Cassava Starch Films with Anthocyanins and Betalains from Agroindustrial by-Products: Their Use for Intelligent Label Development.

The development of biodegradable packaging materials has become a widely addressed topic in recent years. Microparticles generated from Brassica oleracea var. capitata f. rubra (red cabbage, RC) and Beta vulgaris L. var. conditiva (beetroot, BR) which contained anthocyanins or betalains, were included in the formulation of edible films based on cassava starch (CS) giving origin to films CSRC, CSBR, or CSBC (mixture of both particles). The inclusion of the filler determined an increase in the stress at rupture from 0.8 MPa (CS) to 1.2 MPa (CSRC) or 1.0 MPa (CSBC), of the contact angle from 2.6° to 13.8° (CSBR) or 19.6° (CSBC). The use of these films for developing a smart label for hake packaging and the study of the TBV-N content, the microbiological characteristics of the muscle, and the color changes of the label with time, allowed us to conclude that the films CSRC and CSBC would be suitable for sensing the deterioration of packaged and chilled hake and that the color change of the label CSBC was completely consistent with fish muscle deterioration. As the microparticles can be obtained from by-products of the production and industrialization of plant tissues, the composite films and the smart labels developed can contribute not only to the development of safe food but also to the addition of value to those residues and to environmental protection.

How to build a puncture- and breakage-resistant eggshell? Mechanical and structural analyses of avian brood parasites and their hosts.

Evolved eggshell strength is greater in several lineages of obligate avian brood parasites (birds that lay their eggs in other species' nests) than in their hosts. Greater strength is typically indirectly implied by eggshell thickness comparisons between parasites and hosts. Nevertheless, there is strong evidence that the eggshell structural organization differentially influences its mechanical properties. Using instrumental puncture tests and SEM/EBSD and XRD techniques, we studied the most relevant eggshell mechanical, textural, ultrastructural and microstructural features between several host species and their parasitic cowbirds (Molothrus spp.). These parasitic species display different egg-destructive behaviors, reducing host reproductive fitness, including the more frequently host-egg puncturing M. rufoaxillaris and M. bonariensis, and the host egg-removing M. ater. The results, analyzed using a phylogenetic comparative approach, showed interspecific patterns in the mechanical and structural features. Overall, the eggshells of the two egg-puncturing parasites (but not of M. ater) were stronger, stiffer and required greater stress to produce a fracture than the respective hosts' eggs. These features were affected by eggshell microstructure and ultrastructure, related to the increase in the intercrystalline boundary network acting in cooperation with the increase in palisade layer thickness. Both structural features generate more options and greater lengths of intercrystalline paths, increasing the energy consumed in crack or fissure propagation. The reported patterns of all these diverse eggshell features support a new set of interpretations, confirming several hypotheses regarding the impact of the two reproductive strategies (parasitic versus parental) and parasitic egg destruction behaviors (more versus less frequently puncturing).

Papaya by-products for providing stability and antioxidant activity to oil in water emulsions.

The consumption of food with health benefits is growing today worldwide. This study was designed in order to incorporate papaya dietary fibre concentrates (DFCs) from peel and pulp dehydrated with the use of microwave (MW), or convection with hot air (CV) in oil-in- water emulsions. Results of studies indicated that Pulp DFC produced more stability to creaming (18 weeks) than Peel DFC (6 weeks). It was found that peel DFCs exerted up to 30% reduction in lipid peroxidation in comparison to the reference system during storage. Rheological analysis showed a similar behaviour when emulsions were mixed with pulp DFCs either dehydrated by MW or CV, while the dressing with peel DFCs had a much lower consistency than the former. The analysis of the emulsions micro-structure showed a polydisperse system of oil droplets and fiber structures trapping oil. Finally, emulsions with pulp DFCs showed a better consumer´s acceptance. These results also suggested that the use of DFCs may have high industrial potential in contributing to dietary fibre enrichment through technological intervention of emulsion formulation by papaya pulp and peel, increasing antioxidant property, consistency and stability during storage.

Gracilariopsis hommersandii, a red seaweed, source of agar and sulfated polysaccharides with unusual structures.

