Chain-stiffness and excluded-volume effects in solutions of sodium hyaluronate at high ionic strength

Hayashi, Kanako; Tsutsumi, Kikuko; Nakajima, Fumio; Norisuye, Takashi; Teŕamoto, Akio

doi:10.1021/ma00115a012

Cited by 76 publications

(103 citation statements)

References 12 publications

(13 reference statements)

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“…In agreement with this theory, increased binding strength is seen with a decrease in chain stiffness for three polyelectrolytes with similar charge densities: DMF20/25, HA, and pectin. 48 Z c . BSA in the vicinity of Z ) 0 exhibits a relatively flat positive domain (see Figure 8) that accommodates a 5-nm length of the locally stiff polyanion HA; 23 further increase in chain stiffness does not impede binding to this protein domain.…”

Section: Resultsmentioning

confidence: 99%

Effects of Polyelectrolyte Chain Stiffness, Charge Mobility, and Charge Sequences on Binding to Proteins and Micelles

et al. 2006

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The binding affinities of polyanions for bovine serum albumin in NaCl solutions from I ) 0.01-0.6 M, were evaluated on the basis of the pH at the point of incipient binding, converting each such pH c value into a critical protein charge Z c . Analogous values of critical charge for mixed micelles were obtained as the cationic surfactant mole fraction Y c . The data were well fitted as Y c or Z c ) KI a , and values of K and a were considered as a function of normalized polymer charge densities (τ), charge mobility, and chain stiffness. Binding increased with chain flexibility and charge mobility, as expected from simulations and theory. Complex effects of τ were related to intrapolyanion repulsions within micelle-bound loops (seen in the simulations) or negative protein domainpolyanion repulsions. The linearity of Z c with I at I < 0.3 M was explained by using protein electrostatic images, showing that Z c at I < 0.3 M depends on a single positive "patch"; the appearance of multiple positive domains I > 0.3 M (lower pH c ) disrupts this simple behavior.

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Section: Resultsmentioning

confidence: 99%

Effects of Polyelectrolyte Chain Stiffness, Charge Mobility, and Charge Sequences on Binding to Proteins and Micelles

et al. 2006

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“…19 All these [17] values are plotted double-logarithmically against c. in Huggins' constant plotted against log C, for indicated Na hyaluronate samples in aqueous NaCl at 25°C. The data at C,=0.2 and 0.5 M were obtained in our previous work.…”

Section: Resultsmentioning

confidence: 99%

“…The previously investigated 12 fractions 19 of Na hyaluronate, designated HAI, HA2, ···,and HA12 in order of decreasing molecular weight, were used for the present study. Their weight-average molecular weights Mw (determined by light scattering or sedimentation equilibrium in 0.5 M aqueous NaCl) ranged from 3.8 x 10 3 to 3.5 x 10 5 (see Table I).…”

Section: Samplesmentioning

confidence: 99%

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Electrostatic Contributions to Chain Stiffness and Excluded-Volume Effects in Sodium Hyaluronate Solutions

Hayashi

Tsutsumi

Norisuye

et al. 1996

Polym J

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ABSTRACT:Intrinsic viscosities [11] for sodium hyaluronate in aqueous sodium chloride at 25°C were determined for 12 samples ranging in weight-average molecular weight Mw from 3.8 x 10 3 to 3.5 x 10 5 at NaCl concentrations C, between 0.005 and 2.5 M. They were analyzed on the basis of the Yamakawa-Fujii-Yoshizaki theory for [11] ofan unperturbed wormlike chain combined with the Yamakawa-Stockmayer-Shimada theory for excluded-volume effects to estimate the total persistence length q and the excluded-volume strength B as functions of C,. At any C, studied, excluded-volume effects on [11] became appreciable when Mw exceeded 1 x 10 4~2 x 10 4 . The C, dependence of q yielded 4.0 nm for q0 (the intrinsic persistence length) of the polysaccharide chain at infinite ionic strength. It was found that the values of q-q0 (i.e., the electrostatic contribution to q) at C,<0.02M were roughly 70% larger than predicted by the Le Bret theory and the Odijk-Skolnick-Fixman theory. On the other hand, the estimated B values agreed fairly well with Fixman and Skolnick's theory for the excluded-volume interaction between a pair of charged rodlike segments unless C, was lower than 0.05 M, KEY WORDS Polyelectrolyte / Hyaluronic Acid / Wormlike Chain / Chain Stiffness / Electrostatic Persistence Length/ Excluded-Volume Effect/The current polyelectrolyte theory 1 -4 predicts that the persistence length q of a charged linear polymer in aqueous salt increases with lowering salt concentration c., provided the polyelectrolyte is modeled by the Kratky-Porod wormlike chain. 5 This prediction for the electrostatic stiffening effect seems to be substantiated experimentally for intrinsically stiff polymers undergoing no appreciable intramolecular excluded-volume effect. Notably for double-stranded DNA, 6 almost quantitative agreement was obtained between theoretical and experimental values for the electrostatic persistence length q.1 (the electrostatic contribution to q).On the other hand, our understanding of q. 1 for polyelectrolytes with intrinsically weak stiffness is far from satisfactory. The primary difficulty in the experimental determination of q. 1 or q for those polymers is that the effects of chain stiffness and volume exclusion on measured properties can hardly be separated without resort to a relevant excluded-volume theory. Some previous workers 7 -9 deliberately or undeliberately ignored the latter effect in their estimation of q and discussed apparent values so estimated for q or q. 1 • Others 10 -12 took account of volume effects, but they invoked the Fixman-Skolnick theory 13 for the electrostatic binary cluster integral and early theories 14 · 15 for the radius expansion factor a. based on the random flight model.Here, °' • is defined as the ratio of the perturbed to unperturbed radius of gyration. It is probably fair to say that no established way of estimating the chain stiffness is as yet known for intrinsically flexible or weakly stiff polyelectrolytes unless the ionic strength is high enough. We note that although scatt...

