Distinct Diffusion in Macromolecule‐Solvent Mixtures

Vergara, Alessandro

doi:10.1002/mats.200400069

Cited by 3 publications

(2 citation statements)

References 18 publications

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“…Hartley–Crank Equations – seem useless for such nonideal systems, and it was previously reported efficient only for ideal systems. A value in the HC reference can be only in the solvent–solvent term.…”

Section: Resultsmentioning

confidence: 99%

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Use of Kirkwood-Buff Integrals for Extracting Distinct Diffusion Coefficients in Macromolecule-Solvent Mixtures

Vergara

2016

Macromol. Theory Simul.

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The possibility to extract velocity correlation quantities from fluctuation thermodynamic properties is explored in the case of macromolecule–solvent mixtures. Indeed, Kirkwood–Buff integrals, Gij, together with self‐diffusion and viscosity data can provide an approximation for distinct diffusion coefficients (DDCs), Ddij. Herein, Ddij for binary polyethyleneglycol (PEG)(i)–water(0) systems is calculated. These systems show positive values of Ddii coefficients, indicating strong PEG–PEG interaction, and providing marker of water mediated PEG–PEG networks. The efficiency of several standard DDCs present in literature for Ddij analysis is compared, summarizing the usefulness of each one, depending on the nonideality degree.

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Section: Resultsmentioning

confidence: 99%

“…All the above standards refer to an ideal mixture behavior, far away from the nonideality of the macromolecule‐solvent systems. Therefore, a successive standard was proposed based on molecular exclusion concepts, but it accounts only for the repulsive part of the nonideality.…”

Section: Theorymentioning

confidence: 99%

Use of Kirkwood-Buff Integrals for Extracting Distinct Diffusion Coefficients in Macromolecule-Solvent Mixtures

Vergara

2016

Macromol. Theory Simul.

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Precise measurement of the self-diffusion coefficient for poly(ethylene glycol) in aqueous solution using uniform oligomers

Shimada

Kato

Saito

et al. 2005

The Journal of Chemical Physics

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Uniform poly(ethylene glycol) (PEG) oligomers, with a degree of polymerization n=1-40, were separated by preparative supercritical fluid chromatography from commercial monodispersed samples. Diffusion coefficients, D, for separated uniform PEG oligomers were measured in dilute solutions of deuterium oxide (D(2)O) at 30 degrees C, using pulsed-field gradient nuclear magnetic resonance. The measured D for each molecular weight was extrapolated to infinite dilution. Diffusion coefficients obtained at infinite dilution follow the scaling behavior of Zimm-type diffusion, even in the lower molecular weight range. Molecular-dynamics simulations for PEG in H(2)O also showed this scaling behavior, and reproduced close hydrodynamic interactions between PEG and water. These findings suggest that diffusion of PEG in water is dominated by hydrodynamic interaction over a wide molecular weight range, including at low molecular weights around 1000.

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