Non-targeted screening of extracts from polyester-phenolic can coatings: Identification of new aldehyde molecules from resole-based resins.

Phenolic and substituted phenol based resoles are commonly used in the formulation of can coatings. However, migration analyses of these coatings are very little described compared to other coating technologies. While epoxy and polyester have well known migrants with defined formation mechanisms, Non-Intentionally Added Substances (NIAS) specifically related to the phenolic resin are hardly studied in the literature. The goal of the publication is to further explore the influence of the phenolic resole, used in the formulation of can coatings, on extracted NIAS's nature. Six different model polyester-phenolic can coatings were formulated each with a specific phenol, cresol or tertbutylphenol-based resole. Can coating films were extracted for 24 h at 40 °C in acetonitrile before analysis. NIAS identification was done using gas chromatography separation coupled to high resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR) spectroscopy analyses. Cyclic polyester oligomers were found in all extracts, with oligomers found in a range of 10 µg/dm2 to 226 µg/dm2, without specific influence of the resole used in formulation. While very few or no peaks were detected from cresol- and phenol-based resoles, 48 peaks were specifically observed in coating extracts of formulas with tertbutylphenol-based resoles as well as in their respective resoles. The most intense peaks were identified as aldehyde compounds by HRMS and NMR analysis. These aldehydes were semi-quantified in similar proportions as polyester oligomers. The presence of such aldehydes has never been reported in the literature regarding NIAS in can coatings. Further study will then be needed to better understand the aldehyde formation mechanism and assess the toxicological profile of such chemicals.

Influence of some formulation and process parameters on the stability of lysozyme incorporated in corn flour- or corn starch-based extruded materials prepared by melt blending processing.

In order to obtain an antimicrobial biodegradable material, corn flour was extruded with 1% of lysozyme. Since the limited stability of natural preservatives such as lysozyme is a common bottleneck to the elaboration of active biomaterials by melt blending processes, the influence of formulation and of extrusion processing temperature on its residual enzymatic activity was investigated. To assess the contribution of process parameters such as temperature, shear stress and of related formulation parameters such as glycerol and moisture contents, the stability of lysozyme following its extrusion or its thermoforming with plasticized corn starch or thermal treatments in aqueous glycerol solutions was also studied. Increasing glycerol content from 25% to 30% significantly limited inactivation of lysozyme during extrusion, while increasing initial moisture content of the mixture from 14.5% to 28.5% had the opposite effect. These observations open the possibility to prepare active materials retaining more than 60±7% of initial lysozyme activity.

Study of a specific lignin model: γ-oxidation and how it influences the hydrolysis efficiency of alcohol-aldehyde dehydrogenation copolymers.

Six coniferyl alcohol-coniferaldehyde dehydrogenation copolymers (DHcoPs) were synthesized in order to determine the influence of an increased number of aldehyde functions on hydrolysis. After heterogeneous hydrolysis using acidic Montmorillonite K10 clay, the DHcoPs were thioacidolyzed and analyzed by gel permeation chromatography (GPC). Comparison of the thioacidolyzed products, with and without the hydrolysis step, showed that there was a greater proportion of condensation reaction in the absence of aldehyde. When the coniferaldehyde content in the initial synthetic mixture was more than 30% (w/w), only a low fraction of condensed products was generated during the K10 clay hydrolysis step. This suggests that condensation pathways are mainly due to the alcohol present in the γ-position in the DHcoPs. Investigation of the reactivity and the potential condensation of aldehyde and alcohol monomers under hydrolysis conditions showed the important conversion of coniferyl alcohol and conversely the stability of coniferaldehyde.

Effect of migrant size on diffusion in dry and hydrated polyamide 6.

Food safety authorities have already allowed the use of mathematical models to predict diffusion from plastic food contact materials. These models use the molecular weight of the migrant as a cornerstone parameter that describes the contribution of the migrant to the diffusion process. In this work, the dependence of the diffusion coefficient on the migrant size was examined through fluorescence recovery after photobleaching (FRAP). A model migrant series of fluorescent probes was used, covering a wide molecular weight range. The advantage and originality of the tested migrant series are associated with the fact that the same shape and chemical functionality are maintained regardless of the molecular weight of the migrants. In this way the dependence of the acquired data on parameters other than size is excluded. The same experiments were carried out in dry and hydrated polyamide 6 to evaluate the effect of polymer matrix mobility in the "diffusion-migrant size" relationship. The experimental data were compared to well-known mathematical or semiempirical approaches, verifying that there is a relationship between the diffusion coefficient and the size of the migrant. However, it is demonstrated that this relationship is also affected by the mobility of the polymer matrix, becoming more pronounced as the mobility of the matrix decreases.

