Solvation carbohydrates

Figure 11.2 Schematic illustration of carbohydrates solvated by Br ions. Hydrogen bonding between hydroxyl groups and Br ions causes the solvation.

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... 

One particular feature of ionic liquids lies in their solvation properties, not only for hydrophobic compounds but also for hydrophilic compounds such as carbohydrates. Park and Kazlauskas reported the regioselective acylation of glucose in 99 % yield and with 93 % selectivity in [MOEMIM][BF4] (MOE = CH3OCH2CH2), values much higher than those obtained in the organic solvents commonly used for this purpose (Entry 18) [22] (Scheme 8.3-4). 

Ludwig s (2001) review discusses water clusters and water cluster models. One of the water clusters discussed by Ludwig is the icosahedral cluster developed by Chaplin (1999). A fluctuating network of water molecules, with local icosahedral symmetry, was proposed by Chaplin (1999) it contains, when complete, 280 fully hydrogen-bonded water molecules. This structure allows explanation of a number of the anomalous properties of water, including its temperature-density and pressure-viscosity behaviors, the radial distribution pattern, the change in water properties on supercooling, and the solvation properties of ions, hydrophobic molecules, carbohydrates, and macromolecules (Chaplin, 1999, 2001, 2004). 

Molecular Dynamics Simulations of Carbohydrates and Their Solvation... 

Molecular dynamics (MD) simulations are a class of molecular mechanics calculation which directly model the motions of molecular systems, often providing considerable information which cannot be obtained by any other technique, theoretical or experimental. MD simulations have only recently been applied to problems of carbohydrate conformation and motions, but it is likely that this technique will be widely used for modeling carbohydrates in the future. This paper introduces the basic techniques of MD simulations and illustrates the types of information which can be gained from such simulations by discussing the results of several simulations of sugars. The importance of solvation in carbohydrate systems will also be discussed, and procedures for including solvation in molecular dynamics simulations will be introduced and again illustrated from carbohydrate studies. 

To date, only a few solution calculations for carbohydrates have been attempted (one such study of mannitol and sorbitol is described in the chapter by Grigera in this volume), but the results of these early studies bear out the expectation that solvation effects in carbohydrate systems can be both significant and difficult to predict. In the case of pyranoid rings, molecular solvation is further complicated by the close juxtaposition of these groups in essentially fixed relative orientations (assuming no conformational changes in the ring). Under such circumstances, molecular stereochemistry could play important physical roles, as is... 

The particular array of chemical shifts found for the nuclei of a given polymer depends, of course, on such factors as bond orientation, substituent effects, the nature of nearby functional groups, solvation influences, etc. As a specific example, derivatives of the carbohydrate hydroxyl moieties may give rise to chemical shifts widely different from those of the unmodified compound, a fact that has been utilized, e.g., in studies (l ) on commercially-important ethers of cellulose. Hence, as illustrated in Fig, 2, the introduction of an 0-methyl function causes (lU,15) a large downfield displacement for the substituted carbon. This change allows for a convenient, direct, analysis of the distribution of ether groups in the polymer. Analogously, carboxymethyl, hydroxyethyl and other derivatives may be characterized as well... 

Especial points which emerge from these studies include (a) the almost complete absence of reactivity of the hydroxy-groups of simple carbohydrates in water, which is attributed to their powerful solvation by water preventing a close approach of any other solute and (b) the ability of ester groups to interact with proton-acceptors. The refractive index tests, examination of m.p. or b.p., and infrared spectra of certain mono- and poly-esters appear to be interpreted most simply by assuming the formation of weak CH bonds by ester groups under the activating influence of the adjacent (5—0 double bond. These bonds can account for certain properties of l 2-diesters and for the adsorption of proton-acceptor solutes by cellulose acetates. 

Carbohydrate (ligand) Salt Molar ratio, ligand salt Solvent of solvation, molecules/cation Solvent medium Refen... 

Whereas solvated electrons react slowly with carbohydrates,4 5 OH radicals4,8,7 and H atoms4,8 react quite readily with them, the former at nearly diffusion-controlled rates. The solvated electron may be converted by N20 into "OH radicals (see reaction 2). In this case, the radicals in the system are then 90% "OH and 10% H. 

In nonaromatic systems, ionization usually plays a major role, as compared to excitation.301 Whereas, in liquids or highly disordered solids, the electron can be solvated,302 no, or very low yields of, solvated electrons are observed in solid carbohydrates, even at low temperatures.275 This implies that the electron may return to the positive hole (reaction 295). However, it cannot be excluded that ion-molecule reactions (reaction 194) precede this reaction, and that recombination occurs with the resulting ion N+, instead of with the parent ion M+ (reaction 196). Process 194 has been studied with simple alcohols in the gas phase.303,304... 

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