Delilah F. Wood

Nanocellulose Reinforced Chitosan Composite Films as Affected by Nanofiller Loading and Plasticizer Content

UNLABELLED Chitosan is a biopolymer obtained by N-deacetylation of chitin, produced from shellfish waste, which may be employed to elaborate edible films or coatings to enhance shelf life of food products. This study was conducted to evaluate the effect of different concentrations of nanofiller (cellulose nanofibers, CNF) and plasticizer (glycerol) on tensile properties (tensile strength-TS, elongation at break-EB, and Youngs modulus-YM), water vapor permeability (WVP), and glass transition temperature (T(g)) of chitosan edible films, and to establish a formulation to optimize their properties. The experiment was conducted according to a central composite design, with 2 variables: CNF (0 to 20 g/100 g) and glycerol (0 to 30 g/100 g) concentrations in the film (on a dry basis), which was produced by the so-called casting technique. Most responses (except by EB) were favored by high CNF concentrations and low glycerol contents. The optimization was based on maximizing TS, YM, and T(g), and decreasing WVP, while maintaining a minimum acceptable EB of 10%. The optimum conditions were defined as: glycerol concentration, 18 g/100 g; and CNF concentration, 15 g/100 g. AFM imaging of films suggested good dispersion of the CNF and good CNF-matrix interactions, which explains the good performance of the nanocomposite films. PRACTICAL APPLICATION Chitosan is a biodegradable polymer which may be used to elaborate edible films or coatings to enhance shelf life of foods. This study demonstrates how cellulose nanofibers (CNF) can improve the mechanical and water vapor barrier properties of chitosan films. A nanocomposite film with 15% CNF and plasticized with 18% glycerol was comparable to some synthetic polymers in terms of strength and stiffness, but with poorer elongation and water vapor barrier, indicating that they can be used for applications that do not require high flexibility and/or water vapor barrier. The more important advantage of such films when compared to synthetic polymer films is their environmentally friendly properties.

Effect of fiber treatments on tensile and thermal properties of starch/ethylene vinyl alcohol copolymers/coir biocomposites.

Coir fibers received three treatments, namely washing with water, alkali treatment (mercerization) and bleaching. Treated fibers were incorporated in starch/ethylene vinyl alcohol copolymers (EVOH) blends. Mechanical and thermal properties of starch/EVOH/coir biocomposites were evaluated. Fiber morphology and the fiber/matrix interface were further characterized by scanning electron microscopy (SEM). All treatments produced surface modifications and improved the thermal stability of the fibers and consequently of the composites. The best results were obtained for mercerized fibers where the tensile strength was increased by about 53% as compared to the composites with untreated fibers, and about 33.3% as compared to the composites without fibers. The mercerization improved fiber-matrix adhesion, allowing an efficient stress transfer from the matrix to the fibers. The increased adhesion between fiber and matrix was also observed by SEM. Treatment with water also improved values of Youngs modulus which were increased by about 75% as compared to the blends without the fibers. Thus, starch/EVOH blends reinforced with the treated fibers exhibited superior properties than neat starch/EVOH.

Rubber particles from four different species, examined by transmission electron microscopy and electron-paramagnetic-resonance spin labeling, are found to consist of a homogeneous rubber core enclosed by a contiguous, monolayer biomembrane

Abstract. The physical characteristics of rubber particles from the four rubber (cis-1,4-polyisoprene) producing species Euphorbia lactiflua Phil., Ficus elastica Roxb., Hevea brasiliensis Müll. Arg., and Parthenium argentatum Gray, were investigated using transmission electron microscopy (TEM) and electron-paramagnetic-resonance (EPR) spin labeling spectroscopy. Transmission electron microscopy showed the rubber particles to be composed of a spherical, homogeneous, core of rubber enclosed by a contiguous, electron-dense, single-track surface layer. The biochemical composition of the surface layer and its single-track TEM suggested that a monolayer biomembrane was the surface structure most compatible with the hydrophobic rubber core. The EPR spectra for a series of positional isomers of doxyl stearic acid, used to label the surface layer of the rubber particles, exhibited flexibility gradients and evidence for lipid-protein interactions for all four rubber particle types that is consistent with a biomembrane-like surface. The EPR spectra confirmed that the surface biomembrane is a monolayer. Thus, rubber particles appear similar to oil bodies in their basic architecture. The EPR spectra also provided information on protein location and degree of biomembrane penetration that correlated with the known properties of the rubber-particle-bound proteins. The monolayer biomembrane serves as an interface between the hydrophobic rubber interior and the aqueous cytosol and prevents aggregation of the particles. An unexpected observation for the probes in pure polyisoprene was evidence of an intrinsic flexibility gradient associated with the stearic acid molecule itself.

Remodeling the isoprenoid pathway in tobacco by expressing the cytoplasmic mevalonate pathway in chloroplasts.

