A Raman and infrared study of crystalline <scp>D</scp>-fructose, <scp>L</scp>-sorbose, and related carbohydrates. Hydrogen bonding and sweetness

Szarek, Walter A.; Korppi-Tommola, Sirkka-Liisa; Shurvell, H. F.; Smith, Vedene H.; Martin, Olivier R.

doi:10.1139/v84-258

Cited by 39 publications

(20 citation statements)

References 28 publications

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“…In 2 the normal order is restored with the HO-2 group being the strongest hydrogen-bond donor and the HO-1 group the strongest hydrogen-bond acceptor. These results are in sharp contrast with the hydrogen-bonding abilities determined from the infrared and Raman spectra of 1 and 2 (22). In particular, the HO-4 group was shown to be involved in the weakest hydrogen bonds in crystalline 1 and 2, and the HO-2 group to participate in the strongest hydrogen bonds in 1.…”

Section: Mulliken Population Analysiscontrasting

confidence: 80%

Examination of the molecular properties of D-fructose and L-sorbose by abinitio LCAO-MO calculations

Szarek¹,

Korppi-Tommola²,

Martin³

et al. 1984

Can. J. Chem.

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Abinitio SCF LCAO-MO calculations at the STO-3G level have been performed on β-D-fructopyranose (1) and α-L-sorbopyranose (2) using crystallographic data as the geometrical input. Molecular properties of 1 and 2 are discussed in terms of orbital energies, total energy, ionization potentials, Mulliken population analysis, and electrostatic potentials, with a particular emphasis on the possible consequences of these features as regards the sweet taste of these two ketoses. No correlation was found, for example, with the electrostatic, point-charge distribution since the calculated hydrogen-bonding abilities would lead to the prediction of 2 being sweeter than 1. On the other hand, non-bonded overlap populations between oxygen and hydroxyl-hydrogen atoms reveal the presence of intramolecular interactions, which may have a determinant influence on the taste of these molecules and which could explain why D-fructose is much sweeter than its epimer at C-5, namely, L-sorbose.

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Section: Mulliken Population Analysiscontrasting

confidence: 80%

Examination of the molecular properties of D-fructose and L-sorbose by abinitio LCAO-MO calculations

Szarek¹,

Korppi-Tommola²,

Martin³

et al. 1984

Can. J. Chem.

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“…It is clear that on increasing the concentration of water, the area of the OÀH stretching region increases, because with dilution the strength of the OÀH bond increases due to hydrogen-bond formation with water. In general, as widely reported in the literature, [30,33,43,44] at room temperature the OÀH stretching band of bulk water is composed of three main components, which could be attributed to three types of water species. The first peak at 3200 cm À1 is ascribed to the inphase vibrations of the coupled OÀH symmetric stretching mode associated with tetrahedrally coordinated water molecules, as in ice.…”

Section: Secondary or Process-ii Relaxationsupporting

confidence: 62%

“…This shift of the absorption spectra of the OHstretching band towards a higher wavenumber with increasing temperature indicates that thermal agitation decreases the extent of formation of hydrogen bonds between hydroxyl groups. Since our main interest is to see how the OH-stretching region is affected by the presence of water, we carried out the detailed analysis of the OH-stretching region at different temperatures by following the scheme given by Szarek et al [33] in the case of d-arabinose. 3.…”

mentioning

confidence: 99%

Broadband Dielectric Spectroscopic, Calorimetric, and FTIR‐ATR Investigations of D‐Arabinose Aqueous Solutions

et al. 2011

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The dielectric relaxation behavior of D-arabinose aqueous solutions at different water concentrations is examined by broadband dielectric spectroscopy in the frequency range of 10(-2) -10(7) Hz and in the temperature range of 120-300 K. Differential scanning calorimetry is also performed to find the glass transition temperatures (T(g)). In addition, the same solutions are analyzed by Fourier transform infrared (FTIR) spectroscopy using the attenuated total reflectance (ATR) method at the same temperature interval and in the frequency range of 3800-2800 cm(-1). The temperature dependence of the relaxation times is examined for the different weight fractions (x(w)) of water along with the temperature dependence of dielectric strength. Two relaxation processes are observed in the aqueous solutions for all concentrations of water. The slower process, the so-called primary relaxation process (process-I), is responsible for the T(g) whereas the faster one (designated as process-II) is due to the reorientational motion of the water molecules. As for other hydrophilic water solutions, dielectric data for process-II indicate the existence of a critical water concentration above which water mobility is less restricted. Accordingly, FTIR-ATR measurements on aqueous solutions show an increment in the intensity (area) of the O-H stretching sub-band close to 3200 cm(-1) as the water concentration increases.

