Oxidation of cellulose: The reaction of cellulose with periodic acid

Rutherford, Henry A.; Minor, Francis W.; Martin, Albert R.; Harris, Milton

doi:10.6028/jres.029.004

Cited by 78 publications

(33 citation statements)

References 8 publications

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“…The agreement with the alkaline methods was contrary to expectations, as the alkali sensitivity of periodate starch is the basis for a method (5) of determining aldehyde groups. Furthermore, periodate cellulose has been found to be very sensitive to alkali (14,18,19). A discussion of the failure of other a k aline methods, copper tartrate and hypoiodite, for periodate starch, is intended for future publication.…”

Section: Discussionmentioning

confidence: 98%

Reaction of Sodium Chlorite with Various Polysaccharides. Rate Studies and Aldehyde Group Determinations

Launer¹,

Tomimatsu²

1959

Anal. Chem.

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Aldehyde contents and degree of polymerization values of polysaccharides were calculated from chlorite results obtained under various conditions and using the corresponding stoichiometric ratios determined for substances of low molecular weight. The polysaccharides were three native dextrans, a series of hydrolyzed dextrans including clinical dextran, a periodate dextran, a series of araban fractions, and starches including pea, wheat, and rice amylopectin, and a series of periodate cornstarch products. The results with various chlorite procedures were self-consistent and agreed well with those of other chemical methods, and fairly well with those of light-scattering for fractionated polymers. For native dextrans, where no agreement was to b e expected, the large divergence demonstrated inhomogeneity of substance. Agreement with osmotic pressure results was fair to poor. HE oxidation by sodium chlorite in T phosphate buffer of a variety of mono-and disaccharides and benzaldehyde was recently studied (12) with respect to the chlorite-aldehyde stoichiometry as affected by buffer strength, reaction rate, and concentration of reactants. Various experimental conditions employing sodium chlorite were dweloped for application t o the determination of aldehyde groups in polysaccharides.This communication describes the study of the rates of oxidation under those conditions and others of a series of periodate cornstarches; of a series of dextrans, including native, periodate, clinical, and more extensively acidhydrolyzed; and of a series of arabans.

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Section: Discussionmentioning

confidence: 98%

Reaction of Sodium Chlorite with Various Polysaccharides. Rate Studies and Aldehyde Group Determinations

Launer¹,

Tomimatsu²

1959

Anal. Chem.

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“…The course of the reaction was followed by means of measurements of carboxyl content (Methylene Blue ab orption), reducing power (copper number), and fluidity in cuprammonium. The possibility of using the fluidity measurement for this purpose is a con equence of the fact that, as was shown by Harris and his collaborators 1 is accompanied by the almost complete stabilization of the oxycelluloses towards alkalis.…”

Section: Determination Of Optimum Onditions For Tile Oxidation Of mentioning

confidence: 93%

26—The Oxidation of the Aldehyde Groups in Periodate Oxycelluloses by Chlorous Acid

Davidson¹,

Nevell²

1955

Journal of the Textile Institute Transactions

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The effects of pH, temperature, and chlorite concentration on the oxidation of the aldehyde groups in periodate oxycelluloses by acidified chlorite solutions have been investigated . From the results it is concluded that a maximum conversion of aldehyde to carboxyl groups is obtained by tre tment of the oxycelluloses at 2o•c with chlorite solution acidified to pH 3 ; the chlorite concentration and the length of the treatment that are required depend upon the extent of the periodate oxidation. This chlorite treatment has been applied to a series of sixteen periodate oxycelluloses, a.nd it has been found that the fina l products contamed, on the average 1 1·78 carboxyl groups for every atom of oxygen consumed in the perioaate oxidation. This yield of carboxyl, although considerably higher than tho e obtained by earlier workers, is still signjficantly less than the theoretical value of 2 ; possible reasons for the discrepancy are discussed. Evidence is presented which suggests that one of the two aldehyde groups in a chain-unit of a perlodate oxycellulose is preferentially oxidized by chlorous acid, and that this group reduces more copper in the copper number determjnation, and contributes more to the alkali-sensitivity of the oxidized chain-molecule, than the other.Chlorous acid was first used a a reagent in the study of o ycelluloses by Rutherford, Minor, Martin, and Harris\ who showed that the aldehyde groups in periodate oxycelluloses may be oxidized to carboxyl group by means of an acidified solution of sodium chlorite. The chlorite treatment adopted by these workers did not, however, effect oxidation of all the aldehyde groups present in the oxycelluloses except when the initial aldehyde content was very low. Later workers 2 -7 have employed a wide variety of conditions of chlorite treatment, but the reaction appears to have been used without adequate preliminary study of the effects of pH, temperature, and chlorite concentration on its rate. The present paper describes an investigation of the effects of these factors, and uggests conditions for the quantitative oxidation of the aldehyde groups in periodate oxycelluloses. The results of an examination of the action of chlorous acid on an extensive series of period ate oxycelluloses are also recorded, and their implications are discussed. I. DETERMINATION OF OPTIMUM ONDITIONS FOR TilE OXIDATION OF THE ALDEHYDE GROUPSIn order to find the optimum conditions for the oxidation of the aldehyde groups in periodate oxycelluloses by acidified chlorite solutions, the effects of pH, temperature, and chlorite concentration on the rate of the reaction were studied. Most of this work was done with an oxycellulose obtained by relatively slight oxidation of cotton cellulose with metaperiodate, but various more highly oxidized materials were also used in the investigation of the effect of chlorite concentration. The periodate oxycelluloses employed are characterized by their 'oxygen con umption ', that is, the proportion of oxygen, expressed in atoms per glucose unit, consumed...

