Chain-length dependence of the electrophoretic mobility in random gels

Arvanitidou, Evangelia; Hoagland, David A.

doi:10.1103/physrevlett.67.1464

Cited by 74 publications

(81 citation statements)

References 22 publications

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“…The expected decrease of the gel pore size with increasing gel density is clearly observed. A least squares fit to the three data points yields g ∼ c -1.1 , which overestimates the expected exponent 74 ( g ∼ c -3/4 for semidilute good solutions) and lies closer to the Θ solvent values ( g ∼ c -1 for semidilute Θ solutions).…”

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

“…Following the suggestion in ref 74, the mass size scaling of the tracer polymer is also described by the Flory behavior, i.e., ν ) 3/5 in eq I. 74. Figure 11 includes fits with the PMC results, eqs I.79 and I.80, for the model of tracer and gel equilibrium structures described above.…”

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

“…We use this consideration also to a priori fix the ratio of entanglement length to gel pore size to the value, δ ) /b ) 0.3, found for solutions in the previous section. Following the suggestion in ref 74, the mass size scaling of the tracer polymer is also described by the Flory behavior, i.e., ν ) 3/5 in eq I. 74.…”

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

“…The low-field mobilities, µ ) DN, from electrophoresis measurements of poly(styrenesulfonate) (PSS) in polyacrylamide (PAA) gels, 74 and the tracer diffusion measurements of PS in poly(vinyl methyl ether) (PVME) gels, 75 are considered.…”

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

“…We will analyze this observation using the finite size effect, namely the constraint porosity, captured by PMC theory for polymer melts and solutions. As the PAA gel structure is assumed to be similar to the solution structure of PAA, 74 the fractal dimension appropriate for polymers in good solvents, D F ) 5/3 in Flory approximation, is chosen in eq I.75. Also, the soft gel model clearly applies as the cross-linked polymer matrix does not exhibit significantly stronger constraints than the entanglement mesh of the corresponding solution, but only time-independent ones.…”

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

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Polymer-Mode-Coupling Theory of Finite-Size-Fluctuation Effects in Entangled Solutions, Melts, and Gels. 2. Comparison with Experiment

Fuchs

Schweizer

1997

Macromolecules

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The predictions of polymer mode coupling theory for the finite size corrections to the transport coefficients of entangled polymeric systems are tested in comparison with various experimental data. It is found that quantitative descriptions of the viscosities, η, dielectric relaxation time, τ , and diffusion coefficients, D, of polymer melts can be achieved with two microscopic structural fit parameters whose values are in the range expected from independent theoretical or experimental information. An explanation for the (apparent) power law behaviors of η, τ , and D in (chemically distinct) melts for intermediate molecular weights as arising from finite size corrections, mainly the self-consistent constraint release mechanism, is given. The variation of tracer dielectric relaxation times from Rouse to reptationlike behavior upon changes of the matrix molecular weight is analyzed. Self-diffusion and tracer diffusion constants of entangled polymer solutions can be explained as well, if one further parameter of the theory is adjusted. The anomalous scaling of the tracer diffusion coefficients in semidilute and concentrated polystyrene solutions, D ∼ N -2.5 , is predicted to arise due to the spatial correlations of the entanglement constraints, termed "constraint porosity". Extensions of the theory to polymer tracer diffusion through poly(vinyl methyl ether) and polyacrylamide gels provide an explanation of the observation of anomalously high molecular weight scaling exponents in a range where the size of the tracer, Rg, already considerably exceeds the gel pore size, g. IntroductionThe microscopic polymer mode coupling (PMC) theory connects the dynamics of entangled polymeric systems to the underlying equilibrium liquid structure. This description therefore naturally includes corrections arising from the finite molecular weights of tracer or matrix polymers. In the preceding paper, 1 referred to as paper I, the PMC predictions with finite size corrections have been worked out for the transport properties of entangled solutions and melts and for polymer tracer motion in gels. In the present paper these results are compared with data from many experiments. As the PMC approach has been detailed in the preceding paper, 1 it shall be summarized only shortly in this section and then compared to alternative approaches. The resulting formulas of paper I will be referenced by the equation numbers of that paper with a prefix I.The PMC approach of paper I treats the Rouseentangled crossover problem in a simple interpolative manner. The PMC contributions capturing the entanglement corrections are combined with the Rouse, unentangled quantities, see eqs I.52 and I.68 for D, eqs I.55 and I.67 for η, and eqs I.58 and I.70 for τ . Appreciable deviations from the asymptotes for high molecular weights are therefore not explained by corrections of the Rouse dynamics to the asymptotic, entangled motion. In stark contrast to the contour length fluctuation model of Doi, 2,3 the repton model of Rubinstein, 4 and the Rouse-fluc...

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Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

Section: Polymer Tracer Motion In Gels: Comparison With Experimentsmentioning

confidence: 99%

See 3 more Smart Citations

Polymer-Mode-Coupling Theory of Finite-Size-Fluctuation Effects in Entangled Solutions, Melts, and Gels. 2. Comparison with Experiment

Fuchs

Schweizer

1997

Macromolecules

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Gel electrophoretic mobility of single-stranded DNA: The two reptation field-dependent factors

2000

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Polyelectrolytes

Hoagland¹

2003

Encyclopedia of Polymer Science and Technology

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Polyelectrolytes are polymers that develop substantial charge when dissolved or swollen in a highly polar solvent medium such as water. The attendant electrostatic interactions — within a single polyelectrolyte, between polyelectrolytes, or with molecules/surfaces — produce physical properties much different than those for neutral polymers. Most polyelectrolyte solution and gel properties vary sharply with addition of simple electrolytes, which screen electrostatic interactions according to concentration. Scientists are just beginning to understand polyelectrolyte electrostatic interactions, which are known to play an important role in the natural world. Important concepts for polyelectrolytes are counterion condensation, electrostatic persistence length, electrostatic excluded volume, and Donnan equilibrium. Properties such as low angle scattered intensity, solution viscosity, osmotic pressure, polyelectrolyte and counterion diffusion coefficients, conductivity, adsorption, complexation, electric and magnetic birefringence, electrophoresis, titration, and gel swelling can only be understood by accounting properly for electrostatic interactions. These distinctive properties underlie applications in colloid stabilization, surface modification, rheology control, and controlled release.

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Chain-length dependence of the electrophoretic mobility in random gels

Cited by 74 publications

References 22 publications

Polymer-Mode-Coupling Theory of Finite-Size-Fluctuation Effects in Entangled Solutions, Melts, and Gels. 2. Comparison with Experiment

Polymer-Mode-Coupling Theory of Finite-Size-Fluctuation Effects in Entangled Solutions, Melts, and Gels. 2. Comparison with Experiment

Gel electrophoretic mobility of single-stranded DNA: The two reptation field-dependent factors

Polyelectrolytes

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