Synthetic Polysaccharides. IV. Preparation of Carboxyl Derivatives of Polyglucose

Mora, Peter T.; Merler, Ezio; Maury, Priscilla B.

doi:10.1021/ja01529a049

Cited by 12 publications

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“…The isolation of glycerol from the acidic fraction was definite evidence for the 1 --t 2 linkage while the isolation of unoxidized glucose may be due to 1 --t 3 linl<ages. MTe believe that this is the first time that definite proof has been obtained for the existence of furanose residues in a synthetic glucan, although their presence has been indicated by the work of Mora (13). EXPERIMEXTAL Paper chromatographic separations were.…”

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confidence: 77%

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The Structure of a Synthetic Glucan: I. General Structural Features

Dutton¹,

Unrau²

1962

Can. J. Chem.

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Only D-glucoSe was obtained on acid hydrolysis of the glucan. Periodate oxidation released formaldehyde, which was believed to arise from Cc of D-glucofuranose units. From the additional formaldehyde liberated from the borohydride-reduced glucan the degree of polymerization was estimated to be about 165. Complete hydrolysis of the derived polyalcohol gave glycerol, erythritol, D-glucose, and D-xylose. Partial hydrolysis gave glycerol, erythritol, and a t least seven non-reducing oligosaccharides. Direct evidence for the existence of relatively large nu~nbers of 1 4 6 and 1 4 4 linkages was found, together with smaller numbers of 1 + 2 linkages. The methylated glucan was freely soluble in chloroform -petroleum ether (5:05), and hydrolysis gave tetra, tri, di, and mono-0-methyl-D-glucoses in a 6:6:3:1 molar ratio.There are many reports in the literature on the polymerization of D-glucose and a few papers on other monosaccharides (e.g. 1-10). Most of these polynierizations have been acid catalyzed a t temperatures ranging froin rooin temperature to about 200" C and the yields of polymeric material have varied greatly. There appears to have been no detailed study 011 the structures of these synthetic glucans, although there is general agreement that 1 --, G liilltages are co~ninonly present and that there is a high proportion of a-glucosidic bonds. In a paper (6) on the glucan obtained by polymerization in the presence of metaboric acid it was inferred, on the grounds of hydrolytic behavior, that there were 110 glucofuranose units present. I t was further stated that the polymer was highly branched, as shown by the large ainouilt of 2,3,4,G-tetra-0-methyl-~-glucose obtained. Another recent paper on the glucan obtained by poly~uerization of 1,G-anhydro-D-glucose again demonstrated the branched nature of the polymer on the basis of periodate oxidation (1 1).Since 1958 there has been a group of papers published by Mora and his associates a t the National Institutes of Health on the preparation of several synthetic polysaccharides (2-4). Since sollie derivatives of these synthetic ~llaterials have been shown to be biologically active (12, 13) it was of interest to look more closely a t the structures of these polymers. The present paper reports the general structural features of the glucan designated as polyglucose I1 in Table I of reference 3. Complete hydrolysis of the glucan by boiling it with 1 N sulphuric acid followed by chromatography of the product showed only glucose, which was isolated in the crystalline state. Alkaline oxidation or bromine oxidation of the sugar to the corresponding aldonic acid followed by adsorption of the acid on an anion exchange resin left no residue which reacted with Tollens (23) or 9-anisidine trichloroacetate (24) spray reagents when the effluent was evaporated, thus de~noilstrating the absence of ally sugar alcohols. The low optical rotation of the glucan, [aID2' 65" (c, 1.0 in water), compared with the high positive rotation of alpha-linked glucans, such as amylose (195-21...

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“…Since sollie derivatives of these synthetic ~llaterials have been shown to be biologically active (12,13) it was of interest to look more closely a t the structures of these polymers. The present paper reports the general structural features of the glucan designated as polyglucose I1 in Table I of reference 3.…”

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confidence: 99%

The Structure of a Synthetic Glucan: I. General Structural Features

Dutton¹,

Unrau²

1962

Can. J. Chem.

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“…The compound d '-methoxy-D-methoxymethyldiglycolic aldehyde (IV) obtained by periodate oxidation of methyl 6-0-methyl-a-D-galactopyranoside also reacted in the cyclic form (V) because upon methylation with silver oxide and methyl iodide 2(D'/),3,5-trimethoxy-6(L',) -methoxymethy 1-1,4 -dioxane (VI)6 was formed. The compound VI which showed [«]22d +150°(in ethanol) as compared with [q:]21d +143°(in ethanol) for the starting (5) Groups designated by d" and l" in this and other formulations of dioxane compounds correspond to positions below and above the plane of the ring of the original formula written according to the Haworth convention (cf. ref.…”

Section: Methodsmentioning

confidence: 99%

Synthetic Polysaccharides. V. Polymerization of Various Aldoses

Mora¹,

Wood²,

McFarland³

1960

J. Am. Chem. Soc.

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“…The linear o-mannan from Dr. Schuerch was tested at levels of 40, 100, 150, 200, 300, and 500 pg against concanavalin A (40 pg N and 120 pg N) and failed to form a precipitate. The synthetic D-mannan prepared by O'Colla and Lee" also failed to react with concanavalin A (5,15,25,50,250, and 500 pg D-mannan against 40 pg and 120 pg of concanavalin A nitrogen, respectively).…”

Section: Sanddies On Periodate-oxidized Reduced Polymer I -mentioning

confidence: 99%

Proteincarbohydrate interaction.

Robinson¹,

Goldstein²

1970

Carbohydrate Research

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1,6-Anhydro-#?-D-mannopyranose was polymerized in the presence of chloroacetic acid. A high-molecular-weight fraction insoluble in 80% ethanol was isolated and studied. Periodate-oxidation studies showed the polymer to contain 42% of (l--&)-like linkages, 36% of (l-+4)-or (142)~like linkages, and 22% (1+3)-like linkages. End-group analysis gave d.p. = 113. The synthetic n-mannan reacted vigorously with concanavalin A, indicating that it was a highly branched polymer containing multiple c+D-mannopyranosyl residues at chain ends. A synthetic Dmannan obtained by the polymerization of D-mannose in the presence of phosphorous acid gave a much weaker reaction with concanavalin A, and two synthetic, linear polymers failed, as expected, to form a precipitate with this plant protein.

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Synthetic Polysaccharides. IV. Preparation of Carboxyl Derivatives of Polyglucose

Abstract: Synthetic polyglucose has been oxidized with sodium periodate to the dialdehyde derivative of polyglucose which, by further oxidation with different amounts of chlorous acid, has been converted to a series of derivatives containing different amounts of carboxyl groups.

Cited by 12 publications

References 2 publications

The Structure of a Synthetic Glucan: I. General Structural Features

The Structure of a Synthetic Glucan: I. General Structural Features

Synthetic Polysaccharides. V. Polymerization of Various Aldoses

Proteincarbohydrate interaction.

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