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S Magazù

Publications and source records attributed to S Magazù.

12 recordsLinked to original sources
PubMed2007

Concentration dependence of vibrational properties of bioprotectant/water mixtures by inelastic neutron scattering.

Neutron scattering has been demonstrated to be a powerful tool for characterizing the structure and dynamics of biological molecules and for investigating the physical and chemical mechanisms of biophysical processes. The aim of the present work is to investigate by inelastic neutron scattering (INS) the vibrational behaviour of a class of bioprotectant systems, such as homologous disaccharides, trehalose, maltose and sucrose, in water mixtures. INS measurements have been performed on trehalose/H2O, maltose/H2O and sucrose/H2O mixtures at very low temperature as a function of concentration by using the thermal original spectrometer with cylindrical analyzers (TOSCA) spectrometer at the ISIS Facility (DRAL, UK). The findings allow the analyses of the vibrational features of the INS spectra in order to study the effect of disaccharides on the H2O hydrogen-bonded tetrahedral network. The obtained neutron scattering findings point out that disaccharides, and in particular trehalose, have a destructuring effect on the water tetrahedral network, as emphasized by the analysis of the librational modes region from 50 to 130 meV energy transfer. On the other hand, the analysis of the bending modes region (130-225 meV) shows a locally ordered structure in the disaccharide/H2O mixtures.Finally, the observed experimental evidences are linked to the different bioprotective effectiveness of disaccharides as a function of concentration.

Cryoprotective Agents↗
PubMed2006

Structural investigation of the confinement of finite amounts of trehalose in water-containing sodium Bis(2-ethylhexyl)sulfosuccinate reversed micelles.

The structural effect of trehalose confined in water-containing sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reversed micelles at water to AOT molar ratio W = 5 and 10 as a function of the trehalose to AOT molar ratio T (0 < T < 0.1) has been investigated by small-angle neutron scattering (SANS). SANS data analysis is consistent with the hypothesis that trehalose is encapsulated within the quite spherical hydrophilic micellar cores of water-containing reversed micelles, causing an increase of the aggregate size and a decrease of the polydispersion. Moreover, SANS results suggest that the trehalose confinement in water-containing reversed micelles involves marked changes on the molecular packing of the water-containing micellar cores. In particular, according to the obtained findings, we can hypothesize the intercalation of the trehalose molecules between the polar surfactant headgroups. The preferential solubilization in this specific nanodomain could explain the trehalose capability to prevent, upon dehydration, the transition to a gel phase, hindering serious damage to biostructures.

Journal Article↗
PubMed2006

Study of the dynamical properties of water in disaccharide solutions.

This work presents quasi-elastic neutron scattering (QENS) and neutron spin echo (NSE) findings on homologous disaccharide (i.e. trehalose, maltose and sucrose)/water solutions as a function of temperature. The dynamical properties of these systems are investigated by QENS, which, on the picosecond scale, allows for the characterisation of the diffusion of both solutes and solvent. On the other hand, NSE investigates the dynamics on the nanosecond scale, allowing for the relaxation times of the disaccharide/water systems to be evaluated. The experimental data highlight a strong slowing down of water in the presence of disaccharides. The whole set of findings indicates, therefore, a noticeable disaccharide-water interaction, which is more intense in the case of trehalose. This feature can justify its higher bioprotective effectiveness.

Disaccharides↗
PubMed2006

Changes in vibrational modes of water and bioprotectants in solution.

Inelastic neutron scattering (INS) measurements have been performed on trehalose and sucrose/H(2)O mixtures at very low temperature as a function of concentration by using the TOSCA spectrometer at the ISIS Facility (DRAL, UK). The aim of this work is to investigate by INS the vibrational behaviour of water in presence of trehalose and sucrose in order to characterize the changes induced by these disaccharides on the H(2)O hydrogen-bonded network. In particular, we obtained information about the effects of the two disaccharides in the translational, librational and bending spectral regions of ice. The disaccharide bioprotective effectiveness can be linked by the high destructuring effect emphasised by the analysis of the librational modes region. On the other hand, the analysis of the vibrational region corresponding to the ice bending modes show a high "crystallinity" degree which can justify the cryptobiotic action of disaccharides.

Cryoprotective Agents↗
PubMed2006

Macro- and microdefinitions of fragility of hydrogen-bonded glass-forming liquids.

In the present paper, the nature of the fragility of liquids with a developed H-bond network is investigated. It is shown that the effective activation energy of the shear viscosity eta and the fragility parameter defined as m=d log eta/d(Tg/T)|t=t+g are immediately connected with the average number nH(T) of the H-bond per molecule. The consistency of the macroscopic (m) and the microscopic [M=d(u(2)(0)/ 2)>loc)/d(Tg/T)|T=T+8, where 2>loc= 2>anharm - 2>harm] definitions of the fragility is established.

