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Aim: The objective of the present study was to investigate in vitro anticoccidial effect of olive pulp (Olea europaea L var. Chemlal) extract on the destruction of Eimeria spp. oocysts isolated from infected chickens naturally., Materials and Methods: The olive pulp (OP) powder was stirred manually in aqueous ethanol in preparation for extraction using the microwave-assisted extraction system. The identification of the phenolic compounds was obtained by ultra-high-performance liquid chromatography-mass spectrometry with electrospray ionisation (HPLC-ESI-MS). The treatment of Eimeria oocyst with OP extract and standard compounds (quercetin and oleuropein) leads to their lysis as shown by the release of substances absorbing at 273 nm., Results: Our results showed that the maximum number of reduced oocysts was recorded after 8 h of incubation of optimum OP extract, quercetin and oleuropein for different periods of time. Also, the number of Eimeria oocysts decreased considerably with increase concentrations after adding the optimum of OP extract in concentration ranging from 0.023 to 0.371 mg/ml. Positive correlation between the optimum OP extract concentrations and the number of Eimeria oocysts reduced was R 2  = 0.959. From this in vitro experiment, it can be concluded that the OP extract possesses an anti-Eimeria spp activity., Conclusion: To our knowledge, this is the first time that quercetin and oleuropein were tested to evaluate their anticoccidial activity. The findings of this study showed that phenolic compound of OP extract tested separately possesses anti-Eimeria spp. effect. Further studies should be carried out to test its in vivo efficacy of the OP bioactive compounds in broiler chickens.

Nontarget analysis of nonvolatile substances in complex samples is a very challenging task that requires powerful analytical techniques and experience of analyzing such samples. An extensive study was conducted in order to identify nonintentionally added substances (NIAS) migrating from 18 polyethylene (PE) samples intended to be in contact with food. The migration assays were performed in five simulants and analyzed by ultrahigh-performance liquid chromatography (UPLC) coupled to an ion-mobility separation (IMS) quadrupole-time-of-flight (QTOF) mass spectrometer. This experimental setup provides a novel and powerful tool for this type of nonvolatile and nontargeted analysis. Thirty-five compounds were identified, 17 of which were NIAS. Methyl and ethyl 3-(3,5-di- tert -butyl-4-hydroxyphenyl) propanoate were found to be degradation products of either Irganox 1010 or Irganox 1076. Additionally, breakdown products including hexa-heptadecanamide, N , N '-1,2-ethanediylbis- and 11-eicosenamide were identified together with impurity reaction products, e.g., dibutyl amine or compounds of unknown origin like phosphine oxide, tributyl-. Forty-five percent of the detected compounds are in the positive list contained in Regulation 10/2011/EU, and their migration values were below their specific migration limits. The risk assessment for the rest of the compounds was carried out by comparing their migration values to the maximum concentration recommended by Cramer, e.g., ethyl 3-(3,5-di- tert -butyl-4-hydroxyphenyl) propanoate and benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, 1,1'-[2,2-bis(hydroxymethyl)-1,3-propanediyl] ester (both class II toxicity), heptadecanamide, N , N '-1,2-ethanediylbis-, and phosphine oxide, tributyl- (both class III toxicity) were above the maximum concentration values for three samples that were migrated to ethanol 95%, and therefore, these samples are not suitable for food contact. The analytical tools and procedures used in this study are presented and discussed in detail.

