
attention to the First Consul’s brother, who had selected for his wife
a niece of the Secretary of the Navy, and of so influential a senator
as General Smith. Yet nothing irritated Napoleon more than Jerome’s
marriage. In some respects it was even more objectionable to him
than that of Lucien, which gave rise to a family feud. Pichon
suspected what would be the First Consul’s feelings, and wrote letter
after letter to clear himself of blame. In doing so he could not but
excite Napoleon’s anger against American society, and especially
against the family of his new sister-in-law.
“It appears, Citizen Minister,” wrote Pichon to Talleyrand,[275] “that
General Smith, who in spite of the contrary assurances he has given
me, has always had this alliance much at heart, has thrown his eyes
on the mission to Paris as a means of appeasing (ramener) the First
Consul. He has long since aimed at the diplomatic career, for which
he is little qualified; this motive and the near return of Mr. Livingston
have decided his taste. For some time there has been much question
of this nomination among the friends of General Smith. There is also
question of promoting, on the part of the First Consul, for minister to
this country, a selection which should be connected with the other. It is
thought that the appointment of M. Jerome Bonaparte would be an
honorable mode of leaving the First Consul’s brother time to have his
fault forgotten, and of preparing his return to favor.”
Such readiness among Jefferson’s advisers to court the favors of
the young First Consul was sure not to escape the eyes of the
embittered Federalists. Pichon’s account, although sharp in allusions
to General Smith’s “vanity,” was mild compared with the scorn of the
New Englanders. Apparently the new matrimonial alliance was taken
seriously by prominent Republican leaders. One of the
Massachusetts senators mentioned in his diary[276] a “curious
conversation between S. Smith, Breckenridge, Armstrong, and
Baldwin, about ‘Smith’s nephew, the First Consul’s brother.’ Smith
swells upon it to very extraordinary dimensions.” Pichon openly
spoke of the whole family connection, including both Robert and
Samuel Smith, and even Wilson Cary Nicholas, as possessed with
“an inconceivable infatuation” for the match; “it was really the young
man who was seduced.” Nothing that Pichon could say affected
them. Senator J. Q. Adams remarked: “the Smiths are so elated with
their supposed elevation by this adventure, that one step more would
fit them for the discipline of Dr. Willis,”—the famous English expert in
mental diseases.[277]
The President and his friends might not know enough of
Napoleon’s character to foresee the irritation which such reports
would create in his mind, but they were aware of the contrast
between their treatment of Jerome Bonaparte and their slights to
Anthony Merry. Had they felt any doubt upon the subject, the free
comments of the British minister and his wife would have opened
their eyes. In truth, no doubt existed. Washington society was in a
manner ordered to proscribe the Merrys and Yrujo, and pay court to
Jerome and the Smiths.
Had this been all, the matter would have ended in a personal
quarrel between the two envoys and the two Virginians, with which
the public would have had no concern. Jefferson’s “canons of
etiquette” would in such a case have had no further importance than
as an anecdote of his social habits. The seriousness of Jefferson’s
experiments in etiquette consisted in the belief that they were part of
a political system which involved a sudden change of policy toward
two great Powers. The “canons” were but the social expression of an
altered feeling which found its political expression in acts marked by
equal disregard of usage. The Spanish minister had already reason
to know what he might expect; for six weeks before Merry’s dinners
John Randolph proclaimed in the House that West Florida belonged
to the United States, and within the week that preceded Merry’s
reception, he brought in the Bill which authorized the President to
annex Mobile. After such a proceeding, no diplomatist would have
doubted what meaning to put upon the new code of Republican
society. Merry’s arrival, at the instant of this aggression upon Spain,
was the signal for taking toward England a higher tone.
Merry could not fail to see what lay before him. From the
President, notwithstanding heelless slippers and “canons of
etiquette,” the British minister heard none but friendly words. After
the formal ceremony of delivering the letter of credence was over,—
“He desired me to sit down,” wrote Merry,[278] “when we
conversed for some time on general affairs. The sentiments which he
expressed respecting those of Europe appeared very properly to be
by no means favorable to the spirit of ambition and aggrandizement of
the present ruler in France, or to the personal character in any respect
of the First Consul, and still less so to his conduct toward all nations.”
From this subject the President passed to Spanish affairs and to
the Spanish protest against the Louisiana cession, founded on
Bonaparte’s pledge never to alienate that province.
“This circumstance,” continued Merry, “as well as the resistance
altogether which Spain had unexpectedly brought forward in words,
Mr. Jefferson considered as highly ridiculous, and as showing a very