Metabolic engineering to enhance production of isoprenoid metabolites for industrial and medical purposes is an important goal. The substrate for isoprenoid synthesis in plants is produced by the mevalonate pathway (MEV) in the cytosol and by the 2-C-methyl-d-erythritol 4-phosphate (MEP) pathway in plastids. A multi-gene approach was employed to insert the entire cytosolic MEV pathway into the tobacco chloroplast genome. Molecular analysis confirmed the site-specific insertion of seven transgenes and homoplasmy. Functionality was demonstrated by unimpeded growth on fosmidomycin, which specifically inhibits the MEP pathway. Transplastomic plants containing the MEV pathway genes accumulated higher levels of mevalonate, carotenoids, squalene, sterols, and triacyglycerols than control plants. This is the first time an entire eukaryotic pathway with six enzymes has been transplastomically expressed in plants. Thus, we have developed an important tool to redirect metabolic fluxes in the isoprenoid biosynthesis pathway and a viable multigene strategy for engineering metabolism in plants.

Composite edible films based on hydroxypropyl methylcellulose reinforced with microcrystalline cellulose nanoparticles.

It has been stated that hydroxypropyl methyl cellulose (HPMC) based films have promising applications in the food industry because of their environmental appeal, low cost, flexibility and transparency. Nevertheless, their mechanical and moisture barrier properties should be improved. The aim of this work was to enhance these properties by reinforcing the films with microcrystalline cellulose (MCC) at the nano scale level. Three sizes of MCC nanoparticles were incorporated into HPMC edible films at different concentrations. Identical MCC nanoparticles were lipid coated (LC) prior to casting into HPMC/LC-MCC composite films. The films were examined for mechanical and moisture barrier properties verifying how the addition of cellulose nanoparticles affected the water affinities (water adsorption/desorption isotherms) and the diffusion coefficients. The expected reinforcing effect of the MCC was observed: HPMC/MCC and HPMC/LC-MCC films showed up to 53% and 48% increase, respectively, in tensile strength values in comparison with unfilled HPMC films. Furthermore, addition of unmodified MCC nanoparticles reduced the moisture permeability up to 40% and use of LC-MCC reduced this value up to 50%. Water vapor permeability was mainly influenced by the differences in water solubility of different composite films since, in spite of the increase in water diffusivity values with the incorporation of MCC to HPMC films, better moisture barrier properties were achieved for HPMC/MCC and HPMC/LC-MCC composite films than for HPMC films.

Effects of processing conditions on nanoclay dispersion in starch-clay nanocomposites

ABSTRACT Wheat starch samples containing Cloisite Na+ and 30B nanoclays were extruded from a twin-screw extruder. Moisture content, temperature, and screw speed were varied to determine their effect on nanoclay dispersion. X-ray diffraction and transmission electron microscopy (TEM) were used to examine nanoclay intercalation and exfoliation. Moisture content had the largest effect on Cloisite Na+ dispersion, with the highest moisture sample containing exfoliated nanoclays. Meanwhile, temperature and screw speed had little effect on Cloisite Na+ dispersion. For Cloisite 30B samples, only an increase in temperature produced slight intercalation of nanoclays. This was due to the incompatibility of starch with the more hydrophobic Cloisite 30B. Also, Cloisite Na+ and 30B intercalation did not depend on specific mechanical energy. In addition, water absorbance tests indicated the Cloisite Na+ sample containing the most well-dispersed nanoclays had the lowest water uptake.

Nanoemulsions prepared by a low-energy emulsification method applied to edible films.

Catastrophic phase inversion (CPI) was used as a low-energy emulsification method to prepare oil-in-water (O/W) nanoemulsions in a lipid (Acetem)/water/nonionic surfactant (Tween 60) system. CPIs in which water-in-oil emulsions (W/O) are transformed into oil-in-water emulsions (O/W) were induced by changes in the phase ratio. Dynamic phase inversion emulsification was achieved by slowly increasing the water volume fraction (fw) to obtain O/W emulsions from water in oil emulsions. Composition and processing variables were optimized to minimize droplet size and polydispersity index (PdI). It was found that addition of the continuous phase to the dispersed phase following the standard CPI procedure resulted in the formation of oil droplets with diameters of 100-200 nm. Droplet size distribution during CPI and emulsification time depended on stirring speed and surfactant concentration. Droplet sizes in the inverted emulsions were compared to those obtained by direct emulsification: The process time to reach droplet sizes of around 100 nm was reduced by 12 times by using CPI emulsification. The Acetem/water nanoemulsion was also used as a carrier to incorporate oregano and cinnamon essential oils into soy protein edible films. The resulting composite films containing oregano oil showed better moisture barrier and mechanical properties compared to soy protein films.

