Effects of thermal denaturation on the solid-state structure and molecular mobility of glycinin.

The effects of moisture and thermal denaturation on the solid-state structure and molecular mobility of soy glycinin powder were investigated using multiple techniques that probe over a range of length and time scales. In native glycinin, increased moisture resulted in a decrease in both the glass transition temperature and the denaturation temperature. The sensitivity of the glass transition temperature to moisture is shown to follow the Gordon-Taylor equation, while the sensitivity of the denaturation temperature to moisture is modeled using Flory's melting point depression theory. While denaturation resulted in a loss of long-range order, the principal conformational structures as detected by infrared are maintained. The temperature range over which the glass to rubber transition occurred was extended on the high temperature side, leading to an increase in the midpoint glass transition temperature and suggesting that the amorphous regions of the newly disordered protein are less mobile. (13)C NMR results supported this hypothesis.

Structure and molecular mobility of soy glycinin in the solid state.

We report a multitechnique study of structural organization and molecular mobility for soy glycinin at a low moisture content (<30% w/w) and relate these to its glass-to-rubber transition. Small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy are used to probe structure and mobility on different length and time scales. NMR (approximately 10(-6) to 10(-3) s) reveals transitions at a higher moisture content (>17%) than DSC or SAXS, which sample for much longer times (approximately 10 to 10(3) s) and where changes are detected at >13% water content at 20 degrees C. The mobility transitions are accompanied by small changes in unit-cell parameters and IR band intensities and are associated with the enhanced motion of the polypeptide backbone. This study shows how characteristic features of the ordered regions of the protein (probed by SAXS and FTIR) and mobile segments (probed by NMR and DSC) can be separately monitored and integrated within a mobility transformation framework.

Influence of storage conditions on the structure, thermal behavior, and formation of enzyme-resistant starch in extruded starches.

Starch structures from an extrusion process were stored at different temperatures to allow for molecular rearrangement (retrogradation); their thermal characteristics (DSC) and resistance to amylase digestion were measured and compared. The structure of four native and processed starches containing different amylose/amylopectin compositions (3.5, 30.8, 32, and 80% amylose content, respectively) before and after digestion was studied with small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD). Rearrangement of the amylose molecules was observed for each storage condition as measured by the DSC endotherm at around 145 degrees C. The crystalline organization of the starches after processing and storage was qualitatively different to that of the native starches. However, there was no direct correlation between the initial crystallinity and the amount of enzyme-resistant starch (ERS) measured after in vitro digestion, and only in the case of high-amylose starch did the postprocess conditioning used lead to a small increase in the amount of starch remaining after the enzymatic treatment. From the results obtained, it can be concluded that retrograded amylose is not directly correlated with ERS and alternative mechanisms must be responsible for ERS formation.

Processing of novel elevated amylose wheats: functional properties and starch digestibility of extruded products.

Different types of novel wheat lines with different starch contents and amylose/amylopectin ratios, relating to defined alterations in the number and activity of starch synthase IIa genes, were processed by pilot-plant extrusion. Two types of products were produced: pure wholemeal products and breakfast cereals made from wholemeal/maize blends. Lower apparent shear viscosity was obtained in the extruder with lower starch content and higher amylose/amylopectin ratio flours (SSIIa-deficient line). The bulk density of the products decreased with increasing extrusion temperature and was always higher for the triple-null line. The bulk density was not completely explained by the melt shear viscosity, suggesting the importance of the fillers (fibers, brans) in the process of expansion and structure acquisition. The different mechanical properties were explained by the density and by the material constituting the cell walls. Enzyme-resistant starch (RS) content and hydrolysis index (HI) were not correlated to the extrusion temperature, but RS was higher in pure wholemeal products and in the SSIIa-deficient line. These results are discussed in terms of starch molecular architecture and product microstructure.

Gelled emulsion particles for the controlled release of lipophilic volatiles during eating.

Gelled emulsion particles are discussed in relation to controlling the release of lipophilic volatiles in the mouth during eating, using a mass spectroscopic technique that enables real time measurement of volatiles on the breath. Our studies have demonstrated that by encapsulating triglyceride oil droplets within biopolymer gelled particles (70-5000 microm), the initial flavour release maxima were reduced by kinetically inhibiting the mass transfer of flavour through the particle. An important feature of this approach was that it was the oil droplets and not the volatiles that were encapsulated. Factors such as particle size, oil phase volume and the partition coefficient of the volatile all affected the rate of volatile release. To control the temporal release profile, gelled emulsion particles have been designed that break down in a controlled manner under physiological conditions in the mouth. The physiological 'trigger mechanisms' investigated included mechanical failure, melting and enzyme hydrolysis.