Polyelectrolyte ‘Catalysis’ in Ionic Reactions

Ise, Norio

doi:10.1007/978-94-010-1783-1_5

Cited by 10 publications

(1 citation statement)

References 46 publications

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“…and the properties of simple ions present in the solution. Thus, it is now well established that ionic reactions can be remarkably influenced by addition of anionic and cationic polyelectrolytes [26], resulting in "catalysis." This catalysis, as well as a variety of basic physicochemical properties of polyelectrolytes, are satisfactorily accounted for by the Brönsted-Bjerrum theory of electrolytes as extended by Manning to polyelectrolytes.…”

Section: Related Sulfated Mucopolysaccharidesmentioning

confidence: 99%

The Chemical and Anticoagulant Nature of Heparin

Jaques¹,

McDuffie²

2008

Semin Thromb Hemost

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Section: Related Sulfated Mucopolysaccharidesmentioning

confidence: 99%

The Chemical and Anticoagulant Nature of Heparin

Jaques¹,

McDuffie²

2008

Semin Thromb Hemost

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Attempts to prepare regularly sequenced polyamides containing oxyethylene and iminoethylene units

Kern

Kämmerer

Böhmer

et al. 1983

Angew. Makromol. Chem.

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Water soluble polyamides with iminoethylene and oxyethylene units in the main chain were obtained by condensation polymerization of diethylenetriamine and triethylenetetramine with suitable dimethylesters containing two or three oxyethylene units. The molecular weights were in the range of M, = 5000-7000. By potentiometric and conductometric titration only 80 -85% of the expected amount of basic groups was found which was probably caused by branching. ZUSAMMENFASSUNG:Durch Polykondensation von Diethylentriamin und Triethylentetramin mit Dimethylestern von Sauren, die zwei oder drei Oxyethyleneinheiten enthalten, wurden wasserlosliche Polyamide mit Iminoethylen-und Oxyethyleneinheiten in der Hauptkette erhalten. Die Molekulargewichte lagen im Bereich von M, = 5000-7000. Durch potentiometrische bzw. konduktometrische Titration wurden nur 80 -85% der erwarteten basischen Gruppen gefunden, was wahrscheinlich durch Verzweigungen zu erklaren ist.

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Catalytic influence of heparin on auramine O hydrolysis: A basis for differentiating heparin from other glycosaminoglycans based on its properties as a polyelectrolyte

Band

Lukton

1984

Biopolymers

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SynopsisThe basis for heparin's ability to accelerate the conversion of auramine 0 (AuO) to Michlers ketone [P. Band & A. Lukton (1982) A n d . Biochem. 120, [19][20][21][22][23][24] is here explained in terms of well-known polyelectrolyte phenomena. Acceleration of this acidcatalyzed hydrolysis appears to be due to colocalization of the cationic dye and hydronium ion within the microenvironment of heparin's electrostatic domain. The dependence of reaction rate on polymer, dye, and hydronium ion concentration, ionic strength, and various ratios of these parameters is consistent with what others have observed for polyelectrolyte catalysts. Dextran sulfate, polyvinyl sulfate, and polyanethole sulfonate likewise accelerate this reaction, thus precluding any explanation of the catalysis in terms of a specific catalytic site. A striking aspect about the polyanionAuO system is the inability of all other natural glycosaminoglycans tested to catalyze this reaction, despite their analogous polyanionic nature. Manning's limiting laws describing counterion condensation in polyelectrolyte solutions provide a simple context within which to interpret these results. Calculation of the structural linear charge density parameter, e, based on analytically determined sulfate-to-hexosamine ratios, reveals that heparin is unique among the glycosaminoglycans in possessing an 5 value greater than unity under the conditions described. Thus, heparin's differential ability to catalyze AuO hydrolysis is a reflection of the fact that only heparin is sulfated to an extent great enough to maintain 5 > 1, even when the negative charge of carboxylate groups is neutralized. It is proposed that this distinction may be important to the unique biochemical attributes of heparin and that such considerations may prove useful in establishing structurefunction relationships when comparing different glycosaminoglycan classes.

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Polyelectrolyte ‘Catalysis’ in Ionic Reactions

Cited by 10 publications

References 46 publications

The Chemical and Anticoagulant Nature of Heparin

The Chemical and Anticoagulant Nature of Heparin

Attempts to prepare regularly sequenced polyamides containing oxyethylene and iminoethylene units

Catalytic influence of heparin on auramine O hydrolysis: A basis for differentiating heparin from other glycosaminoglycans based on its properties as a polyelectrolyte

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