The main goal of this work is the encapsulation of cinnamon essential oil in cyclodextrin nanosponges and the assessment of their antimicrobial activity against foodborne pathogens. After nanosponge synthesis, a headspace-solid phase microextraction coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS) method was validated to quantify essential oil major compounds. Results showed that essential oil was successfully encapsulated in cyclodextrin nanosponges with α-NS and β-NS being able to encapsulate higher essential oil amounts. Cinnamon essential oil, alone and encapsulated in nanosponges, proved to have antimicrobial activity against foodborne bacteria. Time-kill assays proved that the essential oil, alone or encapsulated, had a bacteriostatic effect against all bacteria tested, with the exception of Y. enterocolitica where a bactericidal action was observed. Furthermore, the controlled release achieved by its encapsulation, allowed cinnamon essential oil to be effective at a much lower concentration in culture medium than when solely dissolved in culture medium. Thus, the results described herein encourage the use of cyclodextrin nanosponges as encapsulating agents for active food packaging applications., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A new biodegradable antioxidant active packaging for food applications based on antioxidants from medicinal and aromatic plants incorporated into a polylactic acid matrix was designed and developed. Melt blending processing technique was applied to prepare polylactic acid films loaded by sage and lemon balm leaves. Antioxidant properties of developed active films were investigated using the following methods: 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid), 2,2-diphenyl-1-(2,4,6-trinitrophenyl)hydrazyl and a home-made generator of hydroxyl radicals. In addition, reducing power and total phenolic content of polylactic acid films were checked. The results of antioxidant capacity showed that percentage of hydroxylation for active film with lemon balm and sage was 55.5% ± 0.1% and 67.4% ± 0.3%, respectively. The reducing power of active films increased 8 times in comparison to the blank samples. Moreover, extensive investigation of influence of sage and lemon balm leaves on material safety and type of migrants was performed using migration assays. The composition of both non-volatile and volatile compounds of different active packaging films was compared with neat polylactic acid film. Three different food simulants such as 95% (v/v) ethanol, 10% (v/v) ethanol and 3% (w/v) acetic acid were checked. It was shown that the addition of sage and lemon balm leaves into a polylactic acid structure decreased the migration of both linear and cyclic polylactic acid oligomers, currently not legislated by European Union. Besides, total absence or decrease of migration of volatile compounds were observed when using the active films. Both thermal and mechanical properties of films were also evaluated., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This article presents fabric phase sorptive extraction (FPSE) as a simple and effective pre-concentration method for the enrichment of acrylate compounds in different food simulants and subsequent analysis of the extracts by ultra-high-performance liquid chromatography with mass spectrometric detection (UPLC-MS). Acrylate compounds come from acrylic adhesives used commonly for sticking the paper labels on polyethylene terephthalate (PET) bottles and therefore, they may exist in recycled polyethylene terephthalate (rPET). Four acrylates were studied: ethylene glycol dimethacrylate (EGDM), pentaerythritol triacrylate (PETA), triethylene glycol diacrylate (TEGDA) and trimethylolpropane triacrylate (TMPTA). Five different types of FPSE media coated with different sol-gel sorbents were studied and finally sol-gel polyethylene glycol- polypropylene glycol-polyethylene glycol triblock copolymer (PEG-PPG-PEG) coated FPSE media was chosen for its satisfactory results. The optimal conditions affecting the extraction efficiency of compounds were determined in three different food simulants. Statistical evaluation of this method reveals good linearity and precision. Under the optimized conditions, the method provided limits of detection of the compounds in the range of (0.1-1.9 ng g -1 , 0.1-1.2 ng g -1 , 0.2-2.3 ng g -1 ) in EtOH 10%, HAc 3% and EtOH 20% and the enrichment factor values (EFs) after applying N 2 were in the range of 11.1-25.0, 13.8-26.3, 8.3-21.9, in simulants A, B and C respectively. The optimized method was applied successfully to analyze thirteen types of recycled PET samples. Acrylates were found in some of the samples at ng g -1 levels., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Atmospheric pressure gas chromatography (APGC) coupled to quadrupole time-of-flight (QTOF) and electron ionization mass spectrometry together with commercial library search are two complementary techniques for non-target screening of volatile and semi-volatile compounds. Optimization was first conducted to achieve easier search of correspondent peaks between the two systems. Analytical strategy for the determination of volatile and semi-volatile compound with different identification confidence levels was then proposed and applied to food contact grade polypropylene (PP) samples. Identification was found to be much easier and less time-consuming especially when correspondent peak was found in the two systems with the help of library search, exact mass of precursor and fragment ions as well as Kovats Index (KI). The behavior of APGC-QTOF-MS was also further investigated. Apart from the M +. ion and the well-known adduct [M+H] + others such as [M-3H + O] + , [M-3H+2O] + and [M-H+3O] + were also observed for n-alkanes. Besides, new reaction products were found, formed by diol compounds (1-Monostearoylglycerol, 2-Monostearoylglycerol and NX 8000K) and silanediol dimethyl, which would be a transformation product of the silicone base septum or the methyl 5% phenyl polysiloxane based column. These new compounds were only detected in APGC-MS-QTOF as EI-GC-MS was not enough sensitive for this purpose., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Baby bottles made of polypropylene, Tritan® and silicone were evaluated regarding the migration of non-volatile compounds using UPLC-QTOF-MS. Twenty-seven compounds were identified. In all polypropylene samples the migration of 2.2'-(tridecylimino)bis-ethanol and derivatives thereof were detected in concentrations below the specific migration limit (1.2 mg.kg -1 ). Furthermore, clarifying agents and glycerol derivatives were detected. Tritan baby bottle showed the migration of one slip additive. On the other hand, twenty compounds were detected in silicone baby bottles. Most of them were unknown compounds derived from acrylates. Once the migrants were identified, the risk assessment was carried out using the Threshold of Toxicological Concern (TTC) approach. The risk assessment of migrants coming from silicone samples showed levels above the threshold recommended as safe for babies., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The rapid growth of polymer technology in the field of food contact materials (FCMs) needs to be supported by continuous improvement in material testing, in order to ensure the safety of foodstuff. In this work, a range of different starch-based biopolymer samples, in the shape of pellets and retail samples (cups and dishes) were studied. The optimized extraction process was performed on three different pellet shapes: pellets with no modification (spherical), pellets shattered under high pressure (lentils), and pellets cryogenically ground (powder). The analysis of unknown volatile and semi-volatile compounds was carried out by gas chromatography-mass spectrometry, using both electron ionization with a single quadrupole mass analyzer (GC-EI-MS), and atmospheric pressure gas chromatography with a quadrupole/time of flight mass analyzer (APGC-Q/ToF). The identification process was implemented using the latest advances in the understanding of APGC ionization pathways. Chemical migration was also assessed on prototype samples using the food simulants: ethanol 10% v/v, acetic acid 3% w/V, ethanol 95% v/v, isooctane, and vegetable oil. Each migration test was performed three consecutive times, as recommended for materials intended for repeated use., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The set-off migration from printing inks can cause alterations in the safety and acceptability of food. Therefore, its control in the food industry is of special importance. The aim of this study was the determination of the migration of compounds coming from different types of cardboard-cups used in coffee vending machines. The volatile compounds present in cardboard-cups were studied and specific migration studies were carried out by solid phase microextraction with headspace coupled to gas chromatography (HS-SPME-GC-MS). The migration of compounds from the cardboard-cups manufacturing material, plastic coating (LDPE) and printing inks were identified and quantified. Those migrants listed in the Regulation No. 10/2011 presented values lower than the specific migration limit (SML), although a series of non-listed and non-authorized compounds were identified. From the results obtained the risk assessment of the vending cups from two different companies has been done., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Biopolymers used for food contact materials must be evaluated in order to ensure food safety and quality. In this work, the aroma profile of starch-based packaging materials, presented as pellets and films has been characterized. Headspace solid phase microextraction (HS-SPME) technique and gas chromatography coupled to both mass spectrometry and a sniffing port (GC-MS-O) were used for identification. In total, 35 odorant compounds were detected. The results showed that aldehydes were the odorants with the highest aromatic impact in starch-based films. Eight odorant compounds, such as trimethylamine, 1-octen-3-one, sotolon, (Z) and (E)-2-nonenal, p-vinylguaiacol, eugenol and 1-undecanol, defined as aroma-impact compounds, obtained modified frequency values (MF%) above 60% in at least 3 out of 4 films. A sensory panel evaluated the toasted, sweet/fruity, green, flower, distasteful, fat and spices notes in the films and it was observed that the quality of all samples decreased when the toasted and spices notes increased., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This work was performed to evaluate the antifungal effect of cinnamon and mustard essential oil (EO) alone and in combination against a range of mould strains. A wide range of resistance levels was observed among different mould species, being R. stolonifer the most resistant one. Mustard EO showed the biggest antifungal effect, and for this reason it was selected to study its effect in vapour phase on bread. The shelf life of bread inoculated with R. stolonifer and non- inoculated increased by 3-4 days at 25 °C, while at 4 °C the shelf-life increased beyond 50 days. However, the results from the acceptability test were negative. Based on this, the antifungal effect of cinnamon/mustard EO in combination was evaluated, with results mostly additive and synergistic. The ratio of the combination was defined taking into account the most resistant strain (100:8, cinnamon and mustard respectively) and their application was performed in vapour phase. This combination maintained the antifungal activity presented by mustard EO by itself and masked the mustard flavour, providing positive results in the acceptability tests. It was therefore suggested to be used at industrial scale., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Polylactic acid (PLA) is a biopolymer commonly used in food packaging due to its good characteristics, similar to PET. To evaluate the safety of this material, the analysis of the non-intentionally added substances (NIAS) is required. Oligomers are NIAS and their behavior needs a deep study, especially if they migrate to the food. In this work, the analysis of the polymer and the migration to food simulants was carried out. A total dissolution/precipitation procedure was applied to PLA pellets and films, using dichloromethane and ethanol as solvent and antisolvent system respectively. The migration tests were carried out in three liquid simulants to mimic any kind of food. Since oligomers are not present in the positive list of the Directive 10/2011/EC, their concentration must be below the 0.01 mg/kg of food. UPLC-QTOF-MS, with and without ion mobility (IM), was used for the analysis. Thirty-nine different PLA oligomers made of repeated monomer units of [LA] (C 3 H 4 O 2 ) and with different structures were identified. They corresponded to cyclic oligomers with [LA] n structure and two groups of linear oligomers, one with an hydroxyl group, OH-[LA] n -H, and the other one with an ethoxy group, CH 3 -CH 2 -O-[LA] n -H. Cyclic oligomers only appeared in the material and were not present in migration solutions. Linear oligomers HO-[LA] n -H were already present in the pellets/film and they migrated in a higher extension to aqueous food simulants (EtOH 10% and AcH 3%). However, linear oligomers CH 3 -CH 2 -O-[LA] n -H were not present initially in the pellets/film, but were detected in migration to simulants with ethanol content, EtOH 95% and EtOH 10%. Furthermore, 5 cyclic polyester oligomers were identified in migration. Ethanol 95% and ethanol 10% migration solutions were also analyzed by scanning electron microscopy (SEM), and the presence of microstructures that could be attributed to the oligomers migration was found. They could be seen as microplastics.

