Water Structure at the Water-Polymer Interface: Proceedings of a Symposium held on March 30 and April 1, 1971, at the 161st National Meeting of the American Chemical Society

190 Pages·1972·6.54 MB·English

by  H. H. G. Jellinek (auth.)

WATER STRUCTURE AT THE
WATER-POLYMER INTERFACE
WATER STRUCTURE
at the Water-Polymer Interface
Proceedings of a Symposium held on March 30 and April 1, 1971,
at the 161 st National Meeting of the American Chemical Society
Edited by
H. H. G. Jellinek
Department af Chemistry
Clarkson College of Technology
Potsdam, New York
9:.>
PLENUM PRESS • NEW YORK-LONDON • 1972
Library of Congress Catalog Card Number 70-189943
ISBN-13: 978-1-4615-8683-8 e-ISBN-13: 978-1-4615-8681-4
001: 10.1007/978-1-4615-8681-4
© 1972 Plenum Press, New York
Softcover reprint of the hardcover 1s t edition 1972
A Division of Plenum Publishing Corporation
227 West 17th Street, New York, N.Y. 10011
United Kingdom edition published by Plenum Press, London
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All rights reserved
No part of this publication may be reproduced in any form
without written permission from the publisher
PREFACE
This symposium was held at the l6lst ACS National Meeting,
Los Angeles, March/April 1971. It represents a contribution to
the discussion of problems connected with the state of water
near macromolecules. Some papers are only peripheral to the
problem of water structure but may become quite pertinent in
specific cases.
Questions concerned with water structure, rate of hydration,
and similar problems are of importance for biological processes
and are still not yet well understood. It is hoped that the
papers presented here will be of some help in the clarification
of problems in this area.
H. H. G. Jellinek
Department of Chemistry
Clarkson College of Technology
Potsdam, New York
September, 1971
v
CONTRIBUTORS
S. Ablett, Unilever Research Laboratory, Colworth House,
Sharnbrook, Bedford, England
M. Anbar, Stanford Research Institute, Menlo Park, California
F. W. Cope, Biochemistry Division, Aerospace Medical Research
Laboratory, U. S. Naval Air Development Center, Warminster,
Pennsylvania
B. Crist, Camille Dreyfus Laboratory, Research Triangle Park,
North Carolina
F. Franks, Unilever Research Laboratory, Colworth House,
Sharnbrook, Bedford, England
H. R, Gloria, NASA-Ames Research Center, Moffett Field,
California
G. W. Gross, New Mexico Institute of Mining and Technology,
Socorro, New Mexico
H. R. Hansen, The Procter & Gamble Company, Miami Valley
Laboratories, Cincinnati, Ohio
R. S. Kaiser, Research Laboratories, Eastman Kodak Company,
Rochester, New York
N. Laiken, Department of Chemistry, The University of Oregon,
Eugene, Oregon
C. E. Lamaze, Camille Dreyfus Laboratory, Research Triangle
Park, North Carolina
G. N. Ling, Department of Molecular Biology, Pennsylvania
Hospital, Philadelphia, Pennsylvania
viii CONTRIBUTORS
A. P. MacKenzie, Cryobiology Research Institute, Madison,
Wisconsin
G. The Rockefeller University, New York, New York
N~methy,
H. G. Olf, Camille Dreyfus Laboratory, Research Triangle Park,
North Carolina
A. Peterlin, Camille Dreyfus Laboratory, Research Triangle Park,
North Carolina
D. H. Rasmussen, Cryobiology Research Institute, Madison,
Wisconsin
R. L. Reeves, Research Laboratories, Eastman Kodak Company,
Rochester, New York
R. F. Reinisch, NASA-Ames Research Center, Moffett Field,
California
G. A. St. John, Stanford Research Institute, Menlo Park,
California
M. J. Tait, Unilever Research Laboratory, Colworth House,
Sharnbrook, Bedford, England
H. Yasuda, Camille Dreyfus Laboratory, Research Triangle Park,
North Carolina
W. Yellin, The Procter & Gamble Company, Miami Valley
Laboratories, Cincinnati, Ohio
CONTENTS
Introduction • • • • 1
H. H. G. Je11inek
Water Structure at the Water-Polymer Interface 4
G. N. Ling
Structured Water and Comp1exed Na+ and K+ in
Biological Systems •••••• 14
• • • • • 0 • •
F. W. Cope
NMR and Infrared Spectroscopic Studies of Stratum
Corneum Hydra tion • • • • • • • • • • • 19
J. R. Hansen and W. Yellin
An NMR Investigation of Water in Carbohydrate Systems • • •• 29
M. J. Tait, S. Ab1ett, and F. Franks
Movement of Water in Homogeneous Water-Swollen Polymers 39
H. Yasuda, H. G. 01f, B. Crist, C. E. Lamaze,
and A. Peterlin
Kinetic and Spectral Evidence for Selective Solvation
of a Hydrophobic Quinoneimine Dye in Mixed
Aqueous Solvents • • • • • • • • • • 56
R. L. Reeves and R. S. Kaiser
A Model for the Binding of Chain-like Molecules to
Compact Macromolecular Surfaces • • • 70
N. Laiken and G. N~methy
Effect of State of Condensation on the Ionization
Potential of Associated Liquids • • • • 85
M. Anbar, G. A. St. John, H. R. Gloria, and
