Biopolymer Grafting Thakur Full Chapter

Biopolymer Grafting Thakur
Visit to download the full and correct content document:

https://ebookmass.com/product/biopolymer-grafting-thakur/
Biopolymer Grafting:
Applications
This page intentionally left blank
ADVANCES IN POLYMERS AND FIBERS
Biopolymer Grafting:
Applications
Edited by
Vijay Kumar Thakur
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
Copyright © 2018 Elsevier Inc. All rights reserved.
No part of this publication may be reproduced or transmitted in any form or by any means, electronic
or mechanical, including photocopying, recording, or any information storage and retrieval system,
without permission in writing from the publisher. Details on how to seek permission, further informa-
tion about the Publisher’s permissions policies and our arrangements with organizations such as the
Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website:
www.elsevier.com/permissions.
This book and the individual contributions contained in it are protected under copyright by the
Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and experience
broaden our understanding, changes in research methods, professional practices, or medical treatment
may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating
and using any information, methods, compounds, or experiments described herein. In using such
information or methods they should be mindful of their own safety and the safety of others, including
parties for whom they have a professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume
any liability for any injury and/or damage to persons or property as a matter of products liability,
negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas
contained in the material herein.
Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library
ISBN: 978-0-12-810462-0
For information on all Elsevier publications visit our website at

https://www.elsevier.com/books-and-journals
Publisher: Matthew Deans

Acquisition Editor: David Jackson
Editorial Project Manager: Jennifer Pierce
Production Project Manager: Paul Prasad Chandramohan
Designer: Greg Harris
Typeset by TNQ Books and Journals
To my parents and teachers who helped me become what I am today.
Vijay Kumar Thakur
This page intentionally left blank
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
Another random document with
no related content on Scribd:
The Project Gutenberg eBook of The black
Flemings
This ebook is for the use of anyone anywhere in the United
States and most other parts of the world at no cost and with
almost no restrictions whatsoever. You may copy it, give it away
or re-use it under the terms of the Project Gutenberg License
included with this ebook or online at www.gutenberg.org. If you
are not located in the United States, you will have to check the
laws of the country where you are located before using this
eBook.
Title: The black Flemings
Author: Kathleen Thompson Norris
Release date: October 22, 2023 [eBook #71929]
Language: English
Original publication: Garden City, NY: Doubleday, Doran &

Company, 1926
Credits: David E. Brown and the Online Distributed Proofreading

Team at https://www.pgdp.net (This file was produced
from images generously made available by The
Internet Archive)
*** START OF THE PROJECT GUTENBERG EBOOK THE BLACK