pitiful conduct on her part, since she did not appear to have taken any
measures to support it either by preparation of defence on the spot, or
by sending there a force to endeavor to prevent the occupation of the
country by the troops of the United States. He concluded by saying
that possession of it would, at all events, be taken.”
If Merry did not contrive, after his dinner at the White House, to
impart this conversation to his colleagues Yrujo and Pichon, he must
have been a man remarkably free from malice. Meanwhile he had
his own affairs to manage, and Madison was not so forbearing as the
President. Merry’s first despatch announced to his Government that
Madison had already raised his tone. Without delay the matter of
impressments was brought into prominence. The “pretended”
blockade of Martinique and Guadeloupe was also strongly
characterized.
“It is proper for me to notice,” said Merry in his report of these
remonstrances,[279] “that Mr. Madison gave great weight to them by
renewing them on every occasion of my seeing him, and by his
expressing that they were matters upon which this Government could
not possibly be silent until a proper remedy for the evil should be
applied by his Majesty’s government. His observations were, however,
made with great temper, and accompanied with the strongest
assurances of the disposition of this Government to conciliate, and to
concur in whatever means could be devised which should not be
absolutely derogatory to their independence and interests, to establish
principles and rules which should be satisfactory to both parties....
But, my Lord, while it is my duty to do justice to Mr. Madison’s
temperate and conciliatory language, I must not omit to observe that it
indicated strongly a design on the part of this Government to avail
themselves of the present conjuncture by persisting steadily in their
demands of redress of their pretended grievances, in the hope of
obtaining a greater respect to their flag, and of establishing a more
convenient system of neutral navigation than the interests of the
British empire have hitherto allowed his Majesty to concur in.”
The British government was aware that its so-called right of
impressment and its doctrine of blockade rested on force, and could
not be maintained against superior force; but this consciousness
rendered England only the more sensitive in regard to dangers that
threatened her supremacy. Knowing that the United States would be
justified in declaring war at any moment, Great Britain looked
uneasily for the first symptoms of retaliation. When Madison took so
earnest a tone, Merry might reasonably expect that his words would
be followed by acts.
These shocks were not all that the new British minister was
obliged to meet at the threshold of his residence in Washington. At
the moment when he was, as he thought, socially maltreated, and
when he was told by Madison that America meant to insist on her
neutral rights, he learned that the Government did not intend to ratify
Rufus King’s boundary convention. The Senate held that the
stipulations of its fifth article respecting the Mississippi might
embarrass the new territory west of the river. King knew of the
Louisiana cession when he signed the treaty; but the Senate had its
own views on the subject, and under the lead of General Smith[280]
preferred to follow them, as it had done in regard to the second
article of the treaty with France, Sept. 30, 1800, and as it was about
to do in regard to Pinckney’s claims convention, Aug. 11, 1802, with
Spain. Merry was surprised to find that Madison, instead of
explaining the grounds of the Senate’s hesitation, or entering into
discussion of the precise geographical difficulty, contented himself
with a bald statement of the fact. The British minister thought that
this was not the most courteous way of dealing with a treaty
negotiated after a full acquaintance with all the circumstances, and
he wrote to his Government to be on its guard:[281]—
“Notwithstanding Mr. Madison’s assurances to the contrary, I have
some reason to suspect that ideas of encroachment on his Majesty’s
just rights are entertained by some persons who have a voice in
deciding upon the question of the ratification of this convention, not to
say that I have much occasion to observe, from circumstances in
general, that there exists here a strong impression of the
consequence which this country is supposed to have acquired by the
recent additions to the territory of the United States, as well as by the
actual situation of affairs in Europe.”
In view of the Mobile Act, introduced into Congress by Randolph
on behalf of the government a week before this letter was written,
Merry’s suspicions could hardly be called unreasonable. A like
stretch of authority applied to the northwest territory would have
produced startling results.
Merry’s suspicions that some assault was to be made upon
England were strengthened when Madison, December 5, in
pursuance of a call from the Senate, sent a list of impressments
reported to the Department during the last year. According to this
paper the whole number of impressments was forty-six,—three of
which were made by France and her allies; while of the forty-three
made by Great Britain twenty-seven of the seamen were not
American citizens. Of the entire number, twelve were stated to have
