Effect of water on hydrolytic cleavage of non-terminal α-glycosidic bonds in cyclodextrins to generate monosaccharides and their derivatives in a dimethyl sulfoxide-water mixture.

Hydrolytic cleavage of the non-terminal α-1,4-glycosidic bonds in α-, ß-, and γ-cyclodextrins and the anomeric-terminal one in d-maltose was investigated to examine how the cleavage rate for α-, ß-, and γ-cyclodextrins is slower than that for d-maltose. Effects of water and temperature were studied by applying in situ (13)C NMR spectroscopy and using a dimethyl sulfoxide (DMSO)-water mixture over a wide range of water mole fraction, xw = 0.004-1, at temperatures of 120-180 °C. The cleavage rate constant for the non-anomeric glycosidic bond was smaller by a factor of 6-10 than that of the anomeric-terminal one. The glycosidic-bond cleavage is significantly accelerated through the keto-enol tautomerization of the anomeric-terminal d-glucose unit into the d-fructose one. The smaller the size of the cyclodextrin, the easier the bond cleavage due to the ring strain. The remarkable enhancement in the cleavage rate with decreasing water content was observed for the cyclodextrins and d-maltose as well as d-cellobiose. This shows the important effect of the solitary water whose hydrogen bonding to other water molecules is prohibited by the presence of the organic dipolar aprotic solvent, DMSO, and which has more naked partial charges and higher reactivity. A high 5-hydroxymethyl-2-furaldehyde (5-HMF) yield of 64% was attained in a non-catalytic conversion by tuning the water content to xw = 0.30, at which the undesired polymerization by-paths can be most effectively suppressed. This study provides a step toward designing a new optimal, earth-benign generation process of 5-HMF starting from biomass.

Effect of water content on conversion of D-cellobiose into 5-hydroxymethyl-2-furaldehyde in a dimethyl sulfoxide-water mixture.

Noncatalytic conversion of D-cellobiose (at 0.5 M) into 5-hydroxymethyl-2-furaldehyde (5-HMF), a platform chemical for fuels and synthetic materials, was analyzed at 120-200 °C over a wide range of water mole fraction, xw = 0.007-1 in a binary dimethyl sulfoxide (DMSO)-water mixture by means of the in situ (13)C NMR spectroscopy. Effects of the water content were revealed as follows: (i) The tautomerization of the anomeric residue of D-cellobiose from D-glucose to D-fructose type was not initially observed at a lower water content, in contrast to the significant tautomerization into the D-fructose type in a higher water content and pure water. (ii) The lower the water content, the faster the glycosidic-bond cleavage by hydrolysis, because of the high reactivity of solitary water molecules with the large partial charges more naked as in supercritical water clusters due to the isolation by the organic solvent DMSO. (iii) The amount of D-fructose as the intermediate product was larger at the higher xw; despite the increase of D-fructose, the production of 5-HMF from D-fructose was slowed down. (iv) A high 5-HMF yield of 71% was reached at xw = 0.20-0.30 that was 6-10 times the initial D-cellobiose concentration. The best yield of 5-HMF was attained in the low xw region when the polymerization paths into NMR-undetectable species via 5-HMF and anhydromonosaccharides were effectively suppressed. This study provides a new framework to design optimal, noncatalytic reaction process to produce 5-HMF from cellulosic biomass by tuning the water content as well as the temperature and the reaction time.

Effect of heavy hydrogen isotopes on the vibrational line shape for supercritical water through rotational couplings.

The rotational couplings, which determine the infrared spectral line shape in the low-density supercritical water, were analyzed as functions of the density and the temperature by applying molecular dynamics simulation to a flexible water model, SPC∕Fw and by varying the moment of inertia of the water through substitution for the H atom in H2O by heavy hydrogen isotopes. The differences in the frequency and the relative intensity between the sharp center peak and the rotational broad side-bands were analyzed for the O-H, O-D, and O-T stretch spectra. The frequency differences between the sharp center peak and the rotational broad side-bands are linearly correlated with the inverse of the moment of inertia of the isotope-substituted water species. The intensity of the sharp peak is associated with the long-time component of the reorientational time correlation function for the stretching bond vector. At 400 °C, where a substantial amount of hydrogen bonds are dynamically persisting, an intensity decrease in the rotational broad side-bands was observed with increasing density from 0.01 to 0.40 g cm(-3), respectively, corresponding to 0.56 and 22.2 M (=mol dm(-3)), orders of magnitude higher than the ideal gas densities. This arises from the decrease in the correlation time of the angular velocity and the rotational couplings due to an increase in the hydrogen-bonding perturbation. The intensity decrease of the rotational side-bands with increasing density is more significant for the water isotopes with heavier hydrogens. At a high temperature of 1200 °C, the rotational side-bands at 0.01 to 0.05 g cm(-3) were more distinct than those at 400 °C, and even at a medium density of 0.40 g cm(-3) a significant signal broadening due to the rotational couplings was clearly observed because of the accelerated rotational momentum. The vibrational spectrum cannot be decomposed into definite chemical clusters for the thermodynamic and kinetic analysis because of the dynamic origin.

Density effect on infrared spectrum for supercritical water in the low- and medium-density region studied by molecular dynamics simulation.

The origin of the line shape of the O-H stretch vibrational spectrum is analyzed for supercritical water in the low- and medium-density region by using classical molecular dynamics simulation for the flexible point-charge model, SPC/Fw. The spectrum calculated for the water model is in good agreement with the experimental one in the low-density region. The spectral origins in the low-density region of 0.01-0.04 g cm(-3) are assigned to a sharp peak due to the bond oscillation along the O-H vector and two broad bands due to the rotational coupling, by taking an isolated single molecule as a reference in the low-density limit. The bands due to the rotational coupling reduce in intensity with increasing density as the rotations are more hindered by the hydrogen-bonding interactions, and their intensities increase with increasing temperature due to the accelerated rotational motion. The O-H stretch oscillation in the time correlation function attenuates in a timescale comparable with the lifetime of the hydrogen bonds, and the spectra conditioned by the number of hydrogen bonds are dominantly controlled by the local solvation structure.