FLEMINGS ***
THE BLACK FLEMINGS
THE
BLACK FLEMINGS
BY
KATHLEEN NORRIS
PALO ALTO EDITION
GARDEN CITY NEW YORK

DOUBLEDAY, DORAN & COMPANY, INC.
1929
COPYRIGHT, 1924, 1925, 1926, BY KATHLEEN
NORRIS. ALL RIGHTS RESERVED. PRINTED
IN THE UNITED STATES AT THE COUNTRY
LIFE PRESS, GARDEN CITY, N. Y.
THE BLACK FLEMINGS
THE BLACK FLEMINGS
CHAPTER I
Once through the dark old iron gates, he seemed to have left the
warm and friendly autumn day, the warm and friendly world, behind
him.
David Fleming laughed half aloud at the fancy and stepped back into
the rambling country road, where wheel tracks were so quickly
obliterated in the loose-drifting sand, to contrast once more, for his
own amusement, the peaceful dreaming landscape in the afternoon
sunlight and the sinister shadows of Wastewater.
Five miles away along the rugged coast lay Crowchester, the little
fishing village whose activities tinged the fresh salty air, even here,
with the odour of salted fish. Between Crowchester and Wastewater,
beside whose forbidding great gates he stood, ran the irregular road,
rising through dunes, skirting wind-twisted groves of pine and fir,
disappearing into ragged hollows to emerge again on turfy bluffs,
and finally winding in here toward the old brick house that lay hidden
behind these high walls.
On his right lay the shore, rocky, steep, rough, with pebbles
complaining as the tide dragged them to and fro, surf hammering
restlessly among the rocks or brimming and ebbing with tireless
regularity over the scooped stone of the pools. No two inches of it,
no two drops of its immensity ever the same; it held him now, as it
had held him for so many hours in his very babyhood, in a sort of
tranced contemplation.
The sun was setting in angry red beyond the forest behind him, but a
hard and brilliant light still lay on the water, and the waves were
sculptured harshly in silver-tipped steel. Where the old brick wall of
Wastewater descended to the shore enough sand had been stored
in the lee of the wall to form a triangular strip of beach, and here
scurfy suds were eddying lazily, hemmed back from the tide by a
great jammed log and only stirred now and then by a fringe of the
surf, which formed new bubbles even while it pricked the old.
On the sharp irregular fall of the cliff, distorted, wind-blown pines and
tight-woven mallows clung, with the hardy smaller growths of the
seaside: blown blue lupin, coarse sedge and furzy grasses, yellow-
topped odorous sage and dry fennel. About their exposed,
tenaciously clinging roots was tangled all the litter of the sea: ropes,
slender logs as white and bare as old bones, seaweeds, and
cocoanut shells.
David breathed the salty, murmuring air, faintly scented with fish,
looked back once more toward the shining roofs and the rising faint
plumes of smoke above Crowchester, shrugged his shoulders with a
philosophic laugh, and turned again toward Wastewater’s gates.
These were four: two great wrought-iron wings in the centre, where
carriages had once entered and departed, and, designed ingeniously
in the same enormous framework, two smaller gates, one on each
side, for foot passengers.
The carriage gates had been closed for years and were bedded
deep in dry grass and fallen leaves, and the right-hand smaller gate
had perhaps not been opened three times in its more than one
hundred years’ existence. But the left-hand gate stood slightly ajar,
and beyond it ran a faintly outlined footpath into a deep old garden.
The whole elaborate structure, met by the mossy brick wall on both
sides, was thick with rust, its scrolls and twisted bars shone brick-red
in the last of the sunlight.
David had walked briskly from the village and his blood was moving
rapidly, but he shivered as the familiar atmosphere once more
enveloped him. Once again the dilapidated, stately old garden with
its bottle-edged flower beds, where the ragged rose bushes were
already showing red and yellow hips, where the pines were shedding
their slippery needles, and where the maples and elms looked
tattered and forlorn.
The place had been thickly planted almost two hundred years ago; it
was densely overgrown now; the trees crowded each other, and the
growth underneath them was sickly. The old path was spongy with
wet leaves underfoot, and the air so pungent with their sharp odour
as to be almost anæsthetic. Between the blackened trunks on the
right David could again see the serenely moving, deeply breathing
surface of the ocean, but now the garden and low cliffs shut off the
shore.
On all other sides lay the garden and the thicket of the plantation
through which presently, after some winding, he came upon
Wastewater Hall itself, standing up boldly in the twilight gloom. The
last dying fires of the sunset, burning through black tree trunks
behind it, seemed only to make darker than ever the outlines of the
great dark red brick house, three-storied and with a steep mansard
as well, its uncompromising bulk enhanced rather than softened by a
thickly wooded coat of black ivy.
