Molecular Simulation of Sucrose Solutions near the Glass Transition Temperature

Ekdawi-Sever, N.; Conrad, Paul B.; Pablo, Juan J. de

doi:10.1021/jp002722i

Cited by 87 publications

(91 citation statements)

References 41 publications

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“…This could play a role in preservation processes; indeed, the trehalose glass would hinder molecular motions by binding water molecules more tightly than other sugars. This possibly leads to its superior cryo-and lyoprotective properties [130]. MD simulations have been also performed in ternary LSZsugar-water systems at various sugar concentration [131][132][133][134].…”

Section: Atomistic Levelmentioning

confidence: 99%

“…The two phenomena, either coupling or nanophase separation, are evident only at low hydration, when competition for the few water molecules starts. If less sugar-water-protein connections are present, as could stem from the lower propensity of sucrose to form HBs [130] with respect to trehalose [122], a separation of the mixture components might arise. In this case, the proteins could try to make HB with other partners in the system; this could led to protein clusters, in which the protein are kept together via inter-protein HBs connections, trapped in structures distorted and with a dangerous aggregation potential following rehydration [101].…”

Section: Electron-transfer In Bacterial Photosynthetic Reaction Centementioning

confidence: 99%

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Proteins in Saccharides Matrices and the Trehalose Peculiarity: Biochemical and Biophysical Properties

Cordone¹,

Cupane²,

Emanuele

et al. 2015

COC

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Immobilization of proteins and other biomolecules in saccharide matrices leads to a series of peculiar properties that are relevant from the point of view of both biochemistry and biophysics, and have important implications on related fields such as food industry, pharmaceutics, and medicine. In the last years, the properties of biomolecules embedded into glassy matrices and/or highly concentrated solutions of saccharides have been thoroughly investigated, at the molecular level, through in vivo, in vitro, and in silico studies. These systems show an outstanding ability to protect biostructures against stress conditions; various mechanisms appear to be at the basis of such bioprotection, that in the case of some sugars (in particular trehalose) is peculiarly effective.Here we review recent results obtained in our and other laboratories on ternary protein-sugar-water systems that have been typically studied in wide ranges of water content and temperature. Data from a large set of complementary experimental techniques provide a consistent description of structural, dynamical and functional properties of these systems, from atomistic to thermodynamic level.In the emerging picture, the stabilizing effect induced on the encapsulated systems might be attributed to a strong biomolecule-matrix coupling, mediated by extended hydrogen-bond networks, whose specific properties are determined by the saccharide composition and structure, and depend on water content.

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Section: Atomistic Levelmentioning

confidence: 99%

Section: Electron-transfer In Bacterial Photosynthetic Reaction Centementioning

confidence: 99%

Proteins in Saccharides Matrices and the Trehalose Peculiarity: Biochemical and Biophysical Properties

Cordone¹,

Cupane²,

Emanuele

et al. 2015

COC

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“…The higher glass transition temperature T g of trehalose (T g ≈ 393 K [8,9]) could explain its greater preservation efficiency compared to maltose (T g ≈ 373 K [8, of three homologuous monosaccharides (namely β-D-glucose, β-D-mannose and D-fructose) and pointed out significant effects of the sugar stereochemistry on the diffusion coefficient of water and on the structure and relaxation of the HBN in these solutions. Moreover, Ekdawi-Sever et al [35,37] and Conrad et al [34] have investigated sucrose and trehalose aqueous solutions from 6 wt % up to 80 wt % and even above. They found a larger hydration number for trehalose [35] for each concentration investigated, as well as a diffusion coefficient of sucrose consistently larger than that of trehalose at high concentration (72 wt % or above) [37].…”

Section: Indeed Disaccharides Such As Trehalose [α-D-glucopyranosymentioning

confidence: 99%

How Homogeneous Are the Trehalose, Maltose, and Sucrose Water Solutions? An Insight from Molecular Dynamics Simulations

