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Polyampholytes in Advanced
Polymer Science and Emerging
Technologies

Polyampholytes are unique polymers containing acid/base and/or anionic/cationic


groups in the main or side chains. Water-soluble and water-swelling polyampholytes
exhibit properties that provide broad potential as structural biomaterials, drug delivery
and chemo-mechanical systems, biosensors, energy storage devices, supercapacitors,
and actuators, among others. This monograph reviews the innovative studies in this
feld over the past two decades, with the aim to analyze and systematize the literature
in the context of emerging technologies.

• Offers a multidisciplinary perspective covering polyampholytes,


polybetaines, and polyzwitterions in nanotechnology, biotechnology,
medicine, catalysis, environment protection, and oil industry applications
• Demonstrates a wide range of applications for these materials with enough
depth to provide critical fundamental knowledge for new researchers in
the feld
• Discusses polyampholyte-protected and gel-immobilized metal nanoparticles
and enzymes that catalyze reactions of hydrolysis, decomposition,
hydrogenation, and oxidation of various substrates in batch-type and
continuous fow–type reactors
• Highlights the remaining persistent challenges in the development and
application of these materials

This book will appeal to readers who conduct materials research for biomedical,
water treatment, and environmental remediation applications.

Sarkyt E. Kudaibergenov is a prominent Kazakh polymer scientist known for his


research into water-soluble and water-swelling polyampholytes, macromolecular
complexes, polymer-stabilized nanoparticles, polymeric catalysis, and stimuli-responsive
materials for various applications. Despite having made many successful developments
and contributions in the feld of physical chemistry of polymers, Prof. Kudaibergenov’s
primary research topic remains polyampholytes, a subject he has studied since 1979
and on which he has published a number of reviews and a fundamental monograph.
Emerging Materials and Technologies
Series Editor: Boris I. Kharissov

The Emerging Materials and Technologies series is devoted to highlighting


publications centered on emerging advanced materials and novel technologies.
Attention is paid to those newly discovered or applied materials with potential
to solve pressing societal problems and improve quality of life, corresponding to
environmental protection, medicine, communications, energy, transportation,
advanced manufacturing, and related areas.
The series takes into account that, under present strong demands for energy,
material, and cost savings, as well as heavy contamination problems and worldwide
pandemic conditions, the area of emerging materials and related scalable technologies
is a highly interdisciplinary feld, with the need for researchers, professionals, and
academics across the spectrum of engineering and technological disciplines. The
main objective of this book series is to attract more attention to these materials and
technologies and invite conversation among the international R&D community.

Biodegradable Polymers, Blends and Biocomposites: Trends and Applications


Edited by A. Arun, Kunyu Zhang, Sudhakar Muniyasamy and Rathinam Raja

Bioinspired Materials and Metamaterials: A New Look at the Materials Science


Edward Bormashenko

Computational Studies: From Molecules to Materials


Edited by Ambrish Kumar Srivastava

2D Semiconductors for Environmental Remediation


Edited by Honey John, Nisha T Padmanabhan, Sona Stanly and Jith C Janardhanan

Materials from Natural Sources


Edited by Ramesh Gardas, Neha Patni and Amita Chaudhary

Dielectric Materials for Capacitive Energy Storage


Edited by Haibo Zhang and Hua Tan

Multifunctional Coordination Materials for Green Energy Technologies


Edited by Ghulam Yasin, Anuj Kumar, Sajjad Ali, Tuan Anh Nguyen, and Saira Ajmal

Polyampholytes in Advanced Polymer Science and Emerging Technologies


Sarkyt E. Kudaibergenov

For more information about this series, please visit: www.routledge.com/Emerging-Materials-and-


Technologies/book-series/CRCEMT
Polyampholytes in
Advanced Polymer Science
and Emerging Technologies