It was an enormous old Georgian building, impressive for size if for
nothing more. Wastewater’s twenty acres stood on a sharply jutting
point of cliff, and the house faced the sea on three sides; the garden
was shut off from the road by the long western wall. Immediately
back of the kitchen and stable yards there was a rear gate, buried in
shrubbery and quite out of sight from the house, for delivery wagons
and tradespeople.
The main entrance was on the eastern front, facing straight out to
sea, but this presented now only rows of shuttered windows and
stone steps deep in fallen leaves, and David stopped instead at the
stone steps of the columned side door. Leaves had littered the paths
and lay thick upon the struggling grass of the rose beds, but these
three steps had been swept clean, their dried surfaces still showing
the marks of a wet broom.
David, absorbing the details with the eye of one who perhaps is
reluctant to see confirmed previous impressions or fears, shrugged
again, made a little face between impatience, amusement, and
misgiving, and gave the old-fashioned iron bell-pull a vigorous jerk.
Then came a long wait. But he did not ring again. The first fifteen of
David’s thirty-one years had been spent here, within these grave old
walls, and he knew exactly what was happening now inside.
The jerk on the brass-handled wire would set into convulsive motion
one of a row of precariously balanced bells far down in the enormous
stone-floored kitchen. Most of these bells had not been rung for two
generations at least. They were connected with the bedrooms and
the study—it had been a long time since any resident of Wastewater
had felt it necessary to summon a servant to bedrooms or study. In
the row, David remembered, were also the front-door bell, dining-
room bell, and the side-door bell. He began to wonder if the last
were broken.
No, someone was coming. He could not possibly have heard steps
behind that massive and impenetrable door, but he assuredly sensed
a motion there, stirring, creaking, the distant bang of another door.
Then another wait, not so long. And at last the door was carefully
opened by Hedda, who looked casually at him with squinting old
white-lashed eyes, looked back in concern at her bars and bolts,
closed the door behind him, and then said in a mild old voice in
which traces of her Belgian origin lingered:
“Good. How is Mister David?”
“Splendid,” David answered, with a heartiness that the chill of the
dark old hall already tinged with a certain familiar depression.
“Where’s my aunt, Hedda?”
Hedda had been staring at him with a complacent, vacuous smile,
like the slightly demented creature she really was. Now she roused
herself just a shade and answered in a slightly reproachful voice:
“Where but upstairs shall she be?”
David remembered now that Gabrielle had long ago announced, with
her precocious little-girl powers of observation, that “Hedda always
tells us things the first time as if it were the twentieth, and her
patience quite worn out with telling us!” An affectionate half smile
twitched the corners of David’s mouth as he thought of that old
tawny-headed, rebellious little Gabrielle of ten years before, and he
followed the smile with as sudden a sigh.
He mounted gloomy, wide old stairs through whose enormous
western windows a dim light was struggling. The treads were
covered with a dark carpet strapped in brass rods. Gabrielle, as a
baby, had loved the top-shaped ends of these rods, had stolen them,
been detected, restored them, how many, many times!
The thought of her more than the thought of his old little self, of Tom
and Sylvia, who were the real Flemings, after all, always came to
him strangely when he first returned to the old house after any
absence. Gabrielle, shouting, roaring, weeping, laughing, had roused
more echoes in Wastewater than all the rest of them put together;
she roused more echoes now, poor little Gabrielle!
Poor Gabrielle, and poor Tom! mused David. Life had dealt oddly
with both these long-ago, eager, happy children, as Life seemed to
have a fashion of dealing with the children of so strange and silent,
so haunted and mysterious an old house. The shadow of the house,
as real upon his spirit as was the actual shadow of the autumn
twilight upon these stained old walls, shut heavily upon David as he
crossed the upper hallways and turned the knob of the sitting-room
door.
His aunt, in the widow’s black she had worn for some eighteen
years, was sitting erect in an upholstered armchair by the fire. She
turned to glance toward him as he came in and welcomed him with a
lifeless cheek to kiss and with the warmest smile her face ever knew.
It was not very warm; Flora Fleming had the black colouring of the
clan; her look was always heavy, almost forbidding. She was in the
middle fifties now; there was a heavy threading of gray in her looped,
oily dark hair. Her skin was dark and the rough heavy eyebrows
almost met above her sharply watchful eyes. There were black hairs
at the corners of her lips and against her ears below her temples; her
