Preparation of pH-Indicative and Flame-Retardant Nanocomposite Films for Smart Packaging Applications

There is an increasing demand for sustainable and safe packaging technologies to improve consumer satisfaction, reduce food loss during storage and transportation, and track the quality status of food throughout its distribution. This study reports the fabrication of colorimetric pH-indicative and flame-retardant nanocomposite films (NCFs) based on polyvinyl alcohol (PVA) and nanoclays for smart and safe food packaging applications. Tough, flexible, and transparent NCFs were obtained using 15% nanoclay loading (PVA-15) with superior properties, including low solubility/swelling in water and high thermal stability with flame-retardant behavior. The NCFs showed average mechanical properties that are comparable to commercial films for packaging applications. The color parameters were recorded at different pH values and the prepared NCFs showed distinctive colorimetric pH-responsive behavior during the transition from acidic to alkaline medium with high values for the calculated color difference (∆E ≈ 50). The prepared NCFs provided an effective way to detect the spoilage of the shrimp samples via monitoring the color change of the NCFs during the storage period. The current study proposes the prepared NCFs as renewable candidates for smart food packaging featuring colorimetric pH-sensing for monitoring food freshness as well as a safer alternative choice for applications that demand films with fire-retardant properties.

[1]  E. Sharmin,et al.  Introductory Chapter: Flame Retardants , 2019, Flame Retardants.

[2]  C. Nayak,et al.  Aqueous two phase extraction for purification and concentration of betalains , 2007 .

[3]  B. Guo,et al.  Poly(vinyl alcohol)/halloysite nanotubes bionanocomposite films: Properties and in vitro osteoblasts and fibroblasts response. , 2009, Journal of biomedical materials research. Part A.

[4]  N. Liou,et al.  Preparation and Characterization of Polyvinyl Alcohol-Chitosan Composite Films Reinforced with Cellulose Nanofiber , 2016, Materials.

[5]  Vijay Kumar Thakur,et al.  Recent Advances in Graft Copolymerization and Applications of Chitosan: A Review , 2014 .

[6]  J. Grunlan,et al.  Clay-chitosan nanobrick walls: completely renewable gas barrier and flame-retardant nanocoatings. , 2012, ACS applied materials & interfaces.

[7]  P. Guerrero,et al.  Development of active fish gelatin films with anthocyanins by compression molding , 2018, Food Hydrocolloids.

[8]  Lei Jiang,et al.  Understanding the relationship of performance with nanofiller content in the biomimetic layered nanocomposites. , 2013, Nanoscale.

[9]  Wei Wang,et al.  Preparation of cellulose nanofibril/titanium dioxide nanoparticle nanocomposites as fillers for PVA-based packaging and investigation into their intestinal toxicity. , 2019, International journal of biological macromolecules.

[10]  S. Mousavi,et al.  Optimization of crosslinked poly(vinyl alcohol) nanocomposite films for mechanical properties. , 2017, Materials science & engineering. C, Materials for biological applications.

[11]  I. Davies,et al.  PVA, PVA Blends, and Their Nanocomposites for Biodegradable Packaging Application , 2017 .

[12]  K. Marsh,et al.  Food packaging--roles, materials, and environmental issues. , 2007, Journal of food science.

[13]  A. Bassani,et al.  Bio-Based Smart Materials for Food Packaging and Sensors – A Review , 2020, Frontiers in Materials.

[14]  Isabel C.F.R. Ferreira,et al.  Food colorants: Challenges, opportunities and current desires of agro-industries to ensure consumer expectations and regulatory practices , 2016 .

[15]  B. Kuswandi,et al.  Edible pH sensor based on immobilized red cabbage anthocyanins into bacterial cellulose membrane for intelligent food packaging , 2020, Packaging Technology and Science.

[16]  H. Almasi,et al.  Development of a colorimetric pH indicator based on bacterial cellulose nanofibers and red cabbage (Brassica oleraceae) extract. , 2017, Carbohydrate polymers.

[17]  S. Degoutin,et al.  New crosslinked cast films based on poly(vinyl alcohol): Preparation and physico-chemical properties , 2014 .

