Analysis of Bioactive Aroma Compounds in Essential Oils from Algerian Plants: Implications for Potential Antioxidant Applications.

In samples of Artemisia campestris (AC), Artemisia herba-alba (AHA) and Salvia jordanii (SJ) essential oils, up to 200 distinct volatile compounds were identified. Using headspace solid-phase microextraction combined with gas chromatography-olfactometry-mass spectrometry (HS-SPME-GC-O-MS), different panelists detected 52 of these compounds. This study offers the most detailed analysis of bioactive compound profiles conducted so far. The most abundant compounds identified were curcumene, making up 12.96% of AC, and camphor, constituting 21.67% of AHA and 19.15% of SJ. The compounds with the highest odor activity value (OAV) were (E,Z)-2,4-nonadienal (geranium, pungent), 3-nonenal (cucumber) and 2-undecenal (sweet) in AC, AHA and SJ, respectively. AHA essential oil showed significant antioxidant activity (IC50 = 41.73 ± 4.14 mg/g) and hydroxyl radical generation (hydroxylation percentage = 29.62 ± 3.14), as assessed by the diphenylpicrylhydrazyl (DPPH) method. In terms of oxygen radical absorbance capacity (ORAC), the strongest antioxidant activity was obtained for SJ essential oil (antioxidant activity of the essential oils, AOX = 337.49 ± 9.87).

Phenolic compounds profile of macerates of different edible parts of carob tree (Ceratonia siliqua L.) using UPLC-ESI-Q-TOF-MSE: Phytochemical screening and biological activities.

Locust bean pulp and gum extracts were prepared, and phytochemical tests based on color reactions and chromatographic analyzes were performed. A profile of seventy-six phenolic compounds was obtained by the ultra-high performance liquid chromatography with electrospray ionization and quadrupole time-of-flight mass spectrometry. The main groups of phenolic compounds identified in the both extracts of Ceratonia siliqua L., were flavonoids, tannins and phenolic acids. Moreover, carob pulp and gum extracts were tested for their antimicrobial activity using disk diffusion tests which showed sensitivity of the different strains to the analyzed extracts at a concentration of 100 mg/mL. Additionally, the antioxidant activity of Ceratonia siliqua L. extracts was assessed by the 2,2-diphenyl-1-picrylhydrazyl acid test, which confirmed stronger antioxidant properties in the case of the pulp extract. To sum up, carob pulp and gum extracts present promising alternatives to synthetic additives within the medicinal industry, serving as potential antioxidant agents and preservatives that combat bacterial contamination, thereby offering a more natural approach to enhancing product safety and efficacy.

Application of Ion Mobility Spectrometry and the Derived Collision Cross Section in the Analysis of Environmental Organic Micropollutants.

Ion mobility spectrometry (IMS) is a rapid gas-phase separation technique, which can distinguish ions on the basis of their size, shape, and charge. The IMS-derived collision cross section (CCS) can serve as additional identification evidence for the screening of environmental organic micropollutants (OMPs). In this work, we summarize the published experimental CCS values of environmental OMPs, introduce the current CCS prediction tools, summarize the use of IMS and CCS in the analysis of environmental OMPs, and finally discussed the benefits of IMS and CCS in environmental analysis. An up-to-date CCS compendium for environmental contaminants was produced by combining CCS databases and data sets of particular types of environmental OMPs, including pesticides, drugs, mycotoxins, steroids, plastic additives, per- and polyfluoroalkyl substances (PFAS), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs), as well as their well-known transformation products. A total of 9407 experimental CCS values from 4170 OMPs were retrieved from 23 publications, which contain both drift tube CCS in nitrogen (DTCCSN2) and traveling wave CCS in nitrogen (TWCCSN2). A selection of publicly accessible and in-house CCS prediction tools were also investigated; the chemical space covered by the training set and the quality of CCS measurements seem to be vital factors affecting the CCS prediction accuracy. Then, the applications of IMS and the derived CCS in the screening of various OMPs were summarized, and the benefits of IMS and CCS, including increased peak capacity, the elimination of interfering ions, the separation of isomers, and the reduction of false positives and false negatives, were discussed in detail. With the improvement of the resolving power of IMS and enhancements of experimental CCS databases, the practicability of IMS in the analysis of environmental OMPs will continue to improve.

