Ionic Interactions in Natural and Synthetic Macromolecules

854 Pages·2007·11.55 MB·English

IONIC INTERACTIONS
IN NATURAL
AND SYNTHETIC
MACROMOLECULES
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IONIC INTERACTIONS
IN NATURAL
AND SYNTHETIC
MACROMOLECULES
EDITED BY
ALBERTO CIFERRI
ANGELO PERICO
A JOHN WILEY & SONS, INC., PUBLICATION
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Copyright © 2012 by John Wiley & Sons, Inc. All rights reserved
Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada
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Library of Congress Cataloging-in-Publication Data:
Ionic interactions in natural and synthetic macromolecules / edited by
Alberto Ciferri, Angelo Perico.
p. cm.
Includes bibliographical references.
ISBN 978-0-470-52927-0
1. Macromolecules. 2. Ion-ion collisions. 3. Supramolecular chemistry.
I. Ciferri, A. II. Perico, Angelo.
QD381.I64 2012
547'.7045723–dc23
2011041448
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
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CONTENTS
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
v
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vi CONTENTS
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
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CONTENTS vii
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
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PREFACE
Two editions of Supramolecular Polymers (Dekker 2000 and CRC Press
2005) have dealt with the self - assembly of structures in the nano - and up -
dimensional range in terms of molecular (chemical and shape) recognition
and growth mechanisms. This third book is devoted to a more detailed descrip-
tion of how the components of chemical recognition are modulated to pro-
duce the variety of properties that characterize the supramolecular organization
of functional systems and adaptive polymers. Fundamental approaches are
highlighted, along with descriptions of a selected number of sophisticated
applications.
Ionic interactions defi nitively play a primary role in the self - assembly of
functional biological and synthetic systems. Theoretical features of purely ionic
interactions have been extensively described in the past, and structural fea-
tures of several real systems in which ionic interactions play a prevailing role
have been experimentally characterized. However, in the majority of real
cases, ionic interactions are modulated (reinforced or antagonized) by the
occurrence of other, charge - independent interactions that produce important
alterations of the structure and properties of the systems.
The fi rst section of the book includes chapters focused on fundamental
aspects of purely ionic interactions. The properties of simple salts described
byMarcus are essential for the analysis of specifi c details of their interaction
with organic substrates. Polyelectrolyte theories are presented by P erico , who
places particular emphasis on the role of ion condensation and like - charge
attraction on the stabilization of biological assemblies. Systems with opposite
fi xed charges include host – guest complexes, described by S chneider , which will
facilitate quantitative comparisons with the polymeric ion pair systems such
as polyampholytes, described next by T hirumalai and coworkers, and layered
polyelectrolytes, described by H olm and coworkers.
The second section of the book includes chapters focused on fundamental
aspects of mixed interactions. Ciferri discusses correlations of mixed systems
and the role of mixed interactions in the Hofmeister effects. Polyelectrolytes
with a signifi cant number of hydrophobic groups, described by O lea , and
polyelectrolyte – surfactant/protein assemblies, described by C iferri and Perico ,
ix
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x PREFACE
offer vivid evidence for the variety of supramolecular structures that are pro-
moted by the microsegregation of apolar segments or associated proteins. Also
in the second section, N ikonenko and coworkers describe the structure and
properties of charged membranes resulting from the microsegregation of
hydrophilic channels within a hydrophobic matrix. Metal – ion coordination for
reversible polymers is discussed byMarcelis and coworkers, whereas a broader
range of the ligand interaction is described by Lombardi and coworkers in
terms of protein thermodynamics, and the chapter by H ermans highlights the
role of charges on the conformation of helical polypeptides and proteins
The third section of the book focuses on functions and applications of
various systems, and is opened by the chapter by Crumbliss and Parker Siburt
on ion transport across living cells. The biological transport mechanisms are
brilliant examples of the way nature has engineered a complex sequence of
ionic mixed interactions for a specifi c function. The chapter by C han and Wang
describes DNA – lipid assemblies that generate pseudoliposomic structures
used for targeted gene and drug delivery. The chapters by Chiarelli and De
Rossi and by T iwari and Kim feature stimulus - responsive intelligent gels, with
emphasis on biomedical applications and muscle - like actuators. The electro-
mechanochemical functioning of the gels entails consideration of readjust-
ment kinetics of forces and related fl uxes, which are handled by continuum
mechanics approaches.
The next three chapters deal with functional layered assemblies: Knoll and
coworkers describe a variety of driving interactions exploited for the forma-
tion of nanostructured fi lms; Seantier and Deratani emphasize the sequential
polycation – polyanion approach and the formation of multilayered mem-
branes; and Cavallo and Comoretto discuss the application as photonic crystals
of ordered periodic structures formed by materials having alternating refrac-
tive indices. Next, the chapter by Pourcelly and coworkers describes complex
separation processes (particularly water treatments) using charged mem-
branes, and also the membrane - based energy conversion in fuel cells technol-
ogy. Effi cient energy sources, such as lithium batteries, are characterized by
cationic conductivity even in the absence of water. Polymer gel electrolytes,
described in the fi nal chapter by Ward and Hubbard , are intermediate between
typical liquid and solid polymeric electrolytes, and allow a molecular under-
standing of ionic conductivity.
The goal of this book is to provide a coordinated and comprehensive rep-
resentation of ionic mixed interactions, and actual or potential applications.
Proper design of the molecular structure of self - assembling building blocks
requires the strategic inclusion of groups that will modulate their contribu-
tions so that tailored properties and even complex functions may be produced.
The unifi ed presentation of the systems described here, characterized by dif-
ferent blends of ionic and ionic mixed interactions, allows the identifi cation
of general mechanisms and a correlation between, at fi rst sight, unrelated
phenomena.
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PREFACE xi
The result was made possible by the dedication and patience of the con-
tributors. Extensive discussions followed the preliminary draft, and attempts
were made to reach a consensus over controversial issues. The Editors express
their appreciation to all colleagues who have cooperated in the preparation
of the book, to the Chemistry Department at Duke University, and to the
Institute for Macromolecular Studies (ISMAC) of the National Research
Council.
The editors wish to honor the memory of their late colleague Eligio Patrone
for his lifelong commitment to cultural and scientifi c values.
A lberto C iferri
A ngelo P erico
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CONTRIBUTORS
R igoberto A dvincula
Department of Chemistry
University of Houston
Houston, TX 77204 - 50031
D ario C avallo
Department of Chemistry and Industrial Chemistry
University of Genoa
Via Dodecaneso 31,
16146 Genova
Italy
J uan J. C erd à
Instituto de Fisica Interdisciplinar y Sistemas Complejos
IFISC (CSIC - UIB)
Universitat de les Illes Balears
E - 07122 Palma de Mallorca
Spain
P eggy P.Y. C han
Department of Chemical Engineering
Monash University
Clayton, Vic. 3800
Australia
P iero C hiarelli
Institute of Clinical Physiology CNR
Via Moruzzi 1
56124 Ghezzano (Pi)
Italy
xiii
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