Biomedical subjects

Stephen G Ring

Publications and source records attributed to Stephen G Ring.

13 recordsLinked to original sources

PubMed2005

The effect of thermal history on the maillard reaction in a glassy matrix.

To test whether the extent of physical aging affected the reaction rate, Maillard reaction kinetics were studied in glassy model preservation systems subjected to two different thermal histories. The glass transition temperature and physical aging of the matrix were determined using differential scanning calorimetry, and the normalized heat capacities were modeled using the Tool-Narayanaswamy-Moynihan approach. Samples prepared using the different thermal histories initially had different degrees of aging, but these were practically indistinguishable after 10 h under the reaction conditions (65 degrees C); the samples underwent rapid structural relaxation at that temperature. The reaction of glucose and lysine in an amorphous trehalose/sucrose matrix was followed using spectrophotometric and chromatographic analysis. A difference in reaction rate could only be distinguished in the rate of consumption of glucose, which was approximately 20% faster in the minimally aged matrix; no significant differences were seen in any other indicator of reaction.

Algorithms↗

PubMed2005

Physical aging of starch, maltodextrin, and maltose.

The physical aging of low water content, amorphous starch/water, maltodextrin/water, and maltose/water mixtures in the glassy state was examined using mechanical testing and calorimetry. Stress relaxation measurements showed that upon storage of the glassy materials there was a time-dependent increase in both flexural modulus and mechanical relaxation time. The mechanical relaxation time increased with depth of quench below the calorimetric glass transition temperature and with aging time at the quench temperature. Calorimetry of the aged materials showed an overshoot in heat capacity in the vicinity of the glass transition. The logarithm of the mechanical relaxation time showed a simple linear relationship with the size of the overshoot expressed as an enthalpy change. The calorimetric behavior could be modeled using the Tool-Narayanaswamy-Moynihan method.

Calorimetry, Differential Scanning↗

PubMed2005

Pectin-chitosan multilayer formation.

The deposition of alternating layers of pectin and chitosan at a solid surface was studied using surface plasmon resonance. The binding of biopolymer to the surface was irreversible over the time scales examined. The deposition was dependent on the flow rate through the measurement cell with mass transport limitation at lower flow rates. The thickness of the deposited layer was dependent on the biopolymer concentration and was particularly marked for pectin. This was consistent with a process of initial attachment, followed by a slower structural rearrangement, which was inhibited at high initial surface concentrations of adsorbed biopolymer. Sequential deposition resulted in the formation of multilayers with an essentially linear growth rate.

Adsorption↗

PubMed2005

Oxygen solubility and permeability of carbohydrates.

The saturated oxygen concentration in a series of aqueous solutions of sorbitol (up to 35% w/w) and maltitol (up to 50% w/w) was measured using colorimetric reagent vials based on Rhodazine D. The results indicate that the solubility of oxygen in low-water carbohydrates is considerably lower than its solubility in pure water. It was concluded that the low-oxygen solubility is a major factor contributing to the barrier properties of low-water content carbohydrates used in the encapsulation of flavours, lipids, peptides and other oxidisable species.

Carbohydrates↗

PubMed2005

The nonequilibrium phase and glass transition behavior of beta-lactoglobulin.

Concentrated solutions of bovine beta-lactoglobulin were studied using osmotic stress and rheological techniques. At pH 6.0 and 8.0, the osmotic pressure was largely independent of NaCl concentration and could be described by a hard sphere equation of state. At pH 5.1, close to the isoelectric point, the osmotic pressure was lower at the lower NaCl concentrations (0 mM, 100 mM) and was fitted by an adhesive hard sphere model. Liquid-liquid phase separation was observed at pH 5.1 at ionic strengths of 13 mM and below. Comparison of the liquid-liquid and literature solid-liquid coexistence curves showed these solutions to be supersaturated and the phase separation to be nonequilibrium in nature. In steady shear, the zero shear viscosity of concentrated solutions at pH 5.1 was observed at shear rates above 50 s(-1). With increasing concentration, the solution viscosity showed a progressive increase, a behavior interpreted as the approach to a colloidlike glass transition at approximately 60% w/w. In oscillatory shear experiments, the storage modulus crossed the loss modulus at concentrations of 54% w/w, an indication of the approaching glass transition. Comparison of the viscous behavior with predictions from the Krieger-Dougherty equation indicates the hydrodynamic size of the protein decreases with increasing concentration, resulting in a slower approach to the glass transition than a hard sphere system.

