On the Binding of Calcium by Micelles Composed of Carboxy-Modified Pluronics Measured by Means of Differential Potentiometric Titration and Modeled with a Self-Consistent-Field Theory

Lauw, Y.; Leermakers, F.A.M.; Stuart, Martien A. Cohen; Pinheiro, José Paulo; Custers, Johan P.A.; Broeke, L.J.P. van den; Keurentjes, J.T.F.

doi:10.1021/la061300i

Cited by 6 publications

(3 citation statements)

References 31 publications

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“…In addition, the width of the transition region (from the start of micellization to its completion) is concentration dependent in P85 solutions: with increasing concentration, the width increases from 1.0 C to 5.2 C. In CAE85 solutions, the transition width does not change signicantly and it uctuates around 1.0 C (Table 1) for concentrations between 5 wt% and 15 wt%. The micellization parameters obtained in this work compare favorably with the report of Lauw et al: 41 the CMT of approx. 20 C for the concentration of about 2 wt% at ionic strength of 5 Â 10 À3 M and at pH ¼ 7.…”

Section: Discussionsupporting

confidence: 89%

The effect of micellization-induced deprotonation on the associative behavior of a carboxyl modified Pluronic P85

et al. 2014

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Thermoresponsive polymeric surfactant CAE85 is a telechelic carboxyl group derivative of Pluronic P85 and its carboxyl end-groups undergo deprotonation into carboxylate groups upon micellization. Micelle formation and disintegration were studied here by means of small angle X-ray scattering, FTIR and Raman spectroscopy, quantum mechanical calculations and dynamical mechanical analysis. The deprotonation was observed in aqueous solutions of CAE85 for concentrations from 5 wt% to 30 wt% at temperatures above the corresponding critical micellization temperature (CMT). The most likely cause is a difference between the proton dissociation constant of the micelle (pK(m)) and the proton dissociation constant of the unimers in solution (pK(a)); our observations indicate that pKm < pK(a). For concentrations up to 15 wt%, the presence of carboxylate groups in CAE85 lowered the CMT in comparison with P85. In addition, the behavior of CAE85 was generally not thermo-reversible and reproducible upon cooling. Quantum chemical calculations showed that, in the dense micelle corona, the deprotonated states were more stable than hydrogen-bonded states of neutral molecules, which is likely to affect the equilibrium processes in the micelle. In contrast to the unmodified P85, no gelation was observed in the case of CAE85. By studying the processes at all the levels of organization from nanoscale charge formation through micellization to the macroscale process of gelation, our understanding of polymeric micelle formation may be advanced.

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Section: Discussionsupporting

confidence: 89%

The effect of micellization-induced deprotonation on the associative behavior of a carboxyl modified Pluronic P85

et al. 2014

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“…The results exhibited the expected collapse of the layer with increased ionic strength at low grafting density and the re-entrant phenomena of stretched chains with increased ionic strength at high grafting density. In turn, 1:1 binding of Ca

to micelles composed by carboxylic acid end-standing Pluronic P85 block copolymers was studied both experimentally by differential potentiometric titration measurements and by SF-SCF theory [ 149 ]. The authors included both acid–base equilibrium and ion condensation reactions into the model, and found that Ca

ions bind both electrostatically and specifically.…”

Section: Applicationsmentioning

confidence: 99%

Theoretical Modeling of Chemical Equilibrium in Weak Polyelectrolyte Layers on Curved Nanosystems

et al. 2020

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Surface functionalization with end-tethered weak polyelectrolytes (PE) is a versatile way to modify and control surface properties, given their ability to alter their degree of charge depending on external cues like pH and salt concentration. Weak PEs find usage in a wide range of applications, from colloidal stabilization, lubrication, adhesion, wetting to biomedical applications such as drug delivery and theranostics applications. They are also ubiquitous in many biological systems. Here, we present an overview of some of the main theoretical methods that we consider key in the field of weak PE at interfaces. Several applications involving engineered nanoparticles, synthetic and biological nanopores, as well as biological macromolecules are discussed to illustrate the salient features of systems involving weak PE near an interface or under (nano)confinement. The key feature is that by confining weak PEs near an interface the degree of charge is different from what would be expected in solution. This is the result of the strong coupling between structural organization of weak PE and its chemical state. The responsiveness of engineered and biological nanomaterials comprising weak PE combined with an adequate level of modeling can provide the keys to a rational design of smart nanosystems.

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“…Research on self-assembled amphiphiles in an aqueous solvent has been intensified in the last couple of decades [1][2][3][4][5][6][7][8][9]. Amphiphiles consist of both hydrophobic and hydrophilic parts and they form aggregates (micelles) with particular morphologies in a selective solvent.…”

Section: Introductionmentioning

confidence: 99%

On the Binding of Calcium by Micelles Composed of Carboxy-Modified Pluronics Measured by Means of Differential Potentiometric Titration and Modeled with a Self-Consistent-Field Theory

Cited by 6 publications

References 31 publications

The effect of micellization-induced deprotonation on the associative behavior of a carboxyl modified Pluronic P85

The effect of micellization-induced deprotonation on the associative behavior of a carboxyl modified Pluronic P85

Theoretical Modeling of Chemical Equilibrium in Weak Polyelectrolyte Layers on Curved Nanosystems

Equilibrium morphologies of nonionic lipid–nanoparticle mixtures in water: A self-consistent mean-field prediction

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