Migration of contaminants from printed masks for children to saliva simulant using liquid chromatography coupled to ion mobility-time of flight-mass spectrometry and gas chromatography-mass spectrometry.

The COVID-19 pandemic has led to children using polymeric FFP2 and polymeric surgical masks on a daily basis. Children often bite and suck on such masks as they wear them closed to their mouths. In this work, the migration of contaminants from printed and unprinted children`s masks to a saliva simulant has been studied. Liquid chromatography coupled to ion-mobility quadrupole time-of-flight mass spectrometry has been used for the detection and identification of non-volatile migrants. An orthogonal projection to latent structures - discriminant analysis (OPLS-DA) was applied to compare the data from the printed masks against the data from the unprinted ones. Headspace solid phase microextraction coupled to gas chromatography mass spectrometry was used to assess the migration of volatile compounds. Thirteen compounds were found in the masks with concentrations ranging from 5 ng/g to 254 ng/g. Toluene, chlorobenzene, irganox 1076 and 2-(2-butoxyethoxy)ethyl acetate were all found to migrate from the masks studied. Moreover, differences between the migrants from printed and unprinted FFP2 masks were found. Octocrylene, 4-(dimethylamine)benzoate, methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(3-methylphenyl)phosphate were found to migrate only from printed masks. Toluene that migrated from all the masks studied and tris(3-methylphenyl)phosphate, that migrated only from printed masks, have been listed as hazardous priority substances.

Evaluation the Potential of Onion/Laponite Composites Films for Sustainable Food Packaging with Enhanced UV Protection and Antioxidant Capacity.

Agro-industrial residues have attracted attention for their applications in the field of biodegradable packaging. Recently, our research group has developed onion-based films with promising properties for this type of application due to their non-toxicity, biocompatibility and biodegradability. Therefore, in this study, we investigated the effect of Laponite clay concentration on the physicochemical and antioxidant properties of the onion-based films, which were prepared by a casting method. The XRD and FTIR data confirm the presence of the mineral clay in the onion-based films. These findings are consistent with those obtained from FE-SEM analysis, which revealed the presence of typical Laponite grains. In terms of wettability, the results show that the clay decreases the hydrophilic character of the material but slightly increases the water vapor permeation. Optical characterization revealed that the materials exhibited zero transmittance in the UV region and increased opacity in the visible region for composites containing 5% and 10% Laponite. Furthermore, the antioxidant test demonstrated higher antioxidant potential in the composites compared to the pure films. Consequently, these results suggest that the formation of Laponite and onion composites could be an essential strategy for developing natural polymers in the field of food contact packaging.

A vision for safer food contact materials: Public health concerns as drivers for improved testing.

Food contact materials (FCMs) and food contact articles are ubiquitous in today's globalized food system. Chemicals migrate from FCMs into foodstuffs, so called food contact chemicals (FCCs), but current regulatory requirements do not sufficiently protect public health from hazardous FCCs because only individual substances used to make FCMs are tested and mostly only for genotoxicity while endocrine disruption and other hazard properties are disregarded. Indeed, FCMs are a known source of a wide range of hazardous chemicals, and they likely contribute to highly prevalent non-communicable diseases. FCMs can also include non-intentionally added substances (NIAS), which often are unknown and therefore not subject to risk assessment. To address these important shortcomings, we outline how the safety of FCMs may be improved by (1) testing the overall migrate, including (unknown) NIAS, of finished food contact articles, and (2) expanding toxicological testing beyond genotoxicity to multiple endpoints associated with non-communicable diseases relevant to human health. To identify mechanistic endpoints for testing, we group chronic health outcomes associated with chemical exposure into Six Clusters of Disease (SCOD) and we propose that finished food contact articles should be tested for their impacts on these SCOD. Research should focus on developing robust, relevant, and sensitive in-vitro assays based on mechanistic information linked to the SCOD, e.g., through Adverse Outcome Pathways (AOPs) or Key Characteristics of Toxicants. Implementing this vision will improve prevention of chronic diseases that are associated with hazardous chemical exposures, including from FCMs.

