Summary
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1.
The intense negative electrostatic field of acid polysaccharides excludes negatively charged periodate ions from the domain of the polysaccharide, thus reducing rates of oxidation. This effect is suppressed by adding salt (0.2 M sodium perchlorate). There is a consequent increase in oxidation rates. Polymer charge due to weakly acidic groups (-COOH) is greatly reduced in periodic acid (< pH 3), and oxidation in periodic acid is faster than in equivalent concentrations of sodium periodate (>pH 5). Oxidations of uncharged polysaccharides are largely unaffected by changes in salt concentration or pH.
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2.
The periodate oxidation of hyaluronate and heparin, although considerably increased by the addition of 0.2 M sodium perchlorate, is still slow or very slow in comparison with that of dextran and polygalacturonate. The C2–C3 glycol group of the uronic acid portion is primarily the target for oxidation.
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3.
Comparison of oxidation rates of polyanions are better carried out in the presence of added salt, to reduce the non-specific effects of the electrostatic fields.
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Scott, J.E., Harbinson, R.J. Periodate oxidation of acid polysaccharides inhibition by the electrostatic field of the substrate. Histochemie 14, 215–220 (1968). https://doi.org/10.1007/BF00306317
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DOI: https://doi.org/10.1007/BF00306317