A novel and fast salting out liquid-liquid extraction method was developed for simultaneous determination of food additives with different polarities in juices. Chromatographic separation was achieved in less than 6 min using Acquity UPLC BEH C 18 (100 mm × 2.1 mm d.i. × 1.7 µm) column with ammonium acetate with 0.01% of trifluoroacetic acid as eluent A and acetonitrile as eluent B at a flow rate of 0.2 mL min -1 . The main factors affecting the extraction efficiency were optimized. The method was validated applying accuracy profile based on total error. The extraction recoveries ranged from 84.97 to 122%. Relative standard deviation ranged from 1.24 to 7.99% for intraday assay and from 1.69 to 9.16% for intermediate precision. The limits of detection for five food additives were from 0.3 to 1.42 µg mL -1 . The method was successfully applied to 47 samples of juices from nine brands., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Bioplastic materials are increasingly used due to its benefits for the environment preservation. Among them, food packaging materials based on polylactic acid (PLA) are among the most employed. In this work, a sample treatment methodology based on dissolution/precipitation has been optimized, selecting finally dichloromethane/ethanol as solvent/antisolvent system. The extracts obtained were analysed by UPLC-MS(QTOF), that allowed the identification of the main PLA non-volatile components. The recovery results were between 100.9 to 114.0%. The methodology was applied to the analysis of pellets and films of a PLA-polyester blend sample. A total of 37 different compounds were detected, where the four compounds with the highest intensity in pellet samples were cyclic oligomers coming from the polyester part of the blend and composed by adipic acid (AA), phthalic acid (PA) and butanediol (BD). Migration experiments to 3 food simulants were also performed: ethanol 95% (v/v), ethanol 10% (v/v) and acetic acid 3% (w/v). The results showed that in addition to those compounds previously detected in the film, new compounds coming from the reaction of PLA components with food simulants were present in migration solutions., (Copyright © 2018. Published by Elsevier B.V.)

A flexible multilayer with selenium nanoparticles incorporated has been used to build an antioxidant packaging. The oxidation of hazelnuts, walnuts, and potato chips was tested at laboratory scale. Hexanal released by the nuts, fatty acids oxidation study, TBARS (thiobarbituric acid reactive substances), and tasting were compared to study the oxidation of foods packaged with this antioxidant packaging. Finally, TBARS method in combination with tasting were selected due to their simplicity and accuracy. It was found that hazelnuts packaged in nanoSe active bags released around 20% less malonaldehyde (MDA) than the blanks. In the case of the walnuts, the active ones released 25% less MDA than the blanks. As for potato chips, the improvement was around 22%. Finally, an industrial study was done. Cooked ham, chicken, and a ready-to-eat vegetable mixture seasoned with butter were industrially packaged with the new antioxidant material and improvements higher than 25% were obtained.

Migration of non volatile compounds from twenty six PP films used as food contact materials has been studied in four simulants (ethanol 95% and 10%, acetic acid 3% and Tenax ®) and analyzed by UPLC-MS/QTOF. Seventy six compounds have been identified, where 76% of them were non-intentionally added substances (NIAS) coming from degradation of additives used, such as methyl or ethyl or hexyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) from irganox 1076 and irganox 1010 degradation; or impurities such as N,N-bis(2-hydroxyethyl) amines, or compounds of unknown origin, like hydro-ceramides. The most common compounds found were glyceryl monostearate or monopalmitate, erucamide, irganox 1010, irgafos 168, irgafos 168 OXO, N,N-bis(2-hydroxyethyl) tridecylamine and N,N-bis(2-hydroxyethyl) pentadecylamine. Six films didn't comply with the European Regulation Nº 10/2011/EU, where irganox 1010 and the group of N,N-bis(2-hydroxyethyl) amines exceeded their SMLs. Other films surpassed the maximum concentration recommended by Cramer for the compounds of class II (degradation products) or III (amide compounds) when ethanol 95% was used as simulant., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In the present work, different pre-concentration strategies were evaluated for the analysis of isophthalaldehyde in migration samples from food packaging materials. This compound is a potential migrant in several copolymers used for food packaging, and since it is considered a non-intentionally added substance, its concentration in migration samples must be determined. Derivatisation was the first sample treatment evaluated. o-(2,3,4,5,6-Pentafluorobenzyl)hydroxylamine was tested as derivatisation agent, but no satisfactory results were obtained. Then, hollow-fibre liquid-phase microextraction (HF-LPME) and solid-phase microextraction were optimised. The HF-LPME method showed the highest sensitivity, achieving an enrichment factor of 60-fold. The limit of detection of the method was 10 ng g -1 , the limit of quantification was 30 ng g -1 and the relative standard deviation was 6.1%. Finally, the method was applied to migration studies to evaluate the safety in use of a poly(ethylene terephthalate) packaging material. The content of isophthalaldehyde was determined in two aqueous food simulants: 10% ethanol (v/v) and 3% acetic acid (w/v). Different migration conditions were tested. The results obtained showed a considerable rise in the concentration of isophthalaldehyde when increasing the time and temperature of the migration experiment.

Antimicrobial packaging materials (films or coatings) (APMs) have aroused great interest among the scientists or the experts specialized in material science, food science, packaging engineering, biology and chemistry. APMs have been used to package the food, such as dairy products, poultry, meat (e.g., beef), salmon muscle, pastry dough, fresh pasta, bakery products, fruits, vegetables and beverages. Some materials have been already commercialized. The ability of APMs to extend the shelf-life of the food depends on the release rate of the antimicrobials (AMs) from the materials to the food. The optimum rate is defined as target release rate (TRR). To achieve TRR, the influencing factors of the release rate should be considered. Herein we reviewed for the first time these factors and their influence on the release. These factors mainly include the AMs, food (or food simulant), packaging materials, the interactions among them, the temperature and environmental relative humidity (RH).

