Prog. Polym. Sci.

28 (2003) 173–208
www.elsevier.com/locate/ppolysci

Water-soluble polymer –metal ion interactions

Bernabé L. Rivasa,*, Eduardo D. Pereiraa, Ignacio Moreno-Villosladab
a
Faculty of Chemistry, University of Concepcion, Casilla 160-C, Concepcion, Chile
b
Faculty of Science, Chemistry Institute, Universidad Austral de Chile, Casilla 567, Valdivia, Chile

Received 4 December 2001; revised 30 April 2002; accepted 1 May 2002

Abstract
The interactions between metal ions and water-soluble polymers (WSP) have gained great interest due to their intrinsic
properties as well as their potential applications, such as superconducting materials, ultra-high strength materials, liquid
crystals, and biocompatible polymers. This review attempts to provide a general coverage of various scientific aspects of the
WSP– metal ion interactions in aqueous solution and their applications. It includes fundamental aspects on synthesis of water-
soluble polymers, as well as different activities and properties. A particular emphasis is given to the study the WSP– metal ion
interactions, under different experimental procedures, through the liquid-phase polymer based retention (LPR) technique,
which combines the use of WSP and membrane ultrafiltration. Theoretical work on this WSP– metal ion interaction has been
elaborated to explain the counterion binding to polyelectrolytes, and the polymer– metal ion complex formation. q 2002
Elsevier Science Ltd. All rights reserved.
Keywords: Water-soluble polymers; Metal ions; Ultrafiltration membranes

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
2. Water-soluble polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
3. Ultrafiltration-LPR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
3.1. General principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
3.2. LPR methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3.2.1. The washing method at constant ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3.2.2. The washing method at variable ionic strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
3.2.3. The enrichment method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.3. Ultrafiltration membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
4. The nature of the polymer– metal ion interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
5. Evaluation of the equilibrium distributions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
5.1. Conductometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
5.2. Ultrafiltration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.2.1. The washing method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.2.2. The enrichment method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
5.3. Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
6. Ultrafiltration results as function of different variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
6.1. Nature of the polymer and the metal ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194

Abbreviations: LMWCM, low molecular weight complexing molecules; LPR, liquid-phase polymer based retention; MBC, minimum
bactericide concentration; MIC, minimum inhibitory concentration; MMCO, molar mass cut-off; MRC, maximum retention capacity; WSP,
water soluble polymers; Da, Daltons.
* Corresponding author. Fax: þ 56-41-245974.
E-mail address: brivas@udec.cl (B.L. Rivas).

0079-6700/03/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 7 9 - 6 7 0 0 ( 0 2 ) 0 0 0 2 8 - X
174 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

6.2. Polymer concentration . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197

6.3. Ionic strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
6.4. Effect of the pH . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
7. Biological applications . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
8. Analytical applications . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

1. Introduction fabric, which will display greatly improved contact

Polymers containing metals have emerged as a new
generation of material with tremendous potential in fields
like superconducting materials, ultra-high strength
materials, liquid crystals, catalysts, and biocompatible
polymers [1 –6]. The structures of some polymer – metal
ion complexes have been reported in the literature [1,7 –16].
The continuous increase of world needs for most of the
known metals, the decrease in grade of the available ores,
and strict environmental regulations, make it interesting to
find effective and efficient methods for processing waste
solutions containing metal ions, even at very low concen-
trations. Liquid– liquid extraction, sorption, precipitation,
and other methods, based on two-phase distributions, are
used in most cases for the separation of inorganic species
contained in dissolved matrices, industrial fluids or natural
waters. Although many of these methods have been
developed and successfully used, their application can
cause problems. Some problems can be connected with
heterogeneous reactions and interphase transfer. Other
problems can arise if aqueous solutions are preferred for
the subsequent procedures rather than organic solvents or
solid concentrates. In such cases, additional procedures are
needed, e.g. back extraction, desorption, dissolution of solid
concentrates, etc., which complicate the analysis and can
result in contamination of the sample from the reagent
added. Insoluble polymeric supports are widely investigated
and applied for metal recovery from dilute solutions
[17 – 32]. There are different natural and synthetic products
that show ion-exchange properties. The organic resins are
by far the most important ion exchangers. The main
advantages are high chemical and mechanical stability,
high ion-exchange capacity and ion-exchange rate. Another
advantage is the possibility of selecting the fixed ligand
groups and the degree of cross-linking. For example, a
styrene-based matrix is prepared by suspension polymeriz-
ation of styrene and varying ratios of divinylbenzene to form
an ion exchange bead. These beads are used extensively for
purification and demineralization of water, but also find
application in chemical synthesis, biomedical, pharmaceu-
tical, food processing, hydrometallurgy, and agriculture
industries [25]. Fibrous ion-exchange materials should have
several advantages over the conventional ion-exchange
beads, which include simplification of the overall prep-
aration, and the ability to be fabricated in the form of felts or
efficiency with the media. This enhances both the rates of
reaction and regeneration. Both physical and mechanical
requirements of strength and dimensional stability should be
achieved by reinforcing the resin with glass fiber substrates.
Heterogeneous two-phase system can be avoided by
application of separation methods based on membrane
process, which are among the most promising techniques for
enrichment of various species from solutions [33 – 36].
Thus, a number of soluble and hydrophilic polymers have
been prepared through addition polymerization and by
functionalizing various polymers, and found to be suitable
for the separation and enrichment of metal ions in
conjunction with membrane filtration. Membrane filtration
easily allows the separation of metal ions bound to soluble
polymers from non-bound metals. This method is known as
the liquid-phase polymer-based retention (LPR) technique
[35,36]. Applications of water-soluble polymers to the
homogeneous enrichment or selective separation of various
metal ions from dilute solutions have been reported.
Ultrafiltration is found as the most suitable technique for
LPR studies, and a vast amount of data is being published in
different journals [35– 80].
Under all these considerations, the theoretical and
experimental study of the interactions of water-soluble
polymers with metal ions is emerging as an interesting topic
nowadays. The accumulated knowledge helps in the
synthesis of new and versatile polymer – metal ion com-
pounds, and achieves efficient and selective separations of
metal ions from dilute solutions by the understanding of the
interaction processes and the features of the ultrafiltration
technique. Thus, this review aims at highlighting the
significant developments in the fields of water-soluble
polymer– metal ion interactions with special reference to the
liquid-phase polymer-based retention (LPR) technique.
2. Water-soluble polymers
Water-soluble polymers are commercially available or
can be synthesized by different routes. Among the most
important requirements for technological applications of
these polymers, there are the high solubility in water, and
easy and cheap route of synthesis, an adequate molecular
weight and molecular weight distribution, chemical stab-
ility, high affinity for one or more metal ions, and selectivity
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 175

Nomenclature
cp polymer concentration (mole of monomeric units l21)
cfZ instantaneous concentration of metal ions in the filtrate (mol l21)
kcfZ l concentration of metal ions in the filtration fractions (DF ) (mol l21)
cfree
Z concentration of metal ions not bound to the polymer (mol l21)
Cz concentration of metal ions not bound to the polymer in Manning’s theory (mol l21)
cbound
Z concentration of metal ions bound to the polymer (mol l21)
uZ amount of metal ions bound to the polymer per monomeric unit
umax
Z maximum amount of metal ions that may condense on the polymer surface per monomeric unit
cres
Z concentration of metal ions in the reservoir solution (mol l21)
cinit
Z initial concentration of metal ions in the ultrafiltration cell (mol l21)
Rz retention
F filtration factor
kZm coefficient of membrane retardation
KZL apparent thermodynamic constant derived from Langmuir isotherm (mol21 l)
V filtrate total volume of the filtrate
V cell volume of the cell solution
Vp condensation volume (cm3 mol21)
R2 square linear regression factor
hsp specific viscosity
j linear charge-density parameter

for the metal ion of interest. The most usual synthetic
procedures are addition polymerization, especially radical
polymerization, and functionalizing of polymer backbones
through polymer-analogous reactions. The macromolecules
can be homo- or copolymers, and may contain one or more
coordinating and/or charged groups. These groups are
placed at the backbone, or at the side chain, directly or
through a spacer group. Table 1 shows the most common
structures for these polymers.
Polyelectrolytes may be distinguished from chelating
polymers (polychelatogens). The former have charged
groups, or easily ionizable groups in aqueous solution,
while the latter bear functional groups with the ability to
form coordination bonds. The most investigated ligands
present in the polychelatogens are amines, carboxylic acids,
amides, alcohols, aminoacids, pyridines, thioureas, iminos,
etc. Among them, polymers containing amino groups have
been extensively studied by ultrafiltration, particularly the
functional polyethylenimine [45]. This heterochain polymer
contains three different types of amino groups: secondary
and tertiary groups in the main chain and secondary and
primary amino groups in the side-chain. The ratios are
between 1:1:1 and 1:2:1 for the primary, secondary, and
tertiary species, varying depending on the degree of
branching. The most studied polyelectrolytes include those
with carboxylic acid, phosphoric acid, sulfonic acid, or
ammonium groups in their structure.
One versatile route for the synthesis of different
polymers is copolymerization. With a good selection of
both comonomers it is possible to improve properties such
as water-solubility, metal ion binding capability, and
selectivity. Copolymer composition is normally determined
by 1H NMR or FTIR spectroscopy by comparing the
characteristic absorption signals for each monomer and by
elemental microanalysis.
A water-soluble polymer solution may be considered a
two-phase system. The polymeric functional groups are kept
separated by a distance contained in a range so that they
present a local high and nearly constant concentration. The
water-soluble polymers undergo interactions with solvent
and other high- and low-molecular weight species present in
the aqueous solutions. Due to these interactions, macromol-
ecules in solution exhibit, beyond their chemical structure,
different properties such as conformation of the polymer
chains, excluded volume, surface activity, or formation of
higher-order structures as aggregates, gels, etc.
3. Ultrafiltration-LPR
3.1. General principles
Membrane filtration processes can be successfully used
for the separation of inorganic species and for their
enrichment from dilute solutions with the aid of a water-
soluble polymer. This technique is called the liquid-phase
polymer based retention technique (LPR). Ultrafiltration is
fast emerging as a new and versatile technique in separation
technology, concentration, purification, and separation
processes. Ultrafiltration of water-soluble, high molecular-
weight polymers in the presence of low molecular weight
electrolytes or molecules allows for the detecting of
176 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

Table 1
Water-soluble polymers and the corresponding metal ions whose interactions have been studied by the LPR technique

Water soluble polymers Metal ions pH References

Cd2þ, Pb2þ, Sr2þ, 3, 5, 7 [43,45,55]

Ni2þ, Cu2þ, Zn2þ,
Co2þ, Fe3þ, Cr3þ

Poly(N-hydroxyethyl)ethyleneimine (PHEI)

Cd2þ, Pb2þ, Sr2þ, 3, 5, 7 [44]

Ni2þ, Cu2þ, Zn2þ,
Co2þ, Fe3þ, Cr3þ

Poly(N-acetyl)ethyleneimine (PAEI)

Cd2þ, Pb2þ, Sr2þ, 3, 5, 7 [45,47]

Ni2þ, Cu2þ, Zn2þ,
Co2þ, Fe3þ, Cr3þ

Poly[(N-hydroxyethyl)ethyleneimine-co-N-acetyl)
ethyleneimine] (PHEI-co-PAEI)

Cd2þ, Pb2þ, Sr2þ, 3, 5, 7 [45,47,55]

Ni2þ, Cu2þ, Zn2þ,
Co2þ, Fe3þ, Cr3þ

Poly(ethyleneimine) (PEI)

Cu2þ, Co2þ, Ni2þ 1, 3, 5, 7 [61,66,79]

Poly(allylamine) (PALA)

Cd2þ, Pb2þ, Ni2þ, 5, 7 [57]

Cu2þ, Zn2þ, Co2þ,
Hg2þ, Fe3þ, Cr3þ

Poly(acrylamide) (PAm)

Cd2þ, Pb2þ, Ni2þ, 3, 5, 7 [53]

Cu2þ, Zn2þ, Co2þ,
Hg2þ, Cr3þ

Poly(acrylamide-co-N-maleylglycine) (PAm-co-MGly)

Cd2þ, Pb2þ, Ni2þ, 5 [52,56,57,74]

Cu2þ, Zn2þ, Co2þ,
Cr3þ

Poly(acrylic acid) (PAA)

 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 177

Table 1 (continued)
Water soluble polymers Metal ions pH References

Cd2þ, Pb2þ, Ni2þ, 5, 7 [11,49,57]

Cu2þ, Hg2þ, Co2þ,
Fe3þ, Cr3þ

Poly(acrylamide-co-acrylic acid) (PAm-co-PAA)

