Surfactant-Free Stabilization of Aqueous Graphene Dispersions Using Starch as a Dispersing Agent.

Attention to graphene dispersions in water with the aid of natural polymers is increasing with improved awareness of sustainability. However, the function of biopolymers that can act as dispersing agents in graphene dispersions is not well understood. In particular, the use of starch to disperse pristine graphene materials deserves further investigation. Here, we report the processing conditions of aqueous graphene dispersions using unmodified starch. We have found that the graphene content of the starch-graphene dispersion is dependent on the starch fraction. The starch-graphene sheets are few-layer graphene with a lateral size of 3.2 µm. Furthermore, topographical images of these starch-graphene sheets confirm the adsorption of starch nanoparticles with a height around 5 nm on the graphene surface. The adsorbed starch nanoparticles are ascribed to extend the storage time of the starch-graphene dispersion up to 1 month compared to spontaneous aggregation in a nonstabilized graphene dispersion without starch. Moreover, the ability to retain water by starch is reduced in the presence of graphene, likely due to environmental changes in the hydroxyl groups responsible for starch-water interactions. These findings demonstrate that starch can disperse graphene with a low oxygen content in water. The aqueous starch-graphene dispersion provides tremendous opportunities for environmental-friendly packaging applications.

Comparison of laccase-catalyzed cross-linking of organosolv lignin and lignosulfonates.

Lignin, an underutilized by-product from chemical pulping of wood, can be modified enzymatically through oxidation by laccase. However, little is known about the molecular details surrounding the cross-linking which is a result of the oxidation. To reduce this lack of knowledge, we used oxygen consumption rate data, phenolic content data and molecular weight data together with data from NMR and FTIR spectroscopy to characterize laccase-catalyzed cross-linking of the industrial lignin preparations organosolv lignin and lignosulfonate. The organosolv lignin preparation had a Mn of 780 g/mol, a Mw of 5200 g/mol, and a phenolic content of 1.8 mmol/g. The lignosulfonate preparation had a Mn of 6000 g/mol, a Mw of 19800 g/mol, and a phenolic content of 1.1 mmol/g. Laccase-catalyzed oxidation of organosolv lignin was characterized by a relatively slow increase in molecular weight, decreased intensities for aromatic signals and p-hydroxycinnamyl groups, and increased intensity for ß-O-4' signals, whereas oxidation of lignosulfonates resulted in a very rapid increase in molecular weight, and strongly decreased intensities for aromatic signals. The data suggest that lignosulfonates cross-linked by couplings to the aromatic ring (e.g. 5-5' and 4-O-5'), whereas ß-O-4' coupling characterized cross-linking of organosolv lignin, probably involving cinnamyl alcohol end-groups.

Comparison of lignin derivatives as substrates for laccase-catalyzed scavenging of oxygen in coatings and films.

BACKGROUND: Lignin 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. RESULTS: When 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. CONCLUSIONS: The 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.

Adsorption of proteins involved in hydrolysis of lignocellulose on lignins and hemicelluloses.

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 ß-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.

Mechanical and structural properties of solution-cast high-amylose maize starch films.

Environmental issues have forced the introduction of sustainable solutions such as annually renewable resources being used as a raw material for packaging and disposables. This paper examined the effects of time and temperature during manufacturing and plasticiser content on the molecular structure of high-amylose maize starch films. It also analysed how manufacturing conditions, plasticiser content and molecular structure of the films affected their material properties. It was found that increased time or temperature increased the degradation of amylose and of amylopectin, which in turn negatively affected film cohesiveness. However, neither time nor temperature had any effect on tensile properties.

Plasticization of zein: a thermomechanical, FTIR, and dielectric study.

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.