Reactivity of stable trifluoroacetaldehyde hemiaminals. 1. An unexpected reaction with enolizable carbonyl compounds.

In the presence of enolizable carbonyl compounds, hemiaminals of fluoral and related polyfluoroaldehydes behave as equivalents of fluoroalkyl iminium compounds and provide beta-polyfluoroalkyl beta-dialkylamino ketones, which are easily transformed, under acidic conditions, into beta-polyfluoroalkylenones.

Reaction rate modeling in cryoconcentrated solutions: alkaline phosphatase catalyzed DNPP hydrolysis.

The hydrolysis of disodium p-nitrophenyl phosphate catalyzed by alkaline phosphatase was chosen as a model to study the kinetics of changes in frozen food products. The initial reaction rate was determined in concentrated sucrose solutions down to -24 degrees C, and the enzymatic characteristics K(M) and V(max) were calculated. The experimental data were compared to the kinetics predicted by assuming that the reaction was viscosity dependent. Indeed, an analysis of the enzymatic reaction demonstrated that both the diffusion of the substrate and the flexibility of the enzyme segments were controlled by the high viscosity of the media. When the temperature was too low for the viscosity to be measured simply, the Williams-Landel-Ferry equation was used to predict the viscosity, taking, as reference temperature, the glass transition temperature (T(g)) corresponding to the concentration of the freeze-concentrated phase at the test temperature. Predicted values of the reaction rate were very close to the experimental ones in the studied temperature range.

Rotational and translational mobility of small molecules in sucrose plus polysaccharide solutions.

The effect of different polysaccharides on the rotational (D(rot)) and translational diffusion (D(trans)) coefficients of small molecules in concentrated systems (sucrose solutions) was investigated. Dextran (1 or 10% w/w) with different molecular masses (from 10(4) to 2 x 10(6) Da), gum arabic, or pullulan was added to solutions of sucrose (57.5% w/w). Viscosity measurements of the diffusion medium studied (sucrose and sucrose plus polysaccharide) were made using a Rheometric Scientific viscometer in a temperature range from 20 to -10 degrees C. The rotational mobility of nitroxide radicals (Tempol) dispersed in the concentrated systems was measured by electron spin resonance. The translational diffusion coefficient of fluorescein was determined by the fluorescence recovery after photobleaching method. The studied temperature range for the latter two techniques was from 20 to -16 degrees C. For these conditions of concentration and temperature, there was no ice formation in the samples. No effect of the molecular mass of dextran on D(rot) and D(trans) was observed when solutions with the same dry matter content were compared. Only pullulan and gum arabic, at 10%, had a significant effect on D(trans)( )()of fluorescein. Temperature and total dry matter content were observed to be the most important factors controlling D(rot) and D(trans) in these concentrated systems.

Influence of the physical state of water on the barrier properties of hydrophilic and hydrophobic films.

Water transfer through different films, as a function of the physical state of water in contact with the film, the relative humidity difference, and the water vapor pressure difference, was investigated. The films were two synthetic packagings (hydrophobic polyethylene and hydrophilic cellophane) and an edible film. The physical state of water affects water sensitive films, such as cellophane, inducing a higher liquid water transfer due to interactions with the polymer. For hydrophobic polymers, such as polyethylene, neither the physical state of water nor the relative humidity has an influence on the water permeability. In complex system, such as an edible film composed of hydrophilic particles dispersed in a lipid phase, barrier efficiency is influenced by the continuous hydrophobic phase but could also be affected by the physical state of water due to the presence of hydrophilic compounds.

Impact of melting conditions of sucrose on its glass transition temperature.

The impact of the melting conditions of sucrose crystals on the glass transition temperature (T(g)) of the sucrose melt was studied. Final temperature, heating rate, and the residence time at the final temperature were the experimental conditions considered. The glass transition temperature of the different glasses was measured by differential scanning calorimetry, and the degradation of sucrose during the thermal treatments was studied by high-performance liquid chromatography. The results showed that the T(g) is sensitive to the degradation of sucrose: T(g) decreases with the appearance of small molecules and then increases with the appearance of polymerization products. Thus, the choice of thermal treatment is of the utmost importance for the determination of the T(g) of pure sucrose.

DSC studies and stability of frozen foods.

This paper discusses the role played by the "WLF decrease in viscosity" above the temperature of the glass transition (Tg) in the temperature dependence of the stability of frozen foods. In the first part, the complex features observed before the melting endotherm on DSC/DTA thermograms of sugar-water solutions are examined; they are suggested to be representative of a glass transition associated with enthalpy relaxation. In the second part, the values of Tg for some complex foods are discussed. It is shown that ice melting adds an important contribution to the WLF effect on the decrease of the viscosity of the freeze-concentrated phase. The temperature dependence of the deterioration processes observed in frozen food products is generally smaller than that expected from this viscosity decrease. Several hypotheses are presented to account for the discrepancy.

Velocity of linear crystallization of ice in macromolecular systems.

The velocity of ice crystallization in gelled systems was compared with that in solutions of similar macromolecular materials. Neither the constituting material nor the dimensions of the tubes in which the measurements were made influenced the results. The velocity of linear crystallization of ice was slowed in macromolecular solutions and gels, and this decrease was not associated with changes in dynamic or thermodynamic properties of water. It was probably the consequence of a mechanical effect of the macromolecules directly on ice crystal growth.