had American papers; and of the twelve, nearly half were impressed
on land within British jurisdiction. The grievance, serious as it was,
had not as yet reached proportions greater than before the Peace of
Amiens. Merry drew the inference that Jefferson’s administration
meant to adopt stronger measures than had hitherto been thought
necessary. He soon began to see the scope which the new policy
was to take.
Dec. 22, 1803, Madison opened in a formal conference the
diplomatic scheme which was the outcome of these preliminary
movements.[282] Beginning with a repetition of complaints in regard
to impressments, and dwelling upon the great irritation created by
such arbitrary acts, the secretary next remonstrated against the
extent given to the law of blockade by British cruisers in the West
Indies, and at length announced that the frequent repetition of these
grievances had rendered it necessary for the United States to take
immediate steps to find a remedy for them. Instructions would
therefore be shortly sent to Monroe at London to negotiate a new
convention on these subjects. The American government would wish
that its flag should give complete protection to whatever persons
might be under it, excepting only military enemies of the belligerent.
Further, it would propose that the right of visiting ships at sea should
be restrained; that the right of blockade should be more strictly
defined, and American ships be allowed, in consideration of the
distance, to clear for blockaded ports on the chance of the blockade
being removed before they arrived; and finally that the direct trade
between the West Indies and Europe should be thrown open to
American commerce without requiring it to pass through a port of the
United States.
In return Madison offered to the British government the
unconditional surrender of deserters by sea and land, together with
certain precautions against the smuggling of articles contraband of
war.
Although Madison pressed the necessity of an immediate
understanding on these points, he did so in his usual temperate and
conciliatory manner; while Merry frankly avowed that he could give
no hopes of such propositions being listened to. He did this the more
decisively because Congress seemed about to take the matter of
impressments into its own hands, and was already debating a Bill for
the protection of seamen by measures which tended to hostilities.
Madison disavowed responsibility for the legislation, although he
defended it in principle.[283] Merry contented himself for the time by
saying that if the United States government sought their remedy in
municipal law, the matter would immediately cease to be a subject of
negotiation.
Thus, in one short month, the two governments were brought to
what the British minister supposed to be the verge of rupture. That
any government should take so well-considered a position without
meaning to support it by acts, was not probable. Acts of some kind,
more or less hostile in their nature, were certainly intended by the
United States government in case Great Britain should persist in
contempt for neutral rights; the sudden change of tone at
Washington left no doubt on this point. Edward Thornton, who had
not yet been transferred to another post, wrote in consternation to
the Foreign Office, fearing that blame might be attached to his own
conduct while in charge of the legation:[284]—
“When I compare the complexion of Mr. Merry’s correspondence
with that of my own, particularly during the course of the last summer,
before the intelligence of the Louisiana purchase reached this country,
I can scarcely credit the testimony of my own senses in examining the
turn which affairs have taken, and the manifest ill-will discovered
toward us by the Government at the present moment.... I believe that
the simple truth of the case is, after all, the circumstance ... that a real
change has taken place in the views of this Government, which may
be dated from the first arrival of the intelligence relative to the
Louisiana purchase, and which has since derived additional force and
acrimony from the opinion that Great Britain cannot resist, under her
present pressure, the new claims of the United States, and now, from
the necessity they are under of recurring to the influence of France in
order to support their demands against Spain.... The cession of
Louisiana, notwithstanding that the circumstances under which it was
made ought to convince the vainest of men that he was not the sole
agent in the transaction, has elevated the President beyond
imagination in his own opinion; and I have no doubt that he thinks of
securing himself at the next election by having to boast of
concessions and advantages derived from us, similar to those he has
gained from France,—that is, great in appearance, and at a
comparatively insignificant expense.”
From such premises, the conclusion, so far as concerned
England, was inevitable; and Thornton agreed with Merry in affirming
it without reserve:—
“Everything, as it relates to this government, now depends on our
firmness. If we yield an iota without a real and perfect equivalent (not
such imaginary equivalents as Mr. Madison mentions to Mr. Merry),
we are lost.”
CHAPTER XVII.
Whatever objects the President and the Secretary of State may
have expected to gain by their change of tone in the winter of 1803–
1804 toward Spain and England, they must have been strangely free
