ABSTRACT
New active films based on chitosan and polycaprolactone blends and containing α-tocopherol were designed for food packaging applications. Mechanical properties, stability against temperature and swelling degree in 50 % ethanol (v/v) were evaluated. Migration kinetics of α-tocopherol from the developed films into butter and food simulants [50 % ethanol (v/v), 95 % ethanol (v/v), and isooctane] at different temperatures were studied. α-Tocopherol was quantified in the food simulants by means of high performance liquid chromatography with diode-array detection at 292 nm. The proposed method exhibited a good sensitivity with a limit of detection of 0.1 mg/L. The kinetics release of α-tocopherol was characterized by determining the partition and the diffusion coefficients by using a mathematical modeling based on Fick's Second Law. The diffusion coefficients obtained ranged between 1.03 × 10(-13) and 2.24 × 10(-12) cm(2)/s for 95 % ethanol (v/v) at 4 and 20 °C, respectively. Developed films maintained the antioxidant activity for more than 20 days.
ABSTRACT
It is a well-known fact that amines are not stable in food of a fatty nature. In this study the synthesis and characterisation of the products obtained as a result of the reaction of amines in a fatty medium are reported. Based on the well-known reactions among amines and acid and esters groups, two novel compounds were synthesised using m-xylylenediamine (mXDA), a primary diamine widely used as monomer in the manufacture of food contact materials and two fatty acids, oleic acid and palmitic acid, which occur in most fats. The resulting compounds were two molecules belonging to the family of fatty acid amides, dioleamide and dipalmitamide. A complete characterisation of both products was carried out employing several techniques such as infrared spectroscopy, (1)H- and (13)C-NMR spectroscopy, electron ionisation mass spectrometry, LC-MS/MS and UV spectrometry. The results obtained by the different techniques were well correlated. In the second part of the work, the formation of these compounds in real samples was evaluated. For this purpose a certain volume of olive oil was spiked with a known amount of mXDA. Olive oil was selected as a fatty medium since it is a widely consumed food and additionally is used as a fatty food simulant in migration studies of food contact materials. A method was developed to extract the fatty acid amides from the fatty matrix, which were then identified by LC-MS/MS. The toxicity of the synthesised compounds was predicted using a toxicity estimation software tool.
Subject(s)
Amides/chemical synthesis , Oleic Acid/chemistry , Palmitic Acid/chemistry , Xylenes/chemistry , Amides/analysis , Chromatography, Liquid , Diffusion , Food Contamination , Food Packaging , Humans , Models, Chemical , Olive Oil , Plant Oils/chemistry , Tandem Mass SpectrometryABSTRACT
This paper describes the development of a multi-analyte method for the determination of polyfunctional amines commonly used as monomers in the manufacture of food contact materials. Amines were analyzed by high-performance-liquid chromatography with diode-array detection (HPLC-DAD) after derivatization with dansyl chloride. The chromatographic analysis and the derivatization conditions were optimized. The proposed method was validated in terms of linearity, limits of detection and repeatabilities. The method showed an excellent sensitivity (LOD≤0.05 µg/mL) and appropriate repeatabilites (RSD (n=7)≤5%)). LC-MS/MS was used as a confirmatory technique. The stability of the amines in five food simulants (distilled water, 3% acetic acid, 10% ethanol, 50% ethanol and olive oil) under the most common testing conditions (10 days at 40 °C) was also studied. Results showed that amines had an acceptable stability in aqueous simulants but in the olive oil a loss of 100% was observed for all analytes.
