Ionic Interactions in Natural and Synthetic Macromolecules

This book is a comprehensive study of the subject of ionic interactions in macromolecules. The first parts of the book review and analyze the conventional treatments of fixed charges (e.g. in polyelectrolytes and polyampholytes), including screening and condensation by mobile ions. The interaction of ions with less polar sites on the macromolecule (e.g. amide bonds), and the origin of the lyotropic effects (focusing on binding versus condensation) will also be extensively addressed.

The book also explores complex micellar organizations involving charged macromolecules (e.g. DNA) and low-molecular-weight ampholytes and strong protein associations. The resulting structures are relevant to a variety of functional biological systems and synthetic analogs. The contribution of electrostatic and hydrophobic interaction to the stability of proteins and other supramolecular structures will also be analyzed. There are chapters on applications such as deionization and cosmetic formulation.

This 21-chapter book is divided into three sections:

1. Fundamentals
2. Mixed Interactions
3. Functions and Applications

PREFACE ix

CONTRIBUTORS xiii

PART I FUNDAMENTALS 1

1 ION PROPERTIES 3
Yizhak Marcus

2 IONIC INTERACTIONS IN SUPRAMOLECULAR COMPLEXES 35
Hans-Jörg Schneider

3 POLYELECTROLYTE FUNDAMENTALS 49
Angelo Perico

4 POLYELECTROLYTE AND POLYAMPHOLYTE EFFECTS IN SYNTHETIC AND BIOLOGICAL MACROMOLECULES 91
Ngo Minh Toan, Bae-Yeun Ha, and Dave Thirumalai

5 MODELING THE STRUCTURE AND DYNAMICS OF POLYELECTROLYTE MULTILAYERS 121
Juan J. Cerdà, Christian Holm, and Baofu Qiao

PART II MIXED INTERACTIONS 167

6 IONIC MIXED INTERACTIONS AND HOFMEISTER EFFECTS 169
Alberto Ciferri

7 HYDROPHOBIC POLYELECTROLYTES 211
Andrés F. Olea

8 ASSOCIATION OF POLYELECTROLYTES TO SURFACTANTS AND SUPRAMOLECULAR ASSEMBLIES: COMPETITIVE ROLE OF CHAIN RIGIDITY AND ASSEMBLY STABILITY 235
Alberto Ciferri and Angelo Perico

9 ION TRANSFER IN AND THROUGH CHARGED MEMBRANES: STRUCTURE, PROPERTIES, AND THEORY 267
Victor V. Nikonenko, Andrey B. Yaroslavtsev, and Gérald Pourcelly

10 REVERSIBLE COORDINATION POLYMERS 337
Kim de Lange, Jos M.J. Paulusse, Antonius T.M. Marcelis, and Han Zuilhof

11 STRUCTURAL AND FUNCTIONAL ASPECTS OF METAL BINDING SITES IN NATURAL AND DESIGNED METALLOPROTEINS 361
Ornella Maglio, Flavia Nastri, and Angela Lombardi

12 CHARGE-INDUCED EFFECTS ON ACID-BASE TITRATION AND CONFORMATIONAL STABILITY OF PROTEINS AND POLYPEPTIDES 451
Jan Hermans

PART III FUNCTIONS AND APPLICATIONS 483

13 IRON TRANSPORT IN LIVING CELLS 485
Alvin L. Crumbliss and Claire J. Parker Siburt

14 DNA-LIPID AMPHIPHILES FOR DRUG AND GENE THERAPY 551
Peggy P.Y. Chan and LiShan Wang

15 POLYELECTROLYTE INTELLIGENT GELS: DESIGN AND APPLICATIONS 581
Piero Chiarelli and Danilo De Rossi

16 IONIC POLYMER–METAL COMPOSITES FOR SENSORS AND ARTIFICIAL MUSCLES: MECHANOELECTRIC PERSPECTIVES 621
Rashi Tiwari and Kwang J. Kim