from human passions if they were unconscious of making at least
two personal enemies upon whose ill-will they might count. If they
were unaware of giving their victims cause for bitterness,—or if, as
seemed more probable, they were indifferent to it,—the frequent
chances of retaliation which the two ministers enjoyed soon showed
that in diplomacy revenge was not only sweet but easy. Even the
vehement Spanish hatred felt by Yrujo for Madison fell short of the
patient Anglo-Saxon antipathy rooted in the minds of the British
minister and his wife. When Yrujo, in March, 1804, burst into the
State Department with the Mobile Act in his hand and denounced
Madison to his face as party to an “infamous libel,” he succeeded in
greatly annoying the secretary without violating Jefferson’s “canons
of etiquette.” Under the code of republican manners which the
President and his secretary had introduced, they could not fairly
object to anything which Yrujo might choose to say or do. Absolute
equality and “the rule of pêle-mêle” reached their natural conclusion
between such hosts and guests in freedom of language and
vehemence of passion. What might have been Merry’s feelings or
conduct had he met with more cordiality and courtesy was uncertain;
but the mortifications of his first month at Washington embittered his
temper, and left distinct marks of acrimony in the diplomacy of
America and England, until war wiped out the memory of reciprocal
annoyances. The Spaniard’s enmity was already a peril to Madison’s
ambition, and one which became more threatening every day; but
the Englishman’s steady resentment was perhaps more
mischievous, if less noisy. The first effect of Jefferson’s tactics was to
ally the British minister with Yrujo; the second bound him to Senator
Pickering and Representative Griswold; the third united his fortunes
with those of Aaron Burr. Merry entered the path of secret
conspiracy; he became the confidant of all the intriguers in
Washington, and gave to their intrigues the support of his official
influence.
The Federalists worked mischievously to widen the breach
between the British minister and the President. They encouraged
Merry’s resentment. Late in January, nearly two months after the first
pêle-mêle, Madison officially informed Merry for the first time that the
President meant to recognize no precedence between foreign
ministers, but that all, even including secretaries of legation in
charge, were to be treated with perfect equality, or what Madison
termed “a complete pell-mell,” and would be received, even at their
first audience, with no more ceremony than was practised toward
any other individual. Merry replied that this notice should have been
given to him on his arrival, and that he could not acquiesce in it
without instructions. He then wrote to his Government,[285]—
“I have now but too much reason to fear, what I did not at first
suspect, that the marked inattention toward me of the present
Administration of this country has been a part of their unfriendly
disposition toward his Majesty and toward the nation which I have the
honor to represent.”
At the same moment, in January and February, 1804, Pickering
and Griswold were plotting their New England confederacy. Merry
was taken by them into the secret, and gave them aid. The Senate,
February 9, voted to strike out the fifth article of Rufus King’s
boundary convention, and to approve the other articles, which
provided for fixing the disputed boundary-line of Maine, New
Hampshire, and Vermont. Merry wrote to his Government that the
object of cancelling the fifth article was to deprive Great Britain of her
treaty-right to navigate the Mississippi:[286]—
“It is hardly necessary for me to point out to your Lordship that the
other articles of the convention are of great importance to the Eastern
States of America, which are much interested in the immediate
settlement of the eastern boundary. I am led to believe from the
language of some of the members of this State [Massachusetts] that
their anxiety on this head is so great that the rejection of those articles
by his Majesty would, as having been occasioned by the exclusion on
the part of this government of the fifth article, prove to be a great
exciting cause to them to go forward rapidly in the steps which they
have already commenced toward a separation from the Southern part
of the Union. The members of the Senate have availed themselves of
the opportunity of their being collected here to hold private meetings
on this subject, and I learn from them that their plans and calculations
respecting the event have been long seriously resolved. They think
that whenever it shall take place it will happen suddenly, yet with
quietness and the universal concurrence of the people. Although it
does not appear to be their opinion that any external secret agency
would accelerate the moment, they naturally look forward to Great
Britain for support and assistance whenever the occasion shall arrive.”
As the summer of 1804 came on, Merry’s despatches grew more
sombre. He reported that at Norfolk twelve British ships were
detained at one time in consequence of the desertion of their
seamen, several of whom had entered the United States service on
the frigates which were under orders for Tripoli. Six British seamen
having deserted at Charleston and re-enlisted in the same way,
