Supramolecular Structure in Confined Geometries

283 Pages·1999·25.236 MB·English

by  Srinivas Manne and Gregory G. Warr (Eds.)

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In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
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In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
736
ACS SYMPOSIUM SERIES
Supramolecular Structure
in Confined Geometries
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73 Srinivas Manne, EDITOR
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American Chemical Society, Washington, DC
In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
QD 380 .S879 1999 C.l
Supramolecular structure in
confined geometries
Library of Congress Cataloging-in-Publication Data
Supramolecular structure in confined geometries / Srinivas Manne, editor. Gregory G. Warr,
editor.
p. cm.—(ACS symposium series ; 736)
Includes bibliographical references and index.
ISBN 0-8412-3615-1
1. Macromolecules—Congresses. 2. Chemistry, Physical and Theoretical.
01 I. Manne, Srinivas. II. Warr, Gregory G. III. Series
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6.f QD380.S879 1999
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7 547'.7—dc21 99-23650
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k- The paper used in this publication meets the minimum requirements of American National
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In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
Advisory Board
ACS Symposium Series
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ChemEdit Company AT&T Bell Laboratories
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In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
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In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
Foreword
1HE ACS SYMPOSIUM SERIES was first published in 1974 to provide
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In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
Preface
The behavior of supramolecular structures and assemblies under spatially con­
fined conditions is a central problem in the physics and chemistry of "soft matter."
As the degree of confinement approaches a relevant supramolecular length scale,
significant deviations from bulk behavior are generally observed. These deviations
1 often play a central role in both technological and biological processes, in applica­
0
pr0 tions as diverse as lubrication, liquid spreading, filtration, mesoscopic materials
36. synthesis, and biological pattern formation.
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9-0 The objective of this symposium, and this volume, is to bring together a group
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9 of researchers from a broad range of academic disciplines and industry to explore
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k- the common features of a confining field on supramolecular structure and behav­
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21/ ior. Recent advances in experimental techniques (such as neutron reflectometry,
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0.1 atomic force microscopy, and surface force measurements) have opened this
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Confinement considers the confinement of polymer melts and solutions; these
include boundary layer lubrication between solid surfaces (Chapter 7), glass
transitions in free-standing films (Chapter 8), interfacial confinement effects in
adsorbed block copolymers and homopolymers (Chapters 9, 10, and 12), and
confinement by lyotropic liquid crystalline phases (Chapter 11). Finally, Con­
finement of Biomolecules considers confinement effects in biomolecules; these
can be due to bulk solvent flow (Chapter 13), tethering and confinement between
solid surfaces (Chapters 14 and 15), filtration through porous media (Chapter
16), or organic synthesis inside porous media (Chapter 17).
Although the choice of subjects included in this volume is not intended to be
comprehensive, it is intended to be representative of the multidisciplinary breadth
of research areas that have supramolecular confinement as a common feature.
xi
In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
It is our hope that this symposium and volume will serve as a point of departure
for further systematic study of this fertile common ground between chemistry,
physics, chemical engineering, and materials science.
We acknowledge financial assistance from Rhodia, Inc. (Cranbury, NJ), and
from the American Chemical Society Petroleum Research Fund. Their generous
support enabled us to bring together a large group of researchers, including many
internationally recognized leaders in fields where spatial confinement is important,
and thus contributed significantly to the success of the symposium. We also
thank John Texter for his advice and assistance with both the symposium and
its proceedings.
SRINIVAS MANNE
Department of Physics
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00 University of Arizona
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6. 1118 East 4th Street
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07 Tucson, AZ 85721
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1 Sydney, New South Wales 2006
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xii
In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.
Chapter 1
Supramolecular Structure of Surfactants Confined
to Interfaces
Srinivas Manne1 and Gregory G. Warr2
1Department of Physics, University of Arizona, 1118 East 4th Street,
Tucson, AZ 85721
2School of Chemistry, University of Sydney,
Sydney, New South Wales 2006, Australia
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07 The mounting evidence for the existence of surfactant aggregates at solid/solution
99- interfaces prompts a re-examination of common experimental techniques for studying
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1 surfactant adsorption. The simple models of a surfactant monolayer or bilayer, while
k-
1/b reasonable in the face of older experimental data, are now seen to be inadequate to
02 describe the rich range of order seen by atomic force microscopy and other techniques.
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0. In this manuscript we review the results of atomic force microscopy which demonstrate
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ember 7, blication Introduction
Sept Pu Adsorption of a simple solute at an interface is nothing more than an accumulation over

and above what would normally be present based on bulk solution concentration. The
adsorption of such solutes can easily be modeled by a Langmuir-type mechanism
involving an interaction between a solute and a (not necessarily well-defined) surface
site. This leads to the well-known Langmuir isotherm, which describes adsorption
behavior up to surface coverage of a filled monolayer.
The behavior of surfactants and polymers is much more rich. Interactions between
these compounds give rise to self-assembly in bulk solution and, for polymers, in the
melt. The supramolecular structures thus formed are labile, and may be easily
influenced by external fields. This is perhaps best known from the range of Theological
behaviors of polymer melts and solutions, of surfactant systems,2 and in biopolymer
solutions (see Chapter 13).
2 © 1999 American Chemical Society
In Supramolecular Structure in Confined Geometries; Manne, S., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1999.