Computer Simulation↗

PubMed2005

Starch crystal solubility and starch granule gelatinisation.

The solubility and dissolution behaviour of A- and B-type crystals of short chain amylose were measured both directly and using differential scanning calorimetry in the temperature range 30-110 degrees C. Dissolution in the calorimeter was affected by super-heating to the extent of 24-28 degrees C. Following trends previously found by calorimetry the B-type crystal polymorph was more soluble than the A-type. Analysis of the chain composition of the dissolved material revealed a preferential solubilisation of the short chains at the lower temperatures. The solubility of both crystal polymorphs and the magnitude of the preferential solubilisation effect was reduced in the presence of 30% w/w sucrose. A comparison of calorimetric measurements of crystal dissolution and the gelatinisation of native granular waxy maize and potato starches found some broad similarities, such as transition temperatures and their composition dependence, and some differences, such as the relatively narrow temperature range of granular gelatinisation, which reflects its cooperative nature.

Amylose↗

PubMed2004

Pectin-chitosan interactions and gel formation.

The effect of chitosan concentration on the gelation of pectins differing in charge density and distribution was examined, through the determination of gel stiffness and the binding of chitosan to the gel network. Chitosan acts as a crosslinker of concentrated pectin solutions, with its effectiveness showing a dependency on charge on the pectin. The networks produced are clear even under conditions of charge neutralisation.

Chitosan↗

PubMed2004

Material properties of concentrated pectin networks.

We have examined the mechanical behaviour of different types of pectin at high concentrations (> 30% w/w), relevant to the behaviour of pectin in the plant cell wall, and as a film-forming agent. Mechanical properties were examined as a function of counterion type (K(+), Ca(2+), Mg(2+)), concentration and extent of hydration. Hydration was controlled in an osmotic stress experiment where pectin films were exposed to concentrated polyethylene glycol [PEG] solutions of known osmotic pressure. We investigated the mechanical behaviour under simple extension. The results show that the swelling and stiffness of the films are strongly dependent on pectin source and ionic environment. At a fixed osmotic stress, both Ca(2+) or Mg(2+) counterions reduce swelling and increase the stiffness of the film.

Cations↗

PubMed2004

Physicochemical studies of pectin/poly-L-lysine gelation.

The effect of poly-L-lysine concentration and degree of polymerisation on the gelation of pectins differing in charge density and distribution was examined, through the determination of gel stiffness, swelling behaviour and the binding of poly-L-lysine to the gel network. Poly-L-lysine acts as a crosslinker of concentrated pectin solutions, with its effectiveness showing dependencies on pH and charge distribution on the pectin. Neutralisation of the anionic charge on the pectin with the polycationic peptide leads to gel opacity and eventually network collapse.

Biopolymers↗

PubMed2003

Volumetric behaviour of maltose-water, maltose-glycerol and starch-sorbitol-water systems mixtures in relation to structural relaxation.

The densities of amorphous maltose-water, maltose-glycerol and starch-sorbitol-water mixtures were measured using a vibrating-tube density meter and pycnometry. The volumetric change on mixing was investigated through the calculation of the quantity DeltaV/V, the difference between (experimental) volume of the mixture and the linear composition weighted pure constituent volumes (ideal mixing). For all of the systems studied the quantity DeltaV/V was negative and approached a minimum of -0.03 and -0.015 at mass fractions of maltose in the region of 0.75 and 0.85 for the maltose-water and maltose-glycerol mixtures, respectively. Results are discussed in the context of volume change due to structural relaxation of vitreous materials and related to the phenomenon of antiplasticisation.

