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This book contains a number of articles inspired by the NATO
Advanced Study Institute on 'Charged and Reactive Polymers l' held
in France in June 1972. This general title indicates simply the
intention of a series. The meeting dealt mainly with the
fundamental problems of the physical chemistry of polyelectrolytes
in solution. Some of the articles reproduce the lectures exactly as
they were delivered. Some others have been modified to a greater or
lesser extent, and this as a result of improvements or new
inspiration arising from comments and discussions. In previous
larger conferences on macromolecules, polyelectrolytes constituted
only a marginal problem and few were the individual communications
or short was the time al10tted to this subject. In other meetings
of a biophysical character the uses of the techniques of charged
macromolecules have been exposed with less attention given to the
theories or to the creation or interpretation of these techniques.
AU of us felt that the time had come to enumerate and to evaluate
this increasing science of polyelectrolytes which has become of
major interest. During the whole period of the Institute physical
chemists discussed their mutual problems for more than a week, and
of ten far into the night One of the advantages of such an
Institute is to enable the Directors and the mem bers of the
Scientific Committee to establish a logical order in the lectures;
this order has been respected in the present edition."
The first four volumes of the series on 'Charged and Reactive
Polymers' have been devoted to polymers in solution (Voh. I and II)
or in gel and membrane forms (Vols. III and IV). In correlation
with charges, other physical or chemical properties of macro
molecules have been considered. Understanding of charge and
hydrophobic effects is equally important for synthetic and
biopolymers or their systems. Optically Active Polymers are related
to problems of the same class, since optical activity is an
inherent property of both natural macromolecules as well as a great
variety of polymers synthesized in the Jast twenty years. Optical
activity is a physical spectral property of chiral matter caused by
asymmetrical configurations, conformations and structures which
have no plane and no center of symmetry and consequently have two
mirror image enantiomeric forms of inverse optical rotation. The
racemic mixture of chiral enantiomers is optically inactive. The
most common form of optical activity was first measured at a
constant wavelength by the angle of rotation of linearly polarized
light. More recently the measurements have been extended to the
entire range of visible and attainable ultraviolet regions where
electronic transitions are observed, giving rise to the ORD
technique (Optical Rotatory Dispersion). The Cotton effects appear
in the region of optically active absorption bands; outside of
these bands the plain curve spectrum is also dependent on all the
electronic transitions of the chromophores."
Polyelectrolytes and their Applications is the second volume in the
series 'Charged and Reactive Polymers'. The important areas of
polyelectrolyte applications, i.e., biomedicine, water
purification, petroleum recovery and drag reduction, are pre sented
along with discussions of the fundamental principles of
polyelectrolyte chem istry and physics. This book should be of
interest to scientists such as physicians, biochemists, polymer
chemists and chemical engineers involved in applications of these
materials. The first part of the book is devoted to the basic
properties of polyelectrolytes in general, namely to the factors
influencing the chain conformation of charged polymers in solution
and to their counterion selectivity. It also contains methods of
synthesis and new concepts of charge stabilized polymer colloids
and of polyelectrolyte ca talysis. The second part describes recent
information on the properties and biological effects of already
well-known natural polyelectrolytes such as heparin and DNA and
recently developed polymers such as pyran and polyionenes. The
effects of poly anions and polycations on normal and transformed
cells as well as on acetylcholine receptors follow. This part is of
particular interest to scientists involved in biological research."
The introduction to the first of these two volumes on Charged Gels
and Membranes has recalled already that both were issued from the
second Advanced Study Institute of Forges les Eaux, of which the
co-directors were Professors G. E. Boyd and K. S. Spiegler.
However, it seems necessary to add some further remarks for the
eventual readers of this one volume only or for those of all four
which now constitute the series. * One discovers that each volume
is precisely linked to the next; and the total con tains a large
number of the very fundamental steps by which macromolecular
physical chemistry finds itself simultaneously at thefronNers of
application and of biology. One often wonders how this is possible.