Sarkyt E. Kudaibergenov
Designed cover image: © Amir Sarkyt
First edition published 2025
by CRC Press
2385 NW Executive Center Drive, Suite 320, Boca Raton FL 33431
and by CRC Press
4 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN
CRC Press is an imprint of Taylor & Francis Group, LLC
© 2025 Sarkyt E. Kudaibergenov
Reasonable efforts have been made to publish reliable data and information,
but the author and publisher cannot assume responsibility for the validity of
all materials or the consequences of their use. The authors and publishers
have attempted to trace the copyright holders of all material reproduced in this
publication and apologize to copyright holders if permission to publish in this
form has not been obtained. If any copyright material has not been acknowledged
please write and let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be
reprinted, reproduced, transmitted, or utilized in any form by any electronic,
mechanical, or other means, now known or hereafter invented, including
photocopying, microflming, and recording, or in any information storage or
retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this work, access
www.copyright.com or contact the Copyright Clearance Center, Inc. (CCC), 222
Rosewood Drive, Danvers, MA 01923, 978-750-8400. For works that are not
available on CCC please contact [email protected]
Trademark notice: Product or corporate names may be trademarks or registered
trademarks and are used only for identifcation and explanation without intent to
infringe.
ISBN: 978-1-032-55605-5 (hbk)
ISBN: 978-1-032-55607-9 (pbk)
ISBN: 978-1-003-43140-4 (ebk)
DOI: 10.1201/9781003431404
Typeset in Times
by Apex CoVantage, LLC
To my mother, Zere Kudaibergenova;
to my sister, Kulbagi Kudaibergenova
to my wife, Gulnar Kudaibergenova;
and to my daughter, Azhar Kudaibergenova,
with love.
Contents
Introduction...............................................................................................................xi
Preface.................................................................................................................. xxiii

Chapter 1 Water-Soluble Polyampholytes.............................................................1


1.1 Annealed Polyampholytes .........................................................1
1.2 Quenched Polyampholytes (QPA) or Polyzwitterions ............. 12
1.3 Polymeric Betaines and/or Polyzwitterions.............................22
1.4 Polybetainic (or Polyzwitterionic) Soaps.................................28
1.5 Low and Upper Critical Solution Temperatures (LCST
and UCST) of Polyampholytes ................................................ 35
1.6 Polyampholytic Ionic Liquids.................................................. 41
1.7 Semi-Natural Polyampholytes.................................................44
1.8 Structural and Behavioral Similarity of Synthetic and
Natural Polyampholytes and Intrinsically Disordered
Proteins (IDPs) ........................................................................46
1.9 Polyampholytic Behavior of Interpolyelectrolyte
Complexes (IPEC)...................................................................54
References ..........................................................................................57

Chapter 2 Stimuli-Responsive Properties of Hydrophobically Modifed


Polyampholytes (HMPA) in Solution................................................. 79
2.1 Thermo- and pH-Sensitive HMPA ..........................................80
2.2 Solvent-Sensitive HMPA .........................................................84
2.3 Salt-Sensitive HMPA...............................................................86
2.4 Light-Sensitive HMPA ............................................................87
2.5 Langmuir–Blodgett and LbL Films of HMPA........................ 89
2.6 Solubilization of SWCNT and MWCNT by HMPA ............... 91
References ..........................................................................................92

Chapter 3 Stimuli-Responsive Amphoteric Nano-, Micro-, and


Macroporous Gels ..............................................................................97
3.1 Thermo-, pH-, and Solvent-Responsive Gels ..........................97
3.2 Salt-Responsive Gels ............................................................. 105
3.3 Electric-Responsive Gels....................................................... 109
3.4 Bioresponsive Gels ................................................................ 109
3.5 Self-Healing and Shape Memory Gels .................................. 110

vii
viii Contents

3.6 Amphoteric Nano-, Micro-, and Macroporous Gels ............. 113


3.7 Molecularly Imprinted Polyampholyte Gels ......................... 117
References ........................................................................................120

Chapter 4 Macromolecular Complexes of Polyampholytes.............................. 130


4.1 Intra- and Interpolyelectrolyte Complexes of
Polyampholytes...................................................................... 130
4.2 Polyampholyte–Polyelectrolyte, Polyampholyte–Protein,
and Polyampholyte–DNA Complexes................................... 133
4.3 Polyampholyte–Metal Complexes......................................... 139
4.4 Polyampholyte–Surfactant Complexes.................................. 145
4.5 Polyampholyte–Dye Complexes............................................ 148
4.6 Stabilization of Metal Nanoparticles by Polyampholytes ..... 149
4.7 Isoelectric Effect.................................................................... 152
References ........................................................................................160

Chapter 5 Polyampholytes in Biotechnology and Medicine............................. 170


5.1 Polyampholytes as Protein and Drug Delivery Systems ....... 170
5.2 Mucoadhesive Properties of Natural and Synthetic
Polyampholytes...................................................................... 172
5.3 Amphoteric Hydrogels as Perspective Structural
Biomaterials........................................................................... 178
5.4 Antifouling and Hemocompatible Polyampholytes............... 180
5.5 Cryoprotective Polyampholytes............................................. 185
References ........................................................................................190