Cd2þ, Pb2þ, Ni2þ, 1, 3, 5, 7 [54,57]
Cu2þ, Zn2þ, Co2þ,
Fe3þ, Cr3þ

Poly(N,N-dimethylacrylamide-co-acrylic acid)
(PDAm-co-PAA)
Agþ, Cd2þ, Hg2þ, 1, 3, 5, 7 [63,68]
Ni2þ, Cu2þ, Zn2þ,
Co2þ, Cr3þ

Poly(methacrylic acid) (PMA)

Agþ, Cd2þ, Pb2þ, 3, 5, 7 [69]
Ni2þ, Cu2þ, Zn2þ,
Co2þ, Cr3þ

Poly(a-acetylamino acrylic acid) (PAAA)

Agþ, Cd2þ, Pb2þ, 3, 5, 7 [62]
Ni2þ, Cu2þ, Zn2þ,
Co2þ, Cr3þ

Poly(N-methyl-N0 -methacryloylpiperazine) (PAP)

Cd2þ, Hg2þ, Ni2þ, 3, 5, 7 [181]
Cu2þ, Zn2þ, Co2þ, Cr3þ

Poly[(3-(methacryloylamino)propyl)trimethylammonium
chloride] (PMPTA)
Cd2þ, Hg2þ, Ni2þ, 3, 5, 7 [181]
Cu2þ, Zn2þ, Co2þ, Cr3þ

(continued on next page)

178 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

Table 1 (continued)
Water soluble polymers Metal ions pH References

Poly(diallyl dimethylammonium chloride) (PDDA)

Cd2þ, Pb2þ, Ni2þ, 1, 3, 5, 7 [56,58,59,65,66,77,79]
Cu2þ, Zn2þ, Co2þ,
Cr3þ, Fe3þ

Poly(sodium 4-styrenesulfonate) (PSS)

Agþ, Cd2þ, Hg2þ, 1, 3, 5, 7 [63,68]
Ni2þ, Cu2þ, Zn2þ,
Co2þ, Cr3þ

Poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAPS)

Agþ, Cd2þ, Hg2þ, 1, 3, 5, 7 [63,68]
Ni2þ, Cu2þ, Zn2þ,
Co2þ, Cr3þ

Poly(methacrylic acid-co-2-acrylamido-2-methyl-1-
propanesulfonic acid) (PMA-co-PAPS)
Agþ, Cd2þ, Pb2þ, 3, 5, 7 [76]
Ni2þ, Cu2þ, Zn2þ,
Co2þ, Cr3þ

Poly(N-methyl-N0 -methacryloylpiperazine-co-a-amino
acrylic acid) (PAP-co-PAAA)
Cd2þ, Pb2þ, Ni2þ, 1, 3, 5, 7 [14]
Cu2þ, Zn2þ, Co2þ,
Cr3þ, Fe3þ

Poly(acrylamide-co-N-vinylpyrrolidone) (PAm-co-PVPyrr)
Cd2þ, Pb2þ, Ni2þ, 1, 3, 5, 7 [60]
Cu2þ, Zn2þ, Co2þ,
Cr3þ, Fe3þ

Poly(N,N-dimethylacrylamide-co-N-vinylpyrrolidone)
(PDAm-co-PVPyrr)
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 179

Table 1 (continued)
Water soluble polymers Metal ions pH References

Cd2þ, Pb2þ, Ni2þ, 1, 3, 5, 7 [181]

Cu2þ, Zn2þ, Co2þ,
Cr3þ, Fe3þ

Poly(1-vinylpyrrolidone-co-2-dimethylaminoethylmethacrylate
quaternized) (PVPyrr-co-PDAEM)
Agþ, Hg2þ 3, 5, 7 [67]

Poly(4-vinylpyridine quaternized) (PVPyQ)

Cd2þ, Hg2þ, Ni2þ, 1, 3, 5, 7 [181]
Cu2þ, Zn2þ, Co2þ,
Cr3þ

Poly[2-acrylamido-2-methyl-1-propanesulfonic acid-co-
(3-(methacryloylamino)propyl)trimethylammonium
chloride] (PAPS-co-PMPTA)
Agþ, Cd2þ, Hg2þ, 1, 3, 5, 7 [181]
Ni2þ, Cu2þ, Zn2þ,
Co2þ, Cr3þ

Poly(vinylphosponic acid) (PVPhA)

Ca2þ, Zn2þ 5 [70]

Poly(N-methacryloyl-4-aminosalicylic acid) (PMAAMSA)

Pb2þ, Cd2þ, Fe2þ, 5 [55]
Ni2þ, Cu2þ, Zn2þ,
Co2þ, Cr3þ

Poly[acrylamide-co-1-(2-hydroxyethyl)aziridine] (PAM-co-PHEA)
180 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
Fig. 1. Ultrafiltration principle.
interactions between the macromolecules and the low
molecular weight small species, such as metal ions. The
polymers, prior to being used in the LPR technique, are
fractionated by the same method using different membranes
of known molecular weight exclusion limit. Thus purified,
they are then lyophilized and characterized. For LPR
experiments, the highest molecular weight fractions are
normally used in combination with a low molecular weight
exclusion limit membranes to ensure no macromolecule
exits the ultrafiltration cell. Metal ions with high interaction
rates with the polymer are retained by the polymer, which is
not able to pass through the ultrafiltration membrane, while
other ions are eluted through the membrane (Fig. 1).
The main features of an LPR system are a filtration cell
with a magnetic stirrer containing a membrane filter with a
known exclusion rating, a reservoir and a pressure source,
e.g. a nitrogen bottle (Fig. 2). In ideal cases, this system may
be considered a steady-state mixed flow reactor. Conven-
(1) filtration cell with polymeric and / or metal ion solution;
(2) membrane filtrate; (3) magnetic stirrer; (4) pressure trap;
(5) selector; (6) reservoir with water.
Fig. 2. Instrumental arrangement. Reprinted with permission from J
Appl Polym Sci 1998;69:817. q 1998 John Wiley & Sons, Inc [55].
tional stirred filtration cells or a specially designed
tangential-flow cell equipped with a pump can be used.
Essential parameters are the molar mass exclusion rate in a
wide pH range (1– 12), an appropriate permeate flow rate
(0.5– 12 ml min21), retentate volume (2 –50 ml) and gas
pressure, where 300 kPa is a suitable pressure in most cases.
The most usual molar mass cut-offs (MMCO) range
between 1000 and 300 000 Daltons (Da). A nominal
exclusion rate of 10 000 Da proved to be convenient for
polymers having a molecular mass between 30 and
50 kg mol21.
3.2. LPR methods
3.2.1. The washing method at constant ionic strength
Different modes of separations by LPR can be used for
inorganic ions [35,48]. The washing method is a batch-like
method where a liquid sample containing the polymer and
the metal ions to be separated is placed in the ultrafiltration
cell at a given pH and ionic strength. This is then washed
with water at the same pH and ionic strength. Conditions
may be found at which the ions of interest are retained and
other species are removed. The washing method can also be
applied to purify a macromolecular compound by eliminat-
ing the microsolutes. In order to quantify the separation
process, retention of the metal species is plotted versus the
filtration factor. The binding and elution processes may be
formulated as a chemical reaction, where reversible reaction
in combination with an irreversible transfer of metal ions
across the membrane is responsible for metal retention
(Scheme 1). Retention (RZ) is defined for any species as the
fraction per unit of the species under study remaining in the
cell during filtration. The filtration factor (F ) is defined as
the volume ratio of the filtrate (V f) versus volume in the cell
(V c). The metal ion (M ) remaining in the cell during
filtration consists of the sum of the metal ion bound to the
polymer chain and the metal ion free in the solution. These
values are a function of F, i.e. the extent of the filtration run.
Then, when the volume inside the ultrafiltration cell is kept
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 181

membrane
H2O/NaNO3
pressure
H2O/NaNO3
Polymer

M Polymer/M
K 1f

outside cell inside cell

Scheme 1.

constant during filtration, retention may be formulated as Fig. 3 shows several retention profiles obtained for different
follows: metal ions and different polymers at different conditions.
Note that these retention profiles tend to zero at different
cfree
Z ðFÞ þ cZ
bound
ðFÞ
RZ ðFÞ ¼ init
ð1Þ rates. The rate of decay gives an idea of the strength of the
cZ interaction of the metal ions with the polymers, since the
where cfree
Z is the concentration of M free in the solution, stronger the interaction is, the lower the rate of decay
cbound
Z is the concentration of M bound to the polymer, and appears.
cinit
Z is the initial metal concentration. Z is the valence of the
metal ion considered. Retention can be plotted versus the 3.2.2. The washing method at variable ionic strength
filtration factor, and a retention profile is obtained. RZ is
In the context of the washing method, elution may be
calculated experimentally by calculating the increment of
performed under the same pH value of the initial solution
the retention from the metal ion concentration for the nth
inside the ultrafiltration cell, but avoiding the addition of a
volume fraction analyzed, since
D E simple electrolyte to the eluent, so that, its ionic strength is
ðDRZ Þn ¼ 2 cfZ DVn =cinit
Z ð2Þ very low. In the course of the ultrafiltration run, the ionic
strength of the cell solution diminishes as small ions are
where kcfZ l is the metal ion concentration in the filtration eluted out of the ultrafiltration cell. This affects the retention
fraction corresponding to a DVn. profiles as can be seen in Fig. 4. The profiles are lines that
Then, dividing and multiplying by V c the following tend, in general, to a constant value different from zero. The
expression is obtained: relative strength of the interactions is in relation with the
D E value of the asymptote.
ðDRZ Þn ¼ 2 cfZ DFn =cinit
Z ð3Þ
100
1 90
0.9 80
0.8 70
0.7 60
R (%)

0.6 50
0.5 40
R

0.4 30
0.3 20
0.2 10
0.1 0
0 0 2 4 6 8 10
0 2 4 6 8 10
F
F
Fig. 4. Retention profiles in experiments of ultrafiltration under the
Fig. 3. Retention profiles in experiments of ultrafiltration under the washing method at variable ionic strength. ( £ ) PSS/Cd2þ [58]; (B)
washing method at constant ionic strength. (V) PSS/Cd2þ; (B) PMAAMSA/Ca2þ [70]; (V) PMAAMSA/Zn2þ [70]; (O) PAM-co-
PALA/Ni2þ. Reprinted from J Membrane Sci (in press). q 2002 PHEA/Cu2þ. Reprinted with permission from J Appl Polym Sci
with permission from Elsevier Science [79]. 1998;69:817. q 1998 John Wiley & Sons, Inc [55].
182 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
metal ion concentration (M)
cres
a b
∆F
cZfree
F
Fig. 5. Shape of the curves in enrichment ultrafiltration experiments. Reprinted from J Membrane Sci 2002;208:69. q 2002 with permission
from Elsevier Science [78].
3.2.3. The enrichment method
To achieve enrichment of metal ions, a dilute solution of
metal ions is passed from the reservoir through the filtration
cell containing a solution of the water-soluble polymer [35,
48], keeping constant the volume inside the cell. This
concentration method (enrichment method) is designed for
metal recovery from dilute technological solutions and
for absolute preconcentration of elements in analytical
chemistry. However, interfering components of the test
solution partly remain in the cell after the filtration run, even
if they do not interact with the reagent. This can cause
difficulties, e.g. in trace analysis of highly mineralized
waters. To avoid it a combined procedure is applied to both
absolute and relative preconcentration.
Plotting the concentration of the metal species in the
filtrate versus F allows visualizing the enrichment process
[35,78]. A blank experiment in the absence of the polymer is
needed, and a curve is obtained showing the diffusion
controlled process as it is shown in Fig. 5, plot a. The
concentration in the filtrate, and, in consequence, in the
solution inside the cell, increases until it achieves
the concentration of the reservoir solution. The presence
of the polymer in the solution and the consequent uptake of
metal ions will modify the shape of the curve (Fig. 5). It is
assumed that the polymer does not affect the diffusion of
metal ions since this phenomenon is faster than the flow rate.
Three cases may be regarded. If only an irreversible uptake
of metal ions is carried out, a parallel curve to the plot of the
blank experiment will appear at a higher F value (Fig. 5, plot
b ). As polymer –metal ion interactions are processes in
equilibrium, it is normally found that a lower slope in the
rate of increase of the metal concentration in the filtrate is
observed (Fig. 5 plots c and d ). In curve c, the case of the
unique existence of an equilibrium situation is shown, while
curve d shows the combination of the two effects, the
existence of an equilibrium situation and an irreversible
uptake of metal ions.
3.3. Ultrafiltration membranes
Microfilters, ultrafilters, dialysis and osmosis mem-
c d
branes can be used for analytical separations. The
membranes are usually made of polycarbonate or cellulose
esters, polyamide, polysulfone, etc. The synthetic mem-
branes are thin, solid-phase barriers that allow preferential
passage of certain substances under the influence of a
driving force. Membrane separation is governed by both the
chemical and physical nature of the membrane material.
Microporous membranes control separation by size, shape,
and charge discrimination, whereas non-porous membranes
rely on sorption and diffusion. There are two important
parameters to determine the membrane performance: degree
of separation of fluid mixture (i.e. rejection or selectivity)
and permeation rate (flux).
Dealing with polymeric membranes, the polymer
provides a range of properties important for separations.
In general, a material with high glass-transition temperature
(Tg), high melting point, and high crystallinity is preferred.
Among the most important physical properties to be
considered are the interfacial properties, such as interfacial
tension and adsorption. In this context, the van der Walls
interaction, hydrogen bonding, electrostatic effect, charge
transfer effect, and dipole moments, play a critical role in the
performance of ultrafiltration membranes. For example, the
precipitous drop in membrane permeation flux with
hydrophobic membranes is the result of irreversible
adsorption of particles to the membrane surface (fouling).
In general, hydrophilic membranes are less susceptible to
fouling than hydrophobic membranes. The major limitations
for applications of ultrafiltration processes are the concen-
tration, polarization and membrane fouling phenomena
arising from rejection of solute molecules at the membrane
surface. The causes of fouling vary depending on the nature
of the solute-membrane interactions, and membrane fouling
is frequently confused with concentration polarization. As a
rule, a reversible flux reduction is a result of concentration
polarization, whereas an irreversible one results from
fouling. The flux, in the absence of irreversible fouling,
increases with the shear rate at the membrane surface.
Concentration polarization can be controlled by engineering
parameters such as module design and system hydro-
dynamics, whereas fouling is influenced by various
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 183

