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  4. REACTIVE EXTRUSION OF ACTIVE AND INTELLIGENT MATERIALS FOR PERFORMANCE IN TARGET APPLICATIONS

REACTIVE EXTRUSION OF ACTIVE AND INTELLIGENT MATERIALS FOR PERFORMANCE IN TARGET APPLICATIONS

File(s)
Redfearn_cornellgrad_0058F_14009.pdf (4.51 MB)
Permanent Link(s)
http://doi.org/10.7298/34rw-gh67
https://hdl.handle.net/1813/115738
Collections
Cornell Theses and Dissertations
Author
Redfearn, Halle
Abstract

The USDA estimates that nearly one-third of the global food supply goes to waste, resulting in greenhouse gas emissions and depletion of natural resources. Active and intelligent packaging can be used to mitigate microbial spoilage and physiochemical degradation through incorporation of functional compounds in the packaging matrix. Nonmigratory active packaging offers advantages through covalent immobilization of active ligands, mitigating migration of additives into the product matrix. These materials can be subject to the regulations and labeling requirements of food contact materials rather than direct additives, satisfying consumer desires for clean label products and facilitating commercial translation. Reactive extrusion is a solvent-free, continuous, and efficient manufacturing method that can improve industrial scalability of nonmigratory active packaging. Therefore, the aim of this research was to synthesize nonmigratory active and intelligent packaging through reactive extrusion and demonstrate performance in conditions reflective of real food applications. With that objective in mind, we grafted curcumin to polypropylene (PP-g-Cur) and characterized interfacial, optical, and functional properties. Additionally, poly(lactic acid) was covalently modified with curcumin (PLA-g-Cur) to demonstrate the translation of this technology to bioderived and biodegradable polymers, mitigating use of petroleum-based plastics through value-added sustainable materials. Both PP-g-Cur and PLA-g-Cur materials demonstrated curcumin migration below the EU migratory limit (0.10 mg/cm2) in aqueous, hydrophilic, acidic, and fatty food systems, with a maximum migration of 0.011 mg/cm2 and < 0.000625 mg/cm2 respectively, confirming covalent modification of packaging materials. Both materials blocked 93% of UV light transmittance while retaining 64% and 89% visible light transmittance for modified PP and PLA, respectively, demonstrating the potential of functionalized polymers to inhibit photo degradation of foods and beverages while allowing consumers and manufacturers complete visibility of the packaged product. Furthermore, the preserved mechanical, water barrier, and wettability properties of PLA-g-Cur films compared to native PLA demonstrated inhibition of thermal degradation of the polymer backbone during radical processing, which could be attributed to antioxidant stabilization by curcumin. These results were supported by the increase in thermal stability of curcumin-based films, demonstrating an ~20°C increase in decomposition temperature compared to native PLA. Modified materials were evaluated for radical scavenging activity in DPPH and ABTS assays, in which PP-g-Cur films exhibited 11.71 ± 3.02 TroloxEq(nmol/cm2) and 3.18 ± 1.04 TroloxEq(nmol/cm2), respectively. In contrast, PLA-g-Cur films exhibited 2.52 ± 0.64 TroloxEq (nmol/cm2) DPPH radical scavenging and 0.49 ± 0.16 TroloxEq (nmol/cm2) ABTS radical scavenging activity. These assays supported the slow hydrogen atom transfer (HAT) radical scavenging mechanism of curcumin under aqueous conditions (ABTS) and the fast sequential proton loss electron transfer (SPLET) mechanism under organic conditions (DPPH). Reduced radical scavenging capacity for PLA materials in the DPPH assay could be attributed to differences in incubation solvent, since, compared to PP, PLA materials could not be evaluated under the harsh conditions of pure ethanol. Indeed, the kinetics of radical scavenging mechanisms are strongly dependent on ionization potential of solvents and incubation time, emphasizing the importance of applications studies in measuring antioxidant capacity under relevant conditions. PP-g-Cur films and free curcumin solutions (20 μg/mL and 200 μg/mL) demonstrated no significant inhibition of E. coli or L. monocytogenes growth, suggesting lack of antibacterial activity against the tested Gram-negative and Gram-positive strains. These results contrast with published reports on curcumin-based antimicrobial packaging and the reported minimum inhibitory concentration of free unmodified curcumin, highlighting the importance of applications relevant test systems in evaluating functional performance. These films were also tested against total viable count (TVC) of shrimp during storage in functionalized packaging. However, PP-g-Cur packaging supplied no statistical shelf-life extension compared to control PP material. Finally, the intelligent properties of modified PP and PLA were measured by exposure to both ammonia vapor and shrimp spoilage. All materials demonstrated visible and quantifiable color change in response to ammonia and only quantifiable color change in response to shrimp spoilage, underscoring the importance of applications studies in measuring the performance of materials in real food systems. This research demonstrates the antioxidant and intelligent modification of packaging materials through reactive extrusion, advancing the capabilities of functional materials through industrially scalable manufacturing methods

Description
229 pages
Date Issued
2023-12
Keywords
Active
•
Antioxidant
•
Biodegradable
•
Intelligent
•
Packaging
•
Reactive Extrusion
Committee Chair
Goddard, Julie
Committee Member
Snyder, Abigail
Coates, Geoffrey
Degree Discipline
Food Science and Technology
Degree Name
Ph. D., Food Science and Technology
Degree Level
Doctor of Philosophy
Type
dissertation or thesis
Link(s) to Catalog Record
https://newcatalog.library.cornell.edu/catalog/16454731

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