Mechanism of the Oxidation of Reducing Sugars (Hexoses) by Hexacyanoferrate(III) in Alkaline Medium and Lobry de Bruyn Transformation

Nath, Narendra; Singh, M. P.

doi:10.1021/j100890a040

Cited by 30 publications

(16 citation statements)

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“…The presence of formaldehyde as the oxidation product in case of fructose was identified by forming its 2,4‐dinitrophenyl‐hydrazone and comparing it with an authentic sample 16. The results are in agreement with the earlier reported oxidation products of reducing sugars 17–19.…”

Section: Resultssupporting

confidence: 93%

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Inhibition effect of {surfactant–substrate} aggregation on the rate of oxidation of reducing sugars by alkaline hexacyanoferrate(III)

Shukla

Upadhyay

2007

Int J of Chemical Kinetics

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The effect of cationic (cetyltrimethylammonium bromide, CTAB), anionic (sodium lauryl sulfate, NaLS), and nonionic (Brij-35) surfactants on the rate of oxidation of some reducing sugars (xylose, glucose, and fructose) by alkaline hexacyanoferrate(III) has been studied in the temperature range from 35 to 50 • C. The rate of oxidation is strongly inhibited in the presence of surfactant. The inhibition effect of surfactant on the rate of reaction has been observed below critical micelle concentration (CMC) of CTAB. In case of NaLS and Brij-35, the inhibition effect was above CMC, at which the surfactant abruptly associates to form micelle. The kinetic data have been accounted for by the combination of surfactant molecule(s) with a substrate molecule in case of CTAB and distribution of substrate into micellar and aqueous pseudophase in case of NaLS and Brij-35. The binding parameters (binding constants, partition coefficients, and free-energy transfer from water to micelle) in case of NaLS and Brij-35 have been evaluated with the help of Menger and Portnoy model reported for micellar inhibition.

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Section: Resultssupporting

confidence: 93%

“…The kinetics of oxidation of the reducing sugars by alkaline hexacyanoferrate(III) in the absence of the surfactant is reported in the literature 17,18. The reaction followed a first‐order dependence of rate with respect to each OH − and reducing sugars and a zero‐order dependence of rate with respect to an oxidant.…”

Section: Resultsmentioning

confidence: 99%

Inhibition effect of {surfactant–substrate} aggregation on the rate of oxidation of reducing sugars by alkaline hexacyanoferrate(III)

Shukla

Upadhyay

2007

Int J of Chemical Kinetics

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“…The reactions involving fructose are complicated by the fact that fructose in alkaline solution is in equilibrium with a much more powerful reducing substance. It has been known for some time that ferricyanide (Nath and Singh, 1965) or Cuzt (Singh et al, 1970) oxidise reducing sugars at a rate which is attributed to a slow forward reaction of fructose with alkali to form an enediol. This results in a constant rate independent of the concentration of oxidizing agent.…”

Section: Discussionmentioning

confidence: 99%

Light Production in Alkaline Mixtures of Reducing Agents and Dimethylbiacridylium Nitrate*

Totter¹

1975

Photochem & Photobiology

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Kinetic studies were made of light production and 0, absorption elicited by treatment of dimethylbiacridylium hydroxide [D(OH),] with reducing agents in alkaline aqueous solutions. D(OH), addition stimulated 0, uptake which proceeded with zero-order kinetics until nearly all of the 0, or of the D(OH), was converted to end products. At the termination of the reactions with fructose as reductant the D(OH), was converted to methylacridone and to dimethylbiacridene each compound accounting for approximately one-half the D(OH), consumed. 0, was reduced to H,O,. With hydroxylamine as the reducing agent the emitted light intensity was related to the first power of the D(OH), concentration and the rate of 0, uptake to the square root of the D(OH),. The disappearance of D(OH), in these circumstances was by a first order or pseudo-first order rate. Fructose as a reducing agent by contrast resulted in an 0, uptake nearly independent of NOH), concentration over a range from 1 x lo-' M -1 x M , while the light intensity and disappearance of D(OH), followed a one-half order rate. 0, uptake was by zero order kinetics and the oxidation of fructose proceeded at the same rate as was found with ferricyanide as oxidant. The kinetics, quantum yields and temperature dependence of the fructose reactions were compared with similar reactions employing H,Oz as the light eliciting reagent. The results are interpreted as indicating that D(OH), acts as a chain initiator in a manner analogous to better known, radical producing compounds found to accelerate hydrocarbon autooxidations. 203

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“…This structure provides an easy access to the ferricynide ion to oxidize the carbon in the beta position to produce a carboxylic acid, while ferricynide is reduced to ferrocyanide. The former one is quantified by measuring the oxidizing limiting current from a RDE and its concentration is related to the oligosaccharides concentration by taking into account the stoichiometry of the reaction (7,10,11 The limiting current as a function of the ferrocyanide concentration is described accordingly to Levich's equation [3] (5). But, before applying Levich's equation it is necessary to know the transport properties of the system at different temperatures, e.g., density, viscosity and diffusion coefficients of the ion pair Fe(CN) 6 3-/Fe(CN) 6 4-.…”

Section: Resultsmentioning

confidence: 99%

“…Figure. 2), there are not changes in the limiting current response after adding the oligosaccharide mixture, it is because at these temperatures the oligosaccharides remain in the cyclic hemiacetal structure (i.e., closed-chain). Therefore, it is not possible to form the enediol structure, that allows the oxidation of the carbon at the beta position (7,10,11). Immediately after the temperature start rising e.g., 60, 65, 70, 75, 80, and 85 °C the close-chain hemiacetal structure opens, the reducing limiting current for the Fe(CN) 6 3-ion decreases and the oxidation current for the Fe(CN) 6 4-ion start increasing after each addition of oligosaccharide, until reaching a maximum limiting current that depends on the temperature (1.2-1.8 mA at 60-85 o C respectively).…”

Section: Resultsmentioning

confidence: 99%

Amperometric Titration of Fructan Oligosaccharides of Agave Tequilana Webber, Blue Variety, in a Rotating Disk Electrode

et al. 2011

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This paper deals with a simple, rapid and sensitive method for quantifying oligosaccharides of fructans of Agave Tequilana Webber a Blue Variety. The method is based on the oxidation of the carbonyl group of the oligosaccharide in its linear open-ring with ferricyanide ions in a RDE (rotating disk electrode). The amperometric titration is carried out at different temperatures, e.g., 60, 65, 70, 75, 80 and 85 °C as a strategy to control the amount of oligosaccharides with the open-ring as a function of their molecular size. The proposed method allows us to determine concentrations of oligosaccharides as low as 0.71 mM. A calibration curve between the limiting current of the Fe(CN) 6 3-/Fe(CN) 6 4-pair and the concentration of the oligosaccharides taking into account the effect of temperature in the physical properties of the system, such as, density, diffusion coefficients and viscosity is also presented.

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Mechanism of the Oxidation of Reducing Sugars (Hexoses) by Hexacyanoferrate(III) in Alkaline Medium and Lobry de Bruyn Transformation

Cited by 30 publications

References 0 publications

Inhibition effect of {surfactant–substrate} aggregation on the rate of oxidation of reducing sugars by alkaline hexacyanoferrate(III)

Inhibition effect of {surfactant–substrate} aggregation on the rate of oxidation of reducing sugars by alkaline hexacyanoferrate(III)

Light Production in Alkaline Mixtures of Reducing Agents and Dimethylbiacridylium Nitrate*

Amperometric Titration of Fructan Oligosaccharides of Agave Tequilana Webber, Blue Variety, in a Rotating Disk Electrode

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