Bioactive Compounds and In Vitro Antioxidant and Anticoccidial Activities of Opuntia ficus-indica Flower Extracts.

The objective of the present study is to identify the biochemical compounds extracted from OFI flowers using ultra-high-performance liquid chromatography-electrospray ionization quadrupole time-of-flight mass spectrometry and to evaluate their in vitro antioxidant activities and anticoccidial effects on the destruction of Eimeria oocysts isolated from naturally infected chickens. A domestic microwave was used with a refrigerant to condense the vapors generated during the extraction. The flavonoid and phenolic compound contents of the OFI flowers were determined according to standard methods. DPPH radical and H2O2 scavenging capacities were used to assess the antioxidant activity. Regarding the anticoccidial activity, the Eimeria spp. oocysts used were isolated from the fresh feces of infected broilers and were determined in triplicate by incubation at an ambient temperature for 24 h. The results highlighted the considerable influence of the optimized acetone concentration, ratio, irradiation time, and microwave power parameters on the phenolic content and antioxidant activities. Our results revealed significant matches between the predicted and experimental values of the models. Molecular analysis revealed the presence of several biophenol classes such as quercetin, isorhamnetin 3-O-rutinoside, and quercetin-3-O-rutinoside. OFI flower extracts inhibited sporulation and damaged the morphology of Eimeria oocysts compared with normal sporulated Eimeria oocysts containing sporocysts. In conclusion, the optimized conditions were validated and found to fit very well with the experimental values. These findings suggest that the flowers of OFI should be considered sources of antioxidants. The results of the present study revealed that OFI flower extracts have anticoccidial activities against Eimeria-spp.-induced infection in broiler chickens.

Combination of Structure Databases, In Silico Fragmentation, and MS/MS Libraries for Untargeted Screening of Non-Volatile Migrants from Recycled High-Density Polyethylene Milk Bottles.

Chemical contamination is one of the major obstacles for mechanical recycling of plastics. In this article, we built and open-sourced an in-house MS/MS library containing more than 500 plastic-related chemicals and developed mspcompiler, an R package, for the compilation of various libraries. We then proposed a workflow to process untargeted screening data acquired by liquid chromatography high-resolution mass spectrometry. These tools were subsequently employed to data originating from recycled high-density polyethylene (rHDPE) obtained from milk bottles. A total of 83 compounds were identified, with 66 easily annotated by making use of our in-house MS/MS libraries and the mspcompiler R package. In silico fragmentation combined with data obtained from gas chromatography-mass spectrometry and lists of chemicals related to plastics were used to identify those remaining unknown. A pseudo-multiple reaction monitoring method was also applied to sensitively target and screen the identified chemicals in the samples. Quantification results demonstrated that a good sorting of postconsumer materials and a better recycling technology may be necessary for food contact applications. Removal or reduction of non-volatile substances, such as octocrylene and 2-ethylhexyl-4-methoxycinnamate, is still challenging but vital for the safe use of rHDPE as food contact materials.

Enhanced compatibility and functionality of thermoplastic cassava starch blended PBAT blown films with erythorbate and nitrite.

Improved miscibility between thermoplastic starch (TPS) and polybutylene adipate-co-terephthalate (PBAT) enhances processability and properties of TPS-based biodegradable plastic packaging. This research investigated compatibility and functionality of TPS/PBAT (50/50) blends with sodium nitrite and sodium erythorbate (1-5%) via blown film extrusion. Film morphology and mechanical and barrier properties were investigated. Sodium nitrite and sodium erythorbate improved processing efficiency of TPS, modified film flexibility and enhanced physical and chemical compatibility between TPS and PBAT matrices via hydrolysis, confirmed by 1H NMR and ATR-FTIR analyses. These chemical reactions also affected thermal and phase transition behaviors. Increased starch granule dispersion caused smoother microstructure, resulting in higher oxygen barrier. Sodium nitrite and sodium erythorbate functionalized TPS/PBAT films reduced discoloration of packaged cured meat during storage at 4 °C for 9 days. These compounds provided extra functionality and improved compatibility between TPS and PBAT biodegradable plastic blends for novel and sustainable food packaging.