Fresh poultry meat and poultry products are highly perishable foods and high potential sources of human infection due to the presence of several foodborne pathogens. Focusing on the microbial control of poultry products, the food industry generally implements numerous preventive measures based on the Hazard Analysis and Critical Control Points (HACCP) food safety management system certification together with technological steps, such as refrigeration coupled to modified atmosphere packaging that are able to control identified potential microbial hazards during food processing. However, in recent years, to meet the demand of consumers for minimally processed, high-quality, and additive-free foods, technologies are emerging associated with nonthermal microbial inactivation, such as high hydrostatic pressure, irradiation, and natural alternatives, such as biopreservation or the incorporation of natural preservatives in packaging materials. These technologies are discussed throughout this article, emphasizing their pros and cons regarding the control of poultry microbiota and their effects on poultry sensory properties. The discussion for each of the preservation techniques mentioned will be provided with as much detail as the data and studies provided in the literature for poultry meat and products allow. These new approaches, on their own, have proved to be effective against a wide range of microorganisms in poultry meat. However, since some of these emergent technologies still do not have full consumer's acceptability and, taking into consideration the hurdle technology concept for poultry processing, it is suggested that they will be used as combined treatments or, more frequently, in combination with modified atmosphere packaging.

An oligomer is a molecule that consists of a few monomer units. It can be formed during polymer manufacturing and also due to polymer degradation processes or even during use conditions. Since oligomers are not included in chemical databases, their identification is a complex process. In this work, the oligomers present in 20 different PET pellet samples have been determined. Two different sample treatment procedures, solvent extraction and total dissolution, were applied in order to select the most efficient one. The analyses were carried out by UPLC-MS-QTOF. The use of high resolution mass spectrometry allowed the structural elucidation of these compounds and their correct identification. The main oligomers identified were cyclic as well as lineal from the first, second, and third series. All of them were composed of terephthalic acid (TPA), diethylene glycol (DEG), and ethylene glycol (EG). Quantitative values were very different in both procedures. In total dissolution of PET samples, the concentration of oligomers was always, at least, 10 times higher than in solvent extraction; some of the compounds were only detected when total dissolution was used. Results showed that the oligomers with the highest concentration values were dimers and trimers, cyclic, as well as lineal, from the first and second series. The oligomer with the maximum concentration value was TPA 2 -EG-DEG that was found in all the samples in a concentration range from 2493 to 19,290 ng/g PET. No differences between virgin and recycled PET were found. Migration experiments were performed in two PET bottles, and results showed the transference of most of these oligomers to a fat food simulant (ethanol 95%). Graphical abstract Graphical abstract of the two procedures developd and optimized for identifying oligomers in PET pellets and in migration form PET bottles.

The potential use of cholesterol esterases was tested to avoid alkaline hydrolysis for cleavage of plasma esterified oxysterols. The enzymatic hydrolysis was optimized by testing two sources of enzyme-Pseudomonas and bovine pancreas, presence of surfactants, incubation time and amount of enzyme. Free forms of 4β-, 7-, 24-, 25- and 27-hydroxycholesterol (HC) as well 7-ketocholesterol (7-KC) were analyzed by liquid chromatography and mass-spectrometry using the deuterated internal standard, 25-HC(d6). Enzymatic hydrolysis was more effective using the Pseudomonas enzyme and in presence of surfactants. Compared to alkaline hydrolysis, it generated a cleaner chromatographic baseline and better recovery of the internal standard. Oxysterols were assayed with detection limits between 7 and 31 pg/mL. Interassay coefficients of variation were lower than 10% and extraction recovery efficiencies, higher than 90%. The procedure was used to characterize plasma levels of Cyp7b1-deficient rat, where it showed increased plasma levels of 7, 24 and 25-HC. Due to the low volume of sample required, it may be used in other animal models, particularly rodents, as well as in pediatric samples where sample amount is always a problem. Thus, the proposed new method offers mild enzymatic processing that greatly facilitates oxysterol determinations to delineate their role in physiopathology., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The aim of this work was the study of the main effects of benzyl isothiocyanate (BITC) on A. ochraceus morphology and on its production metabolism of ochratoxins. This compound was evaluated as active agent of an antimicrobial label in food packaging. Microbiological studies showed a slowdown in mould growth when the active material was applied to A. ochraceus and the presence of three different areas of growth. Scanning electron microscopy was successfully used to demonstrate the mode of action of BITC on this strain. A. ochraceus exhibited modifications in morphology compared to the control samples such as the disappearance of sclerotia or cleistothecia An extraction protocol and an analytical method by UPLC-MS/MS to determine ochratoxins (OTs) was developed. The results showed that all these morphological changes were related to a decrease on OTs production, both ochratoxin A (OTA) and ochratoxin B (OTB). The presence of BITC caused a great decrease on OTA that modified the OTA/OTB ratio, increasing the OTB proportion. Furthermore, the active packaging also modified the production of other secondary metabolites. The morphological and metabolic effects observed, as well as the relationship between them, are of great interest since they have not been reported before for A. ochraceus., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The suitability of an acrylic adhesive used on food packaging was studied. Six potential migrants were identified using GC-MS and UPLC-QTOF. Five compounds were intentionally added (2-butoxyethanol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol 10 (TMDD) and TMDD ethoxylates). One of the compounds identified as 2-(12-(methacryloyloxy) dodecyl)malonic acid was a non -intentionally added substance (NIAS), which could be a methyl metacrylate derivative. A migration study from multilayers containing paper-adhesive-film was carried out. The films used were polyethylene (PE), polypropylene, polyethylene terephthalate, polylactic acid (PLA) and Ecovio F2223®, which is a mixture of biodegradable polyester with PLA. All the non-volatile compounds, including the identified NIAS, migrated into the dry food simulant Tenax ®. Five surfactants based on TMDD were found to migrate from all laminates into Tenax at levels from 0.05 to 0.6 mg kg -1 . The results showed that the lowest migration (0.01 mg kg -1 for 2-(12-(methacryloyloxy)dodecyl)malonic acid to 0.07 for TMDD mg kg -1 ) occurred when the compounds passed through PLA, demonstrating its functional barrier properties to these compounds. In contrast, PE showed the worst barrier properties to these compounds. To evaluate the migration results, the threshold of toxicological concern strategy was applied. The migration values of the surfactant identified were above 0.09 mg kg -1 . Thus, it was decided to remove this surfactant from the formulation.