Table 2
Molecular structure of ultrafiltration membranes

Name Molecular structure

Poly(sulfone)

Cellulose acetate

Poly(ethersulfone)

Poly(ethylene)

Poly(vinyldine fluoride)

membrane – solute interactions, membrane morphology, and
solute – solute interactions. Studies of the membrane surface
chemistry and solution environment, which are responsible
for membrane – solute interactions, are important for under-
standing membrane performance and fouling during ultra-
filtration [83,85].
With the development of asymmetric membranes, other
polymeric materials have been the subjects of investigation
[81 – 84]. The study of different polymeric material for use
in membrane filtration involves selection of suitable
polymers, membrane morphology in relation to its use as
an ultrafilter, and effect of fabrication, operational, and
hydraulic variables. The principal factors that should be
considered for application of membranes to aqueous media
are: pore size and pore size distribution, solution flow,
potential drop over membrane, and degree of hydrophilicity.
The methods for analytical applications are based on
utilization of ‘inert’ membranes, i.e. membranes that hardly
adsorb the species to be separated. Of course, any membrane
has some adsorption ability, so certain conditioning should
Table 3
Membrane separation processes
be provided to minimize the adsorption. A classification of
membrane size separation methods and some principles of
the application of such methods for the investigation
of element distribution in aquatic systems have been
described [85]. Examples of membrane separations in
water analysis are reported [85].
The pore size distribution in the membranes is another
factor which influences the reliability of size distribution
patterns. Membranes with a relatively narrow distribution
have been produced [86 – 89]. Very narrow pore size
distribution is obtained when a thin (10 mm) sheet of
polycarbonate or other polymer material is irradiated. Such
sheets for use as filters are called nucleopore filters.
The most common ultrafiltration membranes (Table 2
[85]) are based on cellulose acetate (CA), polysulfone (PS),
poly(ether sulfone) (PES), polyacrylonitrile (PAN) and
polyvinyldiene (PVD). Although CA-based membranes are
less prone to fouling and typically have a higher flux than PS
membranes at equivalent rejection, PS membranes are used
in many applications because of higher stability. Moreover,

Process Mechanism Membrane

Microfiltration Sieving Porous; pore size 0.1–10 mm

Ultrafiltration Sieving Porous; pore size 0.1–100 nm
Nanofiltration Sorption-sieving Porous; pore size 2 nm
Reverse osmosis Preferential sorption, capillary flow Porous; dense skin, pore size 1 nm
Gas separation Solution-diffusion Non-porous thin film
Pervaporation Solution-diffusion Non-porous thin film
Membrane contactor Vacuum Hydrophobic micropores
Continuous deionization Charge Ion exchange
184 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
hydrophobic polymers and membranes can be modified to
increase flux and reduce fouling [90 – 94]. These membrane
modification techniques include the following: entrapping a
hydrophilic moiety, reacting the base polymer with hydro-
philic pendant groups, blending polymers, modifying the
membrane surfaces, modifying the membrane charge and
grafting the ceramic membranes.
Ultrafiltration is based on the same principle as reverse
osmosis but with much larger pore sizes (0.001– 0.1 mm)
(Table 3). Because of the low or negligible osmotic pressure
of macrosolutes, ultrafiltration operates at very low
pressures (30 – 80 psig).
Ultrafiltration membrane separation depends on mem-
brane pore size, solute– membrane interaction, and shape
and size of the macromolecule. For maximum separation
efficiency, there should be a 10-fold difference in the sizes of
the species to be separated. In addition, because all
ultrafiltration membranes have a certain pore size distri-
bution, the molecular mass cut-off (MMCO) of the
membrane (defined as the molecular weight at which 90%
of the macromolecular solute is rejected by the membrane)
should be at least one-half that of the smallest macro-
molecule to be rejected.
4. The nature of the polymer – metal ion interactions
Interactions of metal ions with water-soluble polymers
are mainly due to electrostatic forces and the formation of
coordinating bonds. Other weak interactions may appear
such as trapping metal ions in the bulk of the polymer phase.
The features of coordination between polymers and
metal ions may be described by the usual coordination
theories, but some special aspects may be considered. When
intra-chain complexes are predominant, it is normally
recognized the existence of a polymer domain with near
constant concentration of ligands, since the distances
between them keep in a narrow range for a given polymer
chain [1,66]. This is responsible for that the chelating
reaction appears as a one-step reaction. For relative low
ligand amounts in the solution, completely complexed metal
ions may coexist with free, uncomplexed ones. The
reactivity of the complexes is sometimes strongly affected
by the polymer ligand that exists outside the coordination
sphere and surrounds the metal complex, by means of
special chemical environment and steric effects.
Electrostatic interactions between polymers and metal
ions are found in many important biopolymers and synthetic
polyelectrolytes. There has been great interest in studying
the interactions between polyions and the small ions
(counterions) around the polyions, as this information is
frequently crucial to the functioning of polyelectrolytes in
technological and in vivo processes [58,59,95– 104]. Three
different modes of counterion binding may be distinguished:
territorial binding, site binding, and hydrophobic binding
(adsorption). Under purely long-range electrostatic inter-
actions, counterions tend to be non-specifically bound to the
polyion, and they are able to move along the axis of the
polymer chain. If short-range, site-specific interactions are
dominant, the counterions may bind on specific sites of the
polyion associated to one or more charged groups. Organic
counterions may bind polyions stronger than inorganic ions
due to the hydrocarbon nature of the polymer chains.
Theoretical work has been elaborated to explain the
counterion binding to polyelectrolytes, including counterion
condensation theory, analysis of the cylindrical Poisson–
Boltzmann equation, hypernetted chain theory, and Monte
Carlo computer simulations. Manning’s and Hao – Harvey’s
theories emerge as an extension of Debye –Hückel theories.
Manning’s theory represents the solution as composed
by a polyelectrolyte domain, in which counterions are non-
specifically bound (territorially bound or condensed) to the
polyion and by uncondensed mobile ions diffused in the
zone outside the polyion domain. The condensed counter-
ions are accumulated around the polyion skeleton; the
counterions closest to the polymer chain should be
dehydrated and the farthest should retain the fully hydrated
state. Territorially bound counterions are assumed to be able
to move within their corresponding region. The uncon-
densed mobile ions in the solution are treated by the Debye –
Hückel approximation. Some assumptions are made to
enunciate this theory: (a) the real polyelectrolyte chain is
modeled as an infinite regular linear array of infinite fixed
univalent point charges of spacing b, (b) interactions
between two or more polyions are negligibly small, (c) the
permittivity 1r in the condensation volume of the poly-
electrolyte is that of the pure solvent. The dimensionless
charge-density parameter j introduced by Lifson and
Katchalsky [105] is defined as follows:
j ¼ e2 =1kB Tb ð4Þ
where b is the distance between two charged groups on the
polyion, 1 the dielectric constant of the solvent, e the
elemental charge, T the Kelvin temperature, and kB is
the Boltzmann constant. In the simple condensation theory,
where only the existence of a counterion species is
supposed, the formulation of the free energy of the system,
Gsys, taking in to account the mixing of free counterions,
bound counterions, and solvent molecules, yields in
equilibrium conditions the following expression:
h i
1 þ ln 103 uz =ðVp Cz Þ
¼ 22Z jð1 2 Z uz Þ ln½1 2 expð2kbÞ ð5Þ
that relates the equilibrium binding fraction of the bound
counterions per fixed polyion charge, uz, with the charge-
density parameter j. Cz is the molarity in excess counterion
of valence Z, k is the Debye –Hückel screening parameter,
and the ratio 103uz/Vp is the molarity of the counterions
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
bound within the volume Vp, where Vp is given in
cm3 mol21 (of polymer charge).
This theory provides a limiting law since in the limit
Cz ! 0, the value of uz is given by the expression:
 
1 1
lim uz ¼ 12 ð6Þ
Cz !0 Z Zj
that is to say, in the limit of infinite dilution, a remaining
amount of counterions uZ will stay bound to the polymer
chain.
An analogous treatment is done when two species of
counterions of different valence are present, in the so-called
Manning’s two variable theory [98]. Considering a mixture
of monovalent and divalent counterions, where the mono-
valent metal counterion is in excess in relation with the
divalent metal counterion, the equilibrium values for u1 and
u2 are given by the following two expressions:
h i
1 þ ln 103 u1 =ðVp C1 Þ
¼ 22jð1 2 u1 2 2u2 Þ ln½1 2 expð2kbÞ ð7Þ
h i h i
ln 103 u2 =ðVp C2 Þ ¼ 1 þ 2 ln 103 u1 =ðVp C1 Þ ð8Þ
where the subscripts 1 or 2 represent the mono- or divalent
metal ion, respectively.
Again, when C1 ! 0 and C2 ! 0, a limiting expression
is found from Eq. (7):
j ¼ ð1 2 u1 2 2u2 Þ21 ð9Þ
Eqs. (7) and (8) represent a 2 £ 4 equation system, where the
four variables are u1, u2, C1, and C2. Manning’s two-
variable theory is relevant because it lumps all the variables
together, and puts them in relation with j.
Manning extended his theory [98] with the introduction
of a parameter, dm0, that accounts for short-range inter-
actions of a territorially bound counterion with its local
environment. Manning’s interpretation of these short-range
interactions is consistent with the notion of a highly mobile
binding mode for the counterions: if a counterion A interacts
more attractively with its local bound-state environment
than does B, then, A cannot wander as far from the polyion
as its B counterpart. The new equations derived for the
system considered above, i.e. a mixture of a monovalent
counterion in excess with a divalent species, are:
103 eu1 expðZ1 {u1 ; u2 }Þ
 
C1 V1p exp 2dm01 =RT
¼ ½1 2 expð2kbÞ22jð12u1 22u2 Þ ð10Þ
185
103 eu2 expðZ2 {u1 ; u2 }Þ
 
