the preferred ph depends on the particular type of nitroxyls . for most nitroxyls such as unsubstituted tempo and 4 - hydroxy - tempo , the preferred ph is between 8 . 0 and 9 . 5 , especially between 8 . 3 and 9 . 0 , whereas for 4 - acetamido - tempo the preferred ph is between 7 . 5 and 8 . 2 . polysaccharides that can be oxidized using the process of the invention should contain a hydroxymethyl group , for example at the 6 - position of the monosaccharide unit . such polysaccharides include the starch - type polysaccharides ( α - 1 , 4 - glucans ), pullulan and other α - 1 , 3 - glucans , cellulose - type polysaccharides ( β - 1 , 4 - glucans ) and other β - glucans such as chitin , fructans , galacto - and gluco - mannans ( guar and the like ), xyloglucans , etc . the process of the invention is particularly concerned with the oxidation of starch and starch analogues and derivatives , such as gelatinized starch , hydrolysed starch , amylose , amylopectin , alkylated , hydroxyalkylated , carboxyalkylated , aminoalkylated , acylated starch etc . the only requirement is that at least a part of the 6 - hydroxyl functions is still available as such . the degree of oxidation to be achieved with the process can be determined on the basis of the intended use , by choosing the appropriate amount of hypochlorite . hypochlorite can be used as such or as a precursor , e . g . as molecular chlorine . at low degree of oxidation , a mixture of 6 - aldehyde - starch and 6 - carboxy - starch is obtained , while at high degrees of oxidation ( e . g . more than 50 %), 6 - carboxy - starch is the predominant product . for complete oxidation to 6 - carboxy starch , two moles of hypochlorite are required per mole of starch unit ( i . e . anhydroglucose unit ). if an aldehyde - free product is desired at partial oxidation , any aldehyde product can be either reduced to the alcohol , e . g . with borohydride , or oxidized to the carboxyl product , e . g . with sodium chlorite . the nitroxyl compound to be used can be any organic nitroxyl compounds lacking α - hydrogen atoms , such as 2 , 2 , 6 , 6 - tetramethylpiperidine - n - oxyl ( tempo ), 2 , 2 , 5 , 5 - tetramethylpyrrolidine - n - oxyl ( proxyl ), 4 - hydroxy - tempo , 4 - acetamido - tempo and other derivatives thereof . it is preferred to use a relatively low amount of tempo , in particular between 3 and 7 . 2 mmol of nitroxyl compound per mole of starch unit . potato starch ( 12 . 2 g ; 10 . 0 g dry weight : 62 mmol ) was gelatinized in demineralized water ( 450 ml ) at 95 ° c . under mechanical stirring . the solution was then slowly cooled to 20 ° c . tempo ( 4 - 8 mg per g of starch ) was dissolved in the starch solution . a hypochlorite solution ( concentration 2 . 0 mol / l ) was added in portions of 2 ml . in total 86 mmoles were added , corresponding to a theoretical degree of oxidation of 70 %. the ph was kept at 8 . 5 by addition of 0 . 5m naoh controlled by a ph - stat . after completion of the reaction , remaining carbonyl intermediates were reduced back to the alcohol by sodium borohydride ( 0 . 2 g ). the oxidized material was precipitated in 2 volumes of ethanol , separated by filtration , rinsed with acetone and dried in a vacuum oven at 30 ° c . the product was then redissolved in water , ion - exchanged ( dowex 50wx8 - 100 cation exchanger , sigma ) and freeze - fried , to remove salts and to convert carboxylates to the protonated form . 13 c nmr ( d 2 o ) ( ppm ): 99 . 2 ( c - 1 ), 73 . 2 , 73 . 7 , 74 . 0 , 74 . 5 ( c - 2 - 5 ), 61 . 7 ( c - 6 ), 177 . 6 ( c - 6 oxidized ). the isolated yield was over 90 %, with a degree of oxidation of 65 %. size exclusion chromatography showed very little depolymerization . the elution pattern was almost identical to the pattern resulting from oxidation using bromide at 2 ° c . and it showed less decomposition compared to oxidation using bromide at 20 ° c .