The Polyfructosans and Difructose Anhydrides

Mcdonald, Emma J

doi:10.1016/s0096-5332(08)60013-2

Cited by 51 publications

(21 citation statements)

References 42 publications

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Section: Discussionmentioning

confidence: 99%

“…Although both the action of aqueous acid on D-fructose (2) or inulin (3) and the heating of a concentrated aqueous solution of D-fructose (4, 5 ) lead to mixtures of these anhydrides, the treatment of inulin triacetate in chloroform with fuming nitric acid yields only the hexaacetate of that isomer known as "di-D-fructose anhydride I" (6). The formation of the di-D-fructose anhydrides has been attributed (7,8) to the stability of the 1,4-dioxane ring."Di-D-fructose anhydride I" was first reported allnost simultaneously by Jackson and Goergen (3) and by Irvine and Stevenson (6). Methylation followed by hydrolysis to yield 3,4,6-tri-0-methyl-D-fructose established the con~pound to be the 1,2':lf,2-dianhydride of D-fructose (7).…”

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confidence: 99%

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THE CONFIGURATION AND CONFORMATION OF "DI-D-FRUCTOSE ANHYDRIDE I"

Lemieux¹,

Ramakrishnan²

1964

Can. J. Chem.

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"Di-D-fructose anhydride I", obtained by acid depolymerization of inulin triacetate, was found t o be 1',2-anhydro-[l-(a-~-fructofuranosyl)-~ctofuranose]. The high resistance t o oxidation by periodate found for the a-D-fructofuranoside portion was related t o the conformation for the ring wherein the 3'-and 4'-hydroxyl groups are in quasi-axial orientation. This and other conclusions about the conformations of the anhydride were based on a cornparison of the 100 Mc.p.s. proton inagnetic resonance spectra of the 6,6'-dideoxytetra-0-acetyl derivative of the anhydride, sucrose octaacetate, and 1,6-anhydro-a-D-galactofura~lose triacetate. DISCUSSIONWhen D-fructose reacts with aqueous acid, dimeric D-fructose anhydrides are formed which possess a central 1,4-dioxane ring. Six such di-D-fructose dianhydrides have been described (I). Although both the action of aqueous acid on D-fructose (2) or inulin (3) and the heating of a concentrated aqueous solution of D-fructose (4, 5 ) lead to mixtures of these anhydrides, the treatment of inulin triacetate in chloroform with fuming nitric acid yields only the hexaacetate of that isomer known as "di-D-fructose anhydride I" (6). The formation of the di-D-fructose anhydrides has been attributed (7,8) to the stability of the 1,4-dioxane ring."Di-D-fructose anhydride I" was first reported allnost simultaneously by Jackson and Goergen (3) and by Irvine and Stevenson (6). Methylation followed by hydrolysis to yield 3,4,6-tri-0-methyl-D-fructose established the con~pound to be the 1,2':lf,2-dianhydride of D-fructose (7). The consumption of 2 moles of periodic acid by the con~pound provided additional support for this structure (9). The configurations of the anomeric centers in the di-D-fructose anhydrides have not been established.The alp-configuration was readily established for "di-D-fructose anhydride I" by application of proton magnetic resonance (NMR) spectroscopy. T o achieve better chemical shifts between the various lcinds of protons, the spectrum of the hexa-0-acetyl derivative (I) of I1 was determined a t 100 Mc.p.s. with chlorofornl as solvent. Should the compound contain either the a,a-or p,p-configurations, the conformational equilibration would be expected to lead to time-averaging of the resonances for the protons a t the corresponding positions in each of the rings. Certainly, the chemical shifts of the protons a t the 1-and 1'-positions would be averaged out through rapid conformational change of the dioxane ring (10). This would result in the averaging of the resonances for protons a t corresponding positions in the furanoside rings even though these rings should be conformationally rigid. Therefore, the N M R spectra for the 1,2':1',2-di-D-fructofuranose anhydride hexaacetates with the a,a-and P,P-configurations should show signals for only five ltinds of protons on the sugar residue and three pairs of nonequivalent acetyl groups. However, as seen from the spectrum in Fig. 1, the hexaacetate (1) of "di-D-fructose anhydride I" (11) provided a much more comp...

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Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

THE CONFIGURATION AND CONFORMATION OF "DI-D-FRUCTOSE ANHYDRIDE I"

Lemieux¹,

Ramakrishnan²

1964

Can. J. Chem.