17 FUNCTIONAL LAYER-BY-LAYER POLYELECTROLYTES: ASSEMBLY STRATEGIES, CHARACTERIZATION, AND SELECTED APPLICATIONS 643
Nicel Estillore, Wolfgang Knoll, and Rigoberto Advincula

18 POLYELECTROLYTES AT INTERFACES: APPLICATIONS AND TRANSPORT PROPERTIES OF POLYELECTROLYTE MULTILAYERS IN MEMBRANES 683
Bastien Seantier and André Deratani

19 SELF-ASSEMBLY OF POLYELECTROLYTES FOR PHOTONIC CRYSTAL APPLICATIONS 727
Dario Cavallo and Davide Comoretto

20 APPLICATIONS OF CHARGED MEMBRANES IN SEPARATION, FUEL CELLS, AND EMERGING PROCESSES 761
Gérald Pourcelly, Victor V. Nikonenko, Natalia D. Pismenskaya, and Andrey B. Yaroslavtsev

21 POLYMER GEL ELECTROLYTES: CONDUCTION MECHANISM AND BATTERY APPLICATIONS 817
Ian M. Ward and Hugh V. St. A. Hubbard

LIST OF SYMBOLS 841

INDEX 843

“This is a comprehensive text that explains the latest advances in the large class of natural and synthetic materials influenced by ionic-mixed interactions and their many potential applications. It should be of interest to practitioners and students in chemistry, biochemistry, physics, and engineering.” (Chemistry & Industry, 1 November 2012)

Alberto Ciferri is currently a Visiting Professor at Duke University, an Associate at the National Research Council (ISMAC), and President of the Jepa-Limmat Foundation, which is devoted to advanced education in developing countries. His research has had significant impact in the areas of the rheological properties of natural and synthetic polymers, fibrous proteins, interactions between salts and macromolecules, liquid crystals, and supramolecular assemblies.

Angelo Perico is Research Director at the National Research Council, associated with the Institute for Macromolecular Studies, in Genoa, Italy. Dr. Perico's research is related to theory and modeling of synthetic and biological macromolecules and their dynamics, assembly, and functions, particularly the interactions among oppositely and similarly charged polyelectrolytes and on the electrostatic effects that promote the formation of complex biomolecular structures.

Comprehensive study sheds new light on ionic interactions in macromolecules and their applications

With contributions from leading researchers around the world, Ionic Interactions in Natural and Synthetic Macromolecules offers a carefully structured and comprehensive explanation of how combinations of supramolecular interactions direct a variety of self-assembly modes for nano-architectures and functional biostructures. The text reviews and analyzes charged macromolecules, such as synthetic polyelectrolytes, DNA, and ampholytic proteins, and describes how an understanding of ionic and ionic-mixed interactions in macromolecules has a general impact and potential applications across a broad range of disciplines, spanning biochemistry, medicine, materials science, and organic chemistry.

Ionic Interactions in Natural and Synthetic Macromolecules is divided into three parts:

• Section One, Fundamentals, examines basic aspects of purely ionic interactions within organic systems, and includes a description of the behavior of simple salts.

• Section Two, Mixed Interactions, explores how the superimposition of ionic and other charge-independent electrostatic interactions control Hofmeister effects, the supramolecular organization of hydrophobic polymers, polyelectrolyte-protein complexes, synthetic membranes, metalloproteins, and helical polypeptides.

• Section Three, Functions and Applications, deals with transport processes in both biological and synthetic systems, functioning and applications of intelligent gels, nano-structured films formed by layered polyelectrolytes, and ionic conductivity in highly efficient energy sources.

Readers will discover how the text's unified presentation of systems—characterized by different blends of ionic and ionic-mixed interactions—has led to the identification of general underlying mechanisms and a correlation among seemingly unrelated phenomena.

This text is recommended for practitioners and students in chemistry, biochemistry, physics, and engineering. All readers will discover what is known about the large class of natural and synthetic materials influenced by ionic-mixed interactions and their many potential applications.