Stability of sugar solutions: a novel study of the epimerization kinetics of lactose in water.

This article reports on the stereochemical aspects of the chemical stability of lactose solutions stored between 25 and 60 °C. The lactose used for the preparation of the aqueous solutions was α-lactose monohydrate with an anomer purity of 96% α and 4% ß based on the supplied certificate of analysis (using a GC analytical protocol), which was further confirmed here by nuclear magnetic resonance (NMR) analysis. Aliquots of lactose solutions were collected at different time points after the solutions were prepared and freeze-dried to remove water and halt epimerization for subsequent analysis by NMR. Epimerization was also monitored by polarimetry and infrared spectroscopy using a specially adapted Fourier transform infrared attenuated total reflectance (FTIR-ATR) method. Hydrolysis was analyzed by ion chromatography. The three different analytical approaches unambiguously showed that the epimerization of lactose in aqueous solution follows first order reversible kinetics between 25 to 60 °C. The overall rate constant was 4.4 × 10(-4) s(-1) ± 0.9 (± standard deviation (SD)) at 25 °C. The forward rate constant was 1.6 times greater than the reverse rate constant, leading to an equilibrium constant of 1.6 ± 0.1 (±SD) at 25 °C. The rate of epimerization for lactose increased with temperature and an Arrhenius plot yielded an activation energy of +52.3 kJ/mol supporting the hypothesis that the mechanism of lactose epimerization involves the formation of extremely short-lived intermediate structures. The main mechanism affecting lactose stability is epimerization, as no permanent hydrolysis or chemical degradation was observed. When preparing aqueous solutions of lactose, immediate storage in an ice bath at 0 °C will allow approximately 3 min (180 s) of analysis time before the anomeric ratio alters significantly (greater than 1%) from the solid state composition of the starting material. In contrast a controlled anomeric composition (~38% α and ~62% ß) will be achieved if an aqueous solution is left to equilibrate for over 4 h at 25 °C, while increasing the temperature up to 60 °C rapidly reduces the required equilibration time.

The measurement of the ß/α anomer composition within amorphous lactose prepared by spray and freeze drying using a simple (1)H-NMR method.

PURPOSE: Reports of the anomeric composition of amorphous lactose are rare and state a highly variable range of composition (between 0% and 60% w/w ß content). We aimed to develop a quantitative measurement by (1)H-NMR of α and ß anomer content in amorphous lactose produced by different production methods. METHODS: Amorphous lactose was prepared by spray and freeze drying 10% w/v aqueous solutions of lactose. NMR analysis was performed in DMSO; peak areas of partially resolved doublets at 6.3 and 6.6 ppm were used to calculate % of α and ß lactose present. Polarimetery was used to determine optical rotation of lactose solutions. RESULTS: Observed specific rotation for supplied crystalline alpha lactose monohydrate of 88° recorded in DMSO was constant for the length of a typical NMR experiment (max. 10 min). ß/α anomer contents of amorphous lactose measured by (1)H-NMR had standard deviations as low as 0.1% w/w (n = 6). Drying a lactose solution 4 h after its preparation led to almost 35% w/w difference in anomer composition within solid amorphous material compared to samples dried after only 30 min, e.g. for freeze dried samples, ß content was 60 ± 0.1% w/w (4 h) and 25 ± 1.0% w/w (30 min). Mutarotation leads to this increase in ß anomer concentration in aqueous solution and within the solid amorphous lactose stored at 25°C. e.g. after 56 d storage the ß content of freeze dried lactose (30 min solution) increased from 25±1.0% to 50±0.5% w/w. CONCLUSION: A simple solution-based (1)H-NMR method for measurement of anomeric composition of lactose has been established. The solution ß/α ratio at the time of drying is mirrored in the composition of the resulting solid amorphous material. In order to produce a consistent anomer composition within spray and freeze dried amorphous lactose, the standing time for the feed solution should be greater than 4 h, such that the most dynamic region of the mutarotation profile has been exceeded. If the amorphous material has been formed from a solution that has not been allowed to equilibrate for 4 h, the resulting solid will continue to undergo mutarotation if trace amounts of moisture are present, until the anomeric ß/α ratio slowly approaches 1.7.

Colloidal Particles for Pickering Emulsion Stabilization Prepared via Antisolvent Precipitation of Lignin-Rich Cocoa Shell Extract.

This study concerns the preparation and functionality testing of a new class of Pickering particles for food emulsion stabilization: colloidal lignin-rich particles (CLRPs) derived from ethanol-soluble extract of cocoa shell. A further goal was to achieve Pickering functionality without the need to add co-emulsifying surfactants during emulsion processing. Cocoa shell is a co-product of the food manufacturing industry. As such it is anticipated that the particles would be accepted as a natural food ingredient, provided no harmful solvents are used in any step of their processing. The cocoa shell particles were milled, dispersed in water and exposed to 250 °C for 1 h in a stainless-steel tubular reactor followed by ethanol extraction to obtain a lignin-rich extract (46% (w/w) lignin with the remainder predominantly lipids). CLRPs were then fabricated by the precipitation of ethanol-dissolved extract into water (antisolvent). By employing an agitated process and droplet dosing into a non-agitated process, four particle suspensions of a range of submicron diameters were obtained. All particle suspensions contained the same mass fraction of extract and were surface active, with surface tension decreasing with increasing particle size. The smallest particles were obtained when lipids were removed from the extract prior to particle processing. In contrast to the other four particle suspensions, this one failed to stabilize a 10% (w/w) sunflower oil-in-water emulsion. We hypothesize that the phospholipids indigenously present in these CLRP formulations are a critical component for Pickering functionality. It can be concluded that we have successfully introduced a new class of Pickering particles, fabricated from an industry co-product and anticipated to be food grade.

