Wheat-gluten-based natural polymer nanoparticle composites.

A series of wheat-gluten-based nanocomposites were produced by dispersing Cloisite-30B nanoclay particles into plasticized wheat gluten systems under thermal processing conditions. The exfoliation of the nanoparticles as confirmed by wide-angle X-ray diffraction and transmission electron microscopy has resulted in significant enhancement of the mechanical properties for both deamidated proteins and vital gluten systems under 50% relative humidity (RH). Such strength improvement was also pronounced for wheat gluten (WG) systems under a high humidity condition (RH = 85%). A similar level of further strength enhancement was obtained for the WG systems that had been strengthened by blending with poly(vinyl alcohol) (PVA) and cross-linking with glyoxal. Although the nanoclay modifier, a quaternary ammonium, caused an additional plasticization to the materials, the interactions between the gluten matrix and the nanoparticles were predominant in all of these nanocomposites. A solid-state NMR study indicated that the polymer matrix in all of these nanocomposites displayed a wide distribution of chain mobilities at a molecular level (less than 1 nm). The interactions between the nanoparticles and the natural polymer matrix resulted in motional restriction for all components in the mobile phases including lipid, plasticizers, and plasticized components, although no significant influence from the nanoparticles was obtained in the mobility of the rigid phases (unplasticized components). On a scale of 20-30 nm, the deamidated protein systems tended to be homogeneous. The small domain size of the matrix resulted in modifications of the spin-lattice relaxation of these systems via spin diffusion. The residual starch seemed to remain in a relatively larger domain size in WG systems. The nanoparticles could enhance the miscibility between the starch and the other components in the WG nanocomposite, but such miscibility enhancement did not occur in the WG/PVA blend and the cross-linked system. These polymer matrixes were still heterogeneous on a scale of 20-30 nm.

pH effect on the mechanical performance and phase mobility of thermally processed wheat gluten-based natural polymer materials.

The mechanical properties, phase composition, and molecular motions of thermally processed wheat gluten- (WG-) based natural polymer materials were studied by mechanical testing, dynamic mechanical analysis (DMA), and solid-state NMR spectroscopy. The performance of the materials was mainly determined by the denaturization and cross-linking occurring in the thermal processing and the nature or amount of plasticizers used. The pH effect also played an important role in the materials when water was used as the only plasticizer (WG-w). Alkaline conditions modified the chemical structure of WG, possibly via deamidation; enhanced the thermal cross-linking of WG macromolecules to form a more stable aggregation structure; and promoted intermolecular interactions between water and all components in WG (proteins, starch, and lipid), resulting in a strong adhesion among different components and phases. The saponification of lipid under alkaline conditions also enhanced the hydrophilicity of lipid and the miscibility among lipid, water, and WG components. However, when glycerol was used with water as a plasticizer (WG-wg), the phase mobility and composition of the materials mainly depended on the content of glycerol when the water content was constant. During thermal processing under either acidic or alkaline conditions, glycerol was unlikely to thermally cross-link with WG as suggested previously. The advanced mechanical performance of the WG-wg materials was attributed to the nature of hydrogen-bonding interactions between glycerol and WG components in the materials. This caused the whole material to behave like a strengthened "cross-linked" structure at room temperature due to the low mobility of glycerol. The pH effect on phase mobility and compositions of WG-wg systems was not as significant as that for WG-w materials.

Chemical modification of wheat protein-based natural polymers: cross-linking effect on mechanical properties and phase structures.

Chemical modification of wheat protein-based natural polymer materials was conducted using glyoxal as cross-linker, and the cross-linking effect was studied on mechanical properties under different humidity conditions, the molecular motions of each component, and the phase structures/components of the whole materials. The cross-linking significantly enhanced the mechanical strength of wheat gluten (WG) materials under RH = 50%. The elongation of materials was also increased, which was in contrast to many cross-linked protein systems. The reaction mainly occurred in proteins and starch components, resulting in the formation of a stable cross-linked network with restricted molecular motions and modified motional dynamics. Although the plasticizer glycerol could also take part in the reaction with glyoxal or other components in WG especially when the glyoxal content was higher, the amount of glycerol involved in such reactions was very little. Glycerol was predominantly hydrogen-bonded with the network. The lipid component did not seem to take part in the cross-linking reaction; its mobility was promoted while its interaction with the protein-starch network was weakened after cross-linking. The formation of the cross-linked network did not enhance the hydrophobicity of the materials; the materials still adsorbed a high level of moisture under high humidity conditions (ca. RH = 85%) with no improvement in mechanical strength. In addition, further increasing the amount of glyoxal did not generate an additional strength improvement even at RH = 50%, possibly because the enhanced mobility of lipid promoted the component to be phase-separated from the WG system. To improve the water-resistant properties, the hydrophobicity of the protein macromolecules requires enhancement by other chemical modifications.