Subject(s)
Amines/analysis , Chromatography, High Pressure Liquid/methods , Food Packaging , Tandem Mass Spectrometry/methods , Amines/isolation & purification , Dansyl Compounds , Food Analysis/methods , Methanol , Models, Chemical , Reproducibility of Results , Sensitivity and Specificity , WaterABSTRACT
Photo-initiators are used in printing inks hardened with UV light and one of the most commonly used photo-initiators is benzophenone (BP). Recent notifications under the Rapid Alert System for Food and Feed have shown migration of 4-methylbenzophenone (4-MBP) from packaging into cereals. A specific migration limit exists for BP of 0.6 mg kg(-1) for its use as an additive in plastics. There is no specific European legislation covering cardboard boxes and/or printing inks for food contact use. However, due to the high levels detected, the European Food Safety Authority (EFSA) published recommendations and the Standing Committee for the Food Chain and Animal Health endorsed a limit of 0.6 mg kg(-1) for the sum of BP and 4-MBP. While studies have been published on photo-initiators in the past, there is a fundamental lack of data on 4-MBP especially for its combined analysis with others. We present an HPLC method with diode array detector to simultaneously determine the levels of BP, 4-MBP as well as 7 other possible derivatives from secondary packaging for food applications. The method was tested and applied to 46 samples of paperboard for secondary packaging collected both from supermarkets and directly from a paperboard supplier. In addition, a survey was conducted on recycled paperboard (n = 19) collected from a supplier, to evaluate the background quantity of BP and other derivatives in recycled board. The most abundant photo-initiator found in the survey was BP, in 61% of samples, and 4-MBP was found in 30% of the samples. It seems that these compounds are used to replace one another. Other derivatives were found in minor quantities. Traces of BP were also found in 42% of the samples of recycled, unprinted board.
Subject(s)
Benzophenones/analysis , Food Contamination/analysis , Food Packaging/instrumentation , Paper , Photosensitizing Agents/analysis , Chromatography, High Pressure Liquid/methods , Edible Grain/chemistry , Reproducibility of Results , SolventsABSTRACT
Monitoring of exposure to chemicals from food contact materials is a subject of increasing importance. The concentration of the chemicals and their migration levels, as well as food consumption and packaging usage data, are required to enable calculation of the degree of such exposure. The present study investigated the migration kinetics of diphenylbutadiene (DPBD) from packages into flour, rice, honey, milk powder and toast. Migration was not always negligible, except in honey and skimmed milk powder. Experiments carried out with starch alone enabled us to conclude that diffusion of migrants occurred through starch and fat. Key diffusion parameters were determined (diffusion coefficient and partition coefficient) based on Fick's second equation. The following diffusion coefficients were obtained at 25 degrees C: 2.7 x 10(-10), 3.4 x 10(-11), 3.2 x 10(-10), 8.4 x 10(-11), 8.1 x 10(-11) cm(2) s(-1), for wheat flour, rice, milk powder and toast, with 4 and 21% fat, respectively. A very good fit between experimental and predicted data was achieved. The data obtained in the present study confirm the validity of the mathematical model for predicting migration from Food Contact Materials (FCM) into foods.
Subject(s)
Butadienes/chemistry , Food Additives/chemistry , Food Contamination/analysis , Food Packaging , Diffusion , KineticsABSTRACT
Photoinitiators are used in the curing process during UV printing of food carton labels. The alarm concerning the detection of a photoinitiator, 2-isopropyl thioxanthone (ITX), in food samples packed with cartons printed with UV-cured inks has focused the attention of legislative authorities on the potential migrants from packaging inks into foods. For this reason it is very important to carry out analytical methods for the detection of those compounds in food as potential migrants from packaging. The aim of the present work was to develop a multimethod for the analysis of 6 photoinitiators in milk. The selected photoinitiators were Irgacure 184, benzophenone, Irgacure 651, Irgacure 907, Quantacure ITX, and Quantacure EHA (2-ethylhexyl-4-dimethylaminobenzoate). Milk (10 mL) extraction was carried out by using ammoniac and hexane. The supernatant was evaporated and the residue was redissolved with acetonitrile. Then, the extract was analyzed by HPLC-UV. Calibration lines were carried out over the concentration range of 0.1 to 10 mg/L. The calibration data presented high correlation coefficients (>0.9999). Mean recoveries (n = 6) of the 6 photoinitiators were 83.4% (residual standard deviation = 2.3%) at 0.5 mg/kg and 81.0% (residual standard deviation = 4.6%) at 1 mg/kg. Several milk samples and their respective packaging cartons were analyzed. Results were confirmed by HPLC-mass spectrometry.