Diffusion of homologous model migrants in rubbery polystyrene: molar mass dependence and activation energy of diffusion.

Published diffusion prediction models for the diffusion of additives in food packaging simplify reality by having a small number of parameters only. Therefore, extrapolation of such models to barrier polymers, larger ranges of temperature and/or additive molecular weight (M(W)) is questionable. Extra data is still required to generalize these existing prediction models. In this paper, diffusion of a specifically designed homologous set of model additives (from 236 to 1120 g mol(-1)) was monitored in two polystyrenes in the rubbery state (from 100 to 180 degrees C): syndiotactic semi-crystalline polystyrene and its amorphous equivalent. Variations in associated diffusion coefficient D and activation energy Ea with migrant M(W) and temperature were surprisingly low. Comparison of experimental behaviour with model predictions was performed. In their actual form, none of the models is capable of describing all experimental data, but there is evidence of convergence of the different approaches.

Acidolysis of a lignin model: investigation of heterogeneous catalysis using Montmorillonite clay.

The use of heterogeneous conditions involving Montmorillonite K10 clay was investigated as a mild alternative to homogeneous acidolysis of a lignin model. Guaiacyl Dehydrogenation Oligomers (DHOs) synthesized by horseradish peroxidase were selected as starting material. Hydrolysis products were analyzed by gel permeation chromatography and by HPLC/mass spectrometry. Several experimental parameters were studied such as catalyst and substrate concentration, as well as reaction solvent composition in order to minimize high molar mass product formation generated by recombination mechanisms. In both catalytic modes, the best hydrolysis conditions were similar in terms of solvent composition with dioxane/water (90/10, v/v) and catalyst H(+) concentration of about 0.01 mol/L. Although the homogeneous catalysis generated only 28% of low molecular weight (LMW) products (monomers and dimers), clay catalysis generated 35%. In light of the qualitative analysis, both catalytic methods gave the same products, thus supporting similar hydrolysis mechanisms.

Proposal of a set of model polymer additives designed for confocal FRAP diffusion experiments.

The migration of additives from food packaging to food stuffs is kinetically governed by the diffusion coefficient (D) of the additive within the polymer. Food safety authorities have recently allowed the use of mathematical models to predict D, with the additive molecular weight as a single entry parameter. Such models require experimental values to feed the databases, but these values are often scattered. To deal with this issue, a fluorescent chemically homologous series of model additives was synthesized with molecular weights (MW) ranging from 236 g.mol (-1) to 1120 g.mol (-1). This set was then used to collect diffusion coefficients D through confocal fluorescence recovery after photobleaching (FRAP). This microscopic technique allows in situ packaging micro migration tests. The FRAP method was tested against results from the literature before being applied to two different model polystyrenes in a preliminary study to investigate the relationship D = f(MW). Our intermediate objective was to compare various experimental D = f(MW) from our method with predictions from other mathematical or semiempirical models.

Thermoplastic starch-waxy maize starch nanocrystals nanocomposites.

Waxy maize starch nanocrystals obtained by hydrolysis of native granules were used as a reinforcing agent in a thermoplastic waxy maize starch matrix plasticized with glycerol. Compared to our previous studies on starch nanocrystals reinforced natural rubber (NR) [Macromolecules 2005, 38, 3783; 2005, 38, 9161], the present system presents two particularities: (i) thermoplastic starch is a polar matrix, contrarily to NR, and (ii) the chemical structures of the matrix and the filler are similar. The influence of the glycerol content, filler content, and aging on the reinforcing properties of waxy maize starch nanocrystals (tensile tests, DMA) and crystalline structure (X-ray diffraction) of materials were studied. It was shown that the reinforcing effect of starch nanocrystals can be attributed to strong filler/filler and filler/matrix interactions due to the establishment of hydrogen bonding. The presence of starch nanocrystals leads to a slowing down of the recrystallization of the matrix during aging in humid atmosphere.