C2 V2p exp 2dm02 =RT
¼ ½1 2 expð2kbÞ24jð12u1 22u2 Þ ð11Þ
where Z1 ðu1 ; u2 Þ and Z2 ðu1 ; u2 Þ are defined in Ref. [98].
The Hao– Harvey theory [99] is another extension of
Manning’s theory that includes considerations about short-
range interactions. The counterions are admitted to bind in
some extent site-specifically. Then, the contribution to the
free energy of the counterions site-specifically bound to the
polymer is considered including the corresponding binding
constant KZ for a single site of the polyion. The equilibrium
binding fractions for the mixture of a monovalent and a
divalent counterion are given by the expressions:
u1
¼ K1 ½1 2 expð2kbÞ22jð12u1 22u2 Þ ð12Þ
C1 ð1 2 u1 2 u2 Þ
u2
¼ K2 ½1 2 expð2kbÞ24jð12u1 22u2 Þ ð13Þ
C2 ð1 2 u1 2 u2 Þ
Note that Eqs. (7), (8), (10) and (11) are functionally
dependent on Vp. There is no general accepted theoretical
expression for Vp. Expressions of Vp have been developed
upon the assumption of relative low ionic strengths [100,
104]. The distributions of Cd2þ bound to PSS and free in
solution in the presence of an excess of Naþ have been
calculated by ultrafiltration [58] under the washing method
at variable ionic strength. The values obtained neither
satisfy Eqs. (7) and (8) nor Eqs. (10) and (11) or Eqs. (12)
and (13) [59]. This fact has been interpreted as being caused
by conformational changes: Manning’s theory relates the
concentration of counterions bound and not bound to the
polymer with the charge-density parameter assuming
the polymer has a linear conformation. In salt-free solutions
of polyelectrolytes, the conformation of the polymers tends
to be rodlike due to charge repulsions in the chain. In the
case of PSS, even if the chain is highly charged,
hydrophobicity in the backbone affects its conformation.
But as the ionic strength increases the polymer adopts a
random conformation—this is the ‘polyelectrolyte effect’.
This can influence the ‘observed’ value of the charge-
density parameter, and some authors have used it as an
adjustable parameter [100]. As the charge density parameter
is related with the average spacing between the charges, the
distance between two charged groups on the polyion b can
also be adjusted [59]. It is shown that for low F values, the
distance between the charges decreases notably. This fact
may be modeled visualizing the polymer projected over an
imaginary straight line that will be responsible for the
counterion condensation, as Manning’s models are con-
structed on the basis of a straight linear arrangement. The
polymer coils and the charge-density parameter increases
because b decreases in the projection. Coiling is a function
of the concentration of metal ions in the solution and b is a
function of coiling. The increase of the apparent linear
186 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
Scheme 2.
charge density may justify the increase of the amounts of
metal ions condensed and the increase on the condensation
volume.
The chelating process of a metal ion by a polymer, may
be preceded by long-range attractive electrostatic inter-
actions, and once the metal ion is condensed on the polymer
surface, it is site fixed by the polymer ligands. A great
number of theoretical studies have been carried out namely
for these macroligands. Polymers and copolymers of acrylic
acids and its derivatives, amines, and amides are widely
used as macroligands. Scheme 2 shows the most accepted
mechanisms for these polymer – metal ion interactions. The
carboxylic groups can act as mono and bidentate ligands.
Depending on the pH value ionized PAA may form
complexes with D2h or D4h (dimers) symmetry. At high
pH values, the PAA chain has a drawn shape due to
electrostatic repulsion of charged carboxylate groups; metal
ions are then binding either with one or two neighbor
groups. At a pH value equal to 4.5, the macromolecular
globule contracts and the metal ions are able to coordinate
2 – 4 carboxyls. The interaction of metal ions with polyacids
is an isothermal process. Therefore formed complexes have
to be stabilized due to high changes in entropy factor [1].
Amino groups form stable complexes through the free
electron pair from the nitrogen atom. Due to that, the
stability of the complexes depends strongly on the pH. At
low pH, where the majority of the amino groups are
protonated, the affinity by the metal ions is poor and the
stability of the complex is low. As the pH increases, the
affinity and stability of the polymer – metal complexes
increases [45].
On the contrary, water-soluble polymers with sulfonate
groups favor the electrostatic polymer – metal ion
interaction.
The polymer– metal ion interaction may be intra- and/or
interchain. The former is the most common for a numerous
group of polymer metal chelates showing comparatively
high chemical and thermal stability. Another specific feature
of these compounds is the total saturation of the coordi-
nation sphere of the transition metal ion. The interchain
polymer– metal ion interaction may proceed via binding
functional groups of two different macromolecules; usually
one of them provides ‘acidic’ functional groups, and the
second ‘basic’ groups. These metal binding with mixed
biopolymers is a process of great importance for biological
reactions.
The variables that may affect the polymer– metal ion
interactions are intrinsic to the polymer: nature of atoms in
the backbone chain, nature of the functional groups attached
to the backbone, structure and copolymer composition,
molecular weight and polydispersity, distance between
functional groups and backbone, degree of branching, etc.;
other variables may be extrinsic to the polymer: for example
pH, ionic strength, nature and charge of the metal ion,
temperature, or nature of the counterion of the metal ion.
5. Evaluation of the equilibrium distributions
5.1. Conductometry
Conductometry is an important tool in the analysis of
counterion distributions in metal/polyelectrolyte solutions
[106– 120]. Conductometry measures the transport of all
charged species in the system studied. Association of
counterions with the polyion affects the conductance of
polyelectrolyte solutions. In the last several years, sub-
stantial progress has been made in the development of the
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
theory of polyelectrolytes, in particular with respect to
counterion binding and conductivity [95,96]. For mono-
valent counterions, it is now possible to estimate the
distribution of counterions over the free and bound states by
varying the nature of the counterion.
Using conductometric titrations, the effective charge-
density parameter j can be estimated. This method is based
on conductometric titrations of the polymer, in the acid
form, by two bases (LiOH and KOH). At a neutralization
degree equal to 1, the conductivity measurements of the salt
forms allow the determination of the transport parameters f,
related to the free fraction of counterions controlled by the
charge-density parameter, and the molar conductivity, L.
One may formally express the molar conductivity L of a
salt free polyelectrolyte solution as
L ¼ f l01 þ lp ð14Þ
where l01 and lp represent the ionic conductivities of the free
counterion in pure solvent and the polyion, respectively. In
terms of a two-state representation of the counterion
distribution, one might refer to f as the conductometrically
free fraction of counterions. This is helpful in practice, but it
should not lead us to ignore the real situation where the
degree of interaction between the polyion and the counter-
ions gradually varies as a function of distance.
One of the main issues in treating the conductivity of
polyelectrolyte solutions is quantifying the contribution
from the ions in the diffuse counterionic atmosphere.
Manning [95,96] tackled this by starting from the Nerst –
Planck equation for the migration of the counterions,
taking into account the radial part of the inhomogeneity of
the electric field around the linear polyions and the steady
ionic movement under the influence of the external field.
Ignoring the possible mobility of condensed counterions
along the chain, it was found that for j . lZ 21 l
fZ ¼ 0:866lZ 21 lj21 ð15Þ
The dimensionless coefficient 0.866 results from the
numerical evaluation of the components of the radially
inhomogeneous electric field around the linear polyion
with smeared-out charge. For polyions with j , 1 and
monovalent counterions, the function of f1 is
0:55j2
f1 ¼ 1 2 ð16Þ
pþj
At this point it is useful to emphasize the difference
between condensed counterions and conductometrically
bound counterions. According to the counterion conden-
sation theory [96], the uncondensed fraction 1 2 uZ
includes both the ions in the diffuse double layer and the
free ions. The conductometrically bound ions include (at
least in Manning’s theory) all condensed ions, plus some
part of the diffuse layer ions. Thus, in the case of
monovalent counterions, the ‘free fraction’ f is always
some fraction of j 21 and the bound fraction ð1 2 f Þ is
187
1-ξ -1 condensed
1-f
double layer
-1
ξ
free f
Scheme 3.
always larger than ð1 2 j21 Þ: The following scheme
(Scheme 3) represents that situation and the expression
for fZ may be used in combination with the expression for
the molar conductivity (L ), thus serving as analytical
working equations.
5.2. Ultrafiltration
5.2.1. The washing method
In order to calculate the equilibrium distributions of
metal ions by ultrafiltration, a parameter is introduced, kZm ;
which is the coefficient of membrane retardation, defined as
the ratio concentration of metal ions in a dV f exiting the cell
to the filtrate versus concentration of free (not bound to the
polymer) metal ions in the cell at that instant, so that
kZm ¼ cfZ =cfree
Z ð17Þ
and represents the influence of the membrane in the
retention process.
Some assumptions may be made concerning the
coefficient of membrane retardation: the value of kZm can
be assumed to be independent of F (assumption 1); this
should be the case if kZm is only dependent on the nature of
the membrane and the nature of the metal ion under study.
Related with assumption 1, and corroborated in several
experiments, it can even be assumed that there is no
retention produced by the membrane, i.e. kZm ¼ 1 (assump-
tion 2).
Upon the assumptions that the ultrafiltration system can
be considered a steady-state mixed flow reactor, so that the
uniformly mixed system attains in every instant during
filtration an equilibrium situation (assumption 3) and that
the metal ion species can be considered in two total groups:
bound to the polymer or free in the solution, (assumption 4)
the values of cfree
Z are calculated directly with the aid of Eq.
(17), and the values of cbound
Z are calculated by subtraction of
cfree
Z from the total concentration of metal ions inside the
cell.
The above shown method is effective when cfZ is
measured instantaneously. If filtrate fractions are collected
and then analyzed [79], the metal ion concentration
experimentally measured for each filtration fraction col-
lected ðkcfZ lÞ corresponds to the concentration of the solution
188 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

at a given instant between the two F values that limit the F

filtration fraction (DF ). When constant DF are taken, an
0
exponential decay is normally found, if kcfZ l is represented
0 2 4 6 8 10
versus F, so that
-2
D E D Einit
cfZ ¼ cfZ expð2jFÞ ð18Þ
-4
where j is a parameter and ‘init’ is referred to initial value

ln <c 2f >
(for F ¼ 0). This is related to an exponential decay on the -6
instantaneous cfZ during filtration, so that
-8
cfZ ¼ cf-init
Z expð2jFÞ ð19Þ
-10
where
 init -12
j cfZ DF
cf-init
Z ¼2 ð20Þ
1 2 expðjDFÞ -14
Then, under Eq. (17) and assumption 2 Fig. 6. Plot of ln kcf2 l versus F and the corresponding linear
adjustments. (V) PSS/Cd2þ, linear adjustment: ln 
cfree
Z ¼ cfree-init
Z expð2jFÞ ð21Þ
kcf2 l ¼ 20:8087F 2 5:0735 ðR2 ¼ 0:9990Þ [77]; (B) PSS/Cd2þ
where [77]; ( £ ) PALA/Ni2þ, linear adjustment: ln kcf2 l ¼ 20:3742F 2
8:6956 ðR2 ¼ 0:9903Þ [79]; (O) PSS/Cd2þ, linear adjustment: ln 
cfree-init
Z ¼ cf-init
Z kcf2 l ¼ 20:099F 2 12:094 ðR2 ¼ 0:9253Þ. Reprinted from J Mem-
brane Sci (in press). q 2002 with permission from Elsevier Science
The j parameter gives a measure of the capacity of the
[79].
system of reposition of the metal ions extracted out of the
bulk of the solution. If j , 1, the equilibrium in the solution distributions of metal ions bound to the polymer and free in
inside the cell is furnishing metal ions to the aqueous phase solution in every instant follow a Freundlich isotherm,
from the polymer phase while they are being eluted out of indicating an anti-cooperative binding, good correlations
the cell during filtration; on the contrary, if j . 1, apart from have been found between theory and experiments
the loss of metal ions in the aqueous phase because of performed under the washing method at constant ionic
elution, the polymer is capturing free metal ions from the strength [79].
solution. In the particular case that j ¼ 0; the aqueous phase From Eqs. (3) and (17), it is found that, at the limit of
solution recuperates the same amount of metal ions that are small volume fractions
eluted. When j ¼ 1; the amounts of metal ions bound to the
polymer do not change during filtration and the free metal kZm cfree
Z
dRZ ¼ 2 dF ð22Þ
ions are eluted out of the ultrafiltration cell. cinit
Z
Fig. 6 shows the results obtained under the washing
and dividing and multiplying by RZ, since RZ ¼ ccellZ =cZ ;
init
method for several experiments. Normally good linear cell
where cz is the total concentration of metal ions in the cell
adjustments are found when plotting ln kcfZ l versus F,
following Eq. (18), at least at high ionic strength values. kZm2 cfree
Z
Ultrafiltration of PSS in the presence of 0.005 M of Cd2þ d lnRZ ¼ 2 dF ð23Þ
ccell
Z
and low constant ionic strength (0.01 M of NaNO3) values
yielded in curves that showed deviations from linearity [77]. or, as
This has been interpreted on the basis of conformational
ccell free bound
Z ¼ cZ þ cZ
changes in the macromolecules: the elution of metal ions
and their subsequent release from the polymer induces an 2kZm
increase of the net negative charge on the polymer surface d lnR ¼ dF ð24Þ
cbound
and then in an expansion of the chains in order to increase 1 þ Zfree
cZ
the total surface, minimizing the electrostatic repulsions.
Related with this, the decrease on the linear or surface Ultrafiltered solutions normally consist of a water solution
charge density of the polymer induces a decrease in the containing the water-soluble polymer, traces of a polyvalent
strength of the interactions with the metal ions, and in metal ion, and an excess of a 1:1 simple electrolyte. When
consequence, their easier release to the solution from the elution of a solution in ultrafiltration experiments is carried
polymer domain during filtration, decreasing the j values out with water at the same pH and ionic strength in the initial
found. polymer– metal ion solution, and the concentration of the
The analytical expressions of the retention profiles polymer may be assumed constant since it is in excess over
are under investigation. Upon the assumption that the the polyvalent metal ions (assumption 5), it can be
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 189