Calorimetry, Differential Scanning↗

PubMed2003

Effect of molecular structure on the conductivity of amorphous carbohydrate-water-KCl mixtures in the supercooled liquid state.

The effect of carbohydrate structure on the conductivity of low water content amorphous carbohydrate-water, and carbohydrate-water-KCl mixtures, has been measured using both direct current and alternating current techniques at temperatures in the supercooled liquid and glassy range, ranging from -40 to 80 degrees C. The structures included homologous mono-, di- and trisaccharides (glucose, maltose and maltotriose), a monosaccharide with no exocyclic hydroxymethyl group (xylose) and a second trisaccharide (raffinose). The KCl-mixtures contained 9.3% w/w water and 0.74% w/w KCl which resulted in calorimetric glass transition temperatures, T(g), in the range -29-19 degrees C. At this concentration conduction due to KCl dominated that due to intrinsic conductors originating from the carbohydrates and water. In the supercooled liquid region, as temperature, T, is reduced to T(g), the activation energy of the molar conductivity of KCl, Lambda(m), increased as described by a Vogel-Tamman-Fulcher-type equation, Lambda(m)=Lambda(m0)exp[B/(T-T(0))], where Lambda(m0), B and T(0) are constants. Comparison of the molar conductivity of KCl in the carbohydrate mixtures at T(g) with that in aqueous solutions showed that conductivity is, to varying extents, uncoupled from viscosity. The uncoupling increased in the order D-xylose<D-glucose<maltose<maltotriose and raffinose. The results suggest that the primary structural characteristic determining conductivity is molecular weight, though the presence of the exocyclic hydroxymethyl group in the monosaccharide also has an effect. Whilst at T(g) the D-xylose mixture had the lowest conductivity, at a particular temperature the trisaccharide mixtures of maltotriose and raffinose had the lowest conductivities.

Carbohydrates↗

PubMed2003

The glass transition behavior of the globular protein bovine serum albumin.

The glass-like transition behavior of concentrated aqueous solutions of bovine serum albumin was examined using rheological techniques. At mass fractions >0.4, there was a marked concentration dependence of viscosity with a glass-like kinetic arrest observed at mass fractions in the region of 0.55. At mass fractions >0.6 the material behaved as a solid with a Young's modulus rising from approximately 20 MPa at a mass fraction of 0.62-1.1 GPa at 0.86. The solid was viscoelastic and exhibited stress relaxation with relaxation times increasing from 33 to 610 s over the same concentration range. The concentration dependence of the osmotic pressure was measured, at intermediate concentrations, using an osmotic stress technique and could be described using a hard sphere model, indicating that the intermolecular interactions were predominantly repulsive. In summary, a major structural relaxation results from the collective motion of the globules at the supra-globule length scale and, at 20 degrees C, this is arrested at water contents of 40% w/w. This appears to be analogous to the glass transition in colloidal hard spheres.

Animals↗

PubMed2002

Structural relaxation and physical ageing of starchy materials.

The structural relaxation during the ageing of an amorphous maltose and a starch-sorbitol mixture was examined using a range of physical techniques. Heat capacity, measured by differential scanning calorimetry, showed an overshoot in the glass-transition region, the size of which was temperature and time dependent. Volume relaxation measurements were made at different ageing temperatures in the range T(g) -15 to -30 K. The volume decreased with increasing ageing time, in an essentially linear fashion with log time. The mechanical behaviour of the materials showed a progressive embrittlement on ageing. For both materials, the mechanical relaxation time increased with ageing, and the material became stiffer. Investigation of the effect of physical ageing on transport properties was also performed using conductivity measurements on a maltose-water-KC1 mixture. A decay in conductivity, which was almost linear with log time, was observed. The structural relaxation was modelled using the Tool-Narayanaswamy approach to describe the calorimetric data.

Calorimetry, Differential Scanning↗