R. F. Reinisch
ix
x CONTENTS
Solute Interference Effects in Freezing Potentials
of Dilute Electrolytes • • • • • • 106
G. W. Gross
Effect of Solutes on Ice-Solution Interfacial Free
Energy; Calculation from Measured
Homogeneous Nucleation Temperatures 126
D. H. Rasmussen and A. P. MacKenzie
Interactions in the Water-Polyvinylpyrrolidone System
at Low Temperatures • • • • • • • • • • • • • • •• 146
A. P. MacKenzie and D. H. Rasmussen
Author Index 173
Subject Index 178
Introduction
H. H. G. Jellinek
Questions of water structure, water of hydration and similar
problems are of biological significance e. g. for the structure of
water in living cells, for the role of hydration water around protein
molecules in life processes etc. and work on such problems has been
done for many years.
The first paper (G. N. Ling) is concerned predominantly with
protein hydration. It touches on the controversial problem of
"polywater" (anomalous water) as an example of multilayer oriented
water. It also refers to the work of T. Hori (1956) who apparently
experimented with anomalous water before Derjaguin and his co
workersl ) rediscovered it. Recently, very interesting and careful
work by G. Swinzow has been reported2) dealing with anomalous
water. Amongst other things this author has shown that anomalous
water cannot be explained away on account of "impurities". It is
refreshing to read a report about such careful work after all the
hasty experimental work and theoretical speculations which have
been published in abundance during the recent past. Ling also points
out that hydration of proteins (or macromolecules in general) takes
place along the chains at the polymer side groups mentioning work
by Dole and Faller of water adsorption on polyvinylpyrrolidone.
Work on freezing of aqueous polyvinylpyrrolidone in aqueous solutions3)
is relevant in this connection. Data obtained led to the conclusion
that water bound by polyvinylpyrrolidone is "ice-like" having a
structure between those of liquid water and ice. The importance
of NMR techniques for the problem of water structure is well
illustrated in Ling's paper and also plays a very prominent part in
2 H. H. G. JELLINEK
most of the other papers of this Symposium. Thus, NMR has a
dominant place in the second paper (F. W. Cope) on complexed Na+
and K+ ions in biological systems. It is shown that water in cells
has definitely more structure than liquid water; however the type of
structure cannot be determined by NMR alone and other evidence has
to be utilized for solving this problem such as for instance data from
adsorption phenomena (polarized multilayers). The next paper
(Hansen and Yellin) treats a very specific problem i. e. hydration of
stratum corneum. Here, NMR in conjunction with infrared measure
ments is used. Again there is clear evidence that water is more
structured than liquid water in the vicinity of protein molecules.
Hydration of carbohydrate molecules is the topic of the paper by
Tait et al. Here NMR is the technique of investigation. Apparently,
there are two types of bound water near carbohydrates, one of which
is solid-like forming a monolayer on starch (monohydrate). Long
range interaction between water and a polysaccharide depends on the
type of macromolecule and its concentration in solution.
Peterlin et al. have investigated movement of water in swollen
polymers. This work is also of biological significance (e. g. for
plants). Here diffusion has been studied as a function of hydration.
Diffusion depends on the structure of water and whether it is free,
firmly or lightly bound by the macromolecules. NMR was employed
in this work and in addition differential calorimetric scanning is
used. It is generally found that water in swollen polymers is
different from free water; the actual state of this water is difficult
to characterize.
Reeves and Kaiser use water soluble dyes as indicators for
changes in water structure. These molecules of intermediate size
between small and macro-molecules are assumed to have simi
larities with polymer molecules. This investigation is based on
reaction kinetics and spectral measurements. Solvation of a dye
molecule will influence its hydrolysis by OIt ions.
The paper by Laiken and Nemethy has indirect relevance to
the main theme of the Symposium but such work may become of
importance in specific cases where the presence of water plays a
role. The latter influences interaction energies and temperature
coefficients for binding. The same is true for the paper by Anbar
et al. dealing with hydrated electrons. It is quite feasible that
for detailed investigations of hydration of polymers, considerations
dealt with in this paper will be of importance.