Water mobility in multicomponent model media as studied by 2H and 17O NMR

Molecular mobility of water was studied in a microbiological media containing complex and heterogeneous mixtures of cellulose, l-sorbose, and orange serum broth (OSB) using (2)H and (17)O high-resolution NMR. All mixtures showed Lorentian (17)O NMR spectra but complex (2)H NMR line shapes. Sorbose, when solubilized, caused line-narrowing where as cellulose-OSB mixtures showed wide peaks with flat plateaus. Presence of liquid or solvent water had a profound effect on a marked increase in T(2) relaxation time observed in sorbose-containing samples. (17)O NMR data were not composition dependent, while (2)H NMR data were highly sorbose dependent.     

Maltodextrin-anionic surfactant interactions: isothermal titration calorimetry and surface tension study

Interactions between maltodextrin (DE = 10) and an anionic surfactant (sodium dodecyl sulfate, SDS) were studied in a buffer solution (pH 7.0, 10 mM NaCl, 20 mM Trizma, 30.0 degrees C) using isothermal titration calorimetry (ITC), surface tension, differential scanning calorimetry (DSC), and turbidity techniques. ITC measurements indicated that the binding of SDS to maltodextrin was exothermic and that, on average, one SDS monomer bound per 24 glucose units of maltodextrin at saturation. Surface tension measurements indicated that there was a critical surfactant concentration ( approximately 0.05 mM SDS) below which surfactant and maltodextrin did not interact and that the amount of surfactant bound to the maltodextrin above this concentration increased with increasing maltodextrin concentration. Turbidity measurements indicated that the solutions remained transparent at all maltodextrin (0-1 wt %) and SDS (0-20 mM) concentrations studied, which suggested that phase separation did not occur. DSC measurements indicated that no phase transitions occurred between 10 and 110 degrees C for maltodextrin solutions (0.5 wt %) in the presence or absence of surfactant. A phase diagram was developed to describe the interactions between SDS and maltodextrin.     

Molecular characterization around a glassy transition of starch using (1)H cross-relaxation nuclear magnetic resonance

The aim of this work was to characterize the glassy-rubbery transition in starch gels using molecular (NMR) techniques. Proton cross-relaxation ((1)H CR) NMR spectra of gelatinized starch ( approximately 50% mc) were obtained by cooling stepwise from 20 to -30 degrees C. A significant line broadening was observed in the CR spectra between 0 and -10 degrees C. Deconvolution of the spectra into its component curves (broad and narrow) yielded a peak amplitude, width at half-height, and peak area for each curve. Between 0 and -10 degrees C (temperatures around T(g)), a significant line width change in the broad component (rigid solid) was apparent. These observed qualitative changes may be evidence of a glassy-rubbery transition at a molecular (short-range) level which are strengthened by a similar transition temperature range found previously with (13)C CP-MAS and DMA tan delta(T) measurements. However, the increase in the relative quantity of rigid protons observed by (1)H CR NMR spectra could also be attributed to ice. The (1)H CR NMR method showed its potential application for probing solid components in gels using a simple and economical NMR spectrometer, without the need for a solid-state instrument.     

Relationship of Gelatinization and Recrystallization of Cross‐Linked Rice to Glass Transition Temperature

Nonwaxy rice starch was cross‐linked with sodium trimetaphosphate and sodium tripolyphosphate to obtain different degrees of cross‐linking (9.2, 26.2, and 29.2%). The objective was to investigate the influence of cross‐linking on thermal transitions of rice starch. Starch suspensions (67% moisture) were heated at 2°C/min using differential scanning calorimetry (DSC) to follow melting transition of amylopectin. Biphasic transitions were observed at ≈60–95°C in all samples. Melting endotherms of amylopectin shifted to a higher temperature (≤5°C) with an increasing degree of cross‐linking, while there was no dramatic change in enthalpy. Recrystallization during aging for 0–15 days was significantly suppressed by cross‐linking. The delayed gelatinization and retrogradation in crosslinked starch were evident due to restricted swelling and reduced hydration in starch granules. Glass transition temperature (T_g) measured from the derivative curve of heat flow was ‐3 to ‐4°C. No significant change in T_g was observed over the storage time studied.     

Increasing the oxidative stability of liquid and dried tuna oil-in-water emulsions with electrostatic layer-by-layer deposition technology

Omega-3 Fatty acids have numerous health benefits, but their addition to foods is limited by oxidative rancidity. Engineering the interfacial membrane of oil-in-water emulsion droplets to produce a cationic and/or thick interface is an effective method to control lipid oxidation. Cationic and thick emulsion droplet interfacial membranes can be produced by an electrostatic layer-by-layer deposition technique resulting in droplets that are coated by multiple layers of emulsifiers. Tuna oil-in-water emulsion droplets coated by lecithin and chitosan produce cationic emulsion droplets that are more oxidatively stable than emulsions coated by lecithin alone. Ethylenediaminetetraacetic acid (EDTA) was able to increase the oxidative stability of emulsions stabilized with lecithin and chitosan more effectively than mixed tocopherols. The combination of EDTA and mixed tocopherols was not more effective than EDTA alone suggesting that control of prooxidant metals was the most important antioxidant technology. The production of emulsion droplets coated with lecithin and chitosan could be an excellent technology for stabilization of oxidatively unstable lipids for use in a variety of food products.     

