Influence of cooling rate on ice crystallization and melting in sucrose-water system

The ice crystallization and melting in systems where the equilibrium state is difficult to reach is one of the growing areas in pharmaceutical freeze-drying research. The quality of the final freeze-dried product depends on the parameters of the cooling step, which affect the ice nucleation and growth. In this paper, we present a DSC study of ice crystallization and melting in a sucrose-water system. Using two different types of thermal cycles, we examine the influence of cooling and heating rates on the thermal behavior of sucrose-water solutions with water contents between 50 and 100 wt%. The DSC results show that low cooling rates provide crystallization at higher temperatures and lead to lower amount of nonfreezing water. Consequently, the glass transition and ice melting properties observed upon heating depend on the cooling conditions in the preceding step. Based on the experimental results, we investigate the reasons for the existence of the two steps on DSC heating curves in sucrose-water systems: the glass transition step and the onset of ice melting. We show that diffusion of water can be the limiting factor for ice growth and melting in the sucrose-water system when the amorphous phase is in a liquid state. In particular, when the diffusion coefficient drops below 10−14 m2/sec, the ice crystals growth or melting becomes strongly suppressed even above the glass transition temperature. Understanding the diffusion limitations in the sucrose-water system can be used for the optimization of the freeze-drying protocols for proteins and probiotics

Effect of particle size in chocolate shell on oil migration and fat bloom development

The effects of chocolate shell particle size were investigated by means of its influence on rate of oil migration and fat bloom development. The particle size of the non-fat particles in the chocolate, i.e. sugar and cocoa particles was varied between 15, 22 and 40 mu m. A novel set of analytical techniques was used and by combining migration results with surface topology results clear differences could be observed between the samples. At 23 degrees C storage the samples with a particle size of 15 mu m showed higher rate of oil migration and, further, the earliest development of fat bloom at the surface. This could be observed both macroscopically and microscopically. Thus, it appears as a larger specific surface area of the nonfat particles facilitates migration of filling oil, possibly due to a more heterogeneous and coarser crystal network with higher permeability. Molecular diffusion cannot explain the level of oil migration observed and, thus, convective flow is assumed to be an important contribution in addition to the molecular diffusion. (C) 2014 Elsevier Ltd. All rights reserved

Hydration enthalpies of amorphous sucrose, trehalose and maltodextrins and their relationship with heat capacities

The mechanisms of glass transitions and the behavior of small solute molecules in a glassy matrix are some of the most important topics of modern thermodynamics. Water plays an important role in the physical and chemical stability of lyophilized biologics formulations, in which glassy carbohydrates act as cryoprotectants and stabilizers. In this study, sorption calorimetry was used for simultaneous measurements of water activity and the enthalpy of water sorption by amorphous sucrose, trehalose and maltodextrins. Moreover, the heat capacity of these carbohydrates in mixtures with water was measured by DSC in a broad range of water contents. The hydration enthalpies of glassy sucrose, trehalose and maltodextrins are exothermic, and the enthalpy change of water-induced isothermal glass transitions is higher for small molecules. The partial molar enthalpy of mixing of water in slow experiments is about -18 kJ mol-1, but less exothermic in the case of small molecules at fast hydration scan rates. By measuring the heat capacities of disaccharides and maltodextrins as a function of water content, we separated the contributions of carbohydrates and water to the total heat capacities of the mixtures. The combination of these data allowed testing of thermodynamic models describing the hydration-induced glass transitions. The heat capacity changes calculated by the fitting of the hydration enthalpy data for disaccharides are in good agreement with the heat capacity data obtained by DSC, while for maltodextrins, the effect of sub-Tg transitions should be taken into account. Combining the data obtained by different techniques, we found a distinct difference in the behavior of water in glassy polymers compared to that in glassy disaccharides. By understanding the behavior of water in glassy carbohydrates, these results can be used to improve the design of freeze-dried formulations of proteins and probiotics

Preparation of diglycerides by lipase-catalyzed alcoholysis of triglgicerides

Lipase from Penicillium roquefortii immobilized on porous polypropylene particles was used for enzymatic preparation of 1,2-diglycerides by alcoholysis in organic media. A screening of commercially available lipases showed that lipases from Penicillium species produced high amounts of 1,2-diglycerides from triglycelirles. Reaction parameters such as solvent, alcohol, water activity, and fatty acid chain length wet-e investigated. The positional selectivity of the lipase as well as the selectivity for type of glyceride specie were studied using pure isomers of the partial glycerides. The enzyme showed high selectivity for triglycerides and 1-monoglycerides and very low activity towards diglycerides. The lipase had a clear preference for the 1- and 3-positions. The highest lipase activity was observed at low water activity, but the yield increased with increasing water activity. Above all, the regio-isomeric purity of the diglycerides increased with increasing water activity. The yield of dilaurin was 75% and furthermore, 95% of the the total dilaurin was 1,2-dilaurin. Alcohol concentration and chain length of the alcohol had insignificant effect on yield and enzyme activity, but product stability increased when alcohol was present in the reaction medium. The best solvents were ethers; higher enzyme activities were obtained in aliphatic hydrocarbons bur yields and regio-isomeric purities were low presumably due to acyl migration

