Universal self-diffusion coefficients of macromolecules in polymer solutions and melts as a function of concentration and molecular mass

Skirda, V. D.; Sundukov, V.I.; Maklakov, A.I.; Vasil'ev, G. I.

doi:10.1016/0032-3950(88)90335-8

Cited by 3 publications

(1 citation statement)

References 9 publications

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“…Next, we estimated the rate constants of a series of the previously reported nonconjugated polymers, whose physical diffusion coefficient has not been experimentally determined (Table ). A simple approximation formula, D phys ∝ C E –β (exponential factor β = 1.75 in an ideal case), was used to predict the physical diffusion coefficient, on the basis of an entangled polymer model by de Gennes. − The model predicts that the higher concentration of the polymer chains and redox centers will decrease D phys owing to the entanglement and heavier chains.…”

Section: Resultsmentioning

confidence: 99%

Diffusion-Cooperative Model for Charge Transport by Redox-Active Nonconjugated Polymers

et al. 2018

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Charge transport processes in nonconjugated redox-active polymers with electrolytes were studied using a diffusion-cooperative model. For the first time, we quantitatively rationalized that the limited Brownian motion of the redox centers bound to the polymers resulted in the 10-fold decline of the bimolecular and heterogeneous charge transfer rate constants, which had been unexplained for half a century. As a next-generation design, a redox-active supramolecular system with high physical mobility was proposed to achieve the rate constant as high as in free solution system (>10 M s) and populated site density (>1 mol/L).

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Section: Resultsmentioning

confidence: 99%

Diffusion-Cooperative Model for Charge Transport by Redox-Active Nonconjugated Polymers

et al. 2018

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Study of Self-Diffusion of Silicone MQ Resins in Chloroform Solutions by Pulsed Field-Gradient NMR Spectroscopy

et al. 2014

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Effect of Reducing Agent TCEP on Translational Diffusion and Supramolecular Assembly in Aqueous Solutions of α-Casein

Melnikova

Skirda

Nesmelova³

2019

J. Phys. Chem. B

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The translational diffusion coefficient is highly sensitive to the size change of diffusing species and is ideally suited for the study of molecular association. Here, we used translational diffusion measurements by pulsed-field gradient Nuclear Magnetic Resonance (PFG NMR) technique to investigate the role of disulfide bonds in the formation of a supramolecular gel-like structure in the concentrated solution of α-casein. To reduce disulfide bonds, we added a commonly used reducing reagent tris(2-carboxyethyl)phosphine (TCEP) to α-casein solution. We found that the disruption of a disulfide bond Cys36-Cys40 in αs2-casein does not alter the translational diffusion or secondary structure of α-casein in dilute, 1 and 3 % (wt. %) solution. On the contrary, in concentrated, 15 % (wt. %) α-casein solution, in addition to the disruption of disulfide bonds, TCEP induced significant changes in gel properties. New long-lived intermolecular interactions formed, leading to the irreversible gel formation. While a few side reactions of TCEP (as well as other reducing agents, e.g., DTT) have been reported, this area is still understudied. Here, we provide new data on side reaction of the reducing agent TCEP in concentrated protein solution, suggesting that at high protein concentrations TCEP should be used with caution.

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Universal self-diffusion coefficients of macromolecules in polymer solutions and melts as a function of concentration and molecular mass

Cited by 3 publications

References 9 publications

Diffusion-Cooperative Model for Charge Transport by Redox-Active Nonconjugated Polymers

Diffusion-Cooperative Model for Charge Transport by Redox-Active Nonconjugated Polymers

Study of Self-Diffusion of Silicone MQ Resins in Chloroform Solutions by Pulsed Field-Gradient NMR Spectroscopy

Effect of Reducing Agent TCEP on Translational Diffusion and Supramolecular Assembly in Aqueous Solutions of α-Casein

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