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The oxidation of natural polysaccharides by TEMPO has become by now an “old chemical reaction” which led to numerous studies mainly conducted on cellulose. This regioselective oxidation of primary alcohol groups of neutral polysaccharides has generated a new class of polyuronides not identified before in nature, even if the discovery of enzymes promoting an analogous oxidation has been more recently reported. Around the same time, the scientific community discovered the surprising biological and techno-functional properties of these anionic macromolecules with a high potential of application in numerous industrial fields. The objective of this review is to establish the state of the art of TEMPO chemistry applied to polysaccharide oxidation, its history, the resulting products, their applications and the associated modifying enzymes. [ABSTRACT FROM AUTHOR]

Guar (GG) and locust bean (LBG) galactomannans (GMs) oxidation at C-6 was performed with catalyst TEMPO, in which the reaction progress was monitored by consume of NaOH solution. The products were characterized by spectroscopic analysis, infrared, and 1 H-nuclear magnetic resonance, confirming the presence of aldehydes groups as intermediate of reaction to carboxylic acid. From high performance anion exchange chromatography with pulsed amperometric detection Man/Gal molar ratio was determined and demonstrated a preference to oxidize Man during the reaction on both GMs, following a first order kinetics of oxidation. The comparative macromolecular behavior of native and oxidized GMs was obtained through the analysis by high performance size exclusion chromatography, and the persistence length (L p ) was 6 nm and 4 nm to native LBG and GG, respectively. A more accessible OH-6 at mannose residue in LBG could be related with a two times faster reaction than GG. The selective oxidation with catalyst TEMPO proved to be efficient to increase the flexibility of the GMs during oxidation. Short reaction time and β-elimination process were mainly observed to LBG, probably due to a more favorable oxidation access to the polysaccharide main chain. [ABSTRACT FROM AUTHOR]