Acyl group migrations in 2-monoolein

Acyl migration in 2-monoolein dissolved in solvents under conditions common in lipid modification reactions has been studied. The effects on acyl migration of solvent, incubation temperature, water activity, polar additives and solid additives have been investigated. Extensive acyl migration occured in aliphatic hydrocarbons and water-miscible alcohols under dry conditions. The acyl migration rate could be decreased in several nonpolar solvents by adding a small amount of water or an alcohol. Increasing water activity had no effect in isooctane, but decreased the acyl migration rate dramatically in methyl tert-butyl ether and methyl isobutyl ketone. Several commonly used enzyme supports catalysed acyl migration, showing that supports with surface charges could catalyse acyl migration

Surface Composition and Morphology of Particles Dried Individually and by Spray Drying

This study investigates how the morphology of spray-dried particles is related to the formulation and properties of the components in the formulation. Further, the scale effects in comparisons of levitation-dried single particles and spray-dried particles in a lab-scale spray dryer have been addressed. The Drying Kinetics Analyzer (TM) generates single particles from a levitated drop under simulated spray-drying conditions. A set of surface-active polymers (bovine serum albumin, hydroxypropyl methyl cellulose, and triblock co-polymer Poloxamer), in combination with lactose, were analyzed for their dynamic surface properties in solution, and their effect on particle morphology and surface composition were determined by low-vacuum SEM and XPS analyses. The morphology obtained in spray drying was reproduced in the single-particle drying. The surface compositions were also similar, but higher levels of surface-active materials were found at the surface of the single particles as compared to the spray-dried particles. Further, the adsorption rate of surface-active compounds at the drop surface estimated by dynamic surface tension was found to be an important parameter to estimate the surface composition at different drying scales. The particle morphology was primarily determined by the surface rheological properties of the feed solution and, to a lesser extent, by the surface composition

Phase Segregation in Individually Dried Particles Composed of Biopolymers.

Mixing of two biopolymers can results in phase separation due to their thermodynamically incompatibility under certain conditions. This phenomenon was first reported when the solution was allowed to equilibrate, but it has later been observed also as a consequence of drying. The challenges of this study were to observe phase segregation by confocal Raman microscopy and LV-SEM on dried film, individually dried particles, and spray dried particles. The influence of the solid content and the phase ratio (composition) of a HPMC/maltodextrin mixture on the localization of the ingredients in the individually dried particles was investigated. We observed that phase segregation of HPMC and maltodextrin is induced by solvent evaporation in film drying, single particle drying, as well as spray drying. The phase ratio is an important parameter that influences the localization of the HPMC-enriched phase and maltodextrin-enriched phase, i.e., to the particle surface, to the core, or in a more or less bicontinuous pattern. The drying time, affected by the solids content, was found to control the level of advancement of the phase segregation

Study of the porous structure of white chocolate by confocal Raman microscopy

Confocal Raman microscopy has been shown to be a useful technique for investigation of white chocolate surfaces. The appearance of protrusions and pores, and the distribution of fat, sucrose, and milk powder at and below the surface of white chocolate pralines were investigated using confocal Raman microscopy. Raman horizontal and depth scans showed that the protrusions and pores continue at least 10 mu m into the chocolate shell and that some protrusions and channels mainly consist of fat, while some consisted of a fat layer, leaving a hollow space underneath. Further, the pores and their continuing channels consisted of nothing but air. These findings indicate that the protrusions might be connected to channels where we suggest a pressure driven convective flow of liquid fat from within the chocolate matrix that, depending on temperature, moves up to the surface or goes back into the matrix, leaving an empty pore with a shell of fat at the surface, which in some cases collapse and leaves a hollow pore and channel. Therefore, these findings support that the protrusions could be connected to oil migration in chocolate and, thus, further to fat bloom development. Practical applications: Confocal Raman microscopy can be used to investigate the local distribution of different components in white chocolate. This technique offers the possibility to acquire the local distribution of different components within the sample, with a resolution down to the optical diffraction limit. Further, the analysis can be performed at ambient conditions, without requiring any special sample preparation or marker molecules. The results obtained by using this technique suggest that specific surface imperfections on chocolate could be part of a network of pore structures at and beneath the chocolate surface, which could be related to oil migration and thus, to fat bloom formation