1 where m ¼ kðcfree-init
Z Þn21 cp : Once again, considering that
0.9 for F ¼ 0; RZ ¼ 1; it is obtained that
0.8 2a
K2 ¼ lnð1 þ mÞ ð31Þ
0.7 jðn 2 1Þ
0.6 The adjustments of the experimental profiles to the plot of a
0.5 function of the type of Eq. (30) is also shown in Fig. 7: very
R

good adjustments are found and they reproduce the

0.4
deviations from linearity found in logarithm scale. Note
0.3 that using a Freundlich distribution of metal ions, assump-
0.2 tion 5 is not implemented, since saturation of the polymer is
0.1 regarded in Freundlich’s treatment.
0 When elution is carried out with water at the same pH of
0 2 4 6 8 10 the initial simple electrolyte– polymer – metal ion solution,
but without adding a simple electrolyte, the ionic strength of
F the solution inside the cell will change during filtration, and
Fig. 7. Plot of the retention versus F. (V) experimental values for the then, the apparent thermodynamic equilibrium constant will
system PSS/Cd2þ; (B) experimental values for the system also change, so that integration of Eq. (24) is not possible
PALA/Ni2þ; (—) adjustment from Eq. (30): for PSS/Cd2þ, n ¼ without knowing the expression of the dependence of KZdiss
0:2206; k ¼ 0:13069; j ¼ 0:099; cfree-init
2 ¼ 5:4036 £ 1025 ; for with F. In such cases, the experimental retention profiles
2þ
PALA/Ni , n ¼ 1:4916; k ¼ 3234:7; j ¼ 0:3742; cfree-init 2 ¼ may be adjusted to the plot of a function (retention function)
1:381 £ 1024 ; (- - -) adjustment from Eq. (25): for PSS/Cd2þ, a ¼
whose logarithm could be derived.
0:025; for PALA/Ni2þ, a ¼ 0:43. Reprinted from J Membrane Sci
A proper adjustment for the retention profiles is given by
(in press). q 2002 with permission from Elsevier Science [79].
the expression
considered that the ratio cbound
Z =cfree
Z does not change during RZ ¼ uZ þ vZ expð2kZ ·FÞ ð32Þ
filtration, so that Eq. (24) is directly integrated to
where uZ, vZ, kZ, are the experimental retention parameters
RZ ¼ expð2aFÞ ð25Þ [58], and
where uZ þ vZ ¼ 1 ð33Þ
21 Then, deriving the logarithm of Eq. (32) and identifying
a¼ ð26Þ
1 with Eq. (24) it is found that
1 þ diss
KZ
1
KZdiss ðFÞ ¼ ð34Þ
and kZm uZ kZm
þ 21
kZ vZ kZ expð2kZ FÞ
cfree
Z
KZdiss ¼ ð27Þ
cbound
Z
an expression that gives the value of the apparent
dissociation constant as a function of F and the experimental
The adjustment of some experimental results to the plot of a retention parameters.
function of the type of Eq. (25) is shown in Fig. 7. Good The expressions to calculate the amount of metal ions
adjustments are found but the experimental values show bound to the polymer and free in the solution have been
slight deviations from linearity in logarithm scale that is not developed from the expressions of the retention functions:
explained by the model. On the contrary, if Freundlich
isotherms are considered, whose expression is R cinit
cbound ðFÞ ¼
Z Zdiss 

n Z
1 þ KZ
uZ ¼ k cfree
Z ð28Þ
Z
m
cinit   
where k and n are experimental parameters, Eq. (24) is ¼ k u þ kZm 2 kZ vZ expð2kZ FÞ ð35Þ
kZm Z Z
transformed to
RZ cinit
Z KZ
diss
cinit
2kZm Z ðFÞ ¼

cfree diss
 ¼ Zm kZ vZ expð2kZ FÞ ð36Þ
d lnRZ ¼  free n21 p dF ð29Þ 1 þ KZ kZ
1 þ k cZ c
At these experimental conditions it has been shown the
and under Eq. (21) it yields that evolution of the distribution of Cd2þ (0.0017 M initial
a concentration) in a solution containing PSS (0.02 mol of
ln RZ ¼ ln{1 þ m exp½2jðn 2 1ÞF} þ aF
jðn 2 1Þ sulfonate groups per liter) and NaNO3 (0.14 M initial
concentration) at pH 5, when elution is performed with
þ K2 ð30Þ water at pH 5 [58]. Fig. 8 shows the experimental retention
190 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
1 0.06
0.9
0.8
0.7
0.6
0.5
R
0.4
0.3
0.2
0.1
0 0
0 2 4 6 8 10
F F
Fig. 8. Plot of the retention versus F. (V) experimental values
for the system PSS/Cd 2þ; (-) plot of the function R ¼
0:55 þ 0:45 expð21:9FÞ. Reprinted with permission from J Phys
Chem B 1998;102:6994. q 1998 American Chemical Society [58].
results for Cd2þ. The retention profile adjusts to the plot of a
function of the type of Eq. (32), with a value of kZ greater
than 1. That means that during filtration, the amounts of
Cd2þ that bind PSS increase, despite the total amount of
Cd2þ decreases in the cell. This is due to the large excess
of monovalent metal ions that are being eluted, decreasing
the ionic strength, and rapidly increasing the ability of the
polymer to uptake metal ions. Fig. 9 shows the evolution of
the binding fraction with F calculated from Eq. (35).
5.2.2. The enrichment method
In the enrichment method, a polymer solution is placed
inside the ultrafiltration cell, and a metal ion solution is
placed in the reservoir. When the reservoir solution is passed
through the polymer solution, the macromolecules uptake
metal ions until saturation is achieved. With this procedure,
maximum capacities of the polymer can be calculated,
defined as the maximum amount of metal ions bound to the
polymer per unit polymer. Plotting the concentration of the
metal species in the filtrate versus F helps to do this
calculation. A control experiment, in the absence of the
polymer, is needed. The concentration in the filtrate
increases until it achieves the concentration of the reservoir
solution since it is controlled by diffusion. When the water-
soluble polymer is present in the cell solution, if an
irreversible uptake of metal ions is carried out, a parallel
curve to the plot of the control experiment appears at a
higher F value [35]. In those cases, the dimensionless
enrichment factor (E ) is defined as
E ¼ Ccp =cres
Z ¼ V =V ¼ F sat
fsat c
ð37Þ
where C is the maximum capacity, c p the polymer
concentration in the same units as C is given, cresZ is the
concentration of the metal ion in the reservoir. V fsat is the
total volume in the filtrate when saturation is achieved, so
0.05
0.04
v2
0.03
0.02
0.01
0 2 4 6 8 10
Fig. 9. Plot of the u2 versus F.
that the enrichment factor may be defined as the filtration
factor in conditions of polymer saturation (F sat).
As the metal ion interactions are processes in equili-
brium, a lower slope in the rate of increase of the metal
concentration in the filtrate is normally observed. From the
differences in the slopes, the amounts of metal ions bound to
the polymer and free in the solution can be easily calculated.
As a consequence of Eq. (17), cfree
Z is directly readable from
the experimental curves (Fig. 5). If cbound
Z is the concen-
tration of metal ions bound to the polymer, its value is given
by the formula
cbound
Z ¼ DFcres
Z ð38Þ
where cresZ is the metal ion concentration of the solution in
the reservoir, and DF is the difference between the F actual
value and the F value that have the same image in the
ordinate axis in the control experiment.
Poly[acrylamide-co-1-(2-hydroxyethyl)aziridine] forms
a stable blue complex with Cu2þ. The compositions in
equilibrium of this metal ion at low concentrations in the
presence of the chelating polymer were evaluated by
ultrafiltration using the enrichment method and it was
found that they present a Freundlich and a Langmuir
isotherm behavior [78]. Fig. 10 shows the experimental
results obtained for the enrichment of Co2þ for poly(2-
acrylamido-2-methyl-1-propane sulfonic acid), PAPS, at
three different pH. Table 4 shows the maximum capacities
for the same polymer of binding several metal ions [39].
5.3. Viscosity
The physicochemical properties of solutions of synthetic
water-soluble polymers have gained attention mainly to the
hydrodynamic properties, among which the intrinsic
viscosity is considered in greater detail.
McCormick and co-workers [121–126] have synthesized
and studied the viscosimetry behavior of many water-soluble
polymers. They have studied anionic polyelectrolytes
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 191

250
(a) containing acrylic, methacrylic, and sulfonic groups,
cationic polyelectrolytes containing methyl propanedi-
methylammonium, diallyl alkoxy benzylmethylammonium,
200
and diallylammonium groups, and other amphiphilic
copolymers and terpolymers [127 – 131]. Their studies
have examined the effects of shear rate, concentration,
C (m g/L)

150
surfactants, added electrolyte, and copolymer composition.
100
Yang [132] studied the rheological behavior of poly-
acrylamide solution, as a function of temperature and
concentration. The temperature and concentration ranges
50
studied were 20 –50 8C and 0.2 – 0.5 wt%, respectively. He
found that the viscosity of polyacrylamide solution
0 decreases with increasing temperature following the Arrhe-
0 50 100 150 200 250 nius’ law. Moreover the viscosity of a polyacrylamide
Volum e (m L) solution decreases with an increase in the concentration of
polyacrylamide.
Practically all these water-soluble polymers exhibit
typical polyelectrolyte behavior, i.e. decrease in the reduced
250 (b) viscosity with an increase in polyelectrolyte concentration
(Fig. 11). This behavior is due to that as the polyelectrolyte
concentration decreases, the ionization degree increases and
200
the produced ions form an ionic atmosphere higher than the
diameter of polymeric coil. The repulsion among the ions
increases the rigidity of the chain, expanding the polymeric
C (mg /L)

150
coil with a consequent increase of the viscosity.
At a semidilute polyelectrolyte concentration regime, the
100 ions are placed either inside or outside of the polymeric coil,
but at higher concentrations, they are preferably outside the
polymer domain, yielding an osmotic effect, raising a higher
50
expansion of the coil. Therefore, at low concentration
predominates the electrostatic effect, whereas at higher
0 concentration predominates the osmotic effect [133].
0 50 100 150 200 250 Also observed was the well-known effect of adding a
Vo lu me (mL)
simple salt to polyelectrolyte solutions, i.e. electrostatic
screening of the charged groups and consequent reduction of
the hydrodynamic volume. The most interesting behavior
observed for the amphiphilic copolymers and terpolymers is
250 (c) that the systems are capable of forming hydrophobic
domains in aqueous solution through intramolecular hydro-
phobic associations. The strength of the association
200
increases with increasing either the hydrophobic content
or the length of the hydrophobic group. Addition of
electrolytes allows sufficient shielding of charges to result
C (m g/L)

150
in a collapsed conformation.
100
The intrinsic viscosity is related with the hydrodynamic
volume, molecular weight, and macromolecular confor-
mations of polyelectrolytes in aqueous solution. However,
50 due to the viscosity behavior of the polyelectrolytes in
aqueous media, the viscosity of polyelectrolytes is very
0 difficult to determine. In this sense many authors have used
0 50 100 150 200 250 different methods to obtain the intrinsic viscosity of these
Volum e (m L)
charged polymers [134 – 138].
Viscosimetric measurements may help in the under-
Fig. 10. Co2þ enrichment of PAPS at pH 3 (a); pH 5 (b), and pH 7 standing of the polymer –metal ion interaction phenomena
(c). (B) blank; (V) performed in the presence of the water-soluble in aqueous solution, including polymer – metal complex
polymer. Reprinted with permission from Polym Adv Technol (in formation and counterion binding on polyelectrolytes. The
press). q 2002 John Wiley & Sons Limited [39].
192 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

Table 4
Maximum retention capacities (MCR) for PAPS

Metal ion Initial concentration (mg/l) pH MRC

Mg metal/g polymer mol Metal ion/mol repeat unit

Cr(III) 51.8 3 51.77 0.21

205.0 3 43.64 0.14
Cu(II) 51.6 3 89.22 0.29
171.0 3 79.70 0.26
49.3 5 – –
173.0 5 125.20 0.41
Ni(II) 54.3 3 83.35 0.29
220.0 3 93.97 0.32
– 5 – –
220.0 5 120.50 0.42
– 7 – –
210.0 7 7.00 0.43