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“…Davidson's researches indicate that this need not be so but that fission may occur at an anhydro-glucose along the cellulose chain which has been previously altered in chemical structure by the oxidant. The investigations of Harris [96] indicate that the aldehyde group is the locus of alkaline attack. The fragments, being more soluble than the original cellulose, may dissolve in the alkali where further degradation takes place.…”

Section: C0evolutionmentioning

confidence: 98%

“…Alkali-sensitivity was quite marked for materials resulting from oxidation by periodic acid and appears to be related to specific instability of the glyoxal and/or erythrose units (aldehyde groups). At low degrees of oxidation, Harris and his coworkers [96] showed that the alkali-solubility and cuprammonium fluidity are proportional to the aldehyde content-that is, the degree of oxidation. When the aldehyde groups were oxidized to carboxyl by chlorous acid, the products were no longer alkali-sensitive.…”

Section: C0evolutionmentioning

confidence: 98%

The Formation and Properties of Oxidized Celluloses

Unruh¹,

Kenyon²

1946

Textile Research Journal

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A consideration of several aspects of past research in oxidized cellulose leads to the following summary of the present status of our knowledge of its structure.(a,) Much of the published data relates to heterogeneous products and hence is of little utility in determining chemical structure. (b) Two types of &dquo;oxidized cellulose&dquo; of reasonable chemical and physical homogeneity have been prepared by oxidation of the 2,3-hydroxyls and the primary (6) hydroxyl groups of the anhydro-glucose units of cellulose. (c) These are not truly &dquo;oxidized celluloses&dquo; but new polymers in their own right, with chemical properties distinct from those of cellulose. They should be considered and named as specific chemical entities.(d) Further advance in our knowledge of oxidized cellulose structure and behavior must rest on examination of physically homogeneous products resulting from the application of oxidants which attack specific points of the cellulose structure.(e) Structural elucidation must employ determinations of unambiguous organic groups under controlled conditions.( f ) Only a few methods of structural determinations have been employed to date that can be accepted with some assurance. These are:( 1 ) Estimation of aldehyde groups by reaction with hydroxylamine. The aldehyde endgroup determination by alkaline iodine solutions is satisfactory for the purpose intended but of unproved merit for alkalisensitive oxidized celluloses.(2) Determination of combined uronic acid groups by evolution of carbon dioxide. (3) Determination of total carboxyl groups (including those of uronic acid) by the calcium acetate technique. (4) Determination of residual hydroxyl groups by acetylation or nitration. (5) Degradation of the oxidized celluloses by known reactions and identification of the fission products. (g) Owing to alkali-sensitivity of the oxidized celluloses, the cuprammonium hydroxide and copper number values are unreliable for such materials.

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Oxidation of cellulose: The reaction of cellulose with periodic acid

Cited by 78 publications

References 8 publications

Reaction of Sodium Chlorite with Various Polysaccharides. Rate Studies and Aldehyde Group Determinations

Reaction of Sodium Chlorite with Various Polysaccharides. Rate Studies and Aldehyde Group Determinations

26—The Oxidation of the Aldehyde Groups in Periodate Oxycelluloses by Chlorous Acid

The Formation and Properties of Oxidized Celluloses

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