Red seaweed Gracilariopsis hommersandii produces important amounts of non-gelling galactans, which were extracted with hot water (GrC, yield, 37%, viscosity average molecular weight, Mv 109 kDa), comprising agarose and sulfated galactan structures. The alkali modified derivative, GrCTr (Mv 95 kDa), gave a galactose:3,6-anhydrogalactose molar ratio of 1.0:0.9, and a more regular structure, favouring gelation (melting and gelling temperatures 64 and 14 °C, respectively). The rheological properties of this product suggest possible applications as hydrocolloid. G. hommersandii also biosynthesizes non gelling sulfated galactan fractions with diads constituted by ß-d-galactose and partially cyclized α-l-galactose units or non-cyclized α-d-galactose residues. Sulfation was mainly detected on C6 or C4 of the ß-d-galactose units, and on C6 and, in minor amounts, on C3 of the α-l-galactose units. The presence of ß-apiuronic acid was demonstrated for these fractions as side chains of the galactan backbone. Carrageenan structures were found for the first time in an agarophyte of the Gracilariales.

Cationization of kappa- and iota-carrageenan--Characterization and properties of amphoteric polysaccharides.

Commercial kappa- and iota carrageenans were cationized with 3-chloro-2-hydroxypropyltrimethylammonium chloride in aqueous sodium hydroxide solution. For kappa-carrageenan three derivatives with different degrees of substitution were obtained. Native and amphoteric kappa-carrageenans were characterized by NMR and infrared spectroscopy, scanning electron and atomic force microscopy; methanolysis products were studied by electrospray ionization mass spectrometry. Young moduli and the strain at break of films, differential scanning calorimetry, rheological and flocculation behavior were also evaluated; the native and the amphoteric derivatives showed different and interesting properties. Cationization of iota-carrageenan was more difficult, indicating as it was previously observed for agarose, that substitution starts preferentially on the 2-position of 3,6-anhydrogalactose residues; in iota-carrageenan this latter unit is sulfated.

A study of the effect of dietary fiber fractions obtained from artichoke (Cynara cardunculus L. var. scolymus) on the growth of intestinal bacteria associated with health.

The effect of different fractions enriched in soluble fiber obtained from artichoke using citric acid or citric acid/hemicellulase on the selective growth of Lactobacillus plantarum 8114 and Bifidobacterium bifidum ATCC 11863 was evaluated. Gompertz modeling of Lactobacillus plantarum 8114 growth showed a higher specific growth rate (µ: 0.16 h(-1)) in the presence of fractions isolated from stems using hemicellulase (fraction A) than in the presence of glucose (µ: 0.09 h(-1)). In the case of Bifidobacterium bifidum 11863, the highest µ was obtained for the microorganism grown in the presence of fraction A and for the fraction isolated from stems without hemicellulase, their rate being twice that observed for glucose (0.04 h(-1)). The positive prebiotic activity scores observed with respect to Escherichia coli 25922 indicated that fibers assayed are metabolized as well as glucose by Lactobacillus plantarum 8114 and Bifidobacterium bifidum ATCC 11863 and that they are selectively metabolized by these microorganisms. The potential capacity to selectively stimulate the growth of intestinal bacteria associated with health shown by fraction A can be ascribed to its high inulin and low methylation degree pectin contents.

Protease and hemicellulase assisted extraction of dietary fiber from wastes of Cynara cardunculus.

The action of protease and hemicellulase for the extraction of fractions enriched in soluble fiber from bracts and stems of Cynara cardunculus was evaluated. Using a two-factor simplex design comprising protease amounts of 0-200 µL and hemicellulase amounts of 0-200 mg for 5 g of material, we explored the effect of a 5 h enzymatic treatment at 40 °C on the chemical composition and yield of the fractions isolated. The fractions contained inulin and pectin. In general, the protein, inulin, and polyphenol contents and also the yields were higher for fractions obtained from stems. The most marked effects were observed when enzymes were used at higher concentrations, especially for hemicellulase. The inclusion of a pre-heating step increased the yield and the inulin content for fractions isolated from bracts and stems and decreased the protein and polyphenol contents, and the galacturonic acid for bracts. These fractions, in general, contained the polyphenolic compounds monocaffeoylquinic acid, apigenin, and pinoresinol.