A new crystalline form of αß-D-lactose prepared by oven drying a concentrated aqueous solution of D-lactose.

A new crystalline form of αß-D-lactose (C12H22O11) has been prepared by the rapid drying of an approximately 40% w/v syrup of D-lactose. Initially identified from its novel powder X-ray diffraction pattern, the monoclinic crystal structure was solved from a microcrystal recovered from the generally polycrystalline mixed-phase residue obtained at the end of the drying step. This is the second crystalline form of αß-D-lactose to be identified and it has a high degree of structural three-dimensional similarity to the previously identified triclinic form.

Crystallisation of freeze-dried sucrose in model mixtures that represent the amorphous sugar matrices present in confectionery.

Recrystallisation occurs frequently in confectionery. More information on sucrose re-crystallisation will aid our understanding of popular foods like chocolate. However, progress has been limited due the lack of a robust method for the production of amorphous sucrose, with known purity. Poor control has led to the glass transition temperatures (Tg's) for amorphous sucrose varying between 48-78 °C in the literature. Our objective was to investigate the recrystallization of sucrose in the presence of lactose, NaCl and water. The purity of sucrose was confirmed by ion chromatography, polarimetry and differential scanning calorimetry. Amorphous sucrose was prepared by freeze-drying 10% w/v aqueous solutions. Fisher (99.7%) and Silver Spoon (98.4%) sucrose samples melted at 186 ± 0.6 °C & 189 ± 0.3 °C respectively. For the Fisher sample the absence of invert sugars and low mineral content allowed the observation of a small endotherm (≈ 150 °C). The Tg of amorphous sucrose was 58.3 ± 1.1 °C with a recrystallization enthalpy (ΔHcrys) of 72.8 ± 6.0 J g-1. NaCl reduced both the Tg (54.8 ± 1.8 °C) and the ΔHcrys (35.7 ± 3.8 J g-1) without affecting the onset temperature of sucrose's re-crystallization (Tcrys, 129.5 ± 6.9 °C), suggesting that a proportion of the sample remained amorphous. The presence of water (1.6 ± 0.07%) inside the hermetically sealed pans caused an earlier onset of Tg (52.3 ± 1.3 °C) and Tcrys (85.1 ± 4.0 °C), as well as lowering ΔHcrys (45.2 ± 2.4 J g-1) compared to samples contained in pin-holed pans (where evaporation was possible). The presence of lactose inhibited the crystallization of sucrose completely. On the basis of this study, it is apparent that sucrose crystallization is highly dependent on the presence of other common food ingredients within the matrix.

Material properties of ex vivo milk chocolate boluses examined in relation to texture perception.

The texture perception of chocolate products is a major driver for consumer liking and the popularity of this confectionary category. Whilst some texture attributes are clearly linked to the material properties of the chocolate bar itself, others are closer related to the properties of the chocolate bolus. However, little is known about the material properties of chocolate boluses. Hence the aim of this study was to gain more in-depth insights into this area and to evaluate how chocolate bolus material properties link to texture and mouthfeel perception. Boluses prepared from four milk chocolates were analysed for microstructure, particle size, composition and friction properties. The boluses showed the expected oil-in-water emulsion microstructure. The emulsion droplets were composed of fat and milk protein with clear evidence for the presence of milk protein not only at the droplet interface but also in the droplet bulk phase. The type of adsorbed milk protein depended on the presence or absence of interfacially adsorbed cocoa solids, grouping the four chocolates into two pairs. The chocolate boluses showed increased friction compared to saliva and at low sliding speed the friction coefficients were lower for boluses with interfacially adsorbed cocoa solids. The perceived differences in mouthcoating were reflected in the mixed regime of the Stribeck curve. Thickness perception on the other hand was reflected in the hydrodynamic regime of the friction curves. This research has highlighted the promise in analysing the material properties of chocolate boluses in view of understanding the perceived texture.

The role of the exine coating in pollen-stigma interactions in Brassica oleracea L.

When the dehydrated pollen grain of Brassica oleracea L. alights on a receptive stigma the pollen coat flows out from the exine to form an appresoria-like 'foot' and, within a matter of some 30 min, gross ultrastructural changes become visible both within the protoplast and in the foot itself. These changes are interpreted as reflecting the limited movement of water, and presumably other materials, from the stigma to the grain. The compatible pollen grain then continues to take up water, whilst undergoing other cytoplasmic changes and eventually producing the pollen tube. The tube grows from the colpus towards the point of contact with the stigma, beneath which the outer layer of the papillar wall has become more loosely packed. The pollen tube enters the wall at this point and, as a consequence of its rapid extension, the grain is frequently lifted away from the papilla. The tube then grows between two layers of the pectocellulosic papillar wall into the stigmatic parenchyma, where it follows an intercellular route. These events are discussed in terms of current views of the relationship between male and female cells at these early stages of the pollen stigma interaction.