Co(II) 51.8 3 78.10 0.28

211.0 3 95.45 0.34
49.2 5 – –
208.0 5 118.70 0.41
– 7 – –
210.0 7 121.70 0.43

intrinsic viscosity values of the water-soluble polymer and
the water-soluble polymer– metal complexes may indicate
the type of polymer – metal ion interaction. In this sense, for
a better understanding of the phenomena, it is necessary to
study the behavior in aqueous solution of polymers,
mixtures of polymers and simple electrolytes, and poly-
mer-complexed metal ion. Ogawara and co-workers [139]
have made a comparative study of poly(a-hydroxy acrylic
acid) (PHA) and poly(acrylic acid) (PAA) of their divalent
counterion binding capacity by measuring the reduced
viscosity, apparent turbidity and activity of Mg2þ and Ca2þ
in aqueous solution. The results were analyzed under the
counterion condensation theory to estimate the relative
binding strength. General results show that the hsp/c p (hsp is
the specific viscosity) decreases with decreasing I 21/2
where I is the salt concentration (Fig. 12). Remarkable
counterion binding specificities were noted by the decrease
in the viscosity in the following order: Naþ . Mg2þ .
Ba 2þ $ Ca2þ for sodium poly(a-hydroxy acrylate)
(PHANa) and Naþ . Mg2þ . Ca2þ . Ba2þ for sodium
poly(acrylate) (PAANa). On the other hand, the results
suggest that PHA discriminates Ca2þ and Mg2þ much more
effectively than PAA. Moreover, according to the results,
the binding degrees should be higher in the order: Mg2þ
(PAA) # Mg2þ (PHA) , Ca2þ (PAA) , Ba2þ (PAA) ,
Ba2þ(PHA) # Ca2þ (PHA). The viscosity ratio between
Ca2þ and Mg2þ with PHA compared with those for PAA
suggests that Ca2þ and Ba2þ are specifically bound to PHA,
probably through coordination with the a-hydroxy groups of
the polymer chain.
Liaw and co-workers [140] studied the solution proper-
ties of the anionic polyelectrolyte poly(potassium-2-sulfo-
propylmethacrylate). Their investigation considered the
viscosimetry measurements of aqueous salt solutions in
the presence of different added electrolytes. They discussed
the results in terms of common cations (KF, KCl, KBr, and
KI), common anions (LiCl, NaCl, and KCl), and divalent
cations (MgCl2, CaCl2, and SrCl2). The results show an
increase in the intrinsic viscosity of poly(potassium-2-
sulfopropylmethacrylate) in 0.1 M aqueous salt solution in
the order KF . KCl . KBr . KI. These results coincide
with the Pearson principle, which states that hard acid
species prefer binding with hard base species and soft acid
species prefer binding with a soft base species. The hard
acid species, like the potassium ion, are easily bound to a
small-radius hard base, such as fluoride ion. Hence, the
fluoride ion is more easily attracted to the potassium ion
than the chloride ion, the bromide ion, or the iodide ion.
These results would reduce the site-binding degree of the
potassium ion on the sulfonate group and would decrease
the degree of the potassium ion neutralizing the negative
charge on polymeric side chains for the polymer. The results
yield a higher intrinsic viscosity of the polyelectrolytes in
aqueous salt solutions. In the case of divalent cations, the
results show an increase in the intrinsic viscosity of
poly(potassium-2-sulfopropylmethacrylate) in 0.1 M aqu-
eous salt solution in the order MgCl2 . CaCl2 . SrCl2.
Geckeler and co-workers [141] carried out a viscometric
study based on the interaction of poly(acrylamide-co-4-
vinylpyrydine) with Fe3þ, Co2þ, Ni2þ, Cu2þ, and Zn2þ in
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
Fig. 11. Reduced viscosities as function of (a) concentration of
terpolymer of acrylamide, acrylic acid and N-[(4-decyl)phenyl]
acrylamide in deionized water at 25 8C and a shear rate of 6 s21
and (b) concentration of copolymer of diallylalkoxybenzylmethyl-
ammonium chloride and diallyldimethylammonium chloride in
deionized water at 25 8C and a shear rate 1.28 s21. Reprinted from
Polymer 1994;35(16):3503, 1994;35(29):4429. q 1994 with
permission from Elsevier Science [128,130].
aqueous solutions. Their results show that at constant
copolymer concentration, an increase in the amount of Cu2þ
caused a decrease in the viscosity. This effect is stronger for
the polymers with lower molar fractions of Cu2þ, where the
complex formation makes the macromolecular coil tighter
by reason of the intrapolymer complex formation. In general
all polymer –metal complexes studied (with Fe3þ, Co2þ,
Ni2þ, Cu2þ and Zn2þ) show a decrease in the reduced
viscosity, compared to the reduced viscosity of the
193
polymers, indicating that the complex formation is prefer-
entially intrachain.
In our laboratory [142] we have studied the viscosity
properties of aqueous solutions of poly(allylamine) – metal
(Cu2þ, Co2þ, Ni2þ) complexes obtained through the LPR
method and mixtures of poly(allylamine) with Cu2þ, Co2þ,
Ni2þ nitrates and chloride salts.
All the solutions show a behavior which can be
approximated by the Ostwald model, t ¼ ADB : It is referred
to the description of the Newtonian flow behavior,
pseudoplastic, and dilatant behavior. A is related with the
amount of the resistance to the flow and for Newtonian
fluids corresponds to the viscosity (Pap s). B is called index
of flow and measures the degree of non-Newtonian flow
behavior. If B ¼ 1; the solution is a Newtonian fluid, if
B . 1, a dilatant fluid, and if B , 1, a pseudoplastic fluid. In
this case, all the solutions have a pseudoplastic fluid
behavior with values of B varying between 0.72 and 0.98.
Thus, a high or low apparent viscosity at low or high shear
rate has been observed, respectively. It can be attributed to
the fact that the particles or polymeric chains keep a
disordered state, raising a high internal resistance to a forced
flow, and therefore high viscosity.
By increasing the shear rate the particles are oriented in
the flow direction. In polymer solutions, the chains are
oriented parallel to the flow direction. Some particles are
better shaped yielding a low viscosity. This behavior is
expected for polymers with a rigid rod conformation.
Fig. 13a shows that with a higher CoCl2 ratio, the
apparent viscosity decreases in all range of shear rate
studied. This is characteristic of polyelectrolytes. The
poly(allylamine)– metal solutions with Cu2þ and Co2þ
show similar viscosity values whereas with Ni2þ lower
values (Fig. 13b) are obtained.
On the other hand, the viscosity of the polymer is
highly dependent on the pH, explained by the protona-
tion and deprotonation equilibrium of the amino groups
as well as by the changes in the ionic strength. As the
pH increases, the viscosity increases, and then remains
constant up to pH 5.0, and thereafter decreases. At
pH . 5.0 amino groups remain as the free base to an
important extent. The equilibrium state of the protonated
and free amino group is strongly dependent on the pH
and is shifted to the free amino group as it increases.
Thus, uncharged poly(allylamine) can be obtained,
which allows a higher interaction among the backbone
segments adopting preferentially a coiled globule-like
conformation, and therefore a smaller viscosity. More-
over, the viscosity of poly(allylamine) and its metal
complexes is strongly dependent on the metal salt
concentration. It is basically due to the change in the
ionic strength, which induces polymer conformational
changes to yield a more compact or extended confor-
mation. Either poly(allylamine) or their metal complexes
showed a polyelectrolyte behavior with high intrinsic
viscosity values. The preferred macroconformation is
194 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

Fig. 12. Dependence of the reduced viscosity on I 21/2. (a) PHA; (b) PAA. Reprinted from Polymer 1998;39(20):437. q 1998 with permission
from Elsevier Science [139].

the rigid rod forming compact coils. The excluded
volume of the poly(allylamine) – metal complexes is
lower than that of poly(allylamine) alone indicating that
intrachain polymer – metal ion interaction is preferred, a
fact that was corroborated by FT-IR spectroscopy and
TGA.
6. Ultrafiltration results as function of different variables
6.1. Nature of the polymer and the metal ion
It is of great interest to know what the parameters are
that could allow distinguishing polyelectrolytes from
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 195

Fig. 13. Effects of the shear rate on the apparent viscosity of (a) mixture of poly(allylamine): CoCl2 (V) 1:1; (B) 2:1; (O) 3:1; and (X); 4:1 and
(b) poly(allylamine) –metal complexes, (V) Cu; (B) Co; and (O) Ni at pH 3.0 and 20 8C. 2.0 g/dL of poly(allylamine). Reprinted with
permission from Polym Bull 2000;45:69. q 2000 Springer-Verlag GmbH & Co [142].

water-soluble chelating polymers by ultrafiltration based on ions with both polyelectrolytes and chelating polymers does
their interaction patterns with metal ions. Analyzing some not affect appreciably the retention profiles of each metal
previous literature [35,39,40,45,50,52,55,56,58,72 – 74], it ion considered individually. A more detailed numeric
can be concluded that the nature of the interaction of metal analysis of the retention functions associated with the
196 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
retention profiles shows that only in polyelectrolyte systems
is the retention parameter, kZ, generally found to be greater
than 1 [58]. Despite every individual retention profile would
not allow distinguishing the nature of the interaction, some
specific tendencies are found when comparing the retention
profiles of mixtures of metal ions ultrafiltered under
different conditions. Typical polyelectrolyte behavior,
where electrostatic interactions are dominant, implies that
all like charged metal ions are similarly retained at given
experimental conditions. The interactions between poly-
electrolytes and metal ions are very dependent on the ionic
strength, and low interaction rates are found when the ionic
strength is high [58,97]. Consequently, at pH 1, where the
concentration of the monovalent Hþ ions is high, low
interaction rates are always found. The interaction rates
increase rapidly increasing the pH, and high retention values
are found for divalent and trivalent metal ions at pH above 3.
On the contrary, when interactions occur by formation of
coordinating bonds, the nature of the metal ions and the
effect of the pH may induce differences in the retention
profiles of like charged metal ions and selectivity is often
informed [35,39,40,45,55,72,73].
The polyelectrolyte pattern has been found in homo-
polymer containing sulfonate groups like PSS or PAPS.
Polymers containing carboxylic groups, such as PAA or
PMA, behave as weak polyelectrolytes, and show high
retention values at pH above 3. They also have chelating
properties, and it is found that interactions with Cu2þ are
normally more intense than with other divalent metal ions.
The polychelatogen pattern is found in polychelatogenes
like PAP, PHEI, PEI, etc. When copolymers that contain
both chelating and charged groups are concerned, their
relative comonomer composition influences its behavior.
The retention behavior for the copolymer PAP-co-PAPS
containing sulfonate groups and amino groups in a 1:1
composition is compared in Fig. 14 with the behavior of the
corresponding two homopolymers PAPS and PAP [71]. The
experiments are performed so that 0.01 M of sulfonate
groups are present in the cell solution containing PAPS or
PAP-co-PAPS, and 0.01 M of piperazine pendant groups are
present when using PAP or PAP-co-PAPS. The results for
the retention of Co2þ when the initial solution has been
eluted with a volume of water of 10 times the volume of the
solution inside the ultrafiltration cell [R2(10)] are shown. It
can be seen that the copolymer loses its ability to bind the
metal ion, a fact that can be explained postulating an
interaction of the sulfonate groups with the amino groups by
charge transfer forces or hydrogen-bonded forces that
should block both functional groups. Concerning the
evolution of the R2(10) values with the pH it can be seen
that PAPS shows a typical polyelectrolyte behavior, while
PAP shows a pattern corresponding to a chelating polymer.
The presence of other polymeric species in solution
affects the metal ion binding ability. Higher order structures
may be formed between different polymers in solution. They
are ordinarily observed as phase separation phenomena,
1
0.9
0.8
0.7
0.6
R 2(10)
0.5
0.4
0.3
0.2
0.1
0
0 2 4 6 8
pH
2þ
Fig. 14. Plot of R2(10) of Co as a function of the pH for the
polymers (V) PAP, (B) PAPS, and (O) PAP-co-PAPS. Reprinted
from J Membrane Sci 2001;187:271. q 2001 with permission from
Elsevier Science [71].
such as precipitation, gelation, coacervation, and emulsion,
or crystallization and liquid-crystallization of polymers or
self-assembly of subunits of biopolymers. In dilute solution,
all macromolecular chains undergo interactions with each
other resulting in the so-called intermolecular excluded
volume effect. In these aggregation phenomena, the
formation of intermolecular complexes is attributed to the
fact that macromolecules with complementary binding sites
interact with each other almost stoichiometrically in
solution due to secondary binding forces as Coulombic
forces, hydrogen-bonding forces, van der Waals forces,
charge transfer forces, exchange repulsion, hydrophobic
interactions, ion – dipole interactions and solvophobic inter-
actions. Extended literature has been published about
intermolecular complexes [143 – 150].
Poly(acrylic acid) and polyacrylamide form a complex
containing hydrogen-bonds. The interpolymer complexa-
tion between a polyacid and a proton-acceptor polymer in
water solution has been extensively studied [143,144,
146–150]. Interpolymer complexes between poly(acrylic
acid) and poly(acrylamide)s have been studied by several
authors [148 – 150]. At low pH or high concentrations, the
interpolymer complex is insoluble in water. The behavior of
the interpolymer complex is dependent on the level of
ionization of poly(acrylic acid). Due to these interactions
between poly(acrylic acid) and different polyacrylamides,
the metal ion binding of the polyacid diminishes in the
presence of the polyacrylamides [57]. This decrease is a
function of the amide – acid relative composition (Fig. 15)
and of the amide structure. As it can be seen in Fig. 16, N,N-
dimethylacrylamide units produce less intense decrease than
acrylamide units, probably due to weaker amide – acid
interactions associated with the steric hindrance of the
substituted amide. It was also shown that, under the same
experimental conditions (pH, metal ion initial concen-
tration) a mixture of two complementary homopolymers
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208 197

