Spectroscopic and structural studies on lactose species in aqueous solution combining the HATR and Raman spectra with SCRF calculations

Márquez, María Jimena; Brizuela, Alicia Beatriz; Davies, Lilian; Brandán, Silvia Antonia

doi:10.1016/j.carres.2015.01.019

Cited by 19 publications

(13 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Hence, it is evident that in the polymer exist differences between the properties of both forms. Moreover, in both monomeric species there are volume expansions in solution, as observed for sugars such as lactose and maltose [57,58]. On the other hand, the corrected solvation energy values calculated for both monomeric forms present values comparable to those observed for maltose anhydrous species (183-177 kJ/mol).…”

Section: Structural Analysissupporting

confidence: 58%

“…Analyzing the gap values it is observed that both forms in gas phase have practically the same reactivities but the α-form is more reactive in solution than the other one. The comparison of these values with those calculated for trehalose (8.0-7.9 eV) [67], maltose (7.8-7.6 eV) [58] and lactose (7.5-7.2 eV) [57] shows that the reactivities of both cellulose forms are similar to those found for maltose and lactose probably because the components monosaccharides in maltose, it is glucose 1α→4glucose and in lactose, it is galactose 1β→4glucose, are similar to cellulose where are observed 1→4…”

Section: Homo-lumo and Descriptors Studies Vol-1 Issue-2 Sift Deskmentioning

confidence: 86%

“…On the contrary, the volume contraction observed for the β-dimer could be related to their lower dipole moment in solution (8.49 D) in relation to that observed in the gas phase (8.58 D) as a consequence of higher O---O interactions in these species generating lower solvation energy. Note that the hydration increases the solvation energies as supported by the lactose [57] and maltose monohydrated [58] and sucrose di-and penta-hydrated [56].…”

Section: Structural Analysismentioning

confidence: 91%

“…Taking into account that the equations are generally known these were presented as supporting material. The force fields were computed only for the monomeric species by using the SQMFF methodology [38] and the Molvib program [39] while the internal coordinates for those cellulose species were taken of those reported for carbohydrate compounds with similar rings [55][56][57][58] and, for this reason, these were not presented in this work. The complete vibrational assignments of the monomeric cellulose structures were performed taking into account the potential energy distribution components (PED) 10% while for the dimeric species the GaussV iew program [40] was used as an aid to perform the assignments.…”

Section: Computational Detailsmentioning

confidence: 99%

“…The complete vibrational assignments of the monomeric cellulose structures were performed taking into account the potential energy distribution components (PED) 10% while for the dimeric species the GaussV iew program [40] was used as an aid to perform the assignments. After that, the calculated properties for α-and β-cellulose species were analyzed and compared later with those properties reported for some compounds with similar rings, such as some carbohydrates [55][56][57][58].…”

Section: Computational Detailsmentioning

confidence: 99%

See 4 more Smart Citations

Vibrational characterization of monomers and dimers of cellulose by using DFT calculations and the SQM methodology

Brandán¹,

Desk²

2017

SDRP-JCCMM

View full text Add to dashboard Cite

In this work, monomeric and dimeric species of α-and β-cellulose were vibrationally characterized by using theoretical calculations derived from the density functional theory (DFT) and the scaled quantum mechanical force field (SQMFF) methodology. Here, the experimental available FT-IR and Raman spectra and the experimental available structure for the β-form were used in order to perform the assignments of the 129 normal vibration modes for both α-and β-cellulose forms. Raman bands and shoulders at 1258, 1153, 1123, 918, 907, 897, 864, 744, 727, 721, 483 and 281 cm -1 could probably support the presence of two proposed dimeric species of cellulose in the solid state. The structural properties reveal differences between both monomeric α-and β-cellulose species mainly evidenced by their molecular electrostatic potentials. The high dipole moment values and the higher populations for the β-form could support the major proportion found experimentally for this form. The volume contraction observed for the β-dimer could be related to their lower dipole moment in solution in relation to that observed in the gas phase. The reduction of the glycosidic angles for both forms in solution support their rigid structures, as was experimentally observed. The atomic charges on the O atoms belonging to the glucopyranose rings and to the glycosidic bonds (O33) present the lower values. The NBO and AIM studies suggest the presence of α-and β-cellulose in the two media but the major quantity of H bonds predicted for the β-form and their high donor-acceptor interaction values could support their most important proportion existent of this form in the earth. Similar reactivities were found in gas phase but the α-form is more reactive in solution than the other one probably because the electrophilicity and nucleophilicity for the β-form show lower values than the α ones.

show abstract

Section: Structural Analysissupporting

confidence: 58%

Section: Homo-lumo and Descriptors Studies Vol-1 Issue-2 Sift Deskmentioning

confidence: 86%

Section: Structural Analysismentioning

confidence: 91%

Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

See 3 more Smart Citations

Vibrational characterization of monomers and dimers of cellulose by using DFT calculations and the SQM methodology

Brandán¹,

Desk²

2017

SDRP-JCCMM

View full text Add to dashboard Cite

show abstract

Hyperconjugative and Electrostatic Interactions as Anomeric Triggers in Archetypical 1,4‐Dioxane Derivatives

2015

View full text Add to dashboard Cite

The anomeric effect accounts for the greater thermodynamic stability of axially arranged six-membered heterocycles holding an electronegative substituent at the C1 position. Within a frame of no general consensus, two different theories are typically claimed to justify this effect mostly based on either hyperconjugative or electrostatic factors. Here we report a theoretical-experimental study of the role of both as anomeric triggers in two archetypical 1,4-dioxane derivatives, using a suitable combination of spectroscopic (IR and vibrational circular dichroism) and computational techniques for the analysis of the solvation environment effect in their anomeric choices. VCD and IR spectroscopies are used as conformer-discriminating tools: a detailed analysis of the evolution of the spectral profiles allows assessing the theoretically predicted changes in the experimental α/β ratios when changing the polar solvent, which are fully explained on the basis of an extensive NBO energy partition scheme that provides a detailed view of the role of hyperconjugative and electrostatic interactions as anomeric regulators. Our results suggest that the anomeric equilibrium cannot be described by a single stereoelectronic effect but by the combined contribution of hyperconjugation and electrostatic repulsions, so that the β-anomeric choice in polar solvents is markedly driven by the strong attenuation of electrostatic repulsive interactions that occurs in solution.

show abstract

FTIR, HATR and FT-Raman studies on the anhydrous and monohydrate species of maltose in aqueous solution

Iramain

Davies

Brandán

2016

Carbohydrate Research

View full text Add to dashboard Cite

Spectroscopic and structural studies on lactose species in aqueous solution combining the HATR and Raman spectra with SCRF calculations

Cited by 19 publications

References 36 publications

Vibrational characterization of monomers and dimers of cellulose by using DFT calculations and the SQM methodology

Vibrational characterization of monomers and dimers of cellulose by using DFT calculations and the SQM methodology

Hyperconjugative and Electrostatic Interactions as Anomeric Triggers in Archetypical 1,4‐Dioxane Derivatives

FTIR, HATR and FT-Raman studies on the anhydrous and monohydrate species of maltose in aqueous solution

Contact Info

Product

Resources

About