Effect of natamycin, nisin and glycerol on the physicochemical properties, roughness and hydrophobicity of tapioca starch edible films.

In this paper, films based on tapioca starch and containing nisin, natamycin and glycerol were characterized in relation to their physicochemical properties, roughness and hydrophobicity. The content of glycerol affected the mechanical properties of the films studied and the roughness and it was observed an increase in WVP with the increase in glycerol content. The addition of antimicrobials affected the mechanical properties, being nisin the one that produced the greater decrease in the Young modulus. The color was highly affected by the joint presence of natamycin and nisin, which increased the yellow index. The contact angle increased with antimicrobial addition indicating a decrease in hydrophilicity. Nisin also affected the roughness of the films. Water vapor permeability was slightly reduced by the presence of natamycin. It was observed that water vapor permeability and contact angle were correlated with the roughness of the films.

Upgrading of residues of bracts, stems and hearts of Cynara cardunculus L. var. scolymus to functional fractions enriched in soluble fiber.

Since only the central portion of the immature flowers of artichoke (Cynara cardunculus L. var. scolymus) is consumed (<20%) it is interesting to upgrade its residues to render value added products. In this research, bracts (B), hearts (H) or stems (S) were used to isolate fractions enriched in soluble fiber. Extraction was performed in citrate buffer with or without hemicellulase. Additionally, the effect of preheating (70 °C - 5 min) prior to extraction was also tested. Polysaccharides were precipitated with ethanol and the fractions obtained were freeze-dried. The presence of the enzyme increased fiber yields and preheating produced an additional increment, especially from stems (≈21%). Isolated fibers were constituted by 70-84% of carbohydrates and 2-25% of proteins, and contained phenolics (2.1-8.2 g/100 g). Carbohydrates included uronic acids (12-25%) and neutral sugars (NS, 4-55%) of pectins, and inulin (13-55%). The lowest protein and NS contents and the highest inulin content were obtained with the enzyme and preheating. The behavior of fractions isolated with higher yields was characterized, observing a pseudoplastic behavior in water and gelation with Ca(2+). They also showed antioxidant activity and an inhibitory effect against herpes simplex virus type 1 without cytotoxicity. The isolated fractions retaining bioactive compounds can be useful as functional food ingredients.

Biopolymeric antimicrobial films: study of the influence of hydroxypropyl methylcellulose, tapioca starch and glycerol contents on physical properties.

Mixture design methodology was applied to study the effect of different levels of tapioca starch (TS), hydroxypropyl methylcelullose (HPMC), and glycerol (Gly) on the physical properties of biopolymeric films supporting potassium sorbate (KS; 0.3% w/w) with the goal of contributing to the development of materials for preventing food surface contamination. Mechanical properties, water vapour permeability (WVP), solubility in water (S) and colour attributes were evaluated on the films. HPMC addition produced an increase of elastic modulus (Ec), stress at break (σb) and S. It also decreased the yellow index (YI) values and the strain at break (εb). The study was deepened using the formulation containing 2.67 g/100g of TS, 0.67 g/100g of HPMC, 1.67 g/100g Gly and 0.3g/100g KS, observing that it behaved as an effective antimicrobial barrier against Zygosaccharomyces bailii external contamination. Microstructural analysis allowed us to conclude that HPMC incorporation to a TS network decreased roughness of the films and it also increased permeability to oxygen (PO2).

Effect of gamma irradiation and storage time on microbial growth and physicochemical characteristics of pumpkin (Cucurbita Moschata Duchesne ex Poiret) puree.

The effect of gamma irradiation (0-2 kGy) and storage time (0-28 days) on microbial growth and physicochemical characteristics of a packed pumpkin puree was studied. For that purpose, a factorial design was applied. The puree contained potassium sorbate, glucose and vanillin was stored at 25°C . Gamma irradiation diminished and storage time increased microbial growth. A synergistic effect between both variables on microbial growth was observed. Storage time decreased pH and color of purees. Sorbate content decreased with storage time and gamma irradiation. Mathematical models of microbial growth generated by the factorial design allowed estimating that a puree absorbing 1.63 kGy would have a shelf-life of 4 days. In order to improve this time, some changes in the applied hurdles were assayed. These included a thermal treatment before irradiation, a reduction of irradiation dose to 0.75 kGy and a decrease in storage temperature at 20°C . As a result, the shelf-life of purees increased to 28 days.

