Retaining Oxidative Stability of Emulsified Foods by Novel Nonmigratory Polyphenol Coated Active Packaging.

Oxidation causes lipid rancidity, discoloration, and nutrient degradation that decrease shelf life of packaged foods. Synthetic additives are effective oxidation inhibitors, but are undesirable to consumers who prefer "clean" label products. The aim of this study was to improve oxidative stability of emulsified foods by a novel nonmigratory polyphenol coated active packaging. Polyphenol coatings were applied to chitosan functionalized polypropylene (PP) by laccase assisted polymerization of catechol and catechin. Polyphenol coated PP exhibited both metal chelating (39.3 ± 2.5 nmol Fe(3+) cm(-2), pH 4.0) and radical scavenging (up to 52.9 ± 1.8 nmol Trolox eq cm(-2)) capacity, resulting in dual antioxidant functionality to inhibit lipid oxidation and lycopene degradation in emulsions. Nonmigratory polyphenol coated PP inhibited ferric iron promoted degradation better than soluble chelators, potentially by partitioning iron from the emulsion droplet interface. This work demonstrates that polyphenol coatings can be designed for advanced material chemistry solutions in active food packaging.

Synthesis of Iminodiacetate Functionalized Polypropylene Films and Their Efficacy as Antioxidant Active-Packaging Materials.

The introduction of metal-chelating ligands to the food-contact surface of packaging materials may enable the removal of synthetic chelators (e.g., ethylenediamine tetra-acetic acid (EDTA)) from food products. In this study, the metal-chelating ligand iminodiacetate (IDA) was covalently grafted onto polypropylene surfaces to produce metal-chelating active-packaging films. The resulting films were able to chelate 138.1 ± 26 and 210.0 ± 28 nmol/cm(2) Fe(3+) and Cu(2+) ions, respectively, under acidic conditions (pH 3.0). The films demonstrated potent antioxidant efficacy in two model food systems. In an emulsified-oil system, the chelating materials extended the lag phase of both lipid hydroperoxide and hexanal formation from 5 to 25 days and were as effective as EDTA. The degradation half-life of ascorbic acid in an aqueous solution was extended from 5 to 14 days. This work demonstrates the potential application of surface-grafted chelating IDA ligands as effective antioxidant active food-packaging materials.

Iron chelating active packaging: Influence of competing ions and pH value on effectiveness of soluble and immobilized hydroxamate chelators.

Many packaged foods utilize synthetic chelators (e.g. ethylenediaminetetraacetic acid, EDTA) to inhibit iron-promoted oxidation or microbial growth which would result in quality loss. To address consumer demands for all natural products, we have previously developed a non-migratory iron chelating active packaging material by covalent immobilization of polyhydroxamate and demonstrated its efficacy in delaying lipid oxidation. Herein, we demonstrate the ability of this hydroxamate-functionalized iron chelating active packaging to retain iron chelating capacity; even in the presence of competing ions common in food. Both immobilized and soluble hydroxamate chelators retained iron chelating capacity in the presence of calcium, magnesium, and sodium competing ions, although at pH 5.0 the presence of calcium reduced immobilized hydroxamate iron chelation. A strong correlation was found between colorimetric and mass spectral analysis of iron chelation by the chelating packaging material. Such chelating active packaging may support reducing additive use in product formulations, while retaining quality and shelf life.

Performance of Nonmigratory Iron Chelating Active Packaging Materials in Viscous Model Food Systems.

Many packaged food products undergo quality deterioration due to iron promoted oxidative reactions. Recently, we have developed a nonmigratory iron chelating active packaging material that represents a novel approach to inhibit oxidation of foods while addressing consumer demands for "cleanË® labels. A challenge to the field of nonmigratory active packaging is ensuring that surface-immobilized active agents retain activity in a true food system despite diffusional limitations. Yet, the relationship between food viscosity and nonmigratory active packaging activity retention has never been characterized. The objective of this study was to investigate the influence of food viscosity on iron chelation by a nonmigratory iron chelating active packaging material. Methyl cellulose was added to aqueous buffered iron solutions to yield model systems with viscosities ranging from ∼1 to ∼10(5)  mPa·s, representing viscosities ranging from beverage to mayonnaise. Iron chelation was quantified by material-bound iron content using colorimetry and inductively coupled plasma-optical emission spectrometry (ICP-OES).  Maximum iron chelation was reached in solutions up to viscosity ∼10(2)  mPa·s. In more viscous solutions (up to ∼10(4)  mPa·s), there was a significant decrease in iron chelating capacity (P < 0.05). However, materials still retained at least 76% iron chelating capacity. Additionally, the influence of different food hydrocolloids on the performance of nonmigratory iron chelating active packaging was characterized. Methyl cellulose and carrageenan did not compete with the material for specific iron chelation (P > 0.05). Materials retained 32% to 45% chelating capacity when in contact with competitively chelating hydrocolloids guar gum, locust bean gum, and xanthan gum. This work demonstrates the potential application of nonmigratory iron chelating active packaging in liquid and semi-liquid foods to allow for the removal of synthetic chelators, while maintaining food quality.

Development of Iron-Chelating Poly(ethylene terephthalate) Packaging for Inhibiting Lipid Oxidation in Oil-in-Water Emulsions.