eyes were set a shade too close together, her teeth were slightly
yellowed, too prominent, and rested upon her bitten lower lip. She
wore, as always, a decent handsome silk that seemed never old and
never new; there was a heavy book in her knuckly, nervous hands,
and David noted for the first time to-day a discoloured vein or two in
her somewhat florid, long face.
“This is good of you, David,” she said, dispassionately, putting her
glasses into her book and laying it aside.
“Didn’t wake you from a nap?” David said, glad to sit down after his
brisk walk.
“A nap?” She dismissed it with a quiet, not quite pleased smile.
“Since when have I had that weakness?” she asked. “No. On an
afternoon like this, with the leaves falling, one hears the wind about
Wastewater if it blows nowhere else, and the sea. I can never nap in
the afternoons. I hear—voices,” she finished, as if half to herself.
“Lord, one realizes how lonely the old place is, coming back to it!”
David said, cheerfully.
“Not for me,” his aunt again corrected him in her quiet voice that
seemed full of autumnal reveries and the quiet falling of leaves itself.
“Other places are lonely. Not this.”
“Well, it’s extremely nice to know that you feel so,” David pursued,
resolutely combating the creeping quiet, the something that was
almost depression, always ready to come out of musty corners and
capture one here. “But when the girls are home we’ll have some
young life at Wastewater, and then—when they marry, you’ll have to
move yourself into brighter quarters—into a city apartment, perhaps!”
“When they marry?” she repeated, slightly stressing the pronoun.
“As I suppose they will?” David elucidated, looking up.
“They?”
“Sylvia—and Gabrielle, too!” he reminded her.
“Oh, Gabrielle?” She repeated the name quietly. “To be sure, she will
marry,” she said, musingly. “But I can hardly feel that quite as much
my affair as Sylvia’s future, David,” she finished, mildly.
“Daughter and niece!” David summarized it. “Sylvia rich and
Gabrielle penniless, but both young and both our girls!”
“I can’t see it quite that way,” Mrs. Fleming said, thoughtfully, after a
pause. “Gabrielle gets here to-night—you knew that?”
“That’s what brings me,” he answered. “I thought perhaps you would
like me to meet her in Boston, bring her home?”
“I wired in answer to the Mother Superior’s wire,” Flora said, “that
she was quite capable of making the journey herself. She should be
here at about eight to-night. She is eighteen, David. There is no
necessity of making a child of her!”
“No,” he conceded, good-humouredly. “But it might seem a little
warmer welcome. I’ll go in to Crowchester for her, at least. After all,
we’ve not seen her for years—for more than two years! When I was
in Paris—when Jim Rucker and I were on our way to Spain—it was
midsummer, and she and some of the other girls and nuns were in
Normandy. I shall be glad to see her again.”
“I wish,” said Mrs. Fleming, slowly, “that I could say as much. But her
return brings it all up again, David. I shall do all I can for her, try my
best to place her well. But when I think of my delicate little sister,”
Flora rushed on, in a voice suddenly shaking, “and of her giving her
life for this unwelcome child—the old bitterness rises up in me——!”
She stopped as if she were choking, and with set lips and inflated
nostrils sat breathing quickly and looking into the fire, shaken by the
painful agitation of a passion usually suppressed.
“I know. I know,” David, who came nearer than any one else in the
world to intimacy with this woman, said soothingly. “But it wasn’t
Gabrielle’s fault that poor little Aunt Lily made a stupid marriage with
a—what was he? A travelling agent? Surely—surely, if you loved
Aunt Lily, you can make up all the sorrow and shame of it to
Gabrielle! There was—there was a marriage there, Aunt Flora?”
David added, with a keen look up from his own finely shaped hands,
now linked and hanging between his knees as he sat forward in his
low chair.
“Between Lily and Charpentier? Certainly!” she answered, sharply.
And suspiciously she added: “What makes you ask that?”
“It has sometimes gone through my head that there might not have
been—that that might account for her despair and her death,” David
suggested. “Not that it matters much,” he added, more briskly. “What
matters is that here we have Gabrielle, a young thing of eighteen,
apparently all over her early frailness and delicateness—at least, I
gather so?” he interrupted himself to ask, with another upward
glance.
“The Superior writes that she is in perfect health.”
“Good. So here we have Gabrielle,” resumed David, “eighteen,
finished off most satisfactorily by almost eight years with the good
Sisters and with two post-graduate years in the Paris convent—
discovered not to have a vocation——”
“Which I profoundly hoped she would have!” put in Flora, forcefully.
“Oh, come, Aunt Flora—the poor little thing! Why should she be a
religious if she doesn’t want to? After all, she’s your sister’s child and
