William MacNaughtan

FTIR study of state and phase transitions of low moisture sucrose and lactose.

Mid-infrared spectra of freeze-dried sucrose and lactose systems were acquired over a range of temperatures (30-200 degrees C) and water contents (0-6.3%). Starting from the glassy state, the experimental conditions were selected to cover the main thermal transitions: the glass-rubber transition, the crystallisation and, for some samples, the subsequent melting. The FTIR spectra were very sensitive to the physical state. While subtle but systematic spectral differences between the glassy and rubbery states were detectable throughout the spectrum, a very pronounced increase in spectral resolution was observed as crystallisation occurred and was followed by the expected spectral broadening during melting. The temperatures at which these changes occurred were in satisfactory agreement with the transition temperatures measured by differential scanning calorimetry (DSC). The increase in molecular mobility as a result of increasing temperature or plasticisation by water led to a significant shift of the O-H stretching band to higher wavenumbers indicating a weakening of hydrogen bonding. This shift reached a maximum as the DSC measured crystallisation temperature range was approached. As expected, the crystallisation led to a highly effective hydrogen bonding network. This was more significant for lactose than for sucrose. No significant step change in hydrogen bonding was observed at Tg. As anticipated, the temperature at which these transitions occurred decreased with increasing water content but overlapped when observed in the context of the shifted temperature (T-Tg).

Isothermal and non-isothermal crystallization in amorphous sucrose and lactose at low moisture contents.

Differential scanning calorimetry has been used in isothermal and non-isothermal modes to provide information on the crystallization of sucrose and lactose at low water contents. Using approaches previously applied to polymer crystallization an attempt has been made to combine the isothermal and non-isothermal data into a single curve. This is achieved by the use of appropriate shift factors in the time and temperature domains. This was successful for sucrose but not for lactose. It was suggested that this was because lactose crystallizes into multiple forms whereas sucrose crystallizes in a single form.

The influence of carrageenan on molecular mobility in low moisture amorphous sugars

Abstract The influence of less than 1% of κ-carrageenan on the mobility of glucose syrup was studied in the context of the glass–rubber transition using proton NMR relaxometry. Glass-transition temperatures, ( T g ) were measured by differential scanning calorimetry (DSC) on glucose syrup samples containing 0 or 0.9% κ-carrageenan, between 0 and 1.4% KCl, and at water contents from 3.5 to 16% (wwb). Potassium chloride was added to vary the extent of gelation of the carrageenan in order to assess the effect of the biopolymer network on molecular mobility. Contrary to the reported increase of the rheologically determined glass-transition temperature, in the presence of gelling agents, the addition of 0.9% κ-carrageenan to glucose syrup with and without KCl, had no effect on the DSC measured T g . In addition, there was no effect on molecular mobility in the glassy region. The presence of carrageenan only significantly affected the mobile part of the NMR free induction decay at relatively high temperatures.

The Effect of Drying Temperature on Physical Properties of Thin Gelatin Films

The molecular morphology of thin gelatin films, controlled through the casting temperature, was monitored by wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). Gelatin films dried at lower temperatures had a markedly higher crystalline or helical structure with a slightly higher Tg and lower ΔCp compared with hot dried films, which had a more coiled structure. The relationship between molecular morphology and gelatin-water interaction in terms of hydration behavior and water diffusivity was assessed using dynamic vapor sorption (DVS). The sorption capacity increased and the level of hysteresis decreased with increasing the degree of crystallinity. The difference in the aging behavior of the films was explained in terms of the difference between the glass transition and aging temperatures, (Tg – Ta).

Stability of Lactobacillus rhamnosus GG incorporated in edible films: Impact of anionic biopolymers and whey protein concentrate

The incorporation of probiotics and bioactive compounds, via plasticised thin-layered hydrocolloids, within food products has recently shown potential to functionalise and improve the health credentials of processed food. In this study, choice of polymer and the inclusion of whey protein isolate was evaluated for their ability to stabalise live probiotic organisms. Edible films based on low (LSA) and high (HSA) viscosity sodium alginate, low esterified amidated pectin (PEC), kappa-carrageenan/locust bean gum (κ-CAR/LBG) and gelatine (GEL) in the presence or absence of whey protein concentrate (WPC) were shown to be feasible carriers for the delivery of L. rhamnosus GG. Losses of L. rhamnosus GG throughout the drying process ranged from 0.87 to 3.06 log CFU/g for the systems without WPC, losses were significantly reduced to 0 to 1.17 log CFU/g in the presence of WPC. Storage stability (over 25d) of L. rhamnosus GG at both tested temperatures (4 and 25 °C), in descending order, was κ-CAR/LBG > HSA > GEL > LSA = PEC. In addition, supplementation of film forming agents with WPC led to a 1.8- to 6.5-fold increase in shelf-life at 4 °C (calculated on the WHO/FAO minimum requirements of 6 logCFU/g), and 1.6–4.3-fold increase at 25 °C. Furthermore probiotic films based on HSA/WPC and κ-CAR/LBG/WPC blends had both acceptable mechanical and barrier properties.