Subject(s)
Food Contamination/analysis , Food Packaging/instrumentation , Milk/chemistry , Thioxanthenes/analysis , Animals , Photochemistry , Propane/analogs & derivatives , Ultraviolet RaysABSTRACT
Photoinitiators are ink components used in the printing of food packaging. The aim of the present study was to develop a multimethod for the analysis of photoinitiators in paperboard packages and commercial beverage packages. The proposed method is simple and fairly rapid. Extraction is carried out with acetonitrile. A reverse-phase high performance liquid chromatography (HPLC) method with UV detection was developed to quantify the 6 selected photoionitiators. Total HPLC time analysis was 30 min and the flow-rate was 1 mL/min. Method validation parameters such as linearity and detection limit are reported. Recovery of all photoinitiators (at 1 mg/kg) from orange juice was satisfactory (mean = 88.4%; ranging from 84.6% to 93.4%). Recovery of benzophenone and Irgacure 651 was good (ranging from 85.2% to 98.1% and 86.1% to 92.2%, respectively) at the 4 concentrations studied (0.1, 0.2, 0.5, and 1 mg/kg). Commercial beverage packages were analyzed and when photoinitiators were detected, the beverages were also analyzed.
Subject(s)
Beverages/analysis , Food Contamination/analysis , Food Packaging , Ink , Paper , Chromatography, High Pressure Liquid , Dose-Response Relationship, Drug , Food Packaging/instrumentation , Photochemistry , Ultraviolet RaysABSTRACT
One of the main concerns regarding safety of food packaging is the possible migration of chemical substances (monomers and other starting substances, additives, residues) from food contact materials into foods. To evaluate the effect of the fat content and of the temperature of storage on the migration from plastics packaging films into meat products as an important class of foodstuffs, the kinetic mass transport of a model migrant (diphenylbutadiene) from low density polyethylene (LDPE) film in contact with different meat products was investigated. From the data, the diffusion coefficients were calculated for the applied test conditions, by use of a mathematical model. The results showed that migration increased with fat content and storage temperature. Analysis of migration data corresponding to minced pork meat containing different amounts of fat, stored for 10 days at 25°C, revealed an excellent relationship between migration level and fat content. This behaviour was also found for other types of meat products (chicken and pork neck). A simplifying mathematical model was applied to derive effective diffusion coefficients in the polymer which, however, do take kinetic effects in the meat also into account. In the case of pork meat contact, the effective diffusion coefficients derived from mathematical modelling were ten times higher for storage at 25°C (1.88×10(-9)cm(2)s(-1)) than for storage at 5°C (1.2×10(-10)cm(2)s(-1)).
ABSTRACT
Headspace solid-phase microextraction (HS-SPME) was studied as a solvent free alternative method for the extraction and characterisation of volatile compounds in stored potato crisps by capillary gas chromatography coupled with mass detection. Better results were obtained when extraction was carried out at 70 degrees C using a divinylbenzene (DVB)-carboxen (CAR)-polydimethylsiloxane fiber. The fiber was exposed for 20 min (extraction time) to the sample headspace, immediately after an equilibrium time of 5 min (time needed to reach the equilibrium between sample and above headspace). A total of 31 compounds were identified in oxidised potato crisps and resulted mainly from the degradation/rearrangement of lipids and carbohydrates.
Subject(s)
Gas Chromatography-Mass Spectrometry/methods , Organic Chemicals/analysis , Solanum tuberosum/chemistry , VolatilizationABSTRACT
Hexanal (an oxidative state indicator) formed in the headspace of potato crisps during storage was evaluated using two different procedures. First, solid-phase microextraction, an innovative sampling preparation methodology was used. It consisted on the absorption of analytes directly from samples and subsequent thermal desorption on the gas chromatograph (GC) injector. Then, a reversed-phase high-performance liquid chromatographic technique (HPLC) was employed to quantify hexanal in the form of 2,4-dinitrophenylhydrazone derivative. Methods were evaluated in what concerns to validation parameters such as linearity, repeatibility and detection limit. GC (LOD = 1 ng/ml) method resulted in more sensitive method than HPLC (LOD = 9 ng/ml). The most suitable technique for hexanal measurement was selected.