Typical diffusion behaviour in packaging polymers - application to functional barriers.

When plastics are collected for recycling, possibly contaminated articles might be recycled into food packaging, and thus the contaminants might subsequently migrate into the food. Multilayer functional barriers may be used to delay and to reduce such migration. The contribution of the work reported here is to establish reference values (at 40 degrees C) of diffusion coefficients and of activation energies to predict the functional barrier efficiency of a broad range of polymers (polyolefins, polystyrene, polyamide, PVC, PET, PVDC, [ethylene vinyl alcohol copolymer], polyacrylonitrile and [ethylene vinyl acetate copolymer]). Diffusion coefficients (D) and activation energies (Ea) were measured and were compiled together with literature data. This allowed identification of new trends for the log D=f(molecular weight) relationships. The slopes were a function of the barrier efficiency of the polymer and temperature. The apparent activation energy of diffusion displayed two domains of variation with molecular weight (M). For low M (gases), there was little variation of Ea. Focusing on larger molecules, high barrier polymers displayed a larger dependence of Ea with M. The apparent activation energy decreased with T. These results suggest a discontinuity between rubbery and glassy polymers.

Lignin-polymer blends: evaluation of compatibility by image analysis.

This paper opens onto a general discussion on the development of new polymeric materials obtained from lignin blends. The aim is (i) to look for good polymer candidates to obtain a good compatibility with lignins (that is among semi polar polymers), and (ii) to look for good lignin candidates to obtain a good compatibility with polymers showing extreme behaviours (very polar, e.g. starch, or apolar, e.g. polypropylene). The compatibility is simply assessed through the blend morphology, as studied by visible microscopy. The morphology of the blends obtained from semi polar polymers is very sensitive to the variation of the solubility parameters. In a low range of polymer solubility parameters (delta delta = 1 cal cm(-3)), both heterogeneous and homogeneous systems are obtained. These blends could be easily improved by a careful choice in the polymer structure (particularly in the family of biodegradable polyesters); it could be possible also to take advantage of lignin variability to improve the compatibility. Only low molecular weight lignins are compatible with apolar and very polar matrixes. These compounds induce interesting specific properties, and original methods have to be looked for in order to improve their production.

Stabilization of aroma compounds through sorption-release by packaging polymers.

Plastic packaging materials are often associated to aroma losses and to a decrease of the organoleptic quality of foods. This work defines situations where, on the contrary, plastics play a regulating role on the concentration of reactive aroma compounds in foods. These systems can be described by a two step mechanism; first, aroma is sorbed in the polymer, while the fraction in solution degrades quickly; in a second step, as the concentration is close to zero in the solution, the polymer liberates progressively the sorbed aroma back to the food. A simple numerical model is proposed, describing competitive processes of aroma degradation in solution and sorption by a polymer in contact with a homogeneous aqueous food. The classical limonene/low density polyethylene (LDPE) system is studied experimentally for the validation of the model: in an acidic medium, limonene both degrades quickly and is sorbed quickly, with a large solubility in LDPE. To define which aroma packaging systems could also display this interesting behavior, all types of possible interactions, using thermodynamic and kinetic parameters describing most practical situations, are simulated. For that purpose, 35 values of reference diffusion coefficients and 35 partition coefficients of usual aroma compounds between polymers and water have been measured and combined with the few available data from literature. The situations where polymers regulate the aroma concentration in food correspond to large partition coefficients (above 10), large diffusion coefficients (>10(-9) cm2 x s(-1)), and large degradation constants.

Using transgenic poplars to elucidate the relationship between the structure and the thermal properties of lignins.

In an attempt to draw relationships between the molecular structure and the thermal behavior of lignins, thermomechanical analyses were run on six milled wood and enzyme poplar lignin fractions prepared from genetically modified and control woods. All the lignin samples displayed similar thermal profiles with a clear inflection point assigned to the glass transition point. The temperature (T(g)) at which this transition occurs showed large variations from 170 to 190 degrees C, depending both on the genetic modification and on the age of the tree. These variations were found to be closely related to the condensation degree of lignins evaluated by thioacidolysis.