Marie-Josée Dumont

Review: bio-based films from zein, keratin, pea, and rapeseed protein feedstocks

The development of bio-based films from proteins for their utilization as packaging materials and composites has gained popularity due to the availability, renewable nature, and biodegradability of proteins. The most studied of these polymers is sourced from soy. However, other sources of proteins show great commercial potential when transformed into films. As such, zein from corn and keratin from low-value chicken feather can be plasticized into films which exhibit good mechanical properties. Films derived from pea proteins can resist UV light transmission due to the presence of disulfide bonds within the network and the presence of amino acids such as tyrosine, tryptophan, and phenylalanine. Proteins from rapeseed have not been extensively studied as feedstocks for bio-based films but show great potential since their amino acid composition is similar to soy proteins. This review aims at combining and condensing the body of research performed on the synthesis of zein-, keratin-, pea-, canola-, and rapeseed-based films. The structural diversity of these proteins highly influences their processing methods and the physical properties of the resulting films. The potential applications of these bio-based materials are also highlighted.

Enzyme-catalyzed synthesis and kinetics of ultrasonic-assisted biodiesel production from waste tallow

The use of ultrasonic processing was evaluated for its ability to achieve adequate mixing while providing sufficient activation energy for the enzymatic transesterification of waste tallow. The effects of ultrasonic parameters (amplitude, cycle and pulse) and major reaction factors (molar ratio and enzyme concentration) on the reaction kinetics of biodiesel generation from waste tallow bio-catalyzed by immobilized lipase [Candida antarctica lipase B (CALB)] were investigated. Three sets of experiments namely A, B, and C were conducted. In experiment set A, two factors (ultrasonic amplitude and cycle) were investigated at three levels; in experiment set B, two factors (molar ratio and enzyme concentration) were examined at three levels; and in experiment set C, two factors (ultrasonic amplitude and reaction time) were investigated at five levels. A Ping Pong Bi Bi kinetic model approach was employed to study the effect of ultrasonic amplitude on the enzymatic transesterification. Kinetic constants of transesterification reaction were determined at different ultrasonic amplitudes (30%, 35%, 40%, 45%, and 50%) and enzyme concentrations (4, 6, and 8 wt.% of fat) at constant molar ratio (fat:methanol); 1:6, and ultrasonic cycle; 5 Hz. Optimal conditions for ultrasound-assisted biodiesel production from waste tallow were fat:methanol molar ratio, 1:4; catalyst level 6% (w/w of fat); reaction time, 20 min (30 times less than conventional batch processes); ultrasonic amplitude 40% at 5 Hz. The kinetic model results revealed interesting features of ultrasound assisted enzyme-catalyzed transesterification (as compared to conventional system): at ultrasonic amplitude 40%, the reaction activities within the system seemed to be steady after 20 min which means the reaction could proceed with or without ultrasonic mixing. Reversed phase high performance liquid chromatography indicated the biodiesel yield to be 85.6±0.08%.

An efficient strategy for the synthesis of 5-hydroxymethylfurfural derivative based poly(β-thioether ester) via thiol-Michael addition polymerization

A derivative of 5-hydroxymethylfurfural was synthesized for the thiol-Michael addition reaction. The efficiency of the catalysts (base and nucleophiles) and side reactions during the thiol-Michael addition were investigated. Dimethylphenylphosphine efficiently initiated the thiol-Michael addition polymerization for synthesizing bio-based furan polymers. The product poly(β-thioether ester) showed the potential to be functionalized.

Influence of palm oil, canola oil and blends on characteristics of fried plantain crisps

Purpose – The purpose of this paper is to study the influence of crude palm oil (PO), canola oil (CO) and their blends on characteristics of fried plantain crisps at two different stages of ripening. Design/methodology/approach – Plantain (Musa paradisiaca L.) samples were peeled, sliced into 3 mm slices, blanched at 70 °C for 3 min and dried. The slices were deep fried at 180 °C for different times. Findings – There was no significant difference (p > 0.05) in the moisture loss rate and the crispiness of the crisps produced using PO and CO. Significant differences (p < 0.05) existed in the fat uptake and color properties of the crisps fried in the two oils. PO fried crisps absorbed 15 percent less oil in the unripe crisps samples and 21 percent less oil in the fully ripened crisps than CO. The browning index showed that the PO crisps had greater color changes than the crisps fried using CO. The difference between the crisps from 50:50 blends of PO: CO and CO was not statistically significant, while 70:30 ...