[18]  Hongqi Dai,et al.  Thermally conductive, super flexible and flame-retardant BN-OH/PVA composite film reinforced by lignin nanoparticles , 2019, Journal of Materials Chemistry C.

[19]  M. Musameh,et al.  Functional Cross‐Linked Electrospun Polyvinyl Alcohol Membranes and Their Potential Applications , 2017 .

[20]  M. Doğan,et al.  Preparation and characterization of poly(vinylalcohol)/modified bentonite nanocomposites , 2013 .

[21]  A. Jiménez,et al.  Active edible films: Current state and future trends , 2016 .

[22]  K. Strawhecker,et al.  Structure and Properties of Poly(vinyl alcohol)/Na+ Montmorillonite Nanocomposites , 2000 .

[23]  Andreas Walther,et al.  Nacre-mimetics with synthetic nanoclays up to ultrahigh aspect ratios , 2015, Nature Communications.

[24]  Kunal Pal,et al.  Preparation and characterization of polyvinyl alcohol-gelatin hydrogel membranes for biomedical applications , 2007, AAPS PharmSciTech.

[25]  K. Raghavarao,et al.  Extraction of anthocyanins from red cabbage and purification using adsorption , 2012 .

[26]  C. O. Mohan,et al.  Smart packaging systems for food applications: a review , 2015, Journal of Food Science and Technology.

[27]  C. Tadini,et al.  Development and evaluation of a novel pH indicator biodegradable film based on cassava starch , 2011 .

[28]  Regiane Ribeiro-Santos,et al.  Application of encapsulated essential oils as antimicrobial agents in food packaging , 2017 .

[29]  H. Wagner,et al.  Layer-by-layer assembled PVA/Laponite multilayer free-standing films and their mechanical and thermal properties , 2011, Nanotechnology.

[30]  Shiji Mathew,et al.  Polyvinyl alcohol/silver nanocomposite films fabricated under the influence of solar radiation as effective antimicrobial food packaging material , 2019, Journal of Polymer Research.

[31]  J. Kerry,et al.  Kinetic desorption models for the release of nanosilver from an experimental nanosilver coating on polystyrene food packaging , 2017 .

[32]  Feiyan Liu,et al.  Flame-retardant polyvinyl alcohol membrane with high transparency based on a reactive phosphorus-containing compound , 2017, Royal Society Open Science.

[33]  Canhui Lu,et al.  Mechanically robust, flame-retardant and anti-bacterial nanocomposite films comprised of cellulose nanofibrils and magnesium hydroxide nanoplatelets in a regenerated cellulose matrix , 2014, Cellulose.

[34]  Ana Cristina Mellinas,et al.  Natural additives and agricultural wastes in biopolymer formulations for food packaging , 2014, Front. Chem..

[35]  Nattinee Bumbudsanpharoke,et al.  Nanoclays in Food and Beverage Packaging , 2019, Journal of Nanomaterials.

[36]  Ana María Jiménez,et al.  Analysis and Antioxidant Capacity of Anthocyanin Pigments. Part II: Chemical Structure, Color, and Intake of Anthocyanins , 2012 .

[37]  S. Ramaswamy,et al.  Smart colorimetric sensing films with high mechanical strength and hydrophobic properties for visual monitoring of shrimp and pork freshness , 2020 .

[38]  Lijuan Wang,et al.  Intelligent poly (vinyl alcohol)-chitosan nanoparticles-mulberry extracts films capable of monitoring pH variations. , 2018, International journal of biological macromolecules.

[39]  Soon-Do Yoon,et al.  Mechanical Properties with the Functional Group of Additives for Starch/PVA Blend Film , 2006 .

[40]  M. E. D. Silva,et al.  Alginate and pectin composite films crosslinked with Ca2+ ions: Effect of the plasticizer concentration , 2009 .

[41]  Nedal Y. Abu-Thabit,et al.  A Flexible Optical pH Sensor Based on Polysulfone Membranes Coated with pH-Responsive Polyaniline Nanofibers , 2016, Sensors.

[42]  J. Gómez-Estaca,et al.  Advances in antioxidant active food packaging , 2014 .