Merry remonstrated. He was told that the seamen, having voluntarily
enlisted in the United States service, could not be restored, because
the British government never restored American seamen who had
voluntarily enlisted. Merry could only reply that the British
government did not knowingly enlist deserters. On the other hand,
Madison remonstrated in “high language,” “accompanied even with
some degree of menace,” against the conduct of Captain Bradley of
the frigate “Cambrian,” one of the British squadron cruising off Sandy
Hook, for taking a British seaman out of a British vessel within
American jurisdiction. Merry added that in contrast to this strictness
toward England the authorities had allowed the officers of the French
frigate “La Poursuivante,” at Baltimore, to send armed parties on
shore at night for the purpose of seizing French seamen, one of
whom they had actually taken by force from a Spanish vessel lying
at the wharf.
“From this government having brought into such serious
discussion objects which would certainly have passed unnoticed had
they occurred in relation to the King’s enemies, his Majesty’s ministers
may be led to suspect that such a resolution has been dictated by
some hostile design,” wrote Merry, with increasing solemnity; “but it is
proper for me to observe that ... I cannot persuade myself that they
will dare to provoke hostilities with his Majesty, at least before Mr.
Jefferson’s re-election to the Presidency shall have taken place.”[287]
Merry made a representation to Madison on impressments; but
his arguments did not satisfy the secretary. “This specimen of Merry
shows him to be a mere diplomatic pettifogger,” wrote Madison
privately to the President.[288]
Merry’s temper was in this stage of ever-increasing irritability,
when an event occurred which gave him, as it seemed, a chance to
gratify his resentments. After the adjournment of Congress in March
the British minister heard nothing from Pickering and Griswold. Early
in June he wrote home that the democrats were carrying all the
elections:[289]—
“In addition to this triumph of the reigning party, there have lately
appeared in the prints of this country, which are generally made the
instruments of the measures of all parties, publications of the
discovery that has been made of secret meetings held at this place by
some of the Federal members during the last sitting of Congress for
the purpose of consulting upon the important point of the separation of
the Eastern from the Southern States, which publications seem to
have imposed a complete silence upon the Federal adherents.”
A few weeks afterward, July 11, occurred the duel between Burr
and Hamilton. Merry had no relations with Hamilton, and felt no
peculiar interest in his fate; but he had become intimate with Burr at
Washington, and watched his career with the curiosity which was the
natural result of their common hatred of Jefferson. July 21 Burr fled
from New York, and a few days afterward reached Philadelphia,
where Merry was passing the summer. While there, Burr sent one of
his friends—an Englishman named Williamson—to the British
minister with a startling message, which Merry immediately
transmitted to his Government:[290]—
“I have just received an offer from Mr. Burr, the actual Vice-
President of the United States (which situation he is about to resign),
to lend his assistance to his Majesty’s government in any manner in
which they may think fit to employ him, particularly in endeavoring to
effect a separation of the western part of the United States from that
which lies between the Atlantic and the mountains, in its whole extent.
His proposition on this and other subjects will be fully detailed to your
Lordship by Colonel Williamson, who has been the bearer of them to
me, and who will embark for England in a few days. It is therefore only
necessary for me to add that if after what is generally known of the
profligacy of Mr. Burr’s character, his Majesty’s minister should think
proper to listen to his offer, his present situation in this country, where
he is now cast off as much by the democratic as by the Federal party,
and where he still preserves connections with some people of
influence, added to his great ambition and spirit of revenge against the
present Administration, may possibly induce him to exert the talents
and activity which he possesses with fidelity to his employers.”
Meanwhile a change of ministry occurred in England. Pitt
returned to power, representing a state of feeling toward America
very different from that which prevailed under the mild rule of
Addington. Subordinates were quick to feel such changes in the
temper of their superiors. Every British officer knew that henceforth
he had behind him an energetic government, which required
vigorous action in maintaining what it claimed as British rights. Merry
felt the new impulse like the rest; but Pitt’s return acted most
seriously on the naval service. After the renewal of the war in May,
1803, a small British squadron cruised off Sandy Hook, keeping a
sharp look-out for French frigates in New York Harbor, and searching
every merchant-vessel for enemy’s property. During the summer of
1804 this annoyance became steadily greater, until the port of New
York was almost blockaded, and every vessel that sailed out or in
