Carbohydrates, stabilized electrons

The majority of easily detected compounds at solid anodes under constant applied potentials are self-stabUized via tt-resonance. Therefore, a desirable characteristic of electrodes in dc amperometry is inert. The electrode serves as a sink to provide and remove electrons with no direct involvement in the reaction mechanism. Since TT-resonance does not exist in polar ahphatic compounds (e.g., carbohydrates), stabilization of reaction intermediates is actively achieved via adsorption at clean noble metal electrodes. Faradaic processes that benefit from electrode surface interactions are described as electrocatalytic. Unfortunately, an undesirable consequence of this apiproach is the accumulation of adsorbed carbonaceous materials, which eventually foul the electrode surface. 

It IS not possible to tell by inspection whether the a or p pyranose form of a par ticular carbohydrate predominates at equilibrium As just described the p pyranose form IS the major species present m an aqueous solution of d glucose whereas the a pyranose form predominates m a solution of d mannose (Problem 25 8) The relative abundance of a and p pyranose forms m solution depends on two factors The first is solvation of the anomeric hydroxyl group An equatorial OH is less crowded and better solvated by water than an axial one This effect stabilizes the p pyranose form m aqueous solution The other factor called the anomeric effect, involves an electronic interaction between the nng oxygen and the anomeric substituent and preferentially stabilizes the axial OH of the a pyranose form Because the two effects operate m different directions but are com parable m magnitude m aqueous solution the a pyranose form is more abundant for some carbohydrates and the p pyranose form for others... 

In carbohydrates in which benzyl groups are used extensively for protection, the stability of the benzyl groups toward electrophilic reagents is increased by the presence of electron-withdrawing groups in the ring." ... 

Microscopic structure of texturized water-extracted soy flour and texturized soy concentrate were quite similar to that of texturized soy flour. Scanning electron microgrpahs showed that water extraction of soy flours had little effect on morphological characteristics of texturized soy products (Figure 10). Solubility of soluble sugars was not affected by texturization, whereas solubility of proteins decreased sharply when soy flour was texturized (Table VII). It appears that soluble sugars did not interact with proteins during texturization. Based upon results of microscopy and solubility studies, it is reasonable to speculate that natural soluble carbohydrates are not required (do not play an important role) in development of texture or stabilization of structure. 

The addition of a C-2 (equation 1 R = H > alkyl, aryl > OMe NR2), C-3, or C-4 electron-donating substituent to a 1 -oxa-1,3-butadiene electronically decreases its rate of 4ir participation in a LUMOdiene-controlled Diels-Alder reaction (c/. Table 5). Nonetheless, a useful set of C-3 substituted l-oxa-l,3-buta-dienes have proven to be effective dienes ° and have been employed in the preparation of carbohydrates (Table 6). The productive use of such dienes may be attributed to the relative increased stability of the cisoid versus transoid diene conformation that in turn may be responsible for the Diels-Alder reactivity of the dienes. Clear demonstrations of the anticipated [4 + 2] cycloaddition rate deceleration of 1-oxa-1,3-butadienes bearing a C-4 electron-donating substituent have been detailed (Table 6 entry 4). >> "3 In selected instances, the addition of a strong electron-donating substituent (OR, NR2) to the C-4 position provides sufficient nucleophilic character to the 1-oxa-1,3-butadiene to permit the observation of [4 + 2] cycloaddition reactions with reactive, electrophilic alkenes including ketenes and sul-fenes, often in competition with [2 + 2] cycloaddition reactions. ... 

An additional role for aromatic groups in carbohydrate binding may be to stabilize the exo-anomeric effect [20]. The exo-cyc c 01 lone pair of a pyranose (e. g., glucose) can donate electron density into the C1-05 cr orbital while decreasing electron density in the C1-05... 

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