Chapter 6 Polyampholytes in Catalysis.............................................................200


6.1 Catalysis by Polyampholytes .................................................200
6.2 Catalysis by Polyampholyte–Metal Complexes ....................202
6.3 Polyampholyte-Protected Metal Nanoparticles in Catalysis ....203
6.4 Catalytic Properties of Catalase Immobilized within
Polyampholyte Cryogels........................................................206
References ........................................................................................209

Chapter 7 Application of Polyampholytes in Emerging Technologies ............. 212


7.1 Wastewater Purifcation and Desalination ............................ 212
7.2 Polyampholytes in Enhanced Oil Recovery (EOR) .............. 218
7.3 Polyampholytes as Additives to Drilling Fluids.................... 222
7.4 Polyampholytes in Stabilization of Colloid Dispersions .......224
7.5 Polyampholytes in Drag Reduction ....................................... 227
7.6 Polyampholytes as Pour Point Depressants...........................230
Contents ix

7.7 Application of Polyampholytes in Leather Treatment........... 233


7.8 Polyampholyte-Based Supercapacitors and Sensors ............. 235
7.9 Storage of Information (or Coding) on Amphoteric
Macromolecules..................................................................... 241
References ........................................................................................ 245

Conclusion ............................................................................................................ 259


Index...................................................................................................................... 265
Introduction
An introduction emphasizes the importance of this book in exploring polyampholy-
tes and gives various terms adopted in literature. It briefy describes the different
types of polyampholytes with examples. Several fundamental properties of polyam-
pholytes discovered in the last century are given. Pioneers and contemporary authors
who have made signifcant contributions to the development of polyampholytes are
mentioned. The synthetic aspects of polyampholytes, numerous theoretical models,
and simulations are omitted. Instead, the main attention is paid to hydrodynamic,
conformational, acid–base, volume–phase, complexation, and catalytic properties of
water-soluble and water-swelling polyampholytes together with application felds.
The book consists of an introduction, seven chapters, and a conclusion. For the read-
er’s convenience, each chapter is provided with its own references.
Polyampholytes are unique macromolecules containing acid/base or anionic/cat-
ionic groups in the main or side chains that mimic the behavior of proteins, poly-
peptides, and/or polynucleotides. Water-soluble and water-swelling polyampholytes
exhibit thermal-resistant, salt-tolerant, shear-stable, self-healing, antifouling, self-as-
sembling, and stimuli-responsive properties that provide broad impact as structural
biomaterials, drug delivery and chemo-mechanical systems, biosensors, energy stor-
age devices, supercapacitors, actuators, etc. Functional, confgurational, conforma-
tional, and behavioral similarity of synthetic polyampholytes to natural ones [1–3] is
an emerging platform to protein mimicking [4, 5] and the developing of various bio-
compatible materials, drug delivery systems, tissue-engineering technology, bioreac-
tors, etc. Advances in polyampholytes emphasizing biomedical [6–9], medical [10],
and antifouling aspects [11] were recently reviewed. The advances in synthetic pol-
yampholytes accumulated during the half century are outlined in this book, together
with application in emerging technology.
In current literature, the terms “zwitterionic polyampholytes,” “polybetaines,”
“zwitterionic polyelectrolytes,” and “polyzwitterions” are widely used. A. B. Lowe
and C. L. McCormick [12] suggest the use of the term “polyzwitterion” for all poly-
mers that possess both cationic and anionic groups. They refer to as polyampholyte
those polymers that specifcally possess the charged groups on different monomer
units, while polybetaine refers to those polymers in which the anionic and cationic
groups are replaced on the same monomer unit. According to the defnition of A.
Laschewsky [13], polyampholytes behave mostly either as polyanionic or as polyca-
tionic species, whereas polyzwitterions (or polybetaines), due to their overall charge
neutrality, exhibit a different, hybrid-like property profle. Sometimes a subtle differ-
ence between these defnitions is hardly perceptible.
Conditionally, polyampholytes can be divided into three classes: annealed,
quenched, and betainic (or zwitterionic) [14–17]. Annealed polyampholytes consist
of acid–base monomers that are ionized in dependence of pH, while quenched poly-
ampholytes containing strongly charged cationic and anionic monomers retain their
respective charges independently on pH. The “semi-annealed” or “semi-quenched”
polyampholytes are defned as amphoteric macromolecules that combine the weak

xi
xii Introduction

acid/cationic or weak base/anionic monomers. “Betainic” (or zwitterionic) polyam-