Stability of spray-dried tuna oil emulsions encapsulated with two-layered interfacial membranes

omega-3 Fatty acids have numerous health benefits, but their addition to foods is limited by oxidative rancidity. Spray-drying tuna oil-in-water emulsion droplets with a coating of lecithin and chitosan multilayer system could produce emulsion droplet interfacial membranes that are cationic and thick, both factors that can help control lipid oxidation. Physicochemical and oxidative stability of the spray-dried emulsions were determined as a function of storage temperature and relative humidity (RH). The combination of ethylenediaminetetraacetic acid (EDTA) and mixed tocopherols was able to increase the oxidative stability of dried emulsions. Lipid oxidation was more rapid during storage at low relative humidity (11% and 33% compared to 52% RH). At high moisture, physical modifications in the sample were observed, including reduced dispersibility and formation of brown pigments. Sugar crystallization or Maillard products produced at the higher humidities may have inhibited oxidation. Overall, spray-dried tuna oil-in-water emulsions stabilized by lecithin-chitosan membranes were more oxidatively stable than bulk oils and thus have excellent potential as an omega-3 fatty acid ingredient for functional foods.     

Effects of Glycerol and Moisture Redistribution on Mechanical Properties of White Bread

Effects of glycerol and moisture redistribution on mechanical properties of bread were investigated. Firmness increased in all bread crumb over storage time but firming rate was dependent on the initial moisture content, storage method (stored with and without crust), and the presence of glycerol. Faster firming was observed when bread crumb had low initial moisture content and high glycerol level, and was stored with crust. The effect of glycerol was more pronounced when stored with crust, suggesting a critical role of water loss. Firmness showed a good correlation (r² = 0.95) with the scale factor (C₁) from a mathematical model. Recoverable work rapidly decreased in first three days of storage and then remained relatively unchanged thereafter. Hardening of aged bread (but not fresh bread) by glycerol may be explained by local dehydration of bread polymer due to osmotic dehydration or competition for water, which in turn promote more rapid amorphous network formation but less amylopectin recrystallization.     

Action of Oxidants on Water Sorption, 2H Nuclear Magnetic Resonance Mobility,and Glass Transition Behavior of Gluten

Oxidation of vital wheat gluten with potassium bromate and ascorbic acid significantly extends or broadens glassy-rubber transition to a higher final temperature range or moisture content. Thermomechanical and deuterium nuclear magnetic resonance (NMR) data show that the increased stiffness due to oxidation could be detected from the thermomechanical and deuterium NMR mobility level, indicating increased rigid fractions. The oxidation also resulted in increased water sorption, but no significant change in “freezable” water, and a much decreased mobile deuterium NMR signal. Room temperature sorption of water resulted in a glassy-rubbery transition over a ≈10–20% mc range for the control. For the oxidized sample, it started at ≈10%mc, but the transition was gradual and extended into much higher moisture ranges that corresponded to a more rigid fraction of deuterium (NMR) signal. This suggests that the oxidative interactions led to a more rigid gluten fraction, extending the transition to a higher temperature range, perhaps resulting in a more elastic dough.     

Role of water mobility on mold spore germination

A sugar transport defected strain of Aspergillus nidulans (biA-1 sorA-2) was tested for spore germination in nutrient media containing various water activity (a(w)) values and varying amounts of non-nutritive, nontoxic carbohydrates (L-sorbose and cellulose). Freeze-dried media [containing the same nutrient level but different in sorbose/cellulose (s:c) ratio] were adjusted to 0.75-0.97a(w) at 25 degrees C before inoculation. Minimum a(w) for germination varied with s:c ratio. Because both sorbose and cellulose were not metabolizable and unable to be transported into the cells, the results reflected the molecular mobility of water. (2)H NMR T(2) relaxation time correlated well with spore germination time, and it distinguished the difference between water sorbed to cellulose and water in a solution associated with dissolved sorbose. On the other hand, mold germination time correlated poorly with a(w). It was highly dependent on the s:c ratio. Water mobility was found to correlate better with biological activity than a(w) because it differentiated the availability between water in dissolved sorbose and adsorbed water in cellulose.     

Effects of glycerol and moisture gradient on thermomechanical properties of white bread

The thermomechanical properties of breadcrumb were investigated using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The main transition (T(1), near 0 degrees C) shifted to lower temperature with added glycerol due to freezing point depression. The low-temperature transition (T(3), approximately -50 degrees C), found only in high-glycerol (8.8%) bread, suggested that of excess or phase-separated glycerol. The high-temperature transition (T(2), 60-85 degrees C) appeared only in aged breadcrumbs; its temperature range was correlated well with the amylopectin melting transition (DSC) but its tan delta amplitude did not correlate well with the amylopectin melting enthalpy (r(2) = 0.72). On the other hand, the change of E' ' (viscous behavior) suggested that T(2) might be related to the change in the amorphous region. Domain-to-domain (amorphous) and crumb-to-crust moisture migrations are two critical phenomenological changes associated with aging and could lead to significant local dehydration of some amorphous regions contributing to mechanical firming during storage.