et al. 2005

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The structural properties resulting from the reciprocal influence between water and three well-known homologous disaccharides, namely trehalose, maltose and sucrose, in aqueous solutions have been investigated in the 4 -66 wt % concentration range by means of molecular dynamics computer simulations. Hydration numbers clearly show that trehalose binds to a larger number of water molecules than do maltose or sucrose, thus affecting the water structure to a deeper extent. Two-dimensional radial distribution functions of trehalose solutions definitely reveal that water is preferentially localized at the hydration sites found in the trehalose dihydrate crystal, this tendency being enhanced when increasing trehalose concentration. In a rather wide concentration range (4-49 wt %), the fluctuations of the radius of gyration and of the glycosidic dihedral angles of trehalose indicate a higher flexibility with respect to maltose and sucrose. At sugar concentrations between 33 wt % and 66 wt %, the mean sugar cluster size and the number of sugar-sugar hydrogen bonds (HBs) formed within sugar clusters reveal that trehalose is able to form larger clusters than sucrose but smaller than maltose. These features suggest that trehalose-water mixtures would be more homogeneous than the two others, thus reducing both desiccation stresses and ice formation.

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“…[3][4][5][6][7][8] These studies suggest that MD simulations are useful in estimating the T g of amorphous materials. Our previous MD simulations with isomaltodecaose (a fragment of dextran) and a-glucose (the repeated unit of dextran) demonstrated that MD simulations can provide rational T g values that decrease upon hydration and increase with increasing fragment size, suggesting the usefulness of MD simulations.…”

mentioning

confidence: 94%

Comparison of the Glass Transition Temperature and Fragility Parameter of Isomalto-Olygomer Predicted by Molecular Dynamics Simulations with Those Measured by Differential Scanning Calorimetry

Yoshioka

Aso

2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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Glass transition temperature (T g ) is an important property for amorphous pharmaceutical formulations, because it is closely related to the storage stability. The T g of amorphous materials can usually be determined by calorimetry, but this technique cannot be applied to amorphous formulations containing polymers with widely distributed molecular weights. This is because these formulations often exhibit unclear changes in heat capacity at T g due to the glass transition occurring over a wide temperature range. Molecular dynamics (MD) simulations can be performed for an amorphous matrix model constructed using polymer molecules of a uniform molecular weight, in which the chemical structure of the repeated unit can be modified. If T g prediction is possible based on MD simulations, the dependence of T g on the polymer molecular weight as well as on the chemical structure of the repeated unit can therefore be elucidated, leading to the efficient development of polymer excipients with high T g values suitable for stable amorphous dosage forms. Furthermore, MD simulations can determine the dependence of fragility for polymer matrices on the polymer molecular weight and on the chemical structure of the repeated unit. Thus, it would be possible to estimate the fragility parameter of polymer matrices with widely distributed molecular weights, which usually cannot be determined from the heating-rate dependence of T g nor from the width of glass transition.MD simulations have been utilized to estimate the glass transition temperature (T g ) of amorphous synthetic polymers, 1,2) glass former saccharides and concentrated saccharide-water systems. [3][4][5][6][7][8] These studies suggest that MD simulations are useful in estimating the T g of amorphous materials. Our previous MD simulations with isomaltodecaose (a fragment of dextran) and a-glucose (the repeated unit of dextran) demonstrated that MD simulations can provide rational T g values that decrease upon hydration and increase with increasing fragment size, suggesting the usefulness of MD simulations.9) However, the T g obtained from MD simulations was not compared with experimentally determined T g , in consideration of the heating/cooling-rate dependence. Such comparison is necessary in order to evaluate the reliability of MD simulations. In this study, the T g of an isomalto-oligomer of relatively narrow molecular weight distribution was determined as a function of heating and cooling rates by differential scanning calorimetry (DSC). For the other angle of investigation, MD simulations were carried out with an amorphous matrix constructed from isomaltoheptaose, the molecular weight of which was close to the isomalto-oligomer investigated. The density of the isomaltoheptaose matrix was calculated as a function of temperature, and the T g of the matrix was estimated from a change in the slope of the density versus temperature profile. The T g estimates obtained at various cooling rates were compared with the experimental data in order to examine whether MD simulati...

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Molecular Simulation of Sucrose Solutions near the Glass Transition Temperature

Cited by 87 publications

References 41 publications

Proteins in Saccharides Matrices and the Trehalose Peculiarity: Biochemical and Biophysical Properties

Proteins in Saccharides Matrices and the Trehalose Peculiarity: Biochemical and Biophysical Properties

How Homogeneous Are the Trehalose, Maltose, and Sucrose Water Solutions? An Insight from Molecular Dynamics Simulations

Comparison of the Glass Transition Temperature and Fragility Parameter of Isomalto-Olygomer Predicted by Molecular Dynamics Simulations with Those Measured by Differential Scanning Calorimetry

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