pholytes are macromolecules containing identical numbers of acid–base (or fully
charged anionic-cationic) species in the same monomer units [13, 18]. The macro-
molecules existing via compensation of the cationic-anionic monomer pairs without
counterions also belong to zwitterionic polymers [19–22] or polyampholytic ionic
liquids [23, 24]. Examples of polyampholytes with different chemical structures are
shown in Figure 0.1.
The main difference between the polyelectrolytes’ and polyampholytes’ irre-
spective linear or crosslinked (gel state) structure is related to their response to salt
addition [24]. Expanded (or swollen) in pure water, polyelectrolyte chains shrink in
salt solution due to the screened electrostatic repulsion between uniformly charged
macroions (polyelectrolyte effect). Collapsed (or shrunken) in aqueous solution,
“annealed” polyampholyte at the isoelectric point (IEP) and/or charge-balanced
“quenched” polyampholyte, including polymeric betaines, in quasi-neutral state,
unfold in salt solution due to screening of the electrostatic attraction between oppo-
sitely charged monomers (“antipolyelectrolyte” effect).
The pioneering works of Alfrey, Morawetz, Fuoss [25–28], Katchalsky [29–31],
Ehrlich, and Doty [32] in the 1950s invoked intensive development of this subject due
to several reasons. First is the similarity of the hierarchical structure of amphoteric
macromolecules to structural organization of proteins [33, 34]. Second is modeling

FIGURE 0.1 Repeating monomeric units of (1) annealed, (2) quenched, (3, 4) zwitterionic,
(5) quenched betainic, (6) annealed betainic, and (7, 8) self-annealed (or self-quenched)
polyampholytes.
Introduction xiii

of protein folding mechanism by synthetic polyampholytes [35]. Third is involve-


ment of amino acids for obtaining amphoteric polypeptides [36–41] and intrinsically
disordered proteins [42], as well as fabrication of polyampholytes from natural build-
ing blocks that exhibit protein-like behaviors [43, 44].
Several fundamental properties of polyampholytes have been discovered in the
last century. One of the fascinating properties of polyampholytes is the so-called
“antipolyelectrolyte effect” in aqueous solutions, predicted by Ehrlich and Doty [32],
theoretically justifed by Higgs and Joanny [45], and confrmed experimentally by
many research groups [46–48], including this one [49–53]. The “antipolyelectro-
lyte effect,” in contrast to the “polyelectrolyte effect,” is related to the unfolding
of amphoteric macromolecules at the isoelectric point (IEP) upon the addition of
low-molecular-weight salts in contrast to salt-induced collapse of ordinary polyelec-
trolytes [54]. Recently [55], the antipolyelectrolyte behavior of polybetaine macro-
molecules was detected directly at the single-chain level.
Another recently discovered fundamental property is the “isoelectric effect”
observed for a series of water-soluble polyampholytes, amphoteric hydrogels, and
cryogels [56–68]. The “isoelectric effect” is due to charge inversion at the IEP and
related to cooperative release of low- or high-molecular-weight substances at the
IEP of polyampholytes as a result of a competition between inter- (inter-MMC) and
intramacromolecular (intra-MMC) complexation [65].
The third fnding, but not adopted yet by fne specialists, is the behavioral close-
ness of interpolyelectrolyte complexes (IPEC)—the products of the interactions
between oppositely charged linear polyelectrolytes—and particularly block polyam-
pholytes [69–76].
A renewed interest in polyampholytes is expected to result from an improved
understanding of the fundamental relationships between the microstructure and
properties of linear and crosslinked amphoteric macromolecules, accompanied by
systematic evaluation of the literature [77–84].
According to the Web of Science database (2018), the global key contributors to
research into polyampholytes are Ali, S. A. (Saudi Arabia); Bekturov, E. A. (Kazakhstan);
Bernards, M. (USA); Bohidar, H. B. (India); Candau, F. (France); Dobrynin, A. V.
(USA); Gong, J. P. (Japan); Joanny, I. F. (France); Khokhlov, A. R. (Russia); Koetz,
J. (Germany); Kudaibergenov, S. E. (Kazakhstan); Laschewsky, A. (Germany);
Matsumura, K. (Japan); McCormick, C. L. (USA); Patrickios, C. S. (Cyprus);
Rubinstein, M. (USA); Stamm, M. (Germany); Tsitsilians, C. (Cyprus); and others.
In this book, the synthetic aspects of polyampholytes comprising of free radical
polymerization (FRP), controlled radical polymerization (CRP), atomic transfer radi-
cal polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT)
polymerization, group transfer polymerization (GTP), chemical modifcation, exclu-
sion (deprotection) of protecting groups, click chemistry, via Ugi reaction, etc. are not
considered. Also, numerous theoretical models and simulations of polyampholytes
(or polyampholyte physics) that comprehensively were considered in the fundamen-
tal monograph of the present author, Polyampholytes: Synthesis, Characterization and
Application (New York: Kluwer Academic/Plenum Publishers, 2002), that covered the
literature sources starting from the 1950s are also omitted. Instead, the main attention
is paid to hydrodynamic, conformational and molecular characteristics, acid–base and
xiv Introduction