was liable not only to be stopped and searched, but to lose some
part of its crew by impressment. The British ministry did indeed
instantly recall Captain Bradley of the “Cambrian” for violating
American jurisdiction, and gave strict orders for the lenient exercise
of belligerent rights; but all the more it showed the intention of
insisting upon the submission of America to such rules as England
should prescribe. The President, already in trouble with Spain,
began to feel the double peril; but Congress pressed him forward,
and even while busy with the trial of Judge Chase it found time for
two measures which greatly disturbed the British envoy.
The first of these measures was an “Act for the more effectual
preservation of peace in the ports and harbors of the United States.”
Under this law any United States marshal, on the warrant of any
United States judge, was bound to board any British or other foreign
ship-of-war lying in American waters, and seize every person
charged with having violated the peace. If the marshal should be
resisted, or if surrender was not made, he must call in the military
power, and compel surrender by force of arms. If death should
ensue, he should be held blameless; but the resisting party should
be punished as for felonious homicide. Further, the President was
authorized to interdict at will the ports of the United States to all or
any armed vessels of a foreign nation; and to arrest and indict any
foreign officer who should come within the jurisdiction after
committing on the high seas “any trespass or tort, or any spoliation,
on board any vessel of the United States, or any unlawful
interruption or vexation of trading-vessels actually coming to or going
from the United States.”
Such laws were commonly understood in diplomacy as removing
the subject in question from the field of negotiation, preliminary to
reprisals and war. The Act was passed with little debate in the last
hours of the session, in the midst of the confusion which followed the
acquittal of Judge Chase. Merry immediately called on the Secretary
of State, and asked him for some assurance that might serve to quiet
the apprehensions which his Government would feel on reading the
Act.[291] Madison could give none, except that the President would
probably not exercise for the present his discretionary powers. As for
the words, “any trespass or tort,” Madison frankly avowed “he could
not but confess they were meant to imply the impressment of any
individual whatsoever from on board an American vessel, the
exercise of which pretended right on the part of his Majesty’s officers
was a matter, he said, which the sense of the people at large would
never allow the government of this country to acquiesce in.”
To this announcement Merry replied in substance that the right
was one which would certainly never be abandoned by his
Government; and there the matter rested at the close of Jefferson’s
first term. Madison assured the British minister that the authority
granted to the President by Congress over foreign ships of war in
American waters would not at present be enforced. He went even a
step further toward conciliation. The Legislature of Virginia was
induced quietly to modify the Act which had hitherto offered so much
encouragement to the desertion of British seamen.[292]
The second threatening measure was a Resolution of the
Senate, March 2, 1805, calling upon the Secretary of State for such
Acts of the British Parliament as imposed heavier duties on the
exportation of merchandise to the United States than on similar
goods exported to the nations of Europe. Such an export duty upon
merchandise for the United States and the West Indies had in fact
been imposed by Parliament some two years before; and this
Resolution foreshadowed some commercial retaliation by Congress.
While sending to his Government these warnings to expect from
Jefferson’s second administration a degree of hostility more active
than from the first, Merry suggested means of giving the United
States occupation that should induce them to leave England alone. A
new element of conspiracy disclosed itself to the British minister.
Under the Louisiana treaty of cession, the United States
government had promised that “the inhabitants of the ceded territory
shall be incorporated in the Union of the United States, and admitted
as soon as possible, according to the principles of the Federal
Constitution, to the enjoyment of all the rights, advantages, and
immunities of citizens of the United States.” This pledge had been
broken. The usual display of casuistry had been made to prove that
the infraction of treaty was no infraction at all; but the more
outspoken Republicans avowed, as has been already shown, that
the people of Louisiana could not be trusted, or in the commoner
phrase that they were unfit for self-government, and must be treated
as a conquered race until they learned to consider themselves
American citizens.
The people of New Orleans finding themselves in a position of
dependence, which, owing chiefly to their hatred of Governor
Claiborne, seemed more irritating than their old Spanish servitude,
sent three representatives to Washington to urge upon Congress the
duty of executing the treaty. Messieurs Sauvé, Derbigny, and
Destréhan accordingly appeared at Washington, and in December,
1804, presented a remonstrance so strong that Government was