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“…Since the polymer from most of these is highly polydisperse, mean molecular weights have been derived to allow comparison of different preparations. Techniques u,sed to estimate molecular size have included relative ethanol solubility (Smith & Grotelueschen, 1966), end-group analysis (Pollock, Hall & Roberts, 1979), the glucose:fructose ratio in hydrolysates (Palmer, 1951), relative mobility on gel permeation columns (Suzuki, 1968;Pollock & Jones, 1979) and a variety of physical methods (McDonald, 1946 and references therein). Comparison of results from different sources gives an approximate size for tbe fructan of Helianthus tuberosus of around 5 5 kD [degree of polymerization (DP) = 35] (Edelman & Jefford, 1968).…”

Section: Chemical and Physical Propertiesmentioning

confidence: 99%

Tansley Review No. 5 Fructans and the Metabolism of Sucrose in Vascular Plants

1986

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SUMMARY The occurrence, structure and metabolism of fructose polymers in tissues of vascular plants are discussed in relation to the metabolism of sucrose. Distinctions are made between long‐term and short‐term storage of such polymers and the regulatory mechanisms which govern accumulation are examined. The roles of various fructosyltransferases in the synthesis of the different fructan structures from sucrose are outlined. The potential selective advantages of the possession of fructan metabolism in different species are assessed with reference to possible roles as cryoprotectants, in osmotic control and as storage carbohydrates whose metabolism can continue at low temperatures (0 to 5°C). It is concluded that the complexity and variety of fructan structures and of the associated enzyme systems has resulted in an incomplete understanding of their physiology and biochemistry, but their significance as an alternative storage polysaccharide in both leaves and storage organs should not be underestimated.

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“…This isomer was thus identified as (l,l)-kestotetraose (nystose, Fig. 2>a), a DP 4 fructan isomer first isolated from sugar cane (Binkley & Altenburg, 1965) and commonly found in inulincontaining members of the Compositae (McDonald, 1946;Bacon & Edelman, 1951;Chatterton et al, 1990). The second oligomer of DP 4 to elute (the dominant isomer) contained one terminal glucose, two terminal fructoses and one 1,6-linked fructose (a branch point) ( Table 1).…”

Section: Fructans Of Dpmentioning

confidence: 98%

Structure of fructan oligomers in cheatgrass (Bromus tectorum L.) ^*

et al. 1993

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SUMMARYLeaves of field-grown cheatgrass {Bromus tectorum L.) plants were sampled during early spring when day-and night-time temperatures were relatively cool. Eructan oligomers with a degree of polymerization (DP) 3-6 were extracted and purified using gel and anion-exchange chromatography. The structures of 13 cheatgrass fructans were established. They included two trisaccharides [1-kestotriose (1-kestose) and 6-kestotriose (6-kestose)], four tetrasaccharides [(l,l)-kestotetraose (nystose), (l&6)-kestotetraose (bifurcose), (6,l)-kestotetraose and (6,6)-kestotetraose], three pentasaccharides [(l,l&6)-kestopentaose, (l&6,6)-kestopentaose and (6; l&6)-kestopentaose] plus four hexasaccharides [(1,1 ,l&6)-kestohexaose (l&6,6,6)-kestohexaose, (6; l&6,6)-kestohexaose and (6; 1,6&6)-kestohexaose]. All fructans larger then DP 4 contained a branch point. Each member of the dominant series(l&6)-kestotetraose, (l&6,6)-kestopentaose and (l&6,6,6)-kestohexaose, is a branched fructan in which two fructose moieties are linked to the fructose subunit of each sucrose molecule. 7^hus the dominant series is built upon (l&6)-kestotetraose. Eructans larger than DP 3 with exclusively 2->l-or 2 >6-linkages were absent except for a very small amount of (6,6)-kestotetraose. The unique fructan structures synthesized in cheatgrass, wheat and oats illustrate diversity in the enzymology of fructan biosynthesis among grass species.

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The Polyfructosans and Difructose Anhydrides

Cited by 51 publications

References 42 publications

THE CONFIGURATION AND CONFORMATION OF "DI-D-FRUCTOSE ANHYDRIDE I"

THE CONFIGURATION AND CONFORMATION OF "DI-D-FRUCTOSE ANHYDRIDE I"

Tansley Review No. 5 Fructans and the Metabolism of Sucrose in Vascular Plants

Structure of fructan oligomers in cheatgrass (Bromus tectorum L.) ^*

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The Polyfructosans and Difructose Anhydrides

Cited by 51 publications

References 42 publications

THE CONFIGURATION AND CONFORMATION OF "DI-D-FRUCTOSE ANHYDRIDE I"

THE CONFIGURATION AND CONFORMATION OF "DI-D-FRUCTOSE ANHYDRIDE I"

Tansley Review No. 5 Fructans and the Metabolism of Sucrose in Vascular Plants

Structure of fructan oligomers in cheatgrass (Bromus tectorum L.) *

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Structure of fructan oligomers in cheatgrass (Bromus tectorum L.) ^*