solution properties, complexation and volume-phase properties of water-soluble and


water-swelling polyampholytes, together with catalytic activity and application aspects.
The present monograph also covers the innovative studies accumulated in the last
20 years, with the aim to analyze and systematize the literature survey in the con-
text of emerging technologies. The book chapters describe the theoretical and exper-
imental results on polyampholytes to predict the perspectives for developing and to
bridge the gap between synthetic and natural polymers, between biological materials
and the physics and chemistry of amphoteric macromolecules. The book contains
an introduction, seven chapters, and a conclusion. Starting with the classifcation
and defnition of various types of polyampholytes in the introduction, Chapter 1
describes the solution properties and hydrodynamic, conformational, and molecular
characteristics of annealed, quenched, and betaine-type polyampholytes. The most
important feature of polyampholytes is related to their isoelectric point (IEP), where
the whole macromolecule is in a quasi-neutral state. The infuence of pH and ionic
strength on the viscosity and sedimentation constant of annealed polyampholytes is
shown, in agreement with the prediction of the unfolding of water-soluble amphoteric
macromolecules at the IEP in the presence of neutral salts. The solution properties
of charge-balanced and charge-imbalanced quenched polyampholytes are discussed.
The conformation of imbalanced quenched polyampholytes consists of a core/shell
structure with a polyampholyte core and a polyelectrolyte shell. Added low-molecu-
lar-weight salts can shrink the polyelectrolyte shell and swell the polyampholyte core
at relatively high ionic strengths. Polyampholytes with block chains can form glob-
ular intra-polyelectrolyte complexes in similarity to interpolyelectrolyte complexes
(IPEC) formed between oppositely charged polyelectrolytes. Separate subchapters
are devoted to polybetainic (or polyzwitterionic) soaps which combine the behavior
of polyampholytes and micellar polymers, to lower (LCST) and upper critical solution
temperatures (UCST) of amphoteric macromolecules, to less-considered-in-literature
polyampholytic ionic liquids, to semi-natural polyampholytes that can be prepared
by modifcation of natural polysaccharides by introducing either carboxylic (sulfo) or
amine (ammonium) groups or both into the macromolecular chains. They represent
a new family of functional polymers with particular properties and new applications.
A minor attention is paid to theories of polymer physics that were developed for the
description of large macromolecules, including proteins. The intrinsically disordered
proteins (IDPs) are characterized by their amino acid composition and low sequence
complexity, as well as by their low amount of bulky hydrophobic amino acids and
high proportions of charged and hydrophilic amino acids. Thus, proteins, polyampho-
lytic polypeptides, IDPs, and random, regular, and block polyampholytes can form
globular conformations at the IEP, stabilized by coulombic forces between opposite
charges within single macromolecules. Complex coacervation, or liquid–liquid phase
separation (LLPS), is a common phenomenon in these systems too. The simplifed
molecular design principles developed for synthetic polyampholytes can provide some
insights into the more complicated sequences of IDPs and an understanding of how
charge-driven LLPS can be designed by tuning the patterning of charged monomers.
Chapter 2 deals with the fundamental and applied aspects of hydrophobically
modifed polyampholytes (HMPA), sometimes called hydrophobic polyampholytes,
or amphoteric “polysoaps,” their self-assembly and stimuli-responsiveness triggered
Introduction xv

by environmental conditions. The controlled balance between lyophilic and lyopho-


