The development of nanocomposites is a new strategy to improve physical properties of polymers, including mechanical strength, thermal stability, and gas barrier properties. The most promising nanoscale size fillers are montmorillonite and kaolinite clays. Graphite nanoplates are currently under study. In food packaging, a major emphasis is on the development of high barrier properties against the migration of oxygen, carbon dioxide, flavor compounds, and water vapor. Decreasing water vapor permeability is a critical issue in the development of biopolymers as sustainable packaging materials. The nanoscale plate morphology of clays and other fillers promotes the development of gas barrier properties. Several examples are cited. Challenges remain in increasing the compatibility between clays and polymers and reaching complete dispersion of nanoplates. Nanocomposites may advance the utilization of biopolymers in food packaging.
Zein, a major protein of corn, is rich in α-helical structure. It has an amphiphilic character and is capable of self-assembly. Zein can self-assemble into various mesostructures that may find applications in food, agricultural, and biomedical engineering. Understanding the mechanism of zein self-assembly at the nanoscale is important for further development of zein structures. In this work, high-resolution transmission electron microscopy (TEM) images revealed nanosize zein stripes, rings, and discs containing a 0.35 nm periodicity, which is characteristic of β-sheet. TEM images were interpreted in terms of the transformation of original α-helices into β-sheet conformation after evaporation-induced self-assembly (EISA). The presence of β-sheet was also detected by circular dichroism (CD) spectroscopy. Zein β-sheets self-assembled into stripes, which curled into rings. Rings formed discs and eventually spheres. The formation of zein nanostructures was believed to be the result of β-sheet orientation, alignment, and packing.
A new method for preparation of zein films involving plasticization of zein with oleic acid to form an intermediate moldable resin was presented. The resin was stretched over rigid frames to form thin membranes that were set in flexible films. The objective of the study was to investigate the effect of film preparation method on film properties. Tensile properties, microstructure, and thermal behavior of zein films plasticized with oleic acid were investigated for films prepared by conventional casting from ethanol solutions and by stretching of plasticized resins. Cast films were stiff and brittle, whereas resin films showed more flexibility and toughness. Differential scanning calorimetry thermograms of cast films indicated phase separations were generated when heated that were not observed for resin films. Microstructure images showed a higher degree of structure development and orientation in resin than in cast films. Glass‐transition temperatures of resin films were measured at ‐94 and 104.4° C, indicating the film remained flexible through a wide temperature range. Resin film flexibility and toughness were attributed to effective plasticization that led to fiber formation and orientation.
Zein, a major protein of corn, is soluble in binary mixtures of ethanol and water. It has an amphiphilic character and is capable of self-assembly into nano- and microsized rods, spheres, and films upon solvent evaporation. The formation of microspheres is of particular interest for the development of delivery systems. Control over structure formation requires a better understanding of zein behavior in solution. The objective of this work was to investigate the effect of zein concentration and the effect of ethanol-water ratio on the microphase behavior of zein solutions, believed to govern the morphology of microstructures after solvent evaporation. The Flory-Huggins solution theory was applied to model boundary lines between microphases in solution. The study generated information on the zein concentration-ethanol/water ratio conditions where microspheres are formed and provided insight into the microphase behavior of zein ethanolic solutions.
Corn zein has been investigated for fabrication of biodegradable packaging materials. Our objective was to investigate the effect of added plasticizers, oleic and linoleic acids, on tensile properties and water absorption of zein sheets. Moldable resins were precipitated from aqueous ethanol dispersions of zein and fatty acids and rolled into sheets of approximately 0.5 mm in thickness. To increase plasticization effects, zein-oleic acid sheets were replasticized by heating them in fatty acid baths. Plasticization resulted in flexible sheets of high clarity, low modulus, and high elongation and toughness, although low tensile strength. Water absorption of zein sheets was lowered by plasticization, attributed in part to reduced mass fraction of zein. Polymerization of linoleic acid may have sealed off pores on sheet surfaces, thus slowing water absorption.
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