Ultra-high performance liquid chromatography coupled to ion mobility quadrupole time-of-flight mass spectrometry for the identification of non-volatile compounds migrating from 'natural' dishes.

Although most new biomaterials for food industry applications are labelled '100% natural fabrication' and 'chemical-free', certain compounds may migrate from those materials to the food, compromising the organoleptic characteristics and safety of the product. In this work, the degree of compound migration from dishes made with four different biomaterials: bamboo, palm leaf, wood and wheat pulp was investigated. Migration tests were carried out using three food simulants, 10% ethanol (simulant A), 3% acetic acid (simulant B), and 95% ethanol (simulant D2). Unequivocal identification of non-intentionally added substances (NIAS) is challenging even when using high-resolution mass spectrometry techniques however, a total of 25 different non-volatile compounds from the migration tests were identified and quantified using Ultra-high performance liquid chromatography coupled to ion mobility quadrupole time-of-flight mass spectrometry (UPLC-IMS-MS). In the bamboo samples three oligomers, cyclic diethylene glycol adipate, 3,6,9,16,19,22-hexaoxabicyclo[22.3.1]-octacosa-1(28),24,26-triene-2,10,15,23-tetrone and 1,4,7,14,17,20-hexaoxacyclohexacosane-8,13,21,26-tetrone exceeded the specified limits of migration.

Mechanochemically Scaled-Up Alpha Cyclodextrin Nanosponges: Their Safety and Effectiveness as Ethylene Scavenger.

Aiming at the development of a greener ethylene removal alternative, the goal of this study was to scale up and ensure the safety of α-cyclodextrin nanosponges (α-CD-NS) for further use as ethylene scavengers. The solvent-free synthesis of α-CD-NS was successfully scaled up using α-cyclodextrin and N,N'-carbonyldiimidazole as cross-linkers (1:4 molar ratio) by means of mechanical alloying using a PM 100 ball mill by focusing on varying the rotation frequency, as determined by FTIR-ATR, X-ray diffraction, and TGA. α-CD-NS washing optimization was performed in water by monitoring the imidazole concentration in the washing solution through the validation of a fast and sensitive HPLC-DAD method. After 6 h at 40 °C, all imidazole was extracted, allowing a faster and less energy-dependent extraction. α-CD-NS absorbent capacity and porosity were also evaluated through BET isotherms and ethylene absorption experiments using α-CD-NS and commercially available absorbents (zeolite and bentonite) were performed by means of gas chromatography (GC) coupled to a flame ionization detector (FID). With a 93 µL h-1 kgadsorbent-1 ethylene removal capacity, α-CD-NS revealed the best ethylene scavenging activity when compared to the other absorbents, opening the doors for a safer, innovative, and eco-friendlier ethylene removal active packaging.

Development of an analytical method for the determination of mineral oil aromatic hydrocarbons (MOAH) from printing inks in food packaging.

An analysis method was developed to detect chemical markers of mineral oil aromatic hydrocarbons (MOAH) from offset printing inks in food packaging materials. 16 aromatic hydrocarbons were used as target analytes and different solid phase extraction procedures (SPE) and gas chromatography coupled to mass spectrometry (GC-MS) were tested. The concentration range studied was 0.1-7.5 µg g-1 with R2 higher than 0.9963, intraday RSD values below 5 %, RSD values between days lower than 12 %, recoveries higher than 80 %, LOD and LOQ lower than 0.09 µg g-1. Ten of the target analytes were identified in offset printing inks at concentrations between 2.28 and 8.59 µg g-1. Nine of them were also identified in the food packages examined in concentrations ranging from 0.10 to 0.33 µg g-1. These compounds were: methylnaphthalene, 2-methylnaphthalene, biphenyl, 2,6-dimethylnaphthalene, acenaphthene, 3,3',5,5'-tetramethylbiphenyl, 4,6-dimethyldibenzothiophene, 1-methylpyrene, benzo(b)naphtha(1,2-d)thiophene and 9,9'-dimethylfluorene. Mineral oil in food packaging was previously analysed by GC with flame ionization detection (FID).

