•Heat-induced retrogradation leads to irreversible reduced water interaction abilities.•Particle size is not predictive of water interaction due to internal channel pores.•Complex relationship ...between starch retrogradation, sizing and water interaction.
The particle size, water sorption properties and molecular mobility of high amylose maize starch (HAMS) and high amylose maize starch acylated with acetate (HAMSA), propionate (HAMSP) and butyrate (HAMSB) were investigated. Acylation increased the mean particle size (D4,3) and lowered the specific gravity (G) of the starch granules with an inverse relationship between the length of the fatty acid chain and particle size. Acylation of HAMS with fatty acids lowered the monolayer moisture content with the trend being HAMSB<HAMSA<HAMSP<HAMS, showing that the decrease is affected by factors other than the length of the fatty acid chain. Measurement of molecular mobility of the starch granules by NMR spectroscopy with Carr–Purcell–Meiboom–Gill (CMPG) experiments showed that T2 long was reduced in acylated starches and that drying and storage of the starch granules further reduced T2 long. Analysis of the Free Induction Decay (FID) focussing on the short components of T2 (correlated to the solid matrix), indicated that drying and subsequent storage resulted in alterations of starch at 0.33aw and that these changes were reduced with acylation. In vitro enzymatic digestibility of heated starch dispersions by bacterial α-amylase was increased by acylation (HAMS<HAMSB<HAMSP≤HAMSA) showing that the trend was not related to the length of the fatty acid chain. Digestibility was enhanced with an increase in particle size, or decrease in G, and inversely proportional to the total T2 signal. It is suggested that both external surface area and an internal network of pores and channels collectively influence the digestibility of starch.
The moisture uptake and molecular mobility of freeze-dried powders containing whey protein isolate-carbohydrate matrices (1WPI:2maltodextrin; 1WPI:1maltodextrin:1d-glucose; and ...1WPI:1maltodextrin:1l-glucose) and encapsulated Lactobacillus rhamnosus GG (LGG) in these matrices were investigated at 25 °C and 33% and 70% relative humidity (RH). The inactivation rate constant for probiotics in freeze-dried matrices were positively correlated (R(2) = 0.98) to moisture uptake and molecular mobility measured by NMR relaxometry. The stability of probiotics in glassy protein-carbohydrate matrices was dependent on the composition of the matrix. The partial substitution of maltodextrin with glucose (d- or l-) which improved microbial survival at 33% RH was related to the reduced molecular mobility and lower water uptake of the matrix. This study suggests that moisture uptake properties and molecular mobility of the matrix composition, as opposed to the relative humidity of the environment, are better determinants of probiotic viability during storage. Dynamic vapour sorption and NMR relaxometry are promising tools to assist in the selection of protein-carbohydrate matrices for enhancing probiotic viability during storage.
X-ray fluorescence microscopy (XFM) facilitates high-sensitivity quantitative imaging of trace metals at high spatial resolution over large sample areas and can be applied to a diverse range of ...biological samples. Accurate determination of elemental content from recorded spectra requires proper calibration of the XFM instrument under the relevant operating conditions. Here, we describe the manufacture, characterization, and utilization of multi-element thin-film reference foils for use in calibration of XFM measurements of biological and other specimens. We have used these internal standards to assess the two-dimensional distribution of trace metals in a thin tissue section of a rat hippocampus. The data used in this study was acquired at the XFM beamline of the Australian Synchrotron using a new 384-element array detector (Maia) and at beamline 2-ID-E at the Advanced Photon Source. Post-processing of samples by different fixation techniques was investigated, with the conclusion that differences in solvent type and sample handling can significantly alter elemental content. The present study highlights the quantitative capability, high statistical power, and versatility of the XFM technique for mapping trace metals in biological samples, e.g., brain tissue samples in order to help understand neurological processes, especially when implemented in conjunction with a high-performance detector such as Maia.
The use of nuclear magnetic resonance (NMR) spectroscopy for characterising microencapsulated tuna oil powders (25% and 50% w/w oil) and assessing the behaviour of the microcapsules on their exposure ...to water, simulated gastric fluid or to sequential exposure of simulated gastric and intestinal fluids was examined. The matrices used for encapsulation were physical mixtures of casein or whey protein in combination with carbohydrates (dextrose monohydrate with either dried glucose syrup or a physically modified resistant starch) or heated mixtures of these matrices. Solid-state ¹³C cross-polarised magic angle spinning NMR and dipolar de-coupled magic angle spinning NMR record the ¹³C NMR signals of the encapsulant material and that of the encapsulated oil, respectively. ¹H and ¹³C solution NMR were used to investigate the relative increase in mobility of the various encapsulant matrices due to their dissolution on exposure to gastrointestinal fluids. The results suggested that the dissolution characteristics of matrices of microencapsulated oil powders were dependent on the type of milk protein and carbohydrate used and whether the protein-carbohydrate matrices were heat-treated prior to encapsulation of the oil.
Part I of this paper reviewed the theoretical principles of the macromolecular design of polymer interface/interphase systems for obtaining maximum adhesion and fracture performance of adhesively ...bonded assemblies. In Part II a novel, relatively simple and industry-feasible technology for surface-grafting connector molecules is demonstrated and discussed in detail and supported by a range of experimental examples. It is shown, in agreement with contemporary theory, that the use of chemically attached graft chemicals of controlled spatial geometry and chemical functionality enables a significant increase in the strength and fracture energy of the interphase, to the point of cohesive fracture of the substrate, or that of an adjacent medium such as adhesive, elastomer, or other material. This occurs even after prolonged exposure of investigated systems to adverse environments such as hot water.
This paper reviews the theoretical principles of the macromolecular design of polymer interface/interphase systems for obtaining maximum adhesion and fracture performance of composite materials and ...adhesively bonded assemblies. Subsequently, a relatively simple and industry-feasible technology for surface grafting molecular brushes is discussed in detail and supported by a range of experimental examples. It is shown, in agreement with contemporary theory, that the use of chemically attached graft chemicals of controlled spatial geometry and chemical functionality enables a significant increase in the strength and fracture energy of the interphase, to the point of cohesive fracture of the substrate, or that of an adjacent medium such as adhesive, elastomer or matrix material. This occurs even after prolonged exposure of investigated systems to adverse environments such as hot water.
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