[43]  S. Shaw.  Halogenated Flame Retardants: Do the Fire Safety Benefits Justify the Risks? , 2010, Reviews on environmental health.

[44]  Francesco Stellacci,et al.  Edible sensors for meat and seafood freshness , 2018 .

[45]  C. Pereira,et al.  Flame Retardancy of Fiber-Reinforced Polymer Composites Based on Nanoclays and Carbon Nanotubes , 2014 .

[46]  R. Wrolstad,et al.  Anthocyanins from banana bracts (Musa X paradisiaca) as potential food colorants , 2001 .

[47]  Martin Malmsten,et al.  Delivery systems for antimicrobial peptides. , 2017, Advances in colloid and interface science.

[48]  Tomy J. Gutiérrez,et al.  Bionanocomposite films developed from corn starch and natural and modified nano-clays with or without added blueberry extract , 2017 .

[49]  A. Shrivastav,et al.  Antibacterial activity of poly (vinyl alcohol)—biogenic silver nanocomposite film for food packaging material , 2018, Advances in Natural Sciences: Nanoscience and Nanotechnology.

[50]  T. Steriotis,et al.  Properties of poly(vinyl alcohol)—Bentonite clay nanocomposite films in relation to polymer–clay interactions , 2012 .

[51]  Faridah Salam,et al.  A Colorimetric pH Sensor Based on Clitoria sp and Brassica sp for Monitoring of Food Spoilage Using Chromametry , 2019, Sensors.

[52]  Changyu Shen,et al.  Effects of nanoclays on the thermal stability and flame retardancy of microcellular thermoplastic polyurethane nanocomposites , 2018 .

[53]  Pedro Guerrero,et al.  Valorization of industrial by-products: development of active coatings to reduce food losses , 2015 .

[54]  A. Hussain,et al.  Preparation and characterization of PVA/nanocellulose/Ag nanocomposite films for antimicrobial food packaging. , 2018, Carbohydrate polymers.

[55]  M. Peltzer,et al.  Development of novel nano-biocomposite antioxidant films based on poly (lactic acid) and thymol for active packaging. , 2014, Food chemistry.

[56]  N. L. Vanier,et al.  pH-sensitive films containing anthocyanins extracted from black bean seed coat and red cabbage , 2017 .

[57]  H. Buchtová,et al.  Variability of selected physicochemical characteristics of defrosted whiteleg shrimps (Litopenaeus vannamei) after culinary processing , 2016 .

[58]  P. Allison,et al.  Mechanical, thermal, and microstructural analysis of polyvinyl alcohol/montmorillonite nanocomposites , 2015 .

[59]  S. Ahmad,et al.  Periodate-Modified Gum Arabic Cross-linked PVA Hydrogels: A Promising Approach toward Photoprotection and Sustained Delivery of Folic Acid , 2019, ACS omega.

[60]  G. Titelman,et al.  Discolouration of polypropylene-based compounds containing magnesium hydroxide , 2002 .

[61]  P. Nair,et al.  A biodegradable and biocompatible PVA–citric acid polyester with potential applications as matrix for vascular tissue engineering , 2009, Journal of materials science. Materials in medicine.

[62]  D. Pathania,et al.  Synthesis, characterization and antibacterial activity of biodegradable starch/PVA composite films reinforced with cellulosic fibre. , 2014, Carbohydrate polymers.

[63]  W. Witte,et al.  Antibiotic resistance. , 2013, International journal of medical microbiology : IJMM.

[64]  A. Netravali,et al.  Halloysite nanotube reinforced biodegradable nanocomposites using noncrosslinked and malonic acid crosslinked polyvinyl alcohol , 2013 .

[65]  L. Kong,et al.  Decomposition properties of PVA/graphene composites during melting-crystallization , 2015 .

[66]  R. Wrolstad,et al.  Characterization of Red Radish Anthocyanins , 1996 .

[67]  D. C. Morgan,et al.  Polymer film packaging for food: An environmental assessment , 2013 .

[68]  A. Mohamad,et al.  Properties and Applications of Polyvinyl Alcohol, Halloysite Nanotubes and Their Nanocomposites , 2015, Molecules.

[69]  W. Kujawski,et al.  Chemically