Development of an Innovative Oxygen Scavenging : A journey from the Idea to the Product

Prof. Dr. Selcuk Yildirim Zürich University of Applied Sciences Institute of Food and Beverage Innovation

1 Zurich University of Applied Sciences

• Institute of Biotechnology

• Institute of Chemistry and Biological Chemistry

• Institute of Food and Beverage Innovation

• Institute of Natural Resource Sciences

• Institute of Applied Simulation

Zurich University of Applied Sciences

2 Department of Life Sciences and Facility Management Center for Food Processing and Packaging

Innovative and sustainable processes and packaging development for optimal food quality and safety

Prof. Dr. Selcuk Yildirim

Dr. Nadina Dr. Jürg Beatrice Stella Dr. Janice Dr. Claudia Dr. Mathias Philippe Ramona Patrick Näf Müller Buchli Baumer Cook Sych Müller Kinner Geiger Rüegg

Prof. Dr. Nadine Susanna Bettina Annica Barbara Pius Meier

Selcuk Yildirim Rüegg Miescher Röcker Jucker Beck 3 Research Fields

Innovative Biopackaging Development and Packaging Materials Optimization of simulations Packaging Processes

- Shelf life simulations - - Biobased materials - packaging - Optimal packaging - Biodegradable - Antimicrobial films design materials - Controlled atmosphere - Oxygen Scavengers - Optimization of - packaging - Moisture Scavengers packaging development - Integration in food - Optimization of processing - High barrier materials storage cond.

- New packaging

processes

4 Content

1. Active Packaging

2. Development of Palladium based Oxygen Scavenging Label

 Idea

 Development

 Industrialisation

3. Applications

5 Content

1. Active Packaging

2. Development of Palladium based Oxygen Scavenging Label

 Idea

 Development

 Industrialisation

3. Applications

6 Active Packaging

Active Packaging: „..designed to deliberately incorporate components that would release or absorb substances into or from the packaged food or the environment surrounding the food“ Regulation (EC) No 1935/2004 A

* Yildirim S. Active Packaging for Food Biopreservation, in Protective Cultures, Antimicrobial Metabolites and Bacteriophages for Food and Beverage Biopreservation, Lacroix C (ed). Woodhead Publishing: Cambridge, 2011; 460-489. 7 Yildirim S., Röcker B., Pettersen M.K., Nygaard Julie N., Ayhan Z., Rutkaite R., Radusin T., Suminska P., Marcos B., Coma V., Active Packaging for Food Applications, Comprehensive Reviews in Food Science and Food Safety, 2018, 17: 165–199.

Vilela C., Kurek M., Hayouka Z., Röcker B. Yildirim S., Antunes M. D. C. Nygaard J. N. Pettersen M. K., Freirea, C. S. R. A concise guide to active agents for functional8 , Trends in Food Science & Technology, 2018, 80, 212-222 Content

1. Active Packaging

2. Development of Palladium based Oxygen Scavenging Label

 Idea

 Development

 Industrialisation

3. Applications

9 Oxidation of Food

Growth of aerobic Oxidation O2 microorganisms

Discoloration Moulds and other and rancidity Spoilage organisms

Degraded appearance Impaired sensory Lost freshness, unpleasant and nutritional value qualities taste and aroma

Reduced Shelf life 10 Modified Atmosphere Packaging

- Gas Flushing

- Modified Atmosphere Packaging

Up to 3-5% residual oxygen11 Oxygen Scavengers

12 Palladium-based Oxygen Scavenger

1. 2. step 3. step 4. step H O 2 H step O O H2 O O O O O * H O H H H H O Pd Pd Pd Pd Pd

Nyberg C, Tengstål CG. Adsorption and reaction of water, oxygen, and hydrogen on Pd(100): Identification of adsorbed hydroxyl and implications for the catalytic H2–O2 reaction. The Journal of Chemical Physics 1984. 80(7): pp. 3463-3468, DOI: 10.1063/1.447102. 13 Pd Deposition Thickness