The characterization and influence factors of semi-volatile compounds from mechanically recycled polyethylene terephthalate (rPET) by combining GC×GC-TOFMS and chemometrics.

A non-targeted method was developed for screening the semi-volatile compounds of different mechanically recycled PET intended for food contact materials. The data was further analyzed by multiple chemometrics methods to obtain the difference level, and the potential influence factors were investigated. The results showed that total dissolution with comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry was more effective than other reported methods. Based on the difference level, 97 compounds were characterized into 4 levels. 1-Methyl-2-pyrrolidinone originating from organic solvent was recognized as level IV and could be determined as the primary difference indicator. The contaminant is mainly attributed to the residuum derived from non-food consumer products. The specific types of contaminants and process parameters of the recycling, such as moisture content, properties of rPET, and temperature, were the potential key factors affecting the presence of semi-volatile compounds of mechanically recycled rPET.

Identification of Nonvolatile Migrates from Food Contact Materials Using Ion Mobility-High-Resolution Mass Spectrometry and in Silico Prediction Tools.

The identification of migrates from food contact materials (FCMs) is challenging due to the complex matrices and limited availability of commercial standards. The use of machine-learning-based prediction tools can help in the identification of such compounds. This study presents a workflow to identify nonvolatile migrates from FCMs based on liquid chromatography-ion mobility-high-resolution mass spectrometry together with in silico retention time (RT) and collision cross section (CCS) prediction tools. The applicability of this workflow was evaluated by screening the chemicals that migrated from polyamide (PA) spatulas. The number of candidate compounds was reduced by approximately 75% and 29% on applying RT and CCS prediction filters, respectively. A total of 95 compounds were identified in the PA spatulas of which 54 compounds were confirmed using reference standards. The development of a database containing predicted RT and CCS values of compounds related to FCMs can aid in the identification of chemicals in FCMs.

Prediction of Collision Cross-Section Values for Extractables and Leachables from Plastic Products.

The use of ion mobility separation (IMS) in conjunction with high-resolution mass spectrometry has proved to be a reliable and useful technique for the characterization of small molecules from plastic products. Collision cross-section (CCS) values derived from IMS can be used as a structural descriptor to aid compound identification. One limitation of the application of IMS to the identification of chemicals from plastics is the lack of published empirical CCS values. As such, machine learning techniques can provide an alternative approach by generating predicted CCS values. Herein, experimental CCS values for over a thousand chemicals associated with plastics were collected from the literature and used to develop an accurate CCS prediction model for extractables and leachables from plastic products. The effect of different molecular descriptors and machine learning algorithms on the model performance were assessed. A support vector machine (SVM) model, based on Chemistry Development Kit (CDK) descriptors, provided the most accurate prediction with 93.3% of CCS values for [M + H]+ adducts and 95.0% of CCS values for [M + Na]+ adducts in testing sets predicted with <5% error. Median relative errors for the CCS values of the [M + H]+ and [M + Na]+ adducts were 1.42 and 1.76%, respectively. Subsequently, CCS values for the compounds in the Chemicals associated with Plastic Packaging Database and the Food Contact Chemicals Database were predicted using the SVM model developed herein. These values were integrated in our structural elucidation workflow and applied to the identification of plastic-related chemicals in river water. False positives were reduced, and the identification confidence level was improved by the incorporation of predicted CCS values in the suspect screening workflow.

Polylactide-Based Films with the Addition of Poly(ethylene glycol) and Extract of Propolis-Physico-Chemical and Storage Properties.