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“…[5][6][7][8] The major problem in the estimation of q el is that excluded-volume and stiffness effects can hardly be separated for those polymers without resort to a relevant excluded-volume theory. In previous studies, [5][6][7][8][9][10][11] we utilized the quasi-two-parameter (QTP) theory (the Yamakawa-Stockmayer-Shimada theory) [12][13][14] for the wormlike chain 15 or, more generally, the helical wormlike chain 14 to estimate these effects in aqueous NaCl solutions of sodium hyaluronate and sodium poly(styrenesulfonate) (Na PSS). Except for some details, the QTP scheme satisfactorily explained the molecular weight dependence of intrinsic viscosity [] and mean-square radius of gyration hS 2 i for the two polyelectrolytes at fixed salt concentrations C s higher than 10 À2 M. On the other hand, the available polyelectrolyte theories [1][2][3][4]16 failed to describe the C s dependence of the estimated q el and excluded-volume strength, though the degree of disagreement appeared to depend on the intrinsic chain stiffness.…”

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Chain Stiffness and Excluded-Volume Effects in Polyelectrolyte Solutions: Characterization of Sodium Poly(2-acrylamido-2-methylpropanesulfonate) in Aqueous Sodium Chloride

Yashiro

Hagino

Sato

et al. 2006

Polym J

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ABSTRACT:Fourteen samples of sodium poly(2-acrylamido-2-methylpropanesulfonate) ranging in weight-average molecular weight from 1:7 Â 10 3 to 1:4 Â 10 6 have been studied by static light scattering (or sedimentation equilibrium) and viscometry to characterize the polyelectrolyte in 0.05 and 0.5 M aqueous NaCl at 25 C. The measured intrinsic viscosities (except for the two lowest molecular weights) and radii of gyration in the respective solvents are consistently described by combinations of the theories for unperturbed wormlike chains and excluded-volume effects (in the quasi-two-parameter scheme) with the parameter sets: q (the total persistence length) = 1.5 nm, M L (the linear mass density) = 900 nm À1 , d (the chain diameter) = 1.6 nm, and B (the excluded-volume strength) = 3 nm in 0.5 M aqueous NaCl and q ¼ 3:0 nm, M L ¼ 900 nm À1 , d ¼ 1:7 nm, and B ¼ 6:2 nm in 0.05 M aqueous NaCl. It is shown that the end effect on the electrostatic persistence length hardly affects the estimation of q in the aqueous salts.

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Chain-stiffness and excluded-volume effects in solutions of sodium hyaluronate at high ionic strength

Cited by 76 publications

References 12 publications

Effects of Polyelectrolyte Chain Stiffness, Charge Mobility, and Charge Sequences on Binding to Proteins and Micelles

Effects of Polyelectrolyte Chain Stiffness, Charge Mobility, and Charge Sequences on Binding to Proteins and Micelles

Electrostatic Contributions to Chain Stiffness and Excluded-Volume Effects in Sodium Hyaluronate Solutions

Chain Stiffness and Excluded-Volume Effects in Polyelectrolyte Solutions: Characterization of Sodium Poly(2-acrylamido-2-methylpropanesulfonate) in Aqueous Sodium Chloride

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