Foods such as bulk oils, salad dressings, and nutritionally fortified beverages that are susceptible to oxidative degradation are often packaged in poly(ethylene terephthalate) (PET) bottles with metal chelators added to the food to maintain product quality. In the present work, a metal-chelating active packaging material is designed and characterized, in which poly(hydroxamic acid) (PHA) metal-chelating moieties were grafted from the surface of PET. Biomimetic PHA groups were grafted in a two-step UV-initiated process without the use of a photoinitiator. Surface characterization of the films by attenuated total reflective Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM) suggested successful grafting and conversion of poly(hydroxyethyl acrylate) (PHEA) to PHA chelating moieties from the surface of PET. Colorimetric (ferrozine) and inductively coupled plasma mass spectroscopy (ICP-MS) assays demonstrated the ability of PET-g-PHA to chelate iron in a low-pH (3.0) environment containing a competitive metal chelator (citric acid). Lipid oxidation studies demonstrated the antioxidant activity of PET-g-PHA films in inhibiting iron-promoted oxidation in an acidified oil-in-water (O/W) emulsion model system (pH 3.0). Particle size and ζ-potential analysis indicated that the addition of PET-g-PHA films did not affect the physical stability of the emulsion system. This work suggests that biomimetic chelating moieties can be grafted from PET and effectively inhibit iron-promoted degradation reactions, enabling removal of metal-chelating additives from product formulations.

Fourier transform infrared studies on the dissociation behavior of metal-chelating polyelectrolyte brushes.

The dissociation behavior of surface-grafted polyelectrolytes is of interest for the development of stimuli-responsive materials. Metal-chelating polyelectrolyte brushes containing acrylic acid (PAA) or hydroxamic acid (PHA) chelating moieties were grafted from the surface of polypropylene (PP). Fourier transform infrared (FTIR) spectroscopy was used to determine the effective bulk pKa of the polyelectrolyte brushes (pKa(bulk)) and to characterize metal-chelating behavior. The pKa(bulk) values of PP-g-PAA and PP-g-PHA were 6.45 and 9.65, respectively. Both PP-g-PAA and PP-g-PHA exhibited bridging bidentate and chelating bidentate iron chelation complexes. This is the first reported determination of the pK(a,bulk) of surface-grafted poly(hydroxamic) acid.

Metal-chelating active packaging film enhances lysozyme inhibition of Listeria monocytogenes.

Several studies have demonstrated that metal chelators enhance the antimicrobial activity of lysozyme. This study examined the effect of metal-chelating active packaging film on the antimicrobial activity of lysozyme against Listeria monocytogenes. Polypropylene films were surface modified by photoinitiated graft polymerization of acrylic acid (PP-g-PAA) from the food contact surface of the films to impart chelating activity based on electrostatic interactions. PP-g-PAA exhibited a carboxylic acid density of 113 ± 5.4 nmol cm(-2) and an iron chelating activity of 53.7 ± 9.8 nmol cm(-2). The antimicrobial interaction of lysozyme and PP-g-PAA depended on growth media composition. PP-g-PAA hindered lysozyme activity at low ionic strength (2.48-log increase at 64.4 mM total ionic strength) and enhanced lysozyme activity at moderate ionic strength (5.22-log reduction at 120 mM total ionic strength). These data support the hypothesis that at neutral pH, synergy between carboxylate metal-chelating films (pKa(bulk) 6.45) and lysozyme (pI 11.35) is optimal in solutions of moderate to high ionic strength to minimize undesirable charge interactions, such as lysozyme absorption onto film. These findings suggest that active packaging, which chelates metal ions based on ligand-specific interactions, in contrast to electrostatic interactions, may improve antimicrobial synergy. This work demonstrates the potential application of metal-chelating active packaging films to enhance the antimicrobial activity of membrane-disrupting antimicrobials, such as lysozyme.

Gastric digestion of raw and roasted almonds in vivo.

Almonds are an important dietary source of lipids, protein, and α-tocopherol. It has been demonstrated that the physical form of almond kernels influences their digestion and absorption, but the role of thermal processes on the digestion of almonds has received little attention. The objectives of this study were to examine the gastric emptying and nutrient composition of gastric chyme from pigs (used as a model for the adult human) fed a single meal of either raw or roasted almonds over a 12-h postprandial period (72 pigs total, 6 pigs at each diet-time combination). Concentrations of glucose, triacylglycerols, and α-tocopherol in peripheral plasma during the 12-h postprandial period were determined. For dry matter and lipid, the gastric emptying profile was not different between raw and roasted almonds. Roasting almonds also did not influence gastric pH, or plasma glucose or triacylglycerols levels. In contrast, the gastric emptying of protein was more rapid for raw almonds compared to roasted almonds (P < 0.01) and intragastric protein content exhibited segregation (P < 0.001) throughout the stomach, with raw almonds having a higher level of segregation compared to roasted almonds. Postprandial plasma α-tocopherol levels were, on average 33% greater (P < 0.001) after consumption of raw almonds, most likely as a result of the higher concentration of α-tocopherol in raw almonds compared to roasted almonds. Roasting of almonds did not influence the overall gastric emptying process, but did lead to differences in the distribution of protein in the stomach and to the gastric emptying of protein.

Release and bioaccessibility of ß-carotene from fortified almond butter during in vitro digestion.

The objective of this study was to determine the release and bioaccessibility of ß-carotene from fortified almond butter using in vitro digestion models. Two types of fortifiers were investigated: ß-carotene oil (oil) and whey protein isolate (WPI)-alginate-chitosan capsules containing ß-carotene oil (capsule). Shaking water bath and Human Gastric Simulator (HGS) digestion models assessed the impact of gastric peristalsis on the release of ß-carotene. Bioaccessibility of ß-carotene was measured as percent recovered from the micelle fraction. There was greater release of ß-carotene from oil fortified almond butter in the HGS model (87.1%) due to peristalsis than the shaking water bath model (51.0%). More ß-carotene was released from capsule fortified almond butter during intestinal digestion. However, more ß-carotene was recovered from the micelle fraction of oil fortified almond butter. These results suggest that a WPI-alginate-chitosan capsule coating may inhibit the bioaccessibility of ß-carotene from fortified almond butter.