Vinyltoluene‐styrene copolymer sulfonic acid. I. Viscous properties and ionic character in hydrochloric acid solutions

Mock, Richard A.; Marshall, Charles A.

doi:10.1002/pol.1954.120136906

Cited by 68 publications

(12 citation statements)

References 14 publications

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“…A measure of success was achieved in description of the data, however, through use of the Hindered Access Model [1] (see Equation 2.13). The data were also consistent with an extended PSS conformation in the presence of low concentrations of salt, which is in agreement with other fluorescence data [87,145,150] and light scattering and viscosity measurements [136][137][138][139] Potentiometric [50] and viscometric [151] measurements on poly [2-(dimethylamino) ethyl methacrylate] (PDMAEMA) indicate that the polyelectrolyte undergoes a conformational change from an expanded structure at low pH when the amine unit is fully protonated, to a collapsed structure at high pH. The data were also consistent with an extended PSS conformation in the presence of low concentrations of salt, which is in agreement with other fluorescence data [87,145,150] and light scattering and viscosity measurements [136][137][138][139] Potentiometric [50] and viscometric [151] measurements on poly [2-(dimethylamino) ethyl methacrylate] (PDMAEMA) indicate that the polyelectrolyte undergoes a conformational change from an expanded structure at low pH when the amine unit is fully protonated, to a collapsed structure at high pH.…”

Section: Polystyrene Sulfonic Acidsupporting

confidence: 92%

“…This contrasts to the behavior observed for a similarly labeled PMAA [87], which could only be modeled through use of a double-exponential function of the form of Equation 2.7. The fact that only one excited state species is present in the PSS sample is indicative that the coil is more homogeneous in nature which is consistent with an extended conformation [136][137][138][139] under salt-free conditions. The fact that only one excited state species is present in the PSS sample is indicative that the coil is more homogeneous in nature which is consistent with an extended conformation [136][137][138][139] under salt-free conditions.…”

Section: Polystyrene Sulfonic Acidsupporting

confidence: 53%

“…However, the degree of water penetration and expansion in this conformation is such that PAA is unable to solubilize probes [17] or certainly presents the low molar mass material with a microenvironment very similar to that of the aqueous phase [20]. Viscosity and light scattering measurements [136][137][138][139] indicate that PSS exists in an extended conformation at all pH values but forms a compact coil under high salt concentrations. Viscosity and light scattering measurements [136][137][138][139] indicate that PSS exists in an extended conformation at all pH values but forms a compact coil under high salt concentrations.…”

Section: Discussionmentioning

confidence: 99%

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Optical Properties of Polyelectrolytes

Swanson

2010

Photochemistry and Photophysics of Polymer Materials

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A polyelectrolyte can be defined as a macromolecule with ionizable repeat units, which can consequently display pH-dependent behavior when dissolved in aqueous solution.As the term polyelectrolyte can also be extended to encompass natural biopolymers, which contain ionizable groups such as peptides, proteins, and DNA, it is perhaps not surprising that synthetic polyelectrolytes are often used as simple models for more complex biological systems. Indeed, many of the photophyscial techniques discussed in this chapter were developed by biologists and biophysicists interested in the conformational behavior and interactions of biopolymers [1].

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Section: Polystyrene Sulfonic Acidsupporting

confidence: 92%

Section: Polystyrene Sulfonic Acidsupporting

confidence: 53%

Section: Discussionmentioning

confidence: 99%

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Optical Properties of Polyelectrolytes

Swanson

2010

Photochemistry and Photophysics of Polymer Materials

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“…In this case the expressions for Ye and Yeo are different. We then have: ~= ---41teoB,kBTb (6) Experimental investigations 8 • 9 show that the DebyeHiickel approximation is not always sufficiently accurate to describe the polyion small ion interactions. In many cases, there is a large discrepancy in coion and counterion activities for polyions where is lower than I Ze 1-1 .…”

mentioning

confidence: 99%

Studies of Polyelectrolyte Solutions VI. Effects of Counterion Binding by Dextran Sulfate and Dextran Phosphate in Aqueous/Organic Solvents