Synthesis, characterization and potential applications of 5-hydroxymethylfurfural derivative based poly(β-thioether esters) synthesized via thiol-Michael addition polymerization

Dimethylphenylphosphine was used to efficiently initiate the thiol-Michael addition polymerization to yield 5-hydroxymethylfurfural (HMF) derivative based poly(β-thioether esters) with relatively high molecular weights (over 10 000 g mol−1) under mild conditions. The synthesized linear polymers with hydroxyl groups as side groups could be used as hot melt adhesives. Tests on wood substrates showed an adhesive strength of 1.5 MPa. Additionally, copolymers with various compositions were obtained by adding different ratios of 1,6-hexanedithiol to 1,4-benzenedithiol. 1H NMR analysis revealed that the ratios of these two dithiol monomers present in the copolymers matched well the theoretical ratios. The reversibility of the Diels–Alder reaction between the furan rings and the maleimide groups allowed the poly(β-thioether esters) to be dynamically crosslinked. As the weight ratio of crosslinkers to polymers increased from 1 : 10 to 1 : 2, the storage modulus at room temperature significantly enhanced from 1.5 MPa to 1691 MPa. Additionally, one-pot thiol-Michael polymerization to synthesize HMF derivative based thermoplastic elastomers (TPEs) was investigated. The polymerization reaction was completed within 40 min at room temperature. The maximum elongation at break of TPEs could reach >450%. The use of the Diels–Alder reaction to crosslink TPEs provided an efficient approach to improve their mechanical properties. The HMF derivative based polymers synthesized in this study had a wide range of thermal and mechanical properties. These polymers can be easily synthesized at room temperature via the combination of thiol-Michael and Diels–Alder reactions.

Model Study To Assess Softwood Hemicellulose Hydrolysates as the Carbon Source for PHB Production in Paraburkholderia sacchari IPT 101

Softwood hemicellulose hydrolysates are a cheap source of sugars that can be used as a feedstock to produce polyhydroxybutyrates (PHB), which are biobased and compostable bacterial polyesters. To assess the potential of the hemicellulosic sugars as a carbon source for PHB production, synthetic media containing softwood hemicellulose sugars (glucose, mannose, galactose, xylose, arabinose) and the potentially inhibitory lignocellulose degradation products (acetic acid, 5-hydroxymethylfurfural (HMF), furfural, and vanillin) were fermented with the model strain Paraburkholderia sacchari IPT 101. Relative to pure glucose, individual fermentation for 24 h with 20 g/L mannose or galactose exhibited maximum specific growth rates of 97% and 60%, respectively. On the other hand, with sugar mixtures of glucose, mannose, galactose, xylose, and arabinose, the strain converted all sugars simultaneously to reach a maximum PHB concentration of 5.72 g/L and 80.5% PHB after 51 h. The addition of the inhibitor mixture at the following concentration, sodium acetate (2.11 g/L), HMF (0.67 g/L), furfural (0.66 g/L), and vanillin (0.93 g/L), to the sugar mixture stopped the growth entirely within 24 h. Individually, the inhibitors either had no effect or only reduced growth. Moreover, it was found that a bacterial inoculum with high initial cell density (optical density, OD ≥ 5.6) could overcome the growth inhibition to yield an OD of 13 within 24 h. Therefore, softwood hemicellulose sugars are viable carbon sources for PHB production. Nevertheless, real softwood hemicellulose hydrolysates need detoxification or a high inoculum to overcome inhibitory effects and allow bacterial growth.

