EW: “ Mass spectrometry in support of the environment, food, and health interaction and disease” Characterization of non-intentionally added substances in food packaging nanofilms by analytical approaches based on HRMS María Dolores Hernando Guil
ERANET SUSFOOD: Sustainable food production Title: Improved resource efficiency throughout the post-harvest chain of fresh-cut fruits and vegetables The Fruit and Vegetable Sector is an important segment of the European Agroindustry, with a weight of about 18% of the value of EU agricultural production Fresh cut products: This sector is a major user of water; about 70% of the water consumption is for cleaning and decontamination Proper disinfection technology is required to ensure microbial safety avoiding at the same time the formation of disinfection by-products such as chlorinated chemicals Growth of microorganisms is favoured by cutting/slicing, which remove the natural barrier The quality of fresh-cut products also depends critically on packaging technology, which has to preserve good appearance and flavour, as well . as meet safety requirement Context
Exporters of food products. Water stressed areas, Mediterranean basin. 30.000 Ha 2.900.000 t 1.573.131.000 € Context
washing technologies and packaging materials Resource-efficient food processing: • Water savings • Reduce use of chemicals • Valorization of food residues Critical stages Food quality & safety: • Extension of shelf-life • Avoid harmful disinfection by-products • Good appearance and flavour Context
These goals are to be achieved by the combination of the following nanotechnology- based solutions for fresh-cut products : Washing & desinfection: Introduction of new membranes with biocidal functionality to allow operating in closed loop and the reduction or elimination of chemical disinfectants. Development of a hybrid technology in which the use of ozone combined with ultrafiltration using ceramic membranes with (eventually) active surface. Shelf-life improvement: Development of packaging materials with antimicrobial components, to increase shelf life and, to reduce wastes. Context
Institute for Process Engineering and Packaging Partners
Institute of chemistry and technology of polymers CEREAL approach To design the new packaging materials mainly monolayers by directing the structure and properties of the polymer matrix during crystallisation taking into consideration the material characteristics, the nanoparticles shape (rod shape and plate-like ), the conditions of the manufacturing packaging process (extrusion and blowing). To develop materials having improved physical, mechanical, barrier and antibacterial activity properties that contribute to extend shelf-life and quality of the food Development of industrial scale processes for the synthesis and the post- treatments of metal oxide nano-powders, and fabrication of nanocomposites by melt processing. CEREAL approach for packaging materials
New Food Packaging Packaging m aterials Nanomaterials (FPN) Assessment Selection Assessment Optimization Quality/ Safety of Food; M atrices/ Nanoparticles Packaging properties : Recyclibility/ Degradability Processing Properties 1. Development 2. Optimization of the processing conditions 3. Assessment of properties of the materials : filler/ matrix interactions, thermal stability and rheological behaviour of the nanocomposites, optical properties, UV- absorption and degradation upon illumination, thermal and mechanical properties and processability 4. Evaluation of new materials M igration of substances Antimicrobial activity, shelf life prolongation and impact on fresh-cut produce quality. Relevant test strains: Institute for Process Engineering and Packaging Listeria monocytogenes, E. coli, Pseudomonas fluorescens, Bacillus subtilis (spores) and Aspergillus niger (spores). Development and evaluation of packaging materials
Polypropylene –based nanocomposites (PP)-based nanocomposites functionalized with zinc oxide nanoparticles (ZnO NPs) and polylimonene (PL) PPR3221 (wt%) PL (wt%) ZnONPs (wt%) Composition 100 0 0 PPR 95 5 0 PPR/PL 95/5 97 0 3 PPR/ZnO 97/3 92 5 3 PPR/PL/ZnO 92/5/3 Biopolymer metal oxide nanocomposites Nanocomposites :Poly(lactic acid) (PLA), PL, ZnO NPs, and ZnONPs coated with stearic acid mZnONPs PLA (wt%) PL (wt%) ZnONPs (wt%) Code (wt%) 100 - - - PLA 97 - 3 - PLA/ZnO3% 95 - 5 - PLA/ZnO5% 93 - - 3 PLA/mZnO3% 95 - - 5 PLA/mZnO5% 85 10 5 - PLA/PL/ZnO Composition of packaging materials
