Characterization of natural rubber using size-exclusion chromatography with online multi-angle light scattering. Study of the phenomenon behind the abnormal elution profile.

Natural and synthetic poly(cis-1,4-isoprene) were characterized by size-exclusion chromatography coupled with an online multi-angle light scattering detector (SEC-MALS). Unlike synthetic poly(cis-1,4-isoprene) (SR), natural rubber (NR) samples showed anomalous elution profiles. The beginning of elution was very similar to SR but, after a certain elution volume, the molar masses of the eluting macromolecules increased with elution volume instead of continuing to decrease, which resulted in an upturn curve profile. Adding tetrabutylammonium bromide (TBABr) to THF (solvent and mobile phase) removed this phenomenon. In addition, using different concentrations of TBABr showed that TBABr had two simultaneous actions. TBABr reduced the abnormal elution profiles and the quantity of aggregates (insoluble part or gel). These results mean that the main phenomenon involved in abnormal elution was delayed entities adsorbing on the column packing. Their delayed elution was responsible for the artificial increase in molar masses, especially at high elution volumes. The results obtained suggest that these entities are very compact and have a sphere-like structure.

Polymerization kinetics of wheat gluten upon thermosetting. A mechanistic model.

Size exclusion high-performance liquid chromatography analysis was carried out on wheat gluten-glycerol blends subjected to different heat treatments. The elution profiles were analyzed in order to follow the solubility loss of protein fractions with specific molecular size. Owing to the known biochemical changes involved during the heat denaturation of gluten, a mechanistic mathematical model was developed, which divided the protein denaturation into two distinct reaction steps: (i) reversible change in protein conformation and (ii) protein precipitation through disulfide bonding between initially SDS-soluble and SDS-insoluble reaction partners. Activation energies of gluten unfolding, refolding, and precipitation were calculated with the Arrhenius law to 53.9 kJ x mol(-1), 29.5 kJ x mol(-1), and 172 kJ x mol(-1), respectively. The rate of protein solubility loss decreased as the cross-linking reaction proceeded, which may be attributed to the formation of a three-dimensional network progressively hindering the reaction. The enhanced susceptibility to aggregation of large molecules was assigned to a risen reaction probability due to their higher number of cysteine residues and to the increased percentage of unfolded and thereby activated proteins as complete protein refolding seemed to be an anticooperative process.

Biodegradability of wheat gluten based bioplastics.

A large variety of wheat gluten based bioplastics, which were plasticized with glycerol, were subjected to biodegradation. The materials covered the total range available for the biochemical control parameter Fi, which expresses the percentage of aggregated proteins. This quantity can be related to the density of covalent crosslinks in the wheat gluten network, which are induced by technological treatments. The biodegradability tests were performed in liquid medium (modified Sturm test) and in farmland soil. All gluten materials were fully degraded after 36 days in aerobic fermentation and within 50 days in farmland soil. No significant differences were observed between the samples. The mineralization half-life time of 3.8 days in the modified Sturm test situated gluten materials among fast degrading polymers. The tests of microbial inhibition experiments revealed no toxic effects of the modified gluten or of its metabolites. Thus, the protein bulk of wheat gluten materials is non-toxic and fully biodegradable, whatever the technological process applied.

Interactions of Kraft lignin and wheat gluten during biomaterial processing: evidence for the role of phenolic groups.

The chemical interactions between Kraft lignin and wheat gluten under processing conditions were investigated by determining the extent of the protein network formation. To clarify the role of different chemical functions found in lignin, the effect of Kraft lignin was compared with that of an esterified lignin, in which hydroxyl groups had been suppressed by esterification, and with a series of simple aromatics and phenolic structures with different functionalities (conjugated double bonds, hydroxyl, carboxylic acid, and aldehyde). The protein solubility was determined by using the Kjeldahl method. The role of the hydroxyl function was assessed by the significantly lower effect of esterified lignin. The importance of the phenolic radical scavenging structure is evidenced by the effect of guaiacol, which results in a behavior similar to that of the Kraft lignin. In addition, the significant effect of conjugated double bonds on gluten reactivity, through nucleophilic addition, was demonstrated.

Modification of the wheat gluten network by Kraft lignin addition.

The effect of Kraft lignin (KL) on wheat gluten (WG) network formation during biomaterial processing was investigated. Gluten plasticized with glycerol was blended with a variable content of KL and processed into material by mixing and hot molding. The effect of KL on WG cross-linking was assessed by size-exclusion chromatography coupled with specific detection of KL by fluorescence. Whereas processing of WG usually results in cross-linking and solubility loss, KL addition promoted an increase of gluten protein solubility in sodium dodecyl sulfate buffers. The feature demonstrates that KL functional groups hinder WG aggregation. A radical scavenger activity of KL toward the thiyl radicals produced during gluten mixing is proposed. Mixing also promotes the association of KL with WG as evidenced by the coelution of KL and WG in size exclusion high-performance liquid chromatography. Finally, gluten aggregation and cross-linking can be obtained by immersion of the materials in a dioxane-water solution, thereby demonstrating the occurrence of stabilized radicals on WG material mixed with KL.