Journal Article↗
PubMed2005

Inelastic neutron scattering study on bioprotectant systems.

We collected inelastic neutron scattering (INS) spectra of homologous disaccharide (C12H22O11)/H2O mixtures at a very low temperature by using indirect geometry time-of-flight spectrometer TOSCA at the ISIS pulse neutron facility (DRAL, UK). The aim of this work is to investigate the vibrational behaviour of trehalose, maltose and sucrose/H2O mixtures with INS in order to characterize the structural changes induced by these disaccharides on the H2O hydrogen-bonded network. A higher degree of 'crystallinity' for the trehalose/H2O system is observed in the vibrational region corresponding to the ice bending modes. This feature could justify the better cryptobiotic action of trehalose compared with maltose and sucrose. On the other hand, the better bioprotective effectiveness could be explained by the higher destructuring effect of trehalose, emphasized by the analysis of the librational modes region.

Cryoprotective Agents↗
PubMed2005

Correlation between bioprotective effectiveness and dynamic properties of trehalose-water, maltose-water and sucrose-water mixtures.

The aim of the present work is to link the bioprotective effectiveness to the dynamic properties of a class of homologous disaccharides, that is, trehalose, maltose and sucrose, and their mixtures in water. The findings obtained by elastic neutron scattering point out a harmonic-anharmonic transition for all the three disaccharide mixtures. Using a new operative definition of 'fragility', the different degrees of 'strength' of the investigated systems are determined. The links existing between the degree of fragility and the cryptoprotective action are also discussed.

Maltose↗
PubMed2005

Tetrahedral order in homologous disaccharide-water mixtures.

The present work aims at evidencing the "kosmotrope" nature of trehalose through the analysis of inelastic neutron scattering measurements on trehalose and sucrose water solutions at different temperatures. Neutron spectra were collected by using the spectrometer MARI at the ISIS pulsed neutron source of the Rutherford Appleton Laboratory (Chilton, UK). To study the structural modifications induced on the tetrahedral hydrogen-bond network of water by homologous disaccharides, as a first step, the vibrational properties of pure water at different temperatures have been investigated. In particular, the temperature behavior of the intramolecular OH stretching mode has been analyzed. Successively, the vibrational properties for pure water have been compared with those of the sugar water solutions focusing the attention on the tetrahedral network-forming tendency. Finally, the obtained findings have been compared with previous Raman scattering evidences, and the results interpreted in the frame of recent molecular dynamics simulation works.

Journal Article↗
PubMed2004

Role of polyols in thermal inactivation of shark ornithine transcarbamoylase.

The ability of activity modulators of ornithine transcarbamoylase (OCT) from the liver of the thresher shark Alopias vulpinus to stabilize the enzyme against thermal denaturation was investigated in the tri-buffer at pH 7.8, at temperatures ranging from 60 to 70 (o)C, in the presence of polyhydroxylic molecules such as glycerol and sugars. The study indicated that in the presence of 0.5 M sugars and 1.6 M glycerol in the preincubation medium the OCT activity increases. When trehalose is introduced directly in the reaction mixture in a range of concentration of 0.25-0.5 M, the activity is lower than that with maltose, glycerol and buffer alone. Kinetic data for carbamoyl phosphate and ornithine with and without maltose and glycerol are similar, whereas trehalose increases the kinetic values. Arrhenius plots show an increase of activation energy due to trehalose, whereas values obtained with maltose and glycerol are similar to the control.

Animals↗
PubMed2004

Fragility by elastic incoherent neutron scattering.

The present work furnishes an operative definition for the fragility degree by using elastic incoherent neutron scattering (EINS). Such a definition is based on the relation between viscosity, a macroscopic quantity, and the atomic mean-square displacement, which refers to a nanoscopic property. This procedure has been used to analyze a set of glass-forming systems and it allows to obtain a linear dependence of the fragility parameter M, obtained by EINS, on the fragility parameter m, obtained by viscosity measurements.

Journal Article↗
PubMed2004

Mean-square displacement relationship in bioprotectant systems by elastic neutron scattering.

Neutron intensity elastic scans on trehalose, maltose, and sucrose/H(2)O mixtures as a function of concentration, temperature, and exchanged wave vector are presented. The experimental findings show a crossover in molecular fluctuations between harmonic and anharmonic dynamical regimes. A new operative definition for the degree of fragility of glass-forming systems is furnished by using explicitly the connection between viscosity and mean-square displacement. The procedure is tested for the investigated mixtures and for a set of glass-forming systems. In this frame, the stronger character of trehalose/H(2)O mixture indicates a better attitude in respect to maltose and sucrose/H(2)O mixtures to encapsulate biostructures in a more rigid matrix.

Biophysics↗