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“…This model does not take into consideration the other hydroxyl groups of the molecule and does not explain the considerable difference in sweetness between Dfructose and its C-5 epimer, L-sorbose: as it exists almost exclusively as a-L-sorbopyranose 5 in solution (6), this ketose is, structurally, very closely related to P-D-fructopyranose; it is, however, nearly devoid of sweet taste. The molecular properties of the two ketoses have been compared using IR spectral data (8) and by means of theoretical calculations (9-1 l), in attempts to explain this difference of sweetness. In one of these attempts (lo), the results have suggested that the assignment of the AH-B couple in P-D-fructopyranose should be reversed, making HO-1 the hydrogen bond donor and 0 -2 the acceptor.…”

mentioning

confidence: 99%

Structure–sweetness relationships for fructose analogs. Part III. 3-Deoxy-D-erythro-hexulose (3-deoxy-D-fructose): composition in solution and evaluation of sweetness

Szarek¹,

Rafka²,

Yang³

et al. 1995

Can. J. Chem.

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Abstract:As part of continuing studies on the structural features responsible for the intense sweetness of D-fructose, 3-deoxy-D-erythro-hexulose (3-deoxy-D-fructose, 1) was prepared, its solution composition was determined, and its taste was evaluated. In aqueous solution, 3-deoxy-D-fructose exists as a complex mixture of five tautomeric forms in which the P-D-pyranose form is preponderant (52.5% at 22OC) and the a-D-pyranose form is the least abundant (5%). Quite remarkable is the behavior of the open-chain keto form of 1: its content increases from 7.5% at 22"C, to 36% at 82OC, and to 47% at 97OC, making this form the preponderant one at high temperatures. 3-Deoxy-D-fructose was found to be sweet, albeit probably not as sweet as D-fructose. The hydroxyl group at C-3 is thus not an essential function of the glycophore of D-fructose. The significance of this result is discussed in relation to the evidence already available and the divergent theories that have been proposed to explain the origin of the sweet taste of D-fructose.Key words: 3-deoxy-D-erythro-hexulose (3-deoxy-D-fructose), sweetness, solution composition.Resume : La poursuite d'ttudes sur les attributs structuraux responsables pour la douceur intense du D-fructose nous a conduit B prCparer le 3-dCsoxy-D-Prythro-hexulose (3-dCsoxy-D-fructose, I), B determiner sa composition en solution et h Cvaluer son gotit. En solution aqueuse, le 3-dCsoxy-D-fructose existe sous forme d'un mClange complexe de cinq formes tautomkres dans lequel la forme P-D-pyranose est prtpondtrante (52.5% j. 22°C) et la forme a-D-pyranose est la moins abondante (5%). Le comportement de la forme a chalne ouverte ce'to est tout-i-fait remarquable : prtsente i 7.5% i 22"C, sa concentration augmente i 36% i 82°C et i 47% B 97"C, ce qui en fait la forme la plus abondante i haute tempkrature. Le 3-dCsoxy-D-fructose est doux, cependant probablement pas aussi doux que le D-fructose. Le groupement hydroxyle en C-3 apparait ainsi ne pas &tre une fonction essentielle du glycophore du D-fructose. L'importance de ce rtsultat est discutC en relation avec les donnCes dCji disponibles et les thCories divergentes qui ont Ct C proposCes pour expliquer l'origine de la douceur du D-fructose.Mots clPs : 3-dtsoxy-D-e'rythro-hexulose (3-dtsoxy-D-fructose), caractkre sucrt, composition d'une solution.The origin of the intense sweetness of D-fructose, the sweetest of the natural sugars (I), has been the object of much debate (2). While the lipophilic component X of the presumed tripartite AH-B-X glycophore (3) can be attributed to one of the methylene groups (2), the assignment of the hydrogen bond donor (AH) and acceptor (B)-couple remains unresolved. As part of continuing studies on deoxy ketohexoses designed to probe the role of individual hydroxyl groups in the glycophore of D-fructose, we have already shown (4) that the 5-OH group is not essential for the sweet response since 5-deoxy-D-threohexulose (5-deoxy-D-fructose) is nearly as sweet as D-fructose. We have now completed studies on 3-and 4-deoxy...

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A Raman and infrared study of crystalline D-fructose, L-sorbose, and related carbohydrates. Hydrogen bonding and sweetness

Cited by 39 publications

References 28 publications

Examination of the molecular properties of D-fructose and L-sorbose by abinitio LCAO-MO calculations

Examination of the molecular properties of D-fructose and L-sorbose by abinitio LCAO-MO calculations

Broadband Dielectric Spectroscopic, Calorimetric, and FTIR‐ATR Investigations of D‐Arabinose Aqueous Solutions

Structure–sweetness relationships for fructose analogs. Part III. 3-Deoxy-D-erythro-hexulose (3-deoxy-D-fructose): composition in solution and evaluation of sweetness

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