Packaging m aterials No n-inte ntio na lly a dde d sub sta nc e s (NIAS) a re c o mpo unds pr ia ls (F CM), not e se nt in food c onta c t ma te r a dde d fo r a te c hnic a l purpo se during ma nufa c ture . Re le va nt issue fo r the food pa c ka g ing industr y itie s - b ulk ma te ria ls Impur me dia te s fo rme d during ma nufa c ture Re a c tion inte r a da tion o f pro duc ts. De g r Conta mina nts NIAS-Non-intentionally added substances
LC-HRMS Database Characterization Screening analysis
Test conditions for overall migration Simulant Abbreviation Ethanol 10% (v/v) Simulant A Acetic acid 3% (w/v) Simulant B Ethanol 20% (v/v) Simulant C Ethanol 50% (v/v) Simulant D1 Vegetable Oil Simulant D2 Modified polyphenylene oxides, particle Simulant E for dry foods size 60-80 mesh, pore size 200 nm Migration test conditions
Framework Regulation (EC) No 1935/2004 (EC) No 2023/2006 Good Manufacturing Practice 2007/42/EC 84/500/EEC 1895/2005/EC (EC) No 450/2009 93/11/EEC Regenerated Ceramics, BADGE/BFDGE/ Active and intelligent Nitrosamines cellulose film as amended NOGE materials and nitrosatable substances Plastics (EU) No 321/2011 (EU) No 10/2011 (EC) No 282/2008 (EU) No 284/2011 restriction of use of Plastics Implementation Recycled plastics polyamide and Bisphenol A in plastic Measure, as melamine plastic infant feeding bottles amended/corrected kitchenware EU legislation
LC-QTOF-MS Qualitative analysis full-scan Fragmentation Screening analysis
LC-QTOF-MS Qualitative analysis full-scan Fragmentation Screening analysis
Simulation of fragmentation Tentative assignation of fragment ions
LC-QTOF-MS Polypropylene –films Characterization of NIAS
Da ta proc e ssing L C- QOrbitra p- MS ilte rs: inte nsity sig na ls: 1x10 5 F ma ss e rro r : 5 p p m (A) PLA/ZnO (B) PLA/ZnO (B) PLA/PL/ZnO (B) control (A) control principal component analysis (A) PLA/PL/ZnO Screening analysis
str uc tur al e luc idation
N,N- Die thyldode c a na mide
T e nta tive fr a g me nta tion pa thwa y N,N- Die thyldode c a na mide O OH O H 2 rH C +H N N N m/z 256.2635 m/z 256.26 m/z 116.11 m/z 116.1070 C 16 H 34 NO C 6 H 14 NO rH B OH rH B N H 2 m/z 88.08 m/z 88.0757 C 4 H 10 NO O OH OH rH B +H N N N m/z 256.2635 m/z 102.0913 m/z 102.09 m/z 256.26 C 16 H 34 NO C 5 H 12 NO
L C-QOr bitr ap-MS Biopolymer metal oxide nanocomposites PRECURSOR ION FRAGM ENT IONS accurate formula mass accurate mass formula Rt mass value proposed deviation* mass value deviation* Candidate compounds proposed [M +H] + [M +H] + (ppm) ( m/ z ) (ppm/ mDa) 11.7 256.2635 C 16 H 34 NO -1.2 116.1070 C 6 H 14 NO -2.6 / 0.3 N,N-Diethyldodecanamide 102.0913 C 5 H 12 NO -1.4 / 0.1 11.9 331.2843 C 19 H 39 O 4 -1.0 313.2737 C 19 H 37 O 3 -2.3 / 0.7 1-Palmitoylglycerol 99.0441 C 5 H 7 O 2 -5.0 / 0.5 12.2 359.3156 C 21 H 43 O 4 -0.7 341.3050 C 21 H 41 O 3 -0.6 / 0.2 Glycerol stearate 285.2788 C 18 H 37 O 2 -2.0 / 0.6 12.5 310.3104 C 20 H 40 NO -0.9 268.2999 C 18 H 38 N 0.2 / 0.1 N-[(9Z)-9-Octadecen-1-yl]acetamide 210.1852 C 13 H 24 NO -3.4 / 0.7 Characterization of NIAS; use of standards. Simulant B: 2.7 – 7.6 ng.g -1
GC-HRMS De c o nvo lutio n • Min. inte nsity sig na ls: 2e 6 • Ma ss E rro r (MS) : 5 ppm • Sig na l to no ise : 10 • Io n o ve rla p windo w: 98 • RT Alig nme nt: 10 se c Ma ss spe c tra l lib ra ry (250.000 c he mic als) • # T o p ma tc he s: 4 • SI T hr e shold: 800 • Sc or e T hr e shold: 95 Cha ra c te riza tio n Screening analysis
GC-QTOF-MS Cha ra c te riza tion NIAS in PP films candidate structure Phthalates of the parent compound
Fragmentation pattern of phthalates Diethyl Phthalate Phthalic acid, butyl undecyl ester OH O O 177.05462 223.09649 (m/z) (m/z) Bis(2-ethylhexyl) phthalate Benzyl butyl phthalate 167.0339 206.09375 Not confirmed 279.1509 238.06245 (m/z) (m/z)
GC-QOr bitr ap-MS 165.0910 430.3805 α - T oc ophe r ol a c e ta te Full MS [50-550 Da] 165.0909 C 10 H 13 O 2 430.3801 C 29 H 50 O 2 472.3907 NIST 165.0909 0.109 430.3801 0.871
GC-QOr bitr ap-MS PL A films PRECURSOR ION FRAGM ENT IONS accurate mass formula accurate formula candidate Rt mass value SI* score* HRF* deviation* proposed mass value ( m/ z ) proposed compounds (m/ z) (ppm/ mDa) 9.8 300.1567 C 15 H 24 O 6 827 96.6 98.0 113.0597 C 6 H 9 O 2 1.4 / 0.2 tripropylene glycol 55.0178 C 3 H 3 O 1.6 / 0.1 diacrylate 11.0 294.3281 C 21 H 42 820 96.4 99.0 69.0699 C 5 H 9 0.5 / 0.03 10-Heneicosene 83.0855 C 6 H 11 0.3 / 0.02 29.6 472.3911 C 31 H 52 O 3 898 97.5 99.8 430.3801 C 29 H 50 O 2 0.9 / 0.4 alpha-Tocopherol 165.0909 C 10 H 13 O 2 0.8 / 0.1 acetate Characterization of NIAS
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