100 100
90 90
80 80
70 70
60 60
R (%)

R (%)
50 50
40
40
30
30
20
20
10
10
0
0
0 2 4 6 8 10
0 2 4 6 8 10
F
F
Fig. 15. Retention of Co2þ at pH 5 as a function of F for the systems:
( £ ) PAA, (V) PAm-co-PAA composition 2:1; (B) PAm-co-PAA Fig. 17. Retention of Co2þ at pH 5 as a function of F for the systems:
composition 1:1; (O) P(AAm–AA) composition 1:2. Reprinted ( £ ) PAA, (V) PAm-co-PAA composition 1:1; (B) a 1:1 mixture of
with permission from Macromol Chem Phys 1998;199:1153. PAAm and PAA; (O) PAAm. Reprinted with permission from
q 1998 Wiley-VCH [57]. Macromol Chem Phys 1998;199:1153. q 1998 Wiley-VCH [57].

behaves as the corresponding copolymer of such a
composition that the same concentration of carboxylic and
amide units is kept (Fig. 17). PAA precipitates in the
presence of divalent metal ions as a consequence of charge
cancellation. Precipitation of PAA with Cd2þ in the
presence of PAAm is retarded at a given pH as shown in
Fig. 18. This fact is interpreted considering all interactions
as equilibrium situations and postulating a competitive
reaction between Cd2þ and PAAm to bind the polyacid.
6.2. Polymer concentration
Studies on the formation of polymer– metal ion chelates
suggest that they are formed in a one-step reaction rather
100
90
80
than stepwise [1] when intra-polymer chain chelation
occurs. Even at low ligand ratios, only completely
coordinated metal ions in equilibrium with uncomplexed
ones are found. Physically this fact may be explained
considering the metal ions occluded in a cage of contracted
polymer chains where the concentration of the ligands is
locally higher in the polymer domain. The increase in the
polymer concentration may be interpreted as the increase in
the number of chains and consequently on the number of
polymeric domains with local high and nearly constant
ligand concentration. Comparing experiments under differ-
ent polymer concentration it is found that the influence of
the concentration of the polymer on the formation constants
is of order one, despite that in some cases, at the molecular
0.25
/ mmol PAA

0.2
70
60
R (%)

0.15
50
40
2+

0.1
30
mmol Cd

20
0.05
10
0
0 2 4 6 8 10 0
0 2 4 6 8
F
pH
Fig. 16. Retention of Co2þ at pH 5 as a function of F for the systems:
( £ ) PAA, (V) PDAm-co-PAA composition 2:1; (B) PDAm-co- Fig. 18. Titration of PAA (B) and PAm-co-PAA composition 1:1
PAA composition 2:1. Reprinted with permission from Macromol (V) with Cd2þ as function of pH. Reprinted with permission from
Chem Phys 1998;199:1153. q 1998 Wiley-VCH [57]. Macromol Chem Phys 1998;199:1153. q 1998 Wiley-VCH [57].
198 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

level, the coordination sphere of the metal ion includes 1

several monomeric units. 0.9
This has been observed in ultrafiltration washing 0.8
experiments under variable ionic strength [66]. A linear
0.7
dependency of the logarithm of KZdiss on the logarithm of the
ionic strength in a wide range of ionic strength values has 0.6

u2
been found, and this is related to a linear dependency of the 0.5
logarithm of this magnitude on the filtration factor F. In 0.4
order to compare the retention profiles associated with 0.3
experiments performed with different values of the polymer
0.2
concentration, a formation constant can be defined that
includes the concentration of the polymer in monomeric 0.1
units as: 0

0 0.2 0.4 0.6 0.8 1
KZf ðFÞ ¼ 1= KZdiss ðFÞ·½Ln ð39Þ
c 1init
where [L ] is the concentration of monomeric units, and n is Fig. 19. Plot of u2 versus cinit
1 for the system PSS/Cd2þ: ( £ )
a factor. From experimental data of KZdiss as a function of F, experimental values, (—) predicted values taking the point
the values of n that, for the different experiments, throw a ð0:4; 0:27Þ as reference and k2 ¼ 1:3. Reprinted from J Membrane
unique value of the formation constant at a given F value for Sci 2000;178:65. q 2000 with permission from Elsevier Science
[65].
each polymeric species can be searched.
Three experiments have been performed with each of the concentration of the 1:1 simple electrolyte, since it is in
systems poly(4-sodium styrenesulfonate) PSS/Pb2þ, and excess. The following expression is obtained:
poly(allylamine) PALA/Ni2þ, in the presence of an excess
of Naþ, and the order of the formation constant related with a
!k2
ua2 cinit
1
the concentration of the polymer was quantified [66]. PSS
va2 cinit b

was chosen as a representative of a polyelectrolyte where ub2 ¼ 1

a
!k2 ð40Þ
the sulfonate groups produce typical electrostatic inter- ua cinit
1 þ a2 1
actions with Pb2þ, and PALA was selected as a representa- v2 cinit
1
b

tive of a coordination-predominant polymer due to the high

coordinating ability of the amine groups. In both cases, it
was found that for n ¼ 1 the values of the formation
constants are equivalent, and then, the influence of the
concentration of the polymer on the formation constants is
of order one.
6.3. Ionic strength
As indicated in Section 3.2.2, the ionic strength
influences the ability of the metal ions to bind the polymer.
This is attributed to a change in the value of the dissociation
constant during filtration, due to screening effects, changes
in the polymer conformation, and a competition of
monovalent metal ions with polyvalent ones to bind the
polymer [58,77]. When the ionic strength is high, the
dissociation constant increases, decreasing the retention
ability of the polymer.
Dealing with PSS and Cd2þ in the ultrafiltration washing
method under variable ionic strength, assuming that there is
a unique application between the ionic strength and the
dissociation constant of its interactions with the divalent
metal ion (assumption 6), it is possible to predict the
unknown retention parameters corresponding to an exper-
iment b from the known ones corresponding to another
experiment a performed under different initial ionic
strength. At the initial stages, the ionic strength equals the
where the numeric subscripts are referring the charge of the
metal ions. To deduce this expression it has been assumed
that interactions between the polymer and the monovalent
ions are negligible (assumption 7). The combination of
assumptions 6 and 7 yields the conclusion that the retention
parameter kZ is a parameter inherent to the polymer. It has
been found that this parameter changes from one experiment
to another when changing the experimental conditions.
Assumption 7 is difficult to justify in the case of
polyelectrolytes, but good qualitative predictions have
been made [65], as it is shown in Fig. 19.
6.4. Effect of the pH
The effect of the pH may be regarded in several ways.
For strong polyelectrolytes, very low pH values are
associated to a high ionic strength, and in consequence,
competition of Hþ with divalent metal ions to condense on
the polymer surface is established. It has been described,
however, that Pb2þ easily removes Hþ ions from PSS than
Naþ ions, due to differences in the hydrodynamic volume of
the monovalent metal ions [100]. Thus, in ultrafiltration
experiments performed at pH near 1, elution of divalent
metal ions takes place from the polymer domain; while at
pH 3 significant binding is found, as can be seen in Fig. 20
for PSS. Weak polyelectrolytes such as polycarboxylic
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
100
90 Cd2+
80
70
60
R(%) 50
40
30
20
10
0
1 3 5 7
2þ 2þ 2þ
Fig. 20. Retention values of Cd , Ni , and Co at four different pH and F ¼ 10: Polymers: white, PAA; grey, PSS. Reprinted with
permission from J Appl Polym Sci 1998;70:219. q 1998 Wiley & Sons, Inc [56].
acids, present high retention ability at pH above 4.5, where
most carboxylic units are deprotonated. For these polymeric
compounds, there is not a fixed acidity constant, and
carboxylic units deprotonate successively in a range of pH;
for poly(acrylic acid) this range takes values between 3.5
and 6 (Figs. 18 and 20). This influences the polymer
conformation and the linear or surface charge density,
changing the metal ion binding ability. Unlike to PSS,
PAA does not retain divalent metal ions at pH 3 as shown in
Fig. 20.
Concerning the metal ions, predominant species may be
present as a function of the pH. Precipitation of the hydroxy-
complexes is a phenomenon to avoid for LPR studies, so
that, Cu2þ cannot be studied at relative high concentrations
over pH 5, and Fe3þ may be studied until pH 3, since above
this pH value a gel is formed.
7. Biological applications
In all living systems metal ions, either as isolated ions or
in clusters, play an essential role. This role deals with both
growth and metabolism. However, metal ions may also have
deleterious effects as toxic substances or play an important
role in metal-containing drugs. Examples of these metal-
containing drugs are: gold-thiolate and copper carboxylate
compounds in the treatment of arthritis; bismuth salts in the
treatment of ulcers; lithium salts to suppress symptoms of
manic depression; radiopharmaceutical imaging with tech-
netium coordination compounds; platinum – amine com-
pounds as anti-tumor drugs, etc. [151]. Most well
understood is the mechanism of the action of platinum-
anti-tumor compounds, and particularly their selective
binding to DNA. cis-Dichlorodiamineplatinum(II) has
been widely used for cancer therapy in spite of its severe
renal toxicity. Many approaches have been attempted to
199
Ni2+ Co2+
1 3 5 7 1 3 5 7
pH
synthesize new platinum complexes having a broader
spectrum of anti-tumor activity, reduced side-effects,
greater solubility, and lack of cross-resistance with cis-
platinum. Polymers as drug carriers have been investigated
to achieve efficient delivery of anti-cancer agents to tumor
cells. In comparison with a low-molecular weight prodrug, a
macromolecular prodrug can be expected to overcome the
problem of side-effects by improving the body distribution
of drugs and prolonging their activity [152,153].
Drobnik and Rypácek [154,155] have studied the
behavior of water-soluble polymers such as: poly(acryl-
amide), poly(4-vinylpyridine), derivatives of poly(asparta-
mide), poly(ethyleneimine), and derivates of
poly(methacrylamide) with dextrane, in biological systems.
Duncan [156] studied several polymers and their potential
use as drug carriers. The effect of the molecular weight
distribution on the biological properties has been studied by
Hespe and co-workers [157]. Similar studies were carried
out with copolymers of divinyl ether and maleic anhydride
[158]. The highest molecular weight fractions showed the
highest toxicity. Muck and co-workers [159,160] described
the influence of the molecular weight and tacticity of
poly(acrylic acid) and poly(methacrylic acid) on the
biological properties. Isotactic poly(acrylic acid) shows an
anti-virus activity higher than that of the atactic polymer
fraction, whereas the most active molecular weight fraction
was between 6000 and 15 000. Isotactic poly(acrylic acid)
with a narrowest molecular weight distribution showed a
higher anti-virus activity.
Other important group of polymers with biological
activity has been reported like polyphosphazenes [161],
derivates of poly(methacrylic acid) [162 – 164], synthetic
poly(aminoacids) [165,166], analogues of nucleic acids
[167,168], poly(ethylene oxide) [169], copolymers of vinyl
pyrrolidone [170], polyamides, and polyamines [171]. The
structure of these polymers was modified by incorporating
200 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
hydrophobic interactions [172], as sugar residues and
sulfenil groups to improve the affinity of these polymers
for the biological tissue. Choi and co-workers [173],
synthesized and studied the biological activity of a-
methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophtaloyl-5-fluo-
rouracil and its corresponding polymer. The study in vitro
showed a high anti-tumoral activity. Nonoka and co-workers
[174], synthesize resins from phenol derivatives, which
showed a high bactericide activity for Eschericchia coli and
Staphylococcus aureus. To determine the bactericide
activity they used the decreasing viable cell number method
in a suspension of bacteria at different contact time with the
resin. Taek Oh and co-workers [175], synthesized and
studied the effect of the polymer concentration, exposure
time, and copolymer composition on bactericide activity of
copolymers containing diphenyl ether moiety for E. coli and
S. aureus.
The polymeric biocides are very interesting due to the fact
that they show important advantages with respect to the
monomeric analogues [176]. Some advantages of polymeric
based anti-bacterial agents compared with conventional anti-
bacterial agents of low molecular weight compounds, are that
the former are non-volatile, chemically stable, and difficult to
permeate through the skin of man or animal. So, they can
reduce the loss associated with volatilization, photolytic
decomposition, and transportation. An important group of
synthetic water-soluble polymers, basically polycations, that
contain ammonium and phosphonic groups at the side chain
show a high anti-bacterial activity. Variables like molecular
weight, dose, and contact time were also studied.
The use of polymer– metal ion adducts may open new
strategies in biological applications. In most cases, the
water-soluble polymer– metal complexes exhibit a cationic
polyelectrolyte behavior in aqueous solution. For this reason
they are potentially biologically active compounds. In this
context, Lee and Rashidova [177] studied the biological
activity, toxicity, immunological response and the pharma-
cokinetics of several polymer metal complexes of N-
vinylpyrrolidone and derivatives of N-2-hydroxypropyl-
methacrylamide with transition metals. The effect of the
macroligand type, polyacid behavior, and the comparison of
the biological properties between the polymer – metal
complexes and the polymer bases were performed. Nandi
and co-workers [178] studied the bactericide activity of
metal ions and polymer – metal complexes with Co2þ, Zn2þ
and Cu2þ whereas Nonaka and co-workers [179] studied the
bactericide activity for E. coli and S. aureus of resins
containing the triethylamine and thiols as side groups and
the metal ions Agþ, Cu2þ and Zn2þ. The best results were
observed for the resin containing Agþ. The results were
compared with the free metal ions.
The electrostatic interaction of the positive charges on
the molecules of the anti-bacterial agents with the
negatively charged species present in the cytoplasm
membranes (i.e. acidic phospholipids and membrane
proteins) is the first step for the biocide action of these
compounds. A series of events may then occur leading to the
death of the bacteria. In our laboratory [180,181] some
water-soluble cationic polymers were synthesized: homo-
polymers such as poly(4-vinylpyridine) N-alkylated
(PVPyMe), poly(diallyl dimethylammounim) chloride
(PDDA), poly[((3-methacryloylamino) propyl)trimethylam-
monium chloride] (PMPTA), copolymers such as poly[2-
acrylamido-2-methyl-1-propanesulfonic acid-co-(3-(metha-
cryloylamino) propyl) trimethylammonium chloride
(PAPS-co-PMPTA), and polymer – silver(I) complexes as
PVPyMe – Ag. Their potential bactericide activity for
Gram(þ) and Gram(2) bacteria has been investigated.
Variables such as molecular weight, concentration, contact
time, and metal ratio in polymer –silver(I) complexes were
considered. Moreover, the genotoxicity of anti-bacterial
polymer– silver(I) compounds was also studied.
The results regarding bactericide activity minimum
inhibitory concentration (MIC) and minimum bactericide
concentration (MBC) are summarized in Table 5. All the
compounds, except Ag(I) ion, show bactericide activity only
for S. Aureus. Ag(I) ions had a high bactericide activity
either for S. aureus as well as for E. coli. It is well known
that the structural difference between the Gram(þ) and
Gram(2 ) bacteria is the cell wall. Hence, the different
bactericide action may be explained on the basis of this
difference. The non-bactericide activity of these com-
pounds, except Ag(I) ions toward Gram(þ) bacteria, is
attributed to the presence in this type of bacteria of an
additional membrane at the cell wall whose main com-
ponents are proteins, lipids, and lipopolysaccharides (LPS).
These LPS give negative charges to the surface cell, which,
in principle, could allow interactions with the polycations
PDDA and PVPyMe. However, these LPS repel hydro-
phobic molecules. Nevertheless, the polymers have positive
charges, and hydrophobicity due to the large carbon
backbone and side chains. No important effect of the
molecular weight or macromolecular size on the MBC value
was observed. The compounds show two main different
actions on the anti-bacterial activity. For example, Agþ
ions, PVPyMe (3000 – 10 000, 100 000 – 1 000 000 Da),
PDDA (all fractions), and PVPyMe – Agþ show anti-
bacterial activity. These compounds show their positive
charge close to the backbone, which increases the charge
density, and hence increases also their bactericide action.
The polycation may be placed near the cell wall or penetrate
the cell wall of the S. aureus bacteria, blocking the ion
channels, producing a total blocking of ionic transport,
causing the death of the cell (Fig. 21). On the contrary,
PMPTA, shows only bacteriostatic actions. This compound
has the charged groups in a lateral chain, at a longer distance
from the main chain, and thus the charge density is lower.
This fact induces a weaker interaction between the cell wall
and polycations (Fig. 21).
The kinetics of bacteria death for the polymers PVPy–
Me and PVPyMe – Agþ (polymer/Agþ mol metal ion ratio:
21.6) were investigated with respect to S. aureus. The results
Table 5
Minimum inhibitory concentration (MIC) and minimum bactericide concentration (MBC) of polymers, Ag(I) and polymer –Ag(I) complex