Most multilayer high barrier materials used in food packaging have a polyurethane adhesive layer in their structures. In order to assess the safety of these materials, it is important to determine the compounds intentionally added to the adhesives (IAS) as well as those non-intentionally added substances (NIAS). During the manufacture of polyurethane adhesives, some by-products can be formed, such as cyclic polyester oligomers coming from the reaction between dicarboxylic acids and glycols. Since these compounds are not listed in the Regulation 10/2011/EU, they should not be found in migration above 0.01 mg/kg of simulant. In this study two flexible multilayer packaging materials were used and migration was evaluated in simulant A (ethanol 10% v/v), simulant B (acetic acid 3% w/v) and simulant ethanol 95% v/v during 10 days at 60ºC. Identification and quantification of non-volatile compounds was carried out by UPLC-MS-QTOF. Most of migrants were oligomers such as cyclic polyesters and caprolactam oligomers. Overall migration and specific migration of adipic acid-diethylene glycol and phthalic acid-diethylene glycol were monitored over time and analysed by UPLC-MS-TQ. In most cases, ethanol 95% v/v was the simulant with the highest concentration values. Overall migration kinetics followed a similar pattern than specific migration kinetics.

Recently oxobiodegradable polyethylene gained popularity as food packaging material due to its potential to reduce polymer waste. However, this type of material can release after its oxidation off-odour compounds that affect the organoleptic properties of packaged food. Odour compounds released from both polyethylene and oxobiodegradable polyethylene before and after oxidation under a free radicals flow were investigated after 1 day, 2 days and 3 days of oxidation. The samples were analysed using headspace solid phase microextraction followed by gas chromatography-mass spectrometry and headspace solid phase microextraction coupled to gas chromatography-olfactometry-mass spectrometry. Sixty-two different odorous compounds were identified. 4-methylthio-2-butanone (fruit), nonanal (fat) and 3,6-nonadienal (fat) were present in different materials before oxidation. Multiple headspace-solid phase microextraction has been used to quantify all analytes. The most abundant compound was (Z)-3-hexenyl hexanoate with a concentration range between 1.5791±0.1387µg/g and 4.8181±0.3123µg/g. Compounds such as 2-dodecenal, 2-octenal, 2-pentanol, 3-nonenal, 3,6-nonadienal, ethyl 3-methylbutanoate, ethyl octenoate, hexanone, isopropyl hexanoate, octanal were below their LOD evaluated using MS detector; however, they were detected by gas chromatography-olfactometry. The minimum LOD and LOQ were 0.011µg/g and 0.036µg/g, respectively., (Copyright © 2017 Elsevier B.V. All rights reserved.)

An antioxidant food packaging material was developed and applied to fresh minced pork meat. The material consists of a multilayer polyethylene film in which 4 different concentrations (2%, 5%, 10%, and 15%) of olive leaves (OL) extract were immobilized in an adhesive formula used to build the multilayer. The antioxidants were not in direct contact with the meat. The packaged meat was kept at 4°C during 16days and finally analyzed by two methods: Raman spectroscopy and thiobarbituric acid reactive substances (TBARS). Raman demonstrated a higher sensitivity for antioxidant evaluation than TBARS. Color of fresh meat packaged with the active film was also measured to evaluate the shelf life of packaged meat. The results showed that active film containing natural antioxidants efficiently enhanced the stability of fresh meat against oxidation processes, thus being a promising way to extend the shelf life of fresh minced meat for about two days., (Copyright © 2017. Published by Elsevier Ltd.)

Printing inks are commonly used in multilayer plastics materials used for food packaging, and compounds present in inks can migrate to the food either by diffusion through the multilayers or because of set-off phenomena. To avoid this problem, the right design of the packaging is crucial. This paper studies the safety by design of multilayer materials. First, the migration from four different multilayers manufactured using polyethylene terephthalate (PET), aluminium (Al) and polyethylene (PE) was determined. The structural differences among materials such as the presence of inks or lacquer coatings as well as the differences in layers position allowed the study of a safety-by-design approach. Sixty-nine different compounds were detected and identified; 49 of them were not included in the positive list of Regulation EU/10/2011 or in Swiss legislation and 15 belong to Cramer class III, which means that they have a theoretical high toxicity. Some of the compounds related to ink composition were pyrene, a compound commercially used to make dyes and dye precursors and the antioxidant Irganox 1300. The application of external lacquers decreased the concentration of some migrants but also brought the potential for new migrants coming from its composition. A final risk assessment of the material allowed evaluating food safety for different food simulants and confirm it.

One critical challenge when developing a new antimicrobial packaging material is to demonstrate the mode of action of the antimicrobials incorporated into the packaging. For this task, several analytical techniques as well as microbiology are required. In this work, the antimicrobial properties of benzyl isothiocyanate, allyl isothiocyanate and essential oils of cinnamon and oregano against several moulds and bacteria have been evaluated. Benzyl isothiocyanate showed the highest antimicrobial activity and it was selected for developing the new active packaging material. Scanning electron microscopy and Raman spectroscopy were successfully used to demonstrate the mode of action of benzyl isothiocyanate on Escherichia coli. Bacteria exhibited external modifications such as oval shape and the presence of septum surface, but they did not show any disruption or membrane damage. To provide data on the in vitro action of benzyl isothiocyanate and the presence of inhibition halos, the transfer mechanism to the cells was assessed using solid-phase microextraction-gas chromatography-mass spectrometry. Based on the transfer system, action mechanism and its stronger antimicrobial activity, benzyl isothiocyanate was incorporated to two kinds of antimicrobial labels. The labels were stable and active for 140 days against two mould producers of ochratoxin A; Penicillium verrucosum is more sensitive than Aspergillus ochraceus. Details about the analytical techniques and the results obtained are shown and discussed. Graphical Abstract Antimicrobial evaluation of pure compounds, incorporation in the packaging and study for mode of action on S. coli by Raman, SEM and SPME-GC-MS.

A novel active film material based on hydroxypropyl-methylcellulose (HPMC) containing poly(lactic acid) (PLA) nanoparticles (NPs) loaded with antioxidant (AO) green tea extract (GTE) was successfully developed. The PLA NPs were fabricated using an emulsification-solvent evaporation technique and the sizes were varied to enable a controlled release of the AO from the HPMC matrix. A statistical experimental design was used to optimise the synthesis of the NPs in order to obtain different sizes of nanoparticles and the loading of these into the HPMC matrix was also varied. The physico-chemical properties of the composite films were investigated and the release of the AO was confirmed by migration studies in 50% v/v ethanol/water food simulant. The AO capacity of the GTE released from the active films was studied using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical method and the results suggest that the material could potentially be used for extending the shelf-life of food products with high fat content., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The antioxidant activity of olive leaf (OL) and cake (OC) extracts with different solvents was evaluated. 70% of aqueous ethanol extract of OL was chosen as the most antioxidant extract based on antiradical activity (DPPH) (95.4±0.3%) and oxygen radical absorbance capacity (ORAC) (0.82±0.07g equivalent Trolox per g of solution) assays. This OL extract was incorporated in two multilayer materials consisting of (i) polyethylene/polyethylene (PE/PE) film and (ii) polyethylene/paper (PE/P). These multilayers were exposed to a gas stream enriched in free radicals to evaluate the scavenging capacity of both materials. PE/PE film exhibited the highest scavenging activity of free radicals (78.8%). Migration of the phenolic compounds from olive by-products into two simulants was performed and demonstrated a non-migrating behavior. The limits of detection and quantification for oleuropein were 0.5μgkg(-1) and 1.7μgkg(-1) and for Luteolin-7-O-glucoside 1.3μgkg(-1) and 4.3μg kg(-1) respectively., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Selenium nanoparticles (SeNPs) were incorporated in a flexible multilayer plastic material using a water-base adhesive as vehicle for SeNPs. The antioxidant performance of the original solutions containing spherical SeNPs of 50-60 nm diameter, the adhesive containing these SeNPs, and the final multilayer plastic material to be used as food packaging were quantitatively measured. The radical scavenging capacity due to SeNPs was quantified by a free radical assay developed in the laboratory and by the diphenyl-1-picrylhydrazyl (DPPH) method. DPPH was not efficient to measure the scavenging capacity in the multilayer when the free radical scavenger is not in the surface in contact with it. Several multilayer laminated structures composed by [PET (20 m)-adhesive-LDPE (with variable thickness from 35 to 90 μm)] were prepared and measured, demonstrating for the first time that free radicals derived from oxygen (OH·, O2·, and O2H) cross the PE layer and arrive at the adhesive. SeNPs remain as such after manufacture and the final laminate is stable after 3 months of storage. The antioxidant multilayer is a non-migrating efficient free radical scavenger, able to protect the packaged product versus oxidation and extending the shelf life without being in direct contact with the product. Migration tests of both Se and SeNPs to simulants and hazelnuts demonstrated the non-migrating performance of this new active packaging. Graphical abstract ᅟ.