Subject(s)
Aldehydes/analysis , Chromatography, Gas/methods , Chromatography, High Pressure Liquid/methods , Lipids/chemistry , Solanum tuberosum/chemistry , Oxidation-ReductionABSTRACT
This study presents an HPLC method for the quantification of sterols in edible seaweeds. Sterols were identified by HPLC/mass spectrometry (HPLC-MS) in positive APCI mode. The samples were saponified by refluxing with 1 m ethanolic KOH, and the non-saponifiable fraction was extracted with hexane. Sterols were quantified by HPLC with UV detection (HPLC-UV), on a 15 x 0.4 cm Kromasil 100 C(18) 5 micro m column (mobile phase 30:70 v/v methanol:acetonitrile; fl ow rate 1.2 mL/min; column temperature 30 degrees C; detection wavelength 205 nm). Method repeatability for fucosterol was good (coefficient of variation 2.4%). Sterol contents were determined in canned or dried brown seaweeds (Himanthalia elongata, Undaria pinnatifida, Laminaria ochroleuca) and red seaweeds (Palmaria sp., Porphyra sp.). The predominant sterol was fucosterol in brown seaweeds (83-97% of total sterol content; 662-2320 micro g/g dry weight), and desmosterol in red seaweeds (87-93% of total sterol content; 187-337 micro g/g dry weight).
Subject(s)
Chromatography, High Pressure Liquid/methods , Seaweed/chemistry , Sterols/analysis , Mass Spectrometry , Reproducibility of Results , Spectrophotometry, UltravioletABSTRACT
A reversed-phase high performance liquid chromatographic (RP-HLPC) method was compared with a gas chromatography-flame ionization detection (GC-FID) method for determining fatty acids in potato crisps. Different extraction procedures were used. Fatty acids were quantified by linear regression. Both methods presented good precision (R.S.D. < or = 5.88%) and recovery (> or = 82.31%). The precision using HPLC method was slightly better than for GC-FID method. There was good agreement between the fatty acid composition of potato crisps analysed by both methods. For most purposes the HPLC method would be better. However, when more fatty acids need to be analysed, GC is a more suitable method.
Subject(s)
Chromatography, Gas/methods , Chromatography, High Pressure Liquid/methods , Fatty Acids/chemistry , Solanum tuberosum/chemistry , Reproducibility of ResultsABSTRACT
This study presents a high-performance liquid chromatography (HPLC) method for simultaneous determination of thiamine and riboflavin and the results of its application to a number of edible seaweeds that are sampled in dried form (Himanthalia elongata, Laminaria ochroleuca, Undaria pinnatifida, Palmaria sp., and Porphyra sp.) or as canned food (H. elongata and Saccorhiza polyschides). Samples are prepared by acid and enzymatic hydrolysis. Optimized conditions for reversed-phase HPLC with fluorescence detection are as follow: column, Kromasil 100 C18; column temperature, 35 degrees C; mobile phase, a 72:28 (v/v) mixture of 0.005 M ammonium acetate (pH 6.7)-methanol; and flow rate, 1.35 mL/min. With these conditions, recovery is 95.52% for thiamine and 90.08% for riboflavin, and the method precision (relative standard deviation) is 2.66% for thiamine and 2.21% for riboflavin. On a dry weight basis, thiamine contents range from 0.14 microg/g in dried H. elongata to 2.02 microg/g in dried Porphyra and riboflavin contents from 0.31 microg/g in canned H. elongata to 6.15 microg/g in dried Porphyra.
Subject(s)
Chromatography, High Pressure Liquid/methods , Riboflavin/analysis , Seaweed/chemistry , Thiamine/analysis , Quality Control , Spectrometry, FluorescenceABSTRACT
A high-performance liquid chromatographic (HPLC) method is described for determination of the ratio of beta-d-mannuronic acid to alpha-l-guluronic acid (M/G ratio) in dietary fibre of edible seaweeds. Total dietary fibre (TDF) content was determined gravimetrically. The TDF fraction was hydrolysed with 12 m and 1 m H(2)SO(4), then neutralized with AG 4 x 4 resin. The uronic acids were separated in a Tracer Extrasil SAX 5 micro m column (25 cm x 4 mm) at 35 degrees C, with 2 mm KH(2)PO(4) containing 5% methanol as mobile phase at a fl ow rate of 1.5 mL/min. The detection wavelength was UV 210 nm. The chromatographic identifications of beta-d-mannuronic acid and alpha-l-guluronic acid were confirmed by liquid chromatography-mass spectrometry (LC-MS). The method precision was 1.4% for beta-d-mannuronic acid and 3.5% for alpha-l-guluronic acid. The method was used to determine M/G ratio in canned seaweeds (Saccorhiza polyschides and Himanthalia elongata) and in dried seaweeds (H. elongata, Laminaria ochroleuca, Undaria pinnatifida, Palmaria sp. and Porphyra sp.).