Research has been the best means of unders anding the microscopic
elements oflife. Biomimetic phenomena or bioanalogue compounds in
their turn have led to innumerable practical realisations. On one
hand, the notion of 'vital force' receded and is disap pearing due
to repetitive total and asymmetric synthesis* of always larger, and
more complex, biological molecules. On the other hand discoveries
of inter-relations in physical chemistry disengage the analogies
between living and non-living systems: the interrelations between
phenomena, between phenomena and structures or the appear ance of
these structures under the influence of intermolecular forces or of
gradients of more statistical forces."
This book contains a number of articles inspired by the NATO
Advanced Study Institute on 'Charged and Reactive Polymers l' held
in France in June 1972. This general title indicates simply the
intention of a series. The meeting dealt mainly with the
fundamental problems of the physical chemistry of polyelectrolytes
in solution. Some of the articles reproduce the lectures exactly as
they were delivered. Some others have been modified to a greater or
lesser extent, and this as a result of improvements or new
inspiration arising from comments and discussions. In previous
larger conferences on macromolecules, polyelectrolytes constituted
only a marginal problem and few were the individual communications
or short was the time al10tted to this subject. In other meetings
of a biophysical character the uses of the techniques of charged
macromolecules have been exposed with less attention given to the
theories or to the creation or interpretation of these techniques.
AU of us felt that the time had come to enumerate and to evaluate
this increasing science of polyelectrolytes which has become of
major interest. During the whole period of the Institute physical
chemists discussed their mutual problems for more than a week, and
of ten far into the night One of the advantages of such an
Institute is to enable the Directors and the mem bers of the
Scientific Committee to establish a logical order in the lectures;
this order has been respected in the present edition."
The first four volumes of the series on 'Charged and Reactive
Polymers' have been devoted to polymers in solution (Voh. I and II)
or in gel and membrane forms (Vols. III and IV). In correlation
with charges, other physical or chemical properties of macro
molecules have been considered. Understanding of charge and
hydrophobic effects is equally important for synthetic and
biopolymers or their systems. Optically Active Polymers are related
to problems of the same class, since optical activity is an
inherent property of both natural macromolecules as well as a great
variety of polymers synthesized in the Jast twenty years. Optical
activity is a physical spectral property of chiral matter caused by
asymmetrical configurations, conformations and structures which
have no plane and no center of symmetry and consequently have two
mirror image enantiomeric forms of inverse optical rotation. The
racemic mixture of chiral enantiomers is optically inactive. The
most common form of optical activity was first measured at a
constant wavelength by the angle of rotation of linearly polarized
light. More recently the measurements have been extended to the
entire range of visible and attainable ultraviolet regions where
electronic transitions are observed, giving rise to the ORD
technique (Optical Rotatory Dispersion). The Cotton effects appear
in the region of optically active absorption bands; outside of
these bands the plain curve spectrum is also dependent on all the
electronic transitions of the chromophores."
The series on 'Charged and Reactive Polymers' was set forth in two
volumes concern ing the fundamentals and applications of
polyelectrolytes. A follow-up on 'Charged Gels and Membranes' would
therefore seem appropriate, necessitating, however, some
explanation for non-specialists. Theories of the most dilute gels
originate in that of concentrated polyelectrolytes: the methods and
problems are similar in structural, spectroscopic or thermodynamic
properties. The borderline can be situated in dialysis conducted
with a 'bag' imper meable to polyelectrolytes but not to small
ions, solutes and water. One may recall Donnan's use of such a
system to experiment and discover his famous law of unequal
distribution of ions of different charge inside and out. Remark
ably so, it is the difference in scale which characterizes the
difference between poly electrolyte solutions and gels and
membranes: the colloidal solution of macro molecules is
heterogeneous only on the microscopic level, whereas the
gel-solution system is a macroscopically heterogeneous one. A gel
is formed when weak or strong cohesive forces counterbalance the
dispersing ones (usually by crosslinking) without inhibiting the
penetration of solvent and of small solutes into the polymeric
network. The solvophile macromolecules cannot invade the total
volume of liquid. As a result of phase-segregation excess solution
and gel coexist and interact. The macroscopic swelling depends on
gel cross-linking as well as on ionic concentration and type and
ion-selectivities are observed."
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