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CHAPTER 1 Applications of Graft Copolymerization: A Revolutionary Approach ........ 1

3. Basic Medical Applications of Hydrophilic Monomer Grafted

1.7Grafting: A Promising Technique for Modiﬁcation.................... 159

4.2 Microwave Method........................................................................ 222

CHAPTER 8 Grafted Copolymerized Chitosan and Its Applications as a Green

5.6 Synthesis of Polyacrylamide-g-Chitosan Nanobeads via

5.6 Amino Acid Composition by High-Performance Liquid

Index ............................................................................................................................... 513

Jay Prakash Pandey

Enhanced Composites and Structures Center

School of Aerospace, Transport, and Manufacturing

Cranﬁeld University, Cranﬁeld, Bedfordshire MK43 0AL

Prior to commencing in the School of Aerospace, Transport, and Manufacturing

Vijay is an editorial board member of several international journals, as well

Vijay Kumar Thakur, PhD

Biopolymer Grafting: Applications. http://dx.doi.org/10.1016/B978-0-12-810462-0.00001-6

ﬂocculating agents (Barikani and Mohammadi, 2007), and targeted (Sun

1.1 Graft Copolymerization

1.2 Concept of Molecular Brushes

1.3 Approaches for Graft Copolymerization

n FIGURE 1.1 Hypothetical diagram of molecular brushes.

n FIGURE 1.2 Schematic presentation of grafting on approach of graft copolymerization.

responsible for grafting can be made possible by alterations employing

1.3.2 Grafting From

1.3.3 Grafting Through Method

n FIGURE 1.3 Schematic presentation of grafting from approach of graft copolymerization.

molecular weight, and the polymer involved is acrylate functionalized

1.3.4 Grafting by Chemical Method

n FIGURE 1.4 Schematic presentation of grafting through approach of graft copolymerization.

(AIBN), and ferrous ammonium sulfate in other polymerization techniques

1.3.5 Grafting by Living Systems

Table 1.1 List of Different Types of Initiators Used for Grafting

Cerium(IV) ammonium Starch Acrylamide Mishra et al. (2011a,b)

Potassium persulfate Starch Phenyl methacrylate Worzakowska and

Horseradish peroxidase in the presence of H2O2 initiated the graft copoly-

1.3.5.2 Plasma-Initiated Grafting

1.3.6 Cationic Graft Copolymerization

1.3.7 Grafting by Radiation

1.3.7.1 Individual Radiation Technique

n FIGURE 1.5 General scheme of grafting by radiation.

Peroxidation: irradiated polymer substrate was further treated with monomer

1.3.7.2 Mutual Radiation Technique

1.3.7.3 Advantages of Radiation Technique Over the

1.3.7.4 Types of Radiation-Induced Grafting

acrylic acid using mutual radiation technique, i.e., by using Ce(4þ)-HNO3 as

n FIGURE 1.6 Formulation methodology of grafting of polymers using microwave.

reproducibility of percentage grafting in the grafted copolymer (Singh

is very simple to utilized. The graft copolymerization of acrylamide on

1.4.2 Controlled Drug Delivery

behavior of 5-amino salicylic acid from matrix tablets prepared by

results indicated that microwave-assisted synthesis shortened the copolymeri-

1.4.3 Enhanced Drug Delivery

HPMC capsules, or it can be dispersed from the usually liquid, lipophilic

Merry then received an official explanation that Jefferson

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