Subject(s)
Chromatography, High Pressure Liquid/methods , Dietary Fiber/analysis , Seaweed/chemistry , Uronic Acids/analysis , Mass Spectrometry , Spectrophotometry, UltravioletABSTRACT
Bisphenol A (BPA) is used as an additive in polyvinyl chloride (PVC) products, including stretch films used for food packaging. The BPA contents were investigated of several brands of stretch film bought locally but marketed internationally or throughout Spain and which were presumably produced at different manufacturing plants. Their major components were identified by FTIR (Fourier Transform Infrared Spectrometry) and horizontal attenuated total reflectance, and the migration of BPA from these materials into the standard European Union food simulants was determined by high-performance liquid chromatography (HPLC) using both fluorescence (FL) and ultraviolet (UV) detection, the identity of the analyte being confirmed by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The two HPLC detection methods had different detection limits (30 microg x l(-1) for UV, 3 microg x l(-1) for FL), but afforded virtually identical BPA determinations for the samples tested. BPA contents ranging from 40 to 100 mg x kg(-1) were found in three of the five PVC-based films analysed, and a content of 500 mg x kg(-1) was found in a fourth; for these determinations, extraction into acetonitrile was used. In standard tests of migration into water, 3% acetic acid and olive oil over 10 days at 40 degrees C, migration from a given film was in all cases greatest into olive oil. Migration from the films with non-zero BPA contents ranged from 3 to 31 microg x dm(-2), values higher than those reported for many other food-contact materials, but lower than the European Union specific migration limit for BPA. PVC stretch film nevertheless may make a significant contribution to contamination of foodstuffs by BPA, and should be taken into account in estimating BPA intake or exposure to this substance.
Subject(s)
Food Contamination/analysis , Food Packaging , Phenols/analysis , Polyvinyl Chloride/chemistry , Benzhydryl Compounds , Chromatography, High Pressure Liquid/methods , Gas Chromatography-Mass Spectrometry/methods , Humans , Phenols/chemistry , Spectroscopy, Fourier Transform Infrared/methodsABSTRACT
The behaviour of two commercial oxygen-scavenging products with respect to migration of active ingredients into foodstuffs was investigated. Migrants were identified, and by using appropriate analytical methods, migration was determined in a variety of liquid, solid or gelled food simulants and foods. Simulants were chosen to cover a range of water activities and viscosities. Foods and the gelled food simulant agar were packed with and without vacuum, and with the oxygen scavenger in various locations relative to the packed food. The main migrants, as identified by X-ray fluorescence spectrometry, infrared spectroscopy and scanning electron microscopy with energy-dispersive spectrometry were Na(+) and Cl(-) in non-acidic aqueous simulants, and Na(+), Cl(-) and Fe(2+) in 3% acetic acid. Migration into aqueous simulants exceeded the current European Union limit for total migration from plastic materials (assumed to be currently applicable to these systems) and was probably excessive by any reasonable standard. However, neither oxygen scavenger appeared to release significant quantities of migrants into solid foods when the scavenger was properly located in the package and the packing process does not favour the contents becoming wet by water released from the food.