2.5 100 nm 50 nm 2.0 10 nm 5 nm

1.5

1.0

0.5

Oxygen Concentration [%] Concentration Oxygen

0.0 0 2 4 6 8 10 12 14 16 18 20 Time [h] PET/Pd

14 Patent: EP2236284, 2010, S. Yildirim, J.C-Jammet, W. Lohwasser Pd Coated Surface Analysis

100 nm 50 nm 20 nm 10 nm 5 nm

• Pd coated surfaces were analyzed using scanning electron microscopy

• 100 nm to 20 nm surface is flat

• A sponge like structure in 10 and 5 nm sample

• 10 nm sample is more dense than 5 nm sample

15 Palladium-based Oxygen Scavenging Label

Pd H2 + ½ O2 H2O

Yildirim S, Jammet JC, Lohwasser W. Multi-layer film. European Patent, 2236284, 6/10/2010. Effect of Substrate on the Oxygen Scavenging Activity

Oxygen Scavenger

Palladium Substrate vs.

Palladium SiOx Substrate

Yildirim S, Röcker B, Rüegg N, Lohwasser W. Development of Palladium-based Oxygen Scavenger: Optimization of Substrate and Palladium Layer Thickness. Packaging17 Technology and Science 2015. 28(8): pp. 710-718 Effect of Palladium Deposition Thickness on the Oxygen Scavenging Activity

Oxygen Scavenger

Palladium

SiOx Substrate

Best Substrates: • PET • PET/AlOx • PLA • LDPE • oPP

18

18 Effect of Coating Substrate on the Oxygen Scavenging Activity

Oxygen Scavenger

Palladium

SiOx Substrate

Best Substrates: • PET • PET/AlOx • PLA • LDPE • oPP

19 Oxygen Scavenging Activity in the Presence of Food

2,2

2,2

2,0 2,0 1,8 1,8 1,6 1,6 1,4 1,4 1,2 1,2 1,0 1,0 0,8 0,8 0,6

0,6 Oxygen concentration / vol.% vol.% / concentration Oxygen

Oxygen concentration / vol.% vol.% / concentration Oxygen 0,4 0,4 0,2 0,2 0,0 0,0 0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160 Time / min Time / min Empty Packaging Ham Empty Packaging Potato Chips Roast Beef Cheese Potato Powder Milk Powder Peanuts Par-baked Buns Cereals Röcker B., Rüegg N., Glöss A. N., Yeretzian C., Yildirim S., Inactivation of Palladium-based Oxygen Scavenger by Volatile Sulphur Compounds Present in the20 Headspace of Packaged Food, Packaging Technology and Science, 2017, 30, 8, 427-442 Catalyst Poisoning by Volatile Sulphur compounds (VSCs)

Maxted EB. The Poisoning of Metallic Catalysts, in Advances in Catalysis, Frankenburg WG, Komarewsky VI, Rideal EK, Emmett PH, Taylor HS (ed). Academic Press,

1951 21

Bartholomew CH. Mechanisms of catalyst deactivation. Applied Catalysis A: General 2001. Volatile Sulphur Compounds (VSCs) in Foods

Beef Volatile sulphur compounds Pork Potato Roasted (Roast Cheese Bread (VSCs) (Ham) Chips Peanuts Beef)

Dimethyl sulphide (DMS) x x x x x

Dimethyl disulphide (DMDS) x x x x x x

Dimethyl trisulphide (DMTS) x x x x x

Furfuryl thiol (FFT) x x x x

Methional (MET) x x x x x x 22 Pd Scavenging Activity in the Presence of VSC

(1) Tray

(2) Palladium-coated film

(3) Sensor spot

(4) petri dish + VSC-Solution

(5) Lidding film

23 Pd Scavenging Activity in the Presence of VSC

Buffer solution without VSC Buffer solution without VSC

2,2 2,2 DMS 1E-07 mmol/l DMS 1E-06 mmol/l 2,0 DMDS 1E-08 mmol/l 2,0 DMDS 1E-07 mmol/l 1,8 DMTS 1E-07 mmol/l 1,8 DMTS 1E-06 mmol/l 1,6 FFT 1E-06 mmol/l 1,6 FFT 1E-05 mmol/l MET 1E-05 mmol/l MET 1E-04 mmol/l 1,4 1,4 1,2 1,2 VSC concentration 1,0 1,0