In most cases, food packaging materials contain inks whose components can migrate to food by diffusion through the material as well as by set-off phenomena. In this work, different mass spectrometry approaches had been used in order to identify and confirm the presence of ink components in ethanol (95%) and Tenax(®) as food simulants. Three different sets of materials, manufactured with different printing technologies and with different structures, were analyzed. Sample analysis by ultra performance liquid chromatography mass spectrometry (UPLC-MS), using a quadrupole-time of flight (Q-TOF) as a mass analyser proved to be an excellent tool for identification purposes while ion mobility mass spectrometry (IM-MS) shown to be very useful for the confirmation of the candidates proposed. The results showed the presence of different non-volatile ink components in migration such as colorants (Solvent Red 49), plasticizers (dimethyl sebacate, tributyl o-acetyl citrate) or surfactants (SchercodineM, triethylene glycol caprilate). An oxidation product of an ink additive (triphenyl phosphine oxide) was also detected. In addition, a surface analysis technique, desorption electrospray mass spectrometry (DESI-MS), was used for analyzing the distribution of some ink components (tributyl o-acetyl citrate Schercodine L, phthalates) in the material. The detection of some of these compounds in the back-printed side confirmed the transference of this compound from the non-food to the food contact side. The results also showed that concentration of ink migrants decreased when an aluminum or polypropylene layer covered the ink. When aluminum was used, concentration of most of ink migrants decreased, and for 5 out of the 9 even disappeared., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A new screening method has been explored for direct analysis of tobacco smoke biomarkers in biological matrices (i.e., saliva and urine). Single run analysis using Atmospheric pressure Solid Analysis Probe (ASAP) and high resolution mass spectrometry with quadrupole and time of flight detector has been applied directly to some biological samples (i.e., urine and saliva), providing a fast, efficient and sensitive method of identification. The method has been applied to saliva and urine samples from heavy tobacco smokers for exposure studies. Nicotine itself, nicotine metabolites (i.e., cotinine, trans-3'-hydroxycotinine, nicotine-N-glucuronide) and other related tobacco smoke toxic compounds (i.e., NNK 4-[methyl(nitroso)amino]-1-(3-pyridinyl)-1-butanone, anatabine) were found in the analyzed samples. The identification of compounds was confirmed by ultrahigh performance liquid chromatography with MS-triple quadrupole detector after sample treatment. Different temporal trends and biomarkers behavior have been found in time series related samples. Both methods are compared for screening of these biological matrices., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Raman imaging spectroscopy is a nondestructive analytical method that can be a useful tool to obtain detailed information about the molecular composition and morphology of biological samples. Its high spatial resolution was used to collect spectra of Aspergillus ochraceus, a mold producer of ochratoxin A (OTA), in order to investigate the cell damage caused on it by the action of the antimicrobial benzyl isothiocyanate (BITC). The study was performed in both direct contact and vapor phase, in order to check the use of BITC as active agent in food packaging material. The results showed that there were morphologic alteration and a characteristic Raman spectrum on spore and hyphae exposed to BITC. BITC was accumulated in the mold cells where it caused an enormous amount of alterations in cellular components (lipids, proteins, saccharides, amino acids...) and cellular functions (cell cycle, respiration, metabolism, transcription of genes, fluidity of the cellular wall). All these structural, composition, and metabolic changes will affect the production of OTA. Pattern recognition with chemometrics using principal component analysis (PCA) demonstrated an excellent separation between control and BITC treated samples, both in spores and hyphae. PCA results also showed two different affection levels when samples were exposed to BITC in the vapor phase.

Most fresh sausages are sold with a self-stick adhesive label stuck directly on it. Because of that, the substances in the adhesive could migrate into the fresh sausage. In this work, the multiple headspace-solid-phase microextraction technique has been optimized to quantify the migrants found in the fresh sausage. All the compounds could be analyzed by this technique since its concentration decay exponentially with the number of extractions with good correlation coefficients (0.8258-0.9987). Then, migration assays were carried out and an evaluation of the potential risk for the human health was undertaken with the conclusion that the migration of the compounds from the label does not endanger human health. The results were compared those obtained in migration to casing filled with isooctane used as fat food simulant by Canellas et al. (2014). The values obtained for isooctane (10-600 ng/g) were much higher than the migration values found in the meat stuffed in casing expressed as ng/g of fat content (ranged from 0.02 to 3.3 ng/g of fat content). This finding shows that in some scenarios, it is difficult to simulate the intended contact of materials used in food packaging with simulants., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

61 different non-volatile compounds were determined in Agaricus Bisporus sliced mushrooms using UHPLC/Q-TOF with MS(E) technology. Both positive and negative electrospray ionization were applied. Chemical profile of three parts of mushroom was created: cap, gills and stipe. The analysed mushrooms were oxidized to identify the non-volatile markers in their parts. MarkerLynx(®) was proposed as a powerful tool to distinguish mushrooms purchased in different countries (Spain and Portugal) by determining their non-volatile markers. Some metabolites were identified. Surprisingly a mix of polyethylene glycols (PEGs) was detected in cap and gills of mushrooms. Whole mushrooms were considered as vegetable resistant to migration from packaging compounds. Additionally migration tests were performed to determine the source of migrating compounds., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A recent trend is to use nanocomposites materials for food-packaging applications. Different kinds of nanoparticles are incorporated into the polymers to improve their characteristics, and, among them, nanoclay is used to improve their barrier properties to gases. In this work, the results of migration studies with different food simulants (ethanol 10% and acetic acid 3%), temperatures and times (40 ºC for 10 days and 70 ºC for 2 h) from two commercialised LDPE nanocomposite bags are presented. The migration solutions thus obtained were analysed by ICP-MS to evaluate the amount of aluminium which migrated into the solutions both in dissolved form and as a part of nanoparticles. Aluminium migration was observed for both samples with a maximum migration value of 51.65 ng cm(-)(2) for the Aisaika bags and 24.14 ng cm(-)(2) for the Debbie Meyer bags. The presence of spikes working in single-particle mode using ICP-MS indicated that part of this aluminium was present as nanoparticles. The size and morphology of the nanoclay, in both the original material and the migration solutions, was studied by scanning electron microscopy coupled to energy-dispersive X-ray diffraction (SEM-EDX). In this manner, nanoparticles of different morphologies and sizes were found to migrate into the food simulants.