Subject(s)
Food Contamination/analysis , Food Packaging/methods , Food Preservation/methods , Acetic Acid/chemistry , European Union , Food Analysis/methods , Food Packaging/legislation & jurisprudence , Free Radical Scavengers/chemistry , Iron/chemistry , Legislation, Food , Sodium Chloride/chemistry , Water/chemistryABSTRACT
A high-performance liquid chromatographic (HPLC) method for the microscale determination of alpha-tocopherol in macroalgae is reported. The method includes microscale saponification and extraction with n-hexane. The presence of alpha-tocopherol in macroalgae samples was confirmed by HPLC-MS. Alpha-tocopherol levels as determined in samples by HPLC with UV and fluorescence detection did not differ significantly; however, fluorescence detection has a higher sensitivity (detection limit 10.4 ng/ml, vs. 104 ng/ml with UV detection), as well as good precision (relative standard deviation 1.81%) and recovery (94.3%). Fluorescence detection is also faster. We used this method to determine the alpha-tocopherol contents of four commercial macroalgae products from northwest Spain as part of nutritional studies in dehydrated Himanthalia elongata and Laminaria ochroleuca, and also in canned Himanthalia elongata and Saccorhiza polychides.
Subject(s)
Chromatography, High Pressure Liquid/methods , Eukaryota/chemistry , alpha-Tocopherol/analysis , Reference Standards , Spectrometry, Fluorescence , Spectrophotometry, UltravioletABSTRACT
Changes in the way foods are produced, distributed, stored and retailed, reflecting the continuing increase in consumer demands for improved quality and extended shelf-life for packaged foods, are placing ever-greater demands on the performance of food packaging. Consumers want to be assured that the packaging is fulfilling its function of protecting the integrity, quality, freshness and safety of foods. To provide this assurance and help improve the performance of the packaging, innovative active and intelligent packaging concepts are being developed and applied in various countries. In Europe, however, the development and application of active and intelligent packaging systems have been limited thus far. The main reasons are legislative restrictions and a lack of knowledge about consumer acceptance, the efficacy of such systems, and the economic and environmental impact they may have. Therefore, in 1999, a European study was started within the framework of the EU FAIR R&D programme. It aims to initiate amendments to European legislation for food-contact materials to establish and implement active and intelligent systems within the current relevant regulations for packaged food in Europe. This paper presents an overview of existing active and intelligent systems and their current and future food-related applications. In addition, developments and trends in active and intelligent food packaging are discussed. The objectives and the work programme of the European project are reviewed and the results obtained so far are presented. The benefits for both the European consumer and the European food and food-packaging industries are highlighted.
Subject(s)
Food Packaging/methods , Food Preservation/methods , Legislation, Food , Europe , Food/standards , Food Contamination/prevention & control , Food Microbiology , Food Packaging/legislation & jurisprudence , Food Packaging/trends , Free Radical ScavengersABSTRACT
European Union directive 90/128/EEC prescribes a specific migration limit of 0.05 mg/kg for the aliphatic diamine m-xylylenediamine (m-XDA) into food or food simultants, but there is no generally accepted method of analysis available for compliance testing with the given restriction. A method is described for the determination of m-XDA monomer in the following food simulants: distilled water, 3% (w/v) acetic acid, and 15% (v/v) ethanol. The method is appropriate for the quantitative determination of m-XDA at a minimum level of 0.020 mg/kg in these food simulants. Detection limits are in the range of 0.004 to 0.010 mg m-XDA per kilogram food simulant (depending on the type of food simulant). The method should also be applicable to other aqueous food simulants. m-XDA in aqueous simulant test samples is determined by high-performance liquid chromatography with fluorescence detection following derivatization with fluorescamine. Quantitation is relative to external standards. The identity of m-XDA may be confirmed by the presence of a second peak in the chromatograms obtained from samples derivatized with less fluorescamine or by comparison with authentic samples.
Subject(s)
Food Analysis/standards , Xylenes/analysis , Indicators and Reagents , Mass Spectrometry , Solutions , SolventsABSTRACT
The overall and specific migrations of BADGE n = 0 monomer and m-XDA hardener from a BEPOX LAB 889 (Gairesa internal code), epoxy system cured at room temperature, into three water-based food simulants are studied. Hydrolysis of BADGE n = 0 was observed in all of these simulants, giving more polar products. We thus propose changing the EEC Directives, which at present only legislate for levels of BADGE n = 0 monomer in the simulants, to include the hydrolysis products of BADGE monomers. Another alternative would be to express all the migration levels due to BADGE and its derived products in terms of BADGE itself.