Oxygen concentration / vol.% vol.% / concentration Oxygen increase by 1 order

0,8 of magnitude vol.% / concentration Oxygen 0,8 0,6 0,6 0,4 0,4 0,2 0,2 0,0 0,0 0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160 Time / min Time / min

Röcker B., Rüegg N., Glöss A. N., Yeretzian C., Yildirim S., Inactivation of Palladium-based Oxygen Scavenger by Volatile Sulphur Compounds24 Present in the Headspace of Packaged Food, Packaging Technology and Science, 2017, 30, 8, 427-442 Determination of Minimum Inhibitory Concentrations Range of VOC

VSC Buffer Solutions VSC Buffer Solutions

2,2 2,2 2,0 2,0 1,8 1,8 1,6 1,6 1,4 1,4 1,2

Oxygen concentration / vol.% vol.% / concentration Oxygen 1,2

1,0 vol.% / concentration Oxygen 1,0 0,8 Head Space Analysis 0,8 0,6 0,6 0,4 0,4 0,2 0,2 0,0 0 20 40 60 80 100 120 140 160 Food Products 0,0 2,2 0 20 40 60 80 100 120 140 160 Time / min 2,0 Time / min 1,8 1,6 1,4 1,2 1,0

Oxygen concentration / vol.% vol.% / concentration Oxygen 0,8 0,6 0,4 0,2 0,0 0 20 40 60 80 100 120 140 160 Time / min Empty Packaging Ham 25 Roast Beef Cheese Peanuts Par-baked Buns

25 Minimum Inhibitory Concentration Range of VOC

40 37,5 35 DMS 32,5 30

27,5

25 22,5 FFT 20

17,5 Absolute concentration / ppbv / concentration Absolute 15 DMDS 12,5 10 7,5 Methional 5 2,5 DMTS 0 Volatile Sulphur Compounds 26 27 28 Further VSC

29 Label Development

1. Step: 2. Step: SiOx/Pd-Coating Partial application of Pd SiOx

Adhesive Pd Pd SiOx SiOx PET PET PET Adhesive* Adhesive* Adhesive* Silicone Silicone Silicone PET PET PET

3. Step: 4. Step: Application of FCM Punching

FCM FCM FCM Adhesive Adhesive Adhesive Pd AL Pd Pd SiOx SiOx SiOx PET PET PET Adhesive* Adhesive* Adhesive* Silicone Silicone carrier PET PET Silicone PET

30 Content

1. Research Group Food Packaging @ZHAW

2. Active Packaging

3. Development of Palladium based Oxygen Scavenging Label

 Idea

 Development

 Industrialisation

4. Applications 31 Use of palladium based oxygen scavenger to prevent discoloration of ham

Hutter S., Rüegg N., Yildirim S., Use of palladium based oxygen scavenger to prevent discoloration of ham, Food Packaging and Shelf Life, 2016, 8, 56-62

32 Use of Palladium based Oxygen Scavenger to Prevent Oxidation in Linseed Oil

33 Faas N., Röcker B., Smrke S., Yeretzian C.,Yildirim S. Prevention of lipid oxidation in linseed oil using a palladium-based oxygen scavenging film, Food Pacakging and Shelf Life, to be submitted Use of Palladium based Oxygen Scavenger to Prevent Mould Growth of Bakery Products

Rüegg N, Röcker B. Yildirim S. Use of palladium based oxygen scavenger to prevent mould growth of bakery product. Manuscript in preperation 34 Acknowledgements

Research Group Food Packaging  Nadine Rüegg  Bettina Röcker  Barbara Beck  Simon Hutter  Sanzio Rombini  Maria Ebenreth  Nicole Faas

Research Group Analytical Technologies  Samo Smrke  Alexia Glöss  Chahan Yeretzian

35 Thank you very much for your attention

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