On the origin of sharp peaks in the X-ray diffraction patterns of xanthan powders.

A series of xanthans containing different levels of the charged group pyruvate has been examined. The X-ray diffraction patterns of the powders of these materials had different levels of a sharp pattern superimposed on an amorphous background. As the moisture content increased so the intensity of the sharp pattern increased up to a level between 20% and 40% moisture content where the sharp pattern disappeared. X-ray diffraction pattern identification software and an inorganic X-ray diffraction database showed the origin of the sharp peaks to be due to sodium sulphate polymorphs. The behaviour of the xanthans was thought to be due to the differences in charge on the molecule; however, the increase in the crystalline component observed with increased amounts of water was unexpected. The possibility of the drying of samples was considered but the interplay between ions, the charged polymer and the water present was considered necessary to more closely describe the results.

Effect of granule organisation on the behaviour of starches in the NMMO (N-methyl morpholine N-oxide) solvent system.

The response of starches of different botanical origin to heating in 78% N-methyl morpholine N-oxide (NMMO) is compared with their behaviour in water. For all starches studied an exothermic transition is obtained in the NMMO system rather than the endothermic transition in water. In NMMO the transition temperatures are lower for A-type starches (wheat, rice and tapioca) than the C-type starches (sago and pea) and also potato which has a B-type polymorph. Observations using a hot stage microscope show two different types of initial behaviour in NMMO; erosion of the granule from the surface or disruption into fragments. In both cases the final outcome is dissolution but for the most resistant C-type starches (pea and sago) some intact granules could be seen following heating at 95 °C in 78% NMMO and subsequent precipitation in ethanol. The results are discussed in terms of what is known from previous structural studies on these six starches and the behaviour of maize starch in NMMO and ionic liquids. The work is relevant to the co-dissolution of starch and cellulose to form novel polysaccharide based materials.

The effect of ball milling and rehydration on powdered mixtures of hydrocolloids.

In many applications, particularly in food related work, it is assumed that ball milling merely serves as a means of reducing crystallinity by the steady attrition of crystals. In this work mixtures of cellulose with other biopolymers have been co-ball milled in the dry state typically at moisture contents of <12% (w/w) and the effects of recrystallizing these mixtures studied. We have found that recystallizing the mixtures under a humid (97%RH) atmosphere increases the crystallinity of the cellulose fraction in a fashion governed by the other hydrocolloid present in the mixture. Some of the measured effects occur during ball milling of the dry powders. A relative method of fitting mixtures of type I and type II cellulose is described. Progressive transition between these forms with time was discovered for eucalyptus and microcrystalline cellulose at 97%RH. Locust bean gum (LBG) appeared to exert a protective effect on both eucalyptus and microcrystalline cellulose against the destruction of crystallinity by ball milling. For eucalyptus cellulose high levels of type I were produced during recrystallization with LBG under humid conditions. Both cellulose samples crystallized in the type I form in the presence of LBG whereas type II was produced in the presence of other hydrocolloids. Possible mechanisms for these unusual observations are proposed.

New insights into xanthan synergistic interactions with konjac glucomannan: A novel interaction mechanism proposal.

The interactions of xanthans containing precise acetate and pyruvate concentration with Konjac glucomannan (KGM) were studied at different sodium chloride and polymer concentrations. A new unified model of the interaction is proposed, taking into account previous models in the literature. This study suggests that the interactions occur by two distinct mechanisms dependent on xanthan conformation. These interactions are not mutually exclusive and may co-exist and hence produce complicated traces. Consequently two types of gel which melt at different temperature ranges can be formed. Depending on the xanthan helix coil transition temperature, one or both of the synergistic states may exist in the hydrocolloid blend. The proposed model has been tested rheologically and using differential scanning calorimetry by varying salt concentration and using samples containing different functional group concentrations.

Stabilisation of oil-in-water emulsions with non-chemical modified gelatinised starch

In this research, stabilisation of oil-in-water emulsions with non-chemically modified gelatinised starch is presented. Thus far only octenyl succinic anhydride (OSA) modified gelatinised starch has been known to adsorb at emulsion droplet interfaces, acting as emulsifiers. Screening a range of commercially available food starches revealed that a non-waxy rice starch, a waxy rice starch and the waxy maize starch PRIMA600 showed oil-in-water emulsifying ability following gelatinisation. The microstructure of emulsions formulated with 20% oil and 1% starch was stable for at least 3 months. Thermal, crystallinity and molecular property analyses as well as amylose and protein content revealed no obvious link to this property. Nevertheless, this research has provided the food industry with exciting results for the formulation of clean label emulsions. Moreover, it presents a concept for oral release food emulsions with destabilisation via salivary amylase digestion of the stabilising starch emulsifier.