Baré

Nordmeier

1996

Polym J

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ABSTRACT:The influence of the solvent on the degree of counterion binding of dextran sulfate and dextran phosphate is studied by activity measurements, dye-spectroscopy, and static light scattering. The solvents used are binary mixtures of water and organic solvents such as acetone, alcohol, and formamide. The mixing ratio is varied over a wide range in order to obtain different solvent dielectric constants. The results of investigations are as follows. First of all, in pure water the alkali ions are bound by dextran sulfate in the order Cs+ > K + >Na+> Li+, i.e., the degree of counterion binding for Li+ is lowest while that for Cs+ is largest. The inverse ion sequence is observed for dextran phosphate. In mixed solvents the ion sequence depends on the mixture used. Secondly, there exists no universal correlation between the dielectric constant of the solvent and the degree of counterion binding. However, it is common to all aqueous/organic solvent mixtures that the degree of counterion binding decreases as the fraction of the organic compound in the solvent increases. Thirdly, condensation theory is not valid in mixed solvents, while the Poisson-Boltzmann approach may be applied. Taking into account the size of the solvated small ions we find that the type of counterion binding of a divalent counterion, such as Mg 2 +, depends on the kind of the univalent counterions added in excess. For water/n-propanol it seems that in the presence of Li+, Mg2+ is bound delocalized, while in the presence of K +, Mg 2 + is bound by site binding. Fourthly, in water/formamide and water/dimethyl sulfoxide (DMSO) the organic solvents are adsorbed preferably by dextran sulfate. As a consequence, the dielectric constant at the polyion surface differs from that of the bulk solvent. Nevertheless, if these changes are taken into account, the predictions of condensation theory remain contradictory to the results of measurements.KEY WORDS Dextran Sulfate / Dextran Phosphate / Counterion Binding / Mixed Solvents / Activity Coefficients / Dielectric Constants / Dye Spectroscopy / Static Light Scattering / There has been great interest in studying the interactions between polyion and simple electrolytes, as this information provides a key to the understanding of biological processes since many biopolymers are polyelectrolytes. A well established result has been that an extra amount of counterions will bind on the polyion of almost all bulk counterions. For instance, in previous reports, 1 -3 we have shown that the polyion charge density and the kind of charged groups play an important role for the degree of counterion binding, but it is also expected that the solvent, in which the polyelectrolyte chains are dissolved, have some influence. Studies in water and aqueous/organic solvent mixtures are therefore very important. The reasons are:I. A certain property of the solvent such as a define value of the dielectric constant, s,, or a particular value of the refractive index, n, can be more precisely adjusted in mixed than in single solvents. ...

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“…It should be noted at this point that eqn (4) shows the complex dependence of the elution volume on polyion concentration in s.e.c. using salt-free water as eluent and allows the prediction of V(cp, O) at any c p value with the only requirement that two calibration curves be experimentally obtained at two polyelectrolyte concentrations, (C p)l and (cph.…”

Section: Prediction Of the Effect Of C P On V(cpo)mentioning

confidence: 95%

Solution properties of polyelectrolytes. II. Comparison of the effects of both polyion and eluent salt concentrations on the calibrations in aqueous exclusion chromatography

Abad¹,

Braco²,

Soria³

et al. 1987

Brit. Poly. J.

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The elution behaviour of charged water‐soluble polymers (sodium polystyrene sulphonate) in both salt‐free and NaCl‐containing aqueous mobile phases has been investigated by size‐exclusion chromatography. A comparative analysis has been established between the results as a function of polyion and salt concentrations, which demonstrates that the chromatographic behaviour is similar in both cases. The variation of the slopes of the different concentration‐dependent calibration curves is discussed in terms of polyelectrolyte conformational changes. Finally, a semi‐empirical model has been developed to predict the dependence of the elution volume in either polyion or salt concentration, and its validity has been checked in a range from very dilute to moderate concentrations.

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Vinyltoluene‐styrene copolymer sulfonic acid. I. Viscous properties and ionic character in hydrochloric acid solutions

Abstract: Conductance measurements on dilute polyelectrolyte solutions recently carried out by Doty and Othl and by Wall and co-workers2 have shown that 2 0 0 0.3 0.6 POLYMER CONC. (g./rnI.) Y 10' 9

Cited by 68 publications

References 14 publications

Optical Properties of Polyelectrolytes

Optical Properties of Polyelectrolytes

Studies of Polyelectrolyte Solutions VI. Effects of Counterion Binding by Dextran Sulfate and Dextran Phosphate in Aqueous/Organic Solvents

Solution properties of polyelectrolytes. II. Comparison of the effects of both polyion and eluent salt concentrations on the calibrations in aqueous exclusion chromatography

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