Inks and varnishes used in food packaging multilayer materials can contain different substances that are potential migrants when packaging is in contact with food. Although printing inks are applied on the external layer, they can migrate due to set-off phenomena. In order to assess food safety, migration tests were performed from two materials sets: set A based on paper and set B based on PET; both contained inks. Migration was performed to four food simulants (EtOH 50%, isooctane, EtOH 95% and Tenax(®)) and the volatile compounds profile was analysed by GC-MS. The effect of presence/absence of inks and varnishes and also their position in the material was studied. A total of 149 volatile compounds were found in migration from set A and 156 from set B materials, some of them came from inks. Quantitative analysis and a principal component analysis were performed in order to identify patterns among sample groups.

Biodegradable packagings are made by combination of several materials creating a multilayer with the properties needed. Each material, including the adhesive, could contain substances that could migrate to the food. In this work, gas chromatography coupled with mass spectrometry and ultra-high-pressure liquid chromatography coupled with quadrupole time-of-flight mass spectrometry were used to identify the biodegradable adhesive compounds. Five of the 13 compounds identified were nonintentionally added substances; they were neoformed compounds created by the reaction of added compounds in the adhesive. Moreover, the migration of the compounds through four different biodegradable materials-paper, polylactic acid, ecovio®, and polyvinyl alcohol-was studied for the first time. Three of the 13 compounds identified in the adhesive migrated from the adhesive to Tenax®, which was used as a solid food simulant. One of them, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, was an intentionally added substance, and the other two were 1,6-dioxacyclododecane-7,12-dione and 1,6,13,18-tetraoxacyclotetracosane-7,12,19,24-tetraone, which were nonintentionally added substances identified in this work. Higher migration values (ranging from 0.81 to 2.07 mg/kg) were observed for migration through ecovio® than through the multilayer made by combination of ecovio® and polyvinyl alcohol (0.07-0.39 mg/kg) owing to the barrier effect provided by polyvinyl alcohol. The migration values for migration through paper and polylactic acid were below the limits of detection.

The profile of volatile compounds released from 13 different multilayer polymeric materials for food use, before and after their exposure to gamma radiation, has been assessed by solid-phase microextraction-gas chromatography-mass spectrometry. Thermosealed bags of different materials were filled with either air or nitrogen to evaluate the oxygen influence. One-third of the samples were analyzed without irradiation, whereas the rest were irradiated at 15 and 25 kGy. Half of the samples were processed just after preparation and the other half was stored for 8 months at room temperature prior to analysis. Very significant differences between unirradiated and irradiated bags were found. About 60-80 compounds were released and identified per sample. A huge peak of 1,3-ditertbutylbenzene was present in most of the irradiated samples. An outstanding reproducibility in all the variables evaluated (chromatograms, oxygen percentage, volume of bags) was noticed. Independently of filling gas, the results of unirradiated materials were almost identical. In contrast, the chromatographic profile and the odor of irradiated bags filled with nitrogen were completely different to those filled with air. Principal component analysis was performed and 86.9% of the accumulated variance was explained with the first two components. The migration of compounds from irradiated materials to the vapor phase was much lower than the limits established in the Commission Regulation (EU) No 10/2011., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The antioxidant capacity of two active papers (based on solid and emulsion paraffin) with cinnamon essential oil was studied. Mushroom samples were introduced in macroperforated PET trays covered with the active papers, and weight loss and browning monitored for 9 days. The antioxidant capacity of the different papers was evaluated based on scavenging 1,1-diphenyl-2-picryl-hydrazyl (DPPH) and tyrosinase inhibition kinetics, and the release of aromatic volatile oils was determined by HSPME-GC-MS. Differences in performance were observed: the active papers were more efficient at avoiding weight loss and mushroom browning when compared to the non-active paraffin-based papers. The efficiency increased when the bottom and walls of the trays were covered rather than the bottom alone. Better results were observed when cinnamon was incorporated as emulsion paraffin instead of a solid., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Adhesives are used to manufacture multilayer materials, where their components pass through the layers and migrate to the food. Nine different adhesives (acrylic, vinyl and hotmelt) and their migration in 21 laminates for future use as market samples have been evaluated and risk assessment has been carried out. A total of 75 volatiles and non volatile compounds were identified by gas chromatography-mass spectrometry and ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. Most of the compounds migrated below their specific migration limit (SML), lowest observed adverse effect level (LOAEL), no observed adverse effect level (NOAEL) and values recommended by Cramer. Six compounds classified as high toxicity class III according to Cramer classification, migrated over their SML and exposure values recommended by Cramer, when they were applied in the full area of the packaging. Nevertheless, these adhesives fulfill the threshold in the real application as they are applied in a small area of the packaging., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A new screening and semi-quantitative approach has been developed for direct analysis of polycyclic aromatic hydrocarbons (PAHs) and their nitro and oxo derivatives in environmental and biological matrices using atmospheric pressure solid analysis probe (ASAP) quadrupole-time of flight mass spectrometry (Q-TOF-MS). The instrumental parameters were optimized for the analysis of all these compounds, without previous sample treatment, in soil, motor oil, atmospheric particles (ashes) and biological samples such as urine and saliva of smokers and non-smokers. Ion source parameters in the MS were found to be the key parameters, with little variation within PAHs families. The optimized corona current was 4 µA, sample cone voltage 80 V for PAHs, nitro-PAHs and oxo-PAHs, while the desolvation temperatures varied from 300°C to 500°C. The analytical method performance was checked using a certified reference material. Two deuterated compounds were used as internal standards for semi-quantitative purposes together with the pure individual standard for each compound and the corresponding calibration plot. The compounds nitro PAH 9-nitroanthracene and oxo-PAH 1,4-naphthalenedione, were found in saliva and urine in a range below 1 µg/g while the range of PAHs in these samples was below 2 µg/g. Environmental samples provided higher concentration of all pollutants than urine and saliva., (Copyright © 2014 Elsevier B.V. All rights reserved.)

