Protein adsorption onto eight lignocellulosic substances (six lignin preparations and two hemicelluloses) was investigated at pH 4.8 and at two different temperatures (4°C and 45°C). The kinetics of the adsorption of cellulase, xylanase, and β-glucosidase were determined by enzyme activity measurements. The maximum adsorption capacities, the affinity constants and the binding strengths varied widely and were typically higher for the lignins than for the carbohydrates. As indicated by BET and gel permeation chromatography, different substances had widely different surface area, pore size, weight average molecular weight, and polydispersity index, but these properties were difficult to relate to protein binding. In most cases, an increase in temperature from 4°C to 45°C and a low content of carboxylic acid groups, as indicated by Fourier-Transform Infra-Red (FTIR) spectroscopy, resulted in increased protein adsorption capacity, which suggests that hydrophobic interactions play an important role.

Zein, the main seed storage protein of maize, has been widely studied as a possible source of material for the production of biodegradable plastic films. Plasticization of zein is critical to make functional films. While there have been a number of publications which report the behavior of systems with a wide variety of plasticizers, there have been few which attempt to examine the interactions of protein and plasticizer at the molecular level. In this paper, we report on the plasticizing effects of water, glycerol, and 2-mercaptoethanol, which were examined by a combination of spectroscopy (FTIR and dielectric) and thermomechanical methods. The results suggest that both water and glycerol are adsorbed onto the protein and form hydrogen bonds with the amide groups. The plasticizer then builds up in patches on the protein surface. 2-Mercaptoethanol only exhibited a weak plasticizing effect due probably to disulfide bond breaking.

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BackgroundLignin derivatives are phenylpropanoid biopolymers derived from pulping and biorefinery processes. The possibility to utilize lignin derivatives from different types of processes in advanced enzyme-catalyzed oxygen-scavenging systems intended for active packaging was explored. Laccase-catalyzed oxidation of alkali lignin (LA), hydrolytic lignin (LH), organosolv lignin (LO), and lignosulfonates (LS) was compared using oxygen-scavenging coatings and films in liquid and gas phase systems.ResultsWhen coatings containing lignin derivatives and laccase were immersed in a buffered aqueous solution, the oxygen-scavenging capability increased in the order LO < LH < LA < LS. Experiments with coatings containing laccase and LO, LH or LA incubated in oxygen-containing gas in air-tight chambers and at a relative humidity (RH) of 100% showed that paperboard coated with LO and laccase reduced the oxygen content from 1.0% to 0.4% during a four-day period, which was far better than the results obtained with LA or LH. LO-containing coatings incubated at 92% RH also displayed activity, with a decrease in oxygen from 1.0% to 0.7% during a four-day period. The oxygen scavenging was not related to the content of free phenolic hydroxyl groups, which increased in the order LO < LS < LH < LA. LO and LS were selected for further studies and films containing starch, clay, glycerol, laccase and LO or LS were characterized using gel permeation chromatograpy, dynamic mechanical analysis, and wet stability.ConclusionsThe investigation shows that different lignin derivatives exhibit widely different properties as a part of active coatings and films. Results indicate that LS and LO were most suitable for the application studied and differences between them were attributed to a higher degree of laccase-catalyzed cross-linking of LS than of LO. Inclusion in active-packaging systems offers a new way to utilize some types of lignin derivatives from biorefining processes.

Biodegradable and renewable materials can be manufactured from prolamins, which are the major storage protein fraction of cereals. This paper investigates the material properties of oat prolamin (avenin), corn prolamin (zein), and sorghum prolamin (kafirin). Glass transition temperature, dry solid content, stress at break, strain at break, oxygen permeability, and water vapor permeability were analyzed at different plasticizer contents. Avenin was plasticized with glycerol, and kafirin and zein were plasticized with a mixture of polyethylene glycol, glycerol, and lactic acid. Avenin displayed potential, although it did not exhibit the mechanical qualities of gluten, which resembles avenin at the molecular level. Compared to kafirin and zein, avenin was more extensible at low plasticizer contents, while kafirin and especially zein were more extensible at the highest plasticizer content. Avenin was far weaker than the other two at all plasticizer contents. Kafirin and zein displayed similar barrier properties, whereas avenin was notably more permeable.

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Zein, the main protein fraction in maize, is left as a by-product from bio-ethanol production. The protein has been investigated as a material for a long time, but mainly in the form of films. In contrast, foamed zein is presented in this paper. Zein foams may perhaps be used e.g. as trays for biodegradable food packages or as scaffolds for tissue engineering. A batch method for manufacturing solid foams was successfully developed, the foams being manufactured by evaporation of solvent from zein resins. In order to be suitable for foam formation, a resin must possess gas-retaining properties, which can be predicted by extensional rheology. The presence of plasticizer in some of the resins decreased their extensional viscosity, and this in turn affected the foaming process. Although all the resins displayed strain-hardening behaviour, there was coalescence of pores in all the foams. Insufficient extensional viscosity resulted in the collapse of pore walls during foam expansion. Structure analysis showed e.g. that most pores were elongated along the main axis of the mould in which the foams were manufactured. The plasticizer content in the resins had no significant effect on the mechanical properties of the foams.