Hydrolytic and oxidative stability of L-(+)-ascorbic acid supported in pectin films: influence of the macromolecular structure and calcium presence.

The hydrolytic and oxidative stability of L-(+)-ascorbic acid (AA) into plasticized pectin films were separately studied in view of preserving vitamin C activity and/or to achieve localized antioxidant activity at pharmaceutical and food interfaces. Films were made with each one of the enzymatically tailored pectins (50%, 70%, and 80% DM; Cameron et al. Carbohydr. Polym.2008, 71, 287-299) or commercial high methoxyl pectin (HMP; 72% DM). Since AA stability was dependent on water availability in the network, pectin nanostructure affected the AA kinetics. Higher AA retention and lower browning rates were achieved in HMP films, and calcium presence in them stabilized AA because of higher water immobilization. Air storage did not change AA decay and browning rates in HMP films, but they significantly increased in Ca-HMP films. It was concluded that the ability of the polymeric network to immobilize water seems to be the main factor to consider in order to succeed in retaining AA into film materials.

Characterization of acid-extracted pectin-enriched products obtained from red beet (Beta vulgaris L. var. conditiva) and butternut (Cucurbita moschata Duch ex Poiret).

Chemical and rheological characteristics of fractions enriched in soluble dietary fiber are reported. These fractions were obtained through acid hydrolysis of butternut (Cucurbita moschata Duch ex Poiret) and red beet (Beta vulgaris L. var. conditiva) cell wall enriched powders. Hydrolysis was performed using citric acid at different pH values and reaction times (2 and 3 h). Yields obtained for butternut fractions were between 21 and 28 g/100 g; for red beet, yields were 24 and 31 g/100 g for pH 1.5 and 11 and 17 g/100 g for pH 2.0 for previously mentioned times; in general, the increase of the yield was directly correlated with the decrease of pH and the increase of reaction time. Products enriched in low methoxyl pectins were obtained in all cases. At the lowest pH assayed, pectins were essentially constituted by homogalacturonan; a significant content of neutral sugars was determined at the higher extraction pH. Neutral sugars were constituted mainly by arabinose, galactose, rhamnose, and glucose in different proportions for each fraction; in general, butternut fractions showed high glucose contents. Flow behavior for 2.00% (w/v) aqueous systems of the different products was evaluated. Data obtained for fractions isolated at pH 1.5 fit to Herschel-Bulkley and Cross models while those isolated at pH 2.0 fit to Ostwald and Cross models. All samples showed low viscosity and, hence, poor thickening properties.

Development of a high methoxyl pectin edible film for retention of l-(+)-ascorbic acid.

An edible film to carry l-(+)-ascorbic acid (AA) was formulated for natural antioxidant food protection. Considering previous works where films based on the "rigid" structure of gellan (deacylated) or on a mixture of acylated-deacylated (more "disordered") gellan were used for network development, pectin was herein chosen by considering that the alternating presence of "disordered" (hairy) regions together with ordered (homogalacturonan) ones could sufficiently immobilize water for better AA retention and lower browning. High methoxyl pectin (HMP) was first investigated. AA stability and browning were studied during film storage at 33.3, 57.7, or 75.2% relative humidity (RH) and 25 degrees C; their dependence on water mobility determined through (1)H NMR analysis as well as the correlation between browning and AA degradation were again found. Network characteristics and glycerol (plasticizer) interactions were analyzed through X-ray diffraction and Fourier transform infrared spectroscopy as well as through uniaxial tensile assay. From all results obtained, it was hypothesized that browning development in solidlike systems may be directly related to the water molecules more closely adsorbed on the hydroxyl-polymeric (active) surfaces. The HMP film microstructure produced the best immobilization of water molecules except at 75.2% RH, where it showed lower AA stability than acylated-deacylated gellan film. It is suggested that disordered regions of this pectin network may not be adequately counterbalanced by more transient junction zones of alternating hydrophilic (water) and hydrophobic (methyl ester) interactions, also disturbed by glycerol molecules, for accomplishing enough water immobilization in the whole network at 75.2% RH.