The current study focuses on the effects of the molecular weight on the mechanical behavior of agarose gels. The small strain rheology and large strain deformation/failure behavior of three different molecular weight agarose gels have been examined, with the results expressed in term of molar concentration. For small deformation strains, the gelation temperature at low concentrations and the critical concentration for gel formation are strongly affected by the molecular weight. In addition, the elasticity of the network is also very sensitive to this parameter. It has been demonstrated that the experimental gelation cure curves can be superimposed on a universal gelation master curve, independent of the cure time. This would indicate self-similarity of the network at different scales, irrespective of concentration. A relationship between the elastic modulus and the molecular weight has been extracted from these results, where the molecular weight dependence exhibits a power law exponent of 2.42. For large deformation strains, the Poisson ratio has been estimated to be 0.5 for each of the agarose types examined, which indicates that these gels are incompressible. The strain at failure is largely dependent on the molecular weight, and is essentially independent of the biopolymer concentration. This result highlights the fact that the strain at failure is sensitive to the connectivity distances in the gel network. However, the failure stress and Young's modulus of agarose gels show a dependence on both concentration and molecular weight. The observations regarding Young's modulus are in good agreement with those found for small deformation strain rheology for the shear modulus. One of the primary advantages of using the lowest molecular weight agarose is that higher molar concentrations can be reached (more molecules per unit volume). However, the mechanical response of agarose gels is very sensitive to the molecular weight at fixed molar concentration, and if the present results are extrapolated to very low molecular weight, it can be suggested that below a limiting molecular weight a percolating network will not be formed, as suggested by the Cascade model (Carbohydr. Polym. 1994, 23, 247-251). This speculation is based on the influence of the "connectivity" at long distances, which influences the strain at failure (when the strain at failure is zero, the system is not connective).

ATR-FTIR spectroscopy is useful in investigating the lateral organization of Stratum corneum (SC) lipids in full-thickness skin. Based on studies of the thermotropic phase transitions in n-tricosane and in excised human skin, the temperature dependence of the CH2 scissoring bandwidth emerged as a measure of the extent of orthorhombic and hexagonal phases. This dependence provides a simpler measure of the lateral order in lipid assemblies than the common spectroscopic approaches based on difference spectra, curve fitting of the CH2 scissoring region, and the position of the CH2 stretching vibrations. It has the advantages of ease of determination, relatively low variability, and high discriminative power for the type of lateral intermolecular chain packing. A comparison of the lateral organization of the lipids at the SC surface of mammalian skin using the scissoring bandwidth revealed considerable differences between human abdominal skin (containing mostly orthorhombic phases), porcine ear skin (containing mostly hexagonal phases), and reconstructed human epidermis (containing mostly disordered phases). This parameter also correctly described the different effects of propylene glycol (minimally disturbing) and oleic acid (formation of a highly disordered phase) on the SC lipids in excised human skin. The procedure described here is applicable to in vivo studies in the areas of dermatology, transdermal drug delivery, and skin biophysics.

The gelation kinetics of gelatin has been exhaustively studied using oscillatory rheometry for six molecular weight distributions, three concentrations, and four temperatures. Measurements lasted up to 3 1 /2 months, much longer than previous studies. Remarkably, all of the data can be superimposed on a single master curve using suitable shift factors. The existence of a master curve shows that, over the broad range of variables studied, the gelation processes are identical; altering the variables just changes the scaling factors for elasticity and time. Empirically, it is found that neither high nor low molecular weight chains contribute to the elasticity. A statistical network model has been developed, based on Flory's phantom network formalism. It gives reasonable fits to the experimental gel times and is compatible with the observed dependence of elasticity on molecular weight distribution. A second order reaction kinetics model has also been developed which satisfactorily models the early stages of gelation.

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Empty yeast cells are used as a new delivery system for flavor encapsulation. The flavor release mechanism from yeast cells is characterized using a series of analytical techniques, and limonene is used as a model representing a hydrophobic flavor. Furthermore, the thermal stability of the capsules was assessed. The characterization of the cell wall structure gives rise to the development of an empirical model explaining water adsorption as well as the desorption singularities observed on drying. The study of the rate of flavor release as a function of temperature and water uptake in the cell wall clearly demonstrated a particular behavior of the yeast cell wall permeability. Below a water activity around 0.7, no flavor release is permitted whereas release occurs above it. Surface analysis on dry or wet cells using atomic force microscopy is discussed.