your own Sylvia’s cousin—give her a chance!” David pleaded, good-
naturedly.
Flora looked at him temperately, patiently.
“But of course I shall give her a chance, David!” she said, quietly.
“She will unquestionably have some plan for herself. I shall see that
it is helped, if it is reasonable. But in the old days,” Flora added, “she
was treated exactly as a child of the house. She must not expect that
now. There have been changes since then, David. Poor Tom’s loss,
Roger’s death—poor Mamma’s death——”
She was silent. David, staring thoughtfully into the fire, was silent,
too. The strangely repressive influence of the twilight, the old room,
the cold, reminiscent voice that somehow rang of the tomb, the
autumn winds beginning to whine softly about the old house, and
beyond and above and through all sounds the quiet steady suck and
rising rush of the sea, the scream of little pebbles beneath the shrill
fine crying of gulls in the dusk, had taken possession of his spirit
again. Something mysterious, unhappy about it all—something
especially so about Flora—was oppressing him once more.
But why? David asked himself, angrily. Here was a widowed woman,
living in an old house only a few miles from the very heart of
civilization, contented with her solitude, yet counting the hours until
her idolized daughter’s return to Wastewater for the summer months;
conscientious in the discharge of her duty where Gabrielle, her
sister’s motherless little girl, was concerned, spending her days
peacefully among servants and flowers, books and memories.
Many and many another elderly woman lived so. What was there so
strangely disturbing, so almost menacing about this one? He did not
know. He told himself impatiently now that it was only because she
was his kinswoman that she had power to make him so uneasy; this
was, in short, the disadvantage of knowing her so well.
“The girls will brighten you up!” he remarked, hopefully.
“Perhaps,” his aunt answered, forbiddingly. And again there was
silence, and presently Mrs. Fleming went away, with some murmur
of dinner.
Left alone, David glanced about the familiar room, whose every
detail had been just as it was now in all the days he could remember.
It was a large room with rep-curtained bays on two sides. The
furniture was all dark and heavy, sixty, seventy years old. Carved
walnut, oak, horsehair, heavy-fringed upholstery, stiffly laundered
antimacassars, bookcases whose glass doors mirrored the room,
gas jets on heavy black-and-gilt brass arms.
A hanging lamp was lowered over the centre table, where albums
and gift books, shells and vases were neatly ranged upon a mat of
Berlin wool. A coal fire was smoking sulkily in the steel-rodded grate;
the mantelpiece was of brown marble flanked with columns of
shining black; the mantelshelf bore another fringed specimen of
Berlin wool work and was decorated by a solid black marble clock
with gilt horses mounting it in a mad scramble; two beautiful great
Sèvres vases of blue china wreathed with white roses and filled with
dry teazels, some small photographs in tarnished metal frames, and
several smaller articles: Turkish and Chinese boxes, Japanese
lacquer ash trays, and a tiny Dresden couple.
There were what-nots in two corners, with their flights of graded and
scalloped shelves similarly loaded; here were more photographs,
more gift books, a row of lichen owls on a strip of stiff silvery lichen,
small specimens of Swiss wood-carving and cloisonné, a china clock
that had not moved its hands in all of David’s lifetime, a teacup or
two, a vial of sand from the banks of the Jordan, a bowl of Indian
brass filled with coloured pebbles, bits of branched coral, goldstone,
a chain of Indian beads, and some Aztec pottery in rich brick-brown
and painted stripes.
On the walls were dark old paintings, engravings, and woodcuts in
heavy frames, interspersed here and there with rubbishy later
contributions: “A Yard of Roses” in a white-and-gilt mat and frame,
and a coloured photograph of ladies and children, too sickeningly
pretty, in high-belted empire gowns and curls, dancing to the music
of a spinet.
The only notable thing among all these was a life-size study that
hung above the mantel: the portrait in oil of a man of perhaps thirty
or thirty-five. David ended his inspection with a long look at it, and
his thoughts went to its subject.

Biopolymer Grafting Thakur Full Chapter

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Biopolymer Grafting Thakur Full Chapter

Uploaded by

Copyright:

Available Formats

Biopolymer Grafting Thakur

Visit to download the full and correct content document:

Library of Congress Cataloging-in-Publication Data

For information on all Elsevier publications visit our website at

Publisher: Matthew Deans

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

Title: The black Flemings

Author: Kathleen Thompson Norris

Release date: October 22, 2023 [eBook #71929]

Original publication: Garden City, NY: Doubleday, Doran &

Credits: David E. Brown and the Online Distributed Proofreading