bic interactions due to the introduction of hydrophobic groups into the polyampholyte
chain leads to organized solutions and solvent-depending self-assembly. Therefore,
monolayers, micelles, vesicles, or highly organized structures are spontaneously
formed. Hydrophobically associating polyampholytes combining the properties of
polymer, surfactant, and alkaline can be used in different felds of application, for
example, for heavy oil displacement. It is shown that hydrophobic polyampholytes
can inhibit the wax deposition and consequently decrease the pour point temperature
of crude oils.
Chapter 3 concerns stimuli-responsive polyampholyte bulk hydrogels, nano-
gels, microgels, and microporous cryogels in dependence on the temperature, pH
value, salt addition, solvent quality, DC electric feld, etc. Polyampholyte hydro-
gels and cryogels possess the typical features of polyelectrolytes. By adding
low-molecular-weight salts, anti-polyelectrolyte effects can be induced, due to the
disruption of intra- and interionic contacts. The isoelectric effect also takes place
at the IEP of polyampholyte cryogels. By random copolymerization of oppositely
charged ionic monomers at relatively high monomer concentrations and equi-
molar monomer ratios, a new class of physical hydrogels containing both strong
and weak ionic bonds become available. Permanent crosslinks are responsible for
maintaining the shape of the gel, while the ionic bonds, acting as a sacrifcial net-
work, are responsible for elongation, deformation, adhesion, self-healing, shape
memory, and other important functions. The molecularly imprinted polyampholyte
hydrogels and cryogels designed by crosslinking of acid–base monomers in the
presence of template proteins or drugs within the network are considered as suita-
ble materials for separation and analysis of proteins and drug delivery system and
hopefully will play an important role in molecular recognition, separation science,
and biocatalysis.
Chapter 4 is related to macromolecular complexes of different types of poly-
ampholytes with polyelectrolytes, proteins, surfactants, metal ions, dyes, drugs, and
nanoparticles. The cooperative release of low- or high-molecular-weight substances
at the IEP of polyampholytes is discussed, as a result of a competition between inter-
and intramacromolecular complexation. This so-called “isoelectric effect” can be
used for purifcation and separation processes of proteins and the removal of transi-
tion metal ions, surfactants, and dyes from wastewater.
Chapter 5 is related to the application of polyampholytes in biotechnology
and medicine. Nonfouling, hemocompatibility, and biodegradability of polyam-
pholytes attract much interest as nanocarriers for delivery of chemotherapeutants,
DNA, and proteins, or as contrast agents in magnetic resonance imaging. These
materials can trigger delivery through a bond cleavage or conformational change
under the action of temperature, pH, ionic strength, enzymes, redox potential,
etc. Polyampholyte nanoparticles can be used in photothermal tumor therapy, and
polyampholyte hydrogels are proved as excellent biomaterials in artifcial organs.
Polyampholytes offer special properties as cryoprotectants. The application of
polyampholyte cryogels as a protein-imprinted matrix for the separation and puri-
fcation of biomacromolecules and for sustained release of biologically active
substances is also highlighted in this chapter.
xvi Introduction

In Chapter 6, the catalytic properties of polyampholytes themselves, polyam-


pholyte–metal complexes, polyampholyte-protected metal nanoparticles, and ampho-
teric cryogel-encapsulated enzymes are outlined in catalytic reactions of hydrolysis,
transesterifcation, photocatalytic light-driven hydrogen production from water, decom-
position, hydrogenation, and oxidation of various substrates. Special attention is paid
to macroporous amphoteric cryogels containing metal nanoparticles or enzymes in
pores that are used as batch-type and continuous fow–type catalytic reactors.
The quintessence of the fundamental fndings discovered in the behavior of lin-
ear and crosslinked polyampholytes is considered in Chapter 7 in light of practical
application, in particular in the felds of environmental protection, petroleum industry,
biotechnology, and medicine. Linear and crosslinked polyampholytes exhibit salt-
tolerant, thermal-resistant, shear-stable, self-healing, antifouling, self-assembling,
and stimuli-responsive properties that could have a broad impact in the areas of
wastewater purifcation, desalination, enhanced oil recovery, stabilization of colloid
dispersions, structural biomaterials, controlled drug delivery systems, energy and
information storage devices, supercapacitors, and actuators, among others.
In the conclusion, the state of the art, general problems, and promising directions
of polyampholytes are discussed. This book can open a renewed interest for spe-
cialists on the theory of polyampholytes to make quantitative predictions and vali-
dation of their theoretical fndings. This perspective is related to several conceptual
advances and the remaining persistent challenges in the contexts of charge and size
of polymers, structures in homogeneous solutions, thermodynamic instability and
phase transitions, structural evolution with oppositely charged polymers, dynamics
in polyampholyte solutions, kinetics of phase separation, mobility of charged mac-
romolecules, and implications to biological systems. For the reader’s convenience,
each chapter is provided with its own references.

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