Polymeric Products Derived From Industrial Oils for Paints, Coatings, and Other Applications

Abstract This chapter focuses on the preparation of thermosets, polyesters, and other polymers from industrial oilseeds for use in paints, coatings, adhesives, foams, gels, lubrication, and other applications. Oils enriched in polyunsaturated fatty acids, particularly linseed, tung, and Chinese melon oils, have been used as “drying oils” for coatings, wood varnishes, and linoleum floor covers for decades, with their polymerization occurring in situ via auto-oxidation, followed by free radical polymerization. Castor and vernonia oils are two industrial oils that contain hydroxyl and epoxy fatty acids, respectively, that can be used as monomers for polymer synthesis. Double bonds encountered in industrial oils or their derivatives (e.g., free fatty acids or partial glycerides) can also be converted into hydroxyl and epoxide groups. These groups can also serve as conjugation sites directly or can be converted into more reactive or more reactive functional groups such as dihydroxy (via ring-opening of epoxy groups), terminal double bonds, or primary hydroxyls. Alternatively, metathesis, a novel reaction platform that uses double bonds within fatty acyl groups, can produce terminal double bonds, carboxylic acid, or amine functional groups. Polyols produced by these methods are valuable components of biobased polyurethanes, thermosets that are used in foams for mattresses and furniture, automotive parts, adhesives, and other uses. Branched and highly cross-linked polymers have been made directly from industrial oilseeds through several different reactions involving their double bonds to produce thermosets and additives for the preparation of composites. Several of the approaches reviewed in this chapter have led to monomers and polymers that are commercially available.

Pea Protein Alginate Encapsulated Bacillus subtilis B26, a Plant Biostimulant, Provides Controlled Release and Increased Storage Survival

Plant growth promoting bacteria (PGPB) represent a wide variety of soil and endophytic bacteria that have the ability to promote growth or to protect against stress of its host plant. Encapsulation of PGPB, using vegetable proteins instead of animal or petroleum-derived polymers, is a new technology to crop production and protection. Pea protein isolates (PPI) alginate capsules were synthesized and used for the protection and delivery of Bacillus subtilis B26 as plant inoculum for agricultural applications. The capsules provided a protective site to B26 strain allowing good survival, between 45 to 50%, after 112 days of incubation at different temperatures. The loaded microcapsules sustained a large population of bacteria, up to 8.3 LogCFUg-1 of soil after 3 weeks post application. The soil concentration stabilized to 7.3 Log CFUg-1 after 8 weeks post application. Capsules loaded with B26, once incorporated in the soil, successfully colonized test plants, and cell numbers inside plant tissues were sustained at 3.5 and 3.3 Log 7.3 CFUg-1 in the root and the shoot respectively. These results indicate that PPIalginate technology represents a good choice for commercial application of B. subtilis B26 in agriculture.

Comparative studies of chemical crosslinking reactions and applications of bio-based hydrogels

AbstractSuperabsorbent hydrogels are polymeric materials known for their ability to absorb and retain large amounts of water or aqueous solutions. Due to their unique properties, hydrogels have been useful in disposable diapers and other sanitary products, and in a range of other fields including agriculture and oral delivery of drugs, nutraceutical compounds or other bioactive molecules. The primary aim of this review is to provide an overview of several synthesis pathways for bio-based hydrogels by describing several chemical crosslinking methods and different ways of introducing new chemical functional groups to improve the absorbency of the polymers. In addition, bio-based superabsorbent hydrogels from proteins, carbohydrates and other biological molecules will be discussed, along with some of their applications in treating wastewater contaminated with heavy metals or as soil amendments in agriculture. Finally, some bio-based self-healing polymers and their respective applications will be covered in some details.

Salmon skin gelatin-corn zein composite films produced via crosslinking with glutaraldehyde: Optimization using response surface methodology and characterization

Composite films comprised of salmon (Salmo salar) skin gelatin and zein were prepared via crosslinking with glutaraldehyde. Response surface methodology (RSM) was used to optimize film composition to maximize tensile strength (TS) and elongation at break (EAB), and to minimize water solubility (WS) of the films. The significant (P < 0.05) variables affecting film properties were: glutaraldehyde for TS, and zein and glutaraldehyde for both EAB and WS. The optimum concentrations (g/mL) to maximize TS and EAB and to minimize WS were 3% zein and 0.02% glutaraldehyde, which yielded films having a TS of 3.11 ± 0.01 MPa, EAB of 22.43 ± 1.57%, and WS of 38.82 ± 1.71%. The infrared spectra and morphological analyses demonstrated that the gelatin-zein composite film was successfully crosslinked after the addition of glutaraldehyde, with the formation of crosslinked networks between proteins and a denser packed organization of proteins. Consequently, the resultant crosslinked composite film exhibited improvement on light transparency, water resistance and mechanical strength as a function of increasing humidity.