Trichoderma species form endophytic associations within Theobroma cacao trichomes.

Trichoderma species are usually considered soil organisms that colonize plant roots, sometimes forming a symbiotic relationship. Recent studies demonstrate that Trichoderma species are also capable of colonizing the above ground tissues of Theobroma cacao (cacao) in what has been characterized as an endophytic relationship. Trichoderma species can be re-isolated from surface sterilized cacao stem tissue, including the bark and xylem, the apical meristem, and to a lesser degree from leaves. SEM analysis of cacao stems colonized by strains of four Trichoderma species (Trichoderma ovalisporum-DIS 70a, Trichoderma hamatum-DIS 219b, Trichoderma koningiopsis-DIS 172ai, or Trichoderma harzianum-DIS 219f) showed a preference for surface colonization of glandular trichomes versus non-glandular trichomes. The Trichoderma strains colonized the glandular trichome tips and formed swellings resembling appresoria. Hyphae were observed emerging from the glandular trichomes on surface sterilized stems from cacao seedlings that had been inoculated with each of the four Trichoderma strains. Fungal hyphae were observed under the microscope emerging from the trichomes as soon as 6h after their isolation from surface sterilized cacao seedling stems. Hyphae were also observed, in some cases, emerging from stalk cells opposite the trichome head. Repeated single trichome/hyphae isolations verified that the emerging hyphae were the Trichoderma strains with which the cacao seedlings had been inoculated. Strains of four Trichoderma species were able to enter glandular trichomes during the colonization of cacao stems where they survived surface sterilization and could be re-isolated. The penetration of cacao trichomes may provide the entry point for Trichoderma species into the cacao stem allowing systemic colonization of this tissue.

Sequential Infrared Radiation and Freeze-Drying Method for Producing Crispy Strawberries

Sequential infrared and freeze-drying (SIRFD) as a new processing method was studied for producing high-quality crispy fruit pieces at reduced cost. This research investigated the drying characteristics of strawberry slices and the quality of the finished products under SIRFD. The 4 mm thick strawberry slices were pre-dehydrated to 30%, 40%, and 50% levels of weight reduction with infrared (IR) heating at each of the three different intensities (3000, 4000, and 5000 W m-2). The pre-dehydrated samples were then further freeze-dried to achieve a final moisture content of about 5%. For comparison, the slices were also pre-dehydrated with hot-air drying (62.8°C) followed by freeze-drying (SHAFD) and dried with regular freeze-drying without pre-dehydration. The drying kinetics of strawberry slices under IR, hot-air, and freeze-drying were determined and modeled. The color, shrinkage, rehydration ratio, and crispness of finished products were measured. The IR radiation heating had a much higher drying rate than hot-air during the pre-dehydration. The product produced with SIRFD had more desirable color, higher crispness, and more shrinkage, but a lower rehydration ratio than regular freeze-drying, which, however, did not produce a high-crispness product. The microstructure characteristics of the dried products explained the differences in quality produced with the different methods. IR pre-dehydration to a 40% weight reduction level reduced required freeze time by 42%, indicating a great energy saving potential for SIRFD, since the energy efficiency of freeze-drying is very low. It has been concluded that SIRFD could be a desirable method for producing high-crispness strawberry pieces.

Microstructure of Purified Rubber Particles

Purified rubber particles from Hevea brasiliensis (Brazilian rubber tree), Parthenium argentatum (guayule), Ficus elastica (Indian rubber tree), and Euphorbia lactiflua were examined and compared using conventional scanning electron microscopy (SEM), field‐emission SEM, cryo‐SEM, and transmission electron microscopy (TEM). Rubber particles of all four species were spherical; they varied in size and had a uniform homogeneous material, the rubber core, surrounded by a contiguous monolayer (half‐unit) membrane. Frozen‐hydrated and/or untreated particles from H. brasiliensis and P. argentatum deformed and fused readily, whereas those from F. elastica and E. lactiflua retained their spherical shapes. These results indicate that the surface components of the H. brasiliensis and P. argentatum particles are more fluid than those of F. elastica or E. lactiflua. When fixed in aldehyde, F. elastica particles retained their spherical exterior shapes but had hollow centers, whereas H. brasiliensis and P. argentatum particles completely collapsed. In aldehyde–osmium tetroxide–fixed material, the rubber core of F. elastica was poorly preserved in some particles in which only a small amount of the rubber core remained adhering to the monolayer membrane, leaving a hollow center. Euphorbia lactiflua particles were well preserved in terms of retaining the rubber core; however, the membrane was not as easily discernible as it was in the other three species. Both H. brasiliensis and P. argentatum were well preserved following fixation; their cores remained filled with rubber, and their monolayer membranes were defined. The addition of potassium permanganate to the fixation‐staining regime resulted in higher‐contrast micrographs and more well defined monolayer membranes.