Compound RMS (nm) Mw ( £ 1025 g/mol) MIC (mg/ml) MBC (mg/ml)

B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

S. aureus, 6538P E. coli, ATCC28922 S. aureus, 6538P E. coli, ATCC28922

PVPy –Me (100 000 –1 000 000 Da) 51.4 1.48 64 .128 128 –
PVPy –Me (30 000 –100 000 Da) 41.6 0.85 64 .128 64 –
PMPTA (10 000 –30 000 Da) 23.7 1.92 32 .128 .128 –
PDDA (10 000 –30 000 Da) 24.1 0.59 16 .128 16 –
PDDA (30 000 –10 000 Da) 28.0 1.03 32 .128 32 –
PDDA (.100 000 Da) 36.4 2.44 32 .128 32 –
(PMPTA-co-PAPS)12 (.100 000 Da) 28.4 4.53 .128 .128 – –
PMPTA-co-PAPS)12 (.100 000 Da) 32.8 3.85 .128 .128 – –
PVPyME–Ag (21.6)a (10 000–1 000 000 Da) – – 64 .128 64 –
PVPyME–Ag (10.8)a (10 000–1 000 000 Da) – – 32 .128 64 –
PVPyME–Ag (5.4)a (10 000–1 000 000 Da) – – 32 .128 64 –
(PMPTA-co-PAPS)21Ag (.100 K) (21.6)a – – .128 .128 .128 –
(PMPTA-co-PAPS)21Ag (.100 K) (10.8)a – – .128 .128 .128 –
(PMPTA-co-PAPS)21Ag (.100 K) (21.6)a – – .128 .128 .128 –
(PMPTA-co-PAPS)21Ag (.100 K) (10.8)a – – .128 .128 .128 –
Agþ ðNO2
3 Þ 2.0 2.0 2.0 2.0
a
Polymer/Agþ mol ratio.

201
202 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208

(a) (b)

Fig. 21. Suggested action mechanism of the (a) bactericide compounds and (b) bacteriostatic compound toward Gram(þ ) bacteria.

are shown in Fig. 22. Both compounds show a similar
behavior with a reduction percentage of bacteria higher than
90% before 60 min. On the other hand, all the compounds
showed no evidence of genotoxicity, except silver ions,
which are in the borderline. That means, that the polymer
backbone plays an important role as to the incorporation of
silver ion, a potential genotoxic agent, in this water-
functional polymer, significantly decreasing the
genotoxicity.
8. Analytical applications
The ultrafiltration technique has been used to
indirectly analyze the concentration of low molecular
weight complexing molecules (LMWCM). The retention
profiles associated with the interaction of a water-
soluble polymer with a metal ion may be sensible to the
presence of a LMWCM. Thus, the problem of analyzing
a LMWCM concentration is turned to analyzing a metal
species concentration, yielding in a potential increase on
the sensibility. A linear dependency of the retention
values as a function of F on the amount of LMWCM
present in the initial solutions ultrafiltered under the
washing method at constant ionic strength has been
found [182]. This allowed the quantification of imino-
diacetic acid (IDAA) in a range of concentrations
between 1024 and 1025 M when 1.6 £ 1024 M Cu2þ
solutions at pH 4 are ultrafiltered in the presence of
PSS, NaNO3, and variable amounts of IDAA, maintain-
ing constant the ionic strength (Fig. 23). On the other
hand, the use of the washing method at variable ionic
strength showed a linear dependency of the values of u2
on the initial concentration of LMWCM [183]. The
technique allowed for the measuring of IDAA in a
range of concentrations between 1024 and 5 £ 1026 M
when a 1.0 £ 1024 M Cu2þ solution was ultrafiltered
with water at pH 4 without adding any single electrolyte

100

80
r e d u cctio n o f bacte r ia (%)

60

40

20

0
0 30 60 90 120
tim e (m in )

Fig. 22. Kinetics of bacteria dead for (O ) PVPyMe (100 000–1 000 000 Da) and (W) PVPyMe –Ag(I) (polymer/metal ion ratio: 21.6).
Reprinted with permission from J Appl Polym Sci (in press). q 2002 John Wiley & Sons, Inc [180].
 B.L. Rivas et al. / Prog. Polym. Sci. 28 (2003) 173–208
0.9
0.8
0.7
0.6
0.5
R
0.4
0.3
0.2
0.1
0 0
0 2E-05 4E-05 6E-05 8E-05 1E-04
[IDAA] (M)
Fig. 23. Retention values as a function of the concentration of IDAA
in the samples ultrafiltered ([IDAA]): (B) experimental values, F ¼
5; experimental values, (V) F ¼ 2; (—) linear adjustments: y ¼
23346:2x þ 0:8177; R2 ¼ 0:9793 ðF ¼ 2Þ; y ¼ 22640:0x þ
0:5587; R2 ¼ 0:9833 ðF ¼ 5Þ. Reprinted with permission from
Anal Chem 2001;73:5468. q 2001 American Chemical Society
[182].
as eluent, in the presence of 0.02 mol of monomeric
units per liter of PSS, 0.04 M of NaNO3, and variable
amounts of IDAA (Fig. 24).
Selective separation of metal ions is an important
tool for practical applications of the ultrafiltration
technique. As explained previously, unlike charged
metal ions could be discriminated by polyelectrolytes
[56] but a large excess of the less charged metal ion can
displace the higher charged one from the polymer
domain. Selectivities concerning the metal ion species
can be found using chelating polymers [35,39,40,45,55,
72,73].
Ultrafiltration has also been used to examine the size
fractionation of various metal ions that can induce
spoilage reactions in wine. These spoilages processes
include precipitation of hydrogen tartrate (potassium) or
tartrate salts (calcium), enhanced rate of oxidation
(copper, iron) and haze formation (copper, iron, and
aluminum). Scollary and co-workers [184] have inves-
tigated the size fractionation of lead, copper, iron,
aluminum, calcium, potassium, and sodium in white and
red wines. Fractionation patterns demonstrated that the
behavior of lead is significantly different from other
metal ions. In red wine, there was a sudden decrease for
lead between 100 000 and 30 000 Da (MMCO) and in
white wine, a gradual decrease in the lead concentration
was observed from 100 000 Da (MMCO). Iron was the
only other metal ion, which showed, for red wine, a size
distribution pattern with a reduction in the concentration
between 30 and 50% from 100 000 to 1000 Da
(MMCO).
203
1
0.9
0.8
0.7
0.6
u2
0.5
0.4
0.3
0.2
0.1
0 2E-05 4E-05 6E-05 8E-05 0.0001
[IDAA] (M)
Fig. 24. u2 values as a function of the concentration of IDAA in the
samples ultrafiltered ([IDAA]): (V) experimental values; (—) linear
adjustment: y ¼ 28775:1x þ 0:8527; R2 ¼ 0:9758 [183].
Acknowledgments
The authors thank FONDECYT (Grant Lineas Comple-
mentarias No 8990011), to the Dirección de Investigación,
Universidad de Concepción, (Grant No. 98.24.17-1), and to
the Dirección de Investigación of the Universidad Austral de
Chile (Grant No. 200126) for partial financial support.
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