Polymeric films based on polylactide (PLA) with the addition of poly(ethylene glycol) (PEG) and a chloroformic extract of propolis were obtained. In the case of the studied films, polylactide (PLA) played the role of polymeric matrix and poly(ethylene glycol) was used as a plasticizer, while the extract of propolis was incorporated as a compound that could significantly affect the properties of the obtained materials, especially the water vapour permeation rate and the stability of the food products. Moreover, changes in structure, morphology, mechanical and storage properties as well as differences in colour, thickness and transparency after introducing propolis into the PLA-PEG system were determined. Based on the obtained results, it was established that the addition of the chloroformic extract of propolis significantly influences the most important properties taken into account during food packaging. It was also noticed that films with incorporated propolis were characterised by a significant improvement in the water vapour barrier property. Moreover, the obtained results prove that packaging containing a chloroformic propolis extract allow for the maintenance of the quality of the fruit stored for an extended period of time. To summarise, the application of a chloroformic propolis extract enables the formation of packaging materials that extend the shelf life of stored food products.

Analysis of potential migration compounds from silicone molds for food contact by SPME-GC-MS.

Four commercially available silicone cupcake molds have been studied. An evaluation of the post-cure treatment applied to the silicone molds was carried out and the loss of volatile organic compounds after cure treatment was quantified. The two higher quality molds showed losses at the 0.5% (w/w) (recommended by BfR standard), while the two lower quality molds exceeded this limit. The migration studies were carried out using Tenax® as a solid food simulant. The volatile compounds that migrate were identified and quantified using SPME-GC-MS. Up to fourteen silicone oligomers were quantified. When the molds were subjected to post-cure treatment, none of them exceeded the global migration of 10 mg/dm2; while those lower quality molds showed migrations higher than 10 mg/dm2, so their use in contact with food is not recommended.

A Collision Cross Section Database for Extractables and Leachables from Food Contact Materials.

The chemicals in food contact materials (FCMs) can migrate into food and endanger human health. In this study, we developed a database of traveling wave collision cross section in nitrogen (TWCCSN2) values for extractables and leachables from FCMs. The database contains a total of 1038 TWCCSN2 values from 675 standards including those commonly used additives and nonintentionally added substances in FCMs. The TWCCSN2 values in the database were compared to previously published values, and 85.7, 87.7, and 64.9% [M + H]+, [M + Na]+, and [M - H]- adducts showed deviations <2%, with the presence of protomers, post-ion mobility spectrometry dissociation of noncovalent clusters and inconsistent calibration are possible sources of CCS deviations. Our experimental TWCCSN2 values were also compared to CCS values from three prediction tools. Of the three, CCSondemand gave the most accurate predictions. The TWCCSN2 database developed will aid the identification and differentiation of chemicals from FCMs in targeted and untargeted analysis.

Prediction of Collision Cross Section Values: Application to Non-Intentionally Added Substance Identification in Food Contact Materials.

The synthetic chemicals in food contact materials can migrate into food and endanger human health. In this study, the traveling wave collision cross section in nitrogen values of more than 400 chemicals in food contact materials were experimentally derived by traveling wave ion mobility spectrometry. A support vector machine-based collision cross section (CCS) prediction model was developed based on CCS values of food contact chemicals and a series of molecular descriptors. More than 92% of protonated and 81% of sodiated adducts showed a relative deviation below 5%. Median relative errors for protonated and sodiated molecules were 1.50 and 1.82%, respectively. The model was then applied to the structural annotation of oligomers migrating from polyamide adhesives. The identification confidence of 11 oligomers was improved by the direct comparison of the experimental data with the predicted CCS values. Finally, the challenges and opportunities of current machine-learning models on CCS prediction were also discussed.

Guidance in selecting analytical techniques for identification and quantification of non-intentionally added substances (NIAS) in food contact materials (FCMS).

There are numerous approaches and methodologies for assessing the identity and quantities of non-intentionally added substances (NIAS) in food contact materials (FCMs). They can give different results and it can be difficult to make meaningful comparisons. The initial approach was to attempt to prepare a prescriptive methodology but as this proved impossible; this paper develops guidelines that need to be taken into consideration when assessing NIAS. Different approaches to analysing NIAS in FCMs are reviewed and compared. The approaches for preparing the sample for analysis, recommended procedures for screening, identification, and quantification of NIAS as well as the reporting requirements are outlined. Different analytical equipment and procedures are compared. Limitations of today's capabilities are raised along with some research needs.