An automated method for analyzing free non-cholesterol sterols in human serum using online solid phase extraction-liquid chromatography-mass spectrometry is proposed herein. The method allows the determination of three phytosterols (sitosterol, stigmasterol and campesterol) and two cholesterol precursors (desmosterol and lanosterol). The analysis of sterols in human serum is critical in the study of cholesterol-related disorders, such as inherited familial hypercholesterolemias. Special effort was made to isolate the analytes from the serum lipoproteins, their natural conveyance through the bloodstream. The sample treatment consisted of a Bligh-Dyer extraction followed by dilution of the extract. This treatment allowed the sample to be injected into the online system and ensured the correct detection of the analytes, while avoiding the matrix effects commonly related to serum samples. The analytical performance showed linear ranges that covered two orders of magnitude, with correlation coefficients above 0.99. Limits of detection and quantification ranged from 0.2 ng/mL to 13 ng/mL and from 1.0 ng/mL to 43 ng/mL, respectively. Recovery when spiking serum with a half or a tenth of the average concentration reported in human serum ranged from 99% to 111% and from 102% to 120%, respectively. Intra-day precision and inter-day precision were below 20%., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Pressure-sensitive adhesives (PSA) are used to manufacture labels that are applied directly on the food. These adhesives could contain not only intentionally added compounds (IAS) to the adhesive formula but also non-intentionally added substances (NIAS), due to the impurities from the raw materials used, decomposition of the initial components or from chemical interactions between them. These compounds could migrate to the food and contaminate it. In this study, gas chromatography coupled with mass spectrometry (GC-MS/Q) and atmospheric pressure gas chromatography coupled to a quadrupole hyphenated to a time of flight mass spectrometer (APGC-MS/Q-TOF) have been used for identification of unknown compounds and NIAS coming from a PSA. Seven compounds were identified by GC-MS/Q, and other eight compounds remained initially unknown. The structure of these eight new compounds was elucidated by working with the spectra obtained by APGC-MS/Q-TOF. Finally, two different migration studies were carried out. The first one with Tenax as solid food simulant in contact with the paper label containing the adhesive and the second one with isooctane filled in a natural pork intestine where the label containing the adhesive was applied on the external side. The results are shown and discussed., (Copyright © 2014 John Wiley & Sons, Ltd.)

The ORAC assay is applied to measure the antioxidant capacity of foods or dietary supplements. Sometimes, the manufacturers claim antioxidant capacities that may not correspond to the constituents of the product. These statements are sheltered by the general understanding that antioxidants might exhibit synergistic properties, but this is not necessarily true when dealing with ORAC assay values. This contribution applies the ORAC assay to measure the antioxidant capacity of ten essential oils typically added to foodstuffs: citronella, dill, basil, red thyme, thyme, rosemary, oregano, clove and cinnamon. The major components of these essential oils were twenty-one chemicals in total. After a preliminary discrimination, the antioxidant capacity of eugenol, carvacrol, thymol, α-pinene, limonene and linalool was determined. The results showed that 72-115% of the antioxidant capacity of the essential oils corresponded to the addition of the antioxidant capacity of their constituents. Thus, the ORAC assay showed additive properties., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Aiming at the development of an active food packaging, the goal of this study was to increase stilbenes (resveratrol (RV), pterostilbene (PT) and pinosylvin (PS)) aqueous solubility and stability using hydropropyl-cyclodextrins (HP-CDs) and bile salts. To evaluate stilbene concentration, an HPLC-DAD method was validated. Stilbene solubility was improved by the formation of inclusion complexes and micellar systems with higher solubility values obtained for the inclusion complexes with cyclodextrins. Inclusion complexes revealed a 1:1 stoichiometry for RV and PT and a 1:2 for PS. Solid state characterisation was carried out using X-ray diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry. (1)H NMR studies were also performed to characterise the prepared complexes. Photostability studies revealed that CDs were able to increase stilbene photostability at 4 °C. This work showed that stable stilbene solutions can be achieved using hydroxypropyl-CDs, contributing for their incorporation in several materials for the food and pharmaceutical industries., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Adhesives are commonly used in the manufacture of multilayer food packaging materials. Although they are not in direct contact with the packed food, their compounds may migrate from the adhesive through the substrates to the food. The aim of this work is to determine the migrant concentration in order to evaluate the possible human risk and also to determine if this migration could affect the organoleptic properties of packed food. For this purpose, a total of 12 market samples of multilayer materials (laminates) for packaging dry food (tomatoes, cakes, cookies, breadcrumbs, flour or salt) or fresh food (pizza and pastry) produced with 5 different adhesives were analysed by GC-O-MS. A total of 25 different compounds from adhesives were detected in these laminates. Seventy-six percentage of these compounds migrated into a dry food simulant (Tenax®). Furthermore, compounds with concentrations below the MS detection limit were detected by sniffers with a high modified frequency (MF%). Acetic acid, butyric acid and cyclohexanol with vinegar, cheese and camphor odours were the most abundant compounds. All migration data were below the specific migration limits (SML) and threshold toxicological concern (TTC) recommended values according to the Cramer classification., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The present study deals with the development of a liquid microextraction procedure for enhancing the sensitivity of the determination of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one in adhesives. The procedure involves a three-phase hollow-fiber liquid-phase microextraction using a semipermeable polypropylene membrane, which contained 1-octanol as the organic phase in the pores of the membrane. The donor and acceptor phases are aqueous acidic and alkaline media, respectively, and the final liquid phase (acceptor) is analyzed by HPLC coupled with diode array detection. The most appropriate conditions were extraction time 20 min, stirring speed 1400 rpm, extraction temperature 50°C. The quantification limits of the method were 0.123 and 0.490 μg/g for 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, respectively. Three different adhesive samples were successfully analyzed. The procedure was compared to direct analysis using ultra high pressure liquid chromatography coupled with TOF-MS, where the identification of the compounds and the quantification values were confirmed., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A formula including green tea extract (GTE) was developed as an active food packaging material. This formula was moulded to obtain an independent component/device with antioxidant properties that could be easily coupled to industrial degassing valves for food packaging in special cases. GTE components (i.e., gallic acid, catechins and caffeine) were identified and quantified by HPLC-UV and UPLC-MS and migration/diffusion studies were carried out. Antioxidant properties of the formula alone and formula-valve were measured with static and dynamic methods. The results showed that the antioxidant capacity (scavenging of free radicals) of the new GTE formula was 40% higher than the non-active system (blank). This antioxidant activity increased in parallel with the GTE concentration. The functional properties of the industrial target valve (e.g., flexibility) were studied for different mixtures of GTE, and good results were found with 17% (w/w) of GTE. This new active formula can be an important addition for active packaging applications in the food packaging industry, with oxidative species-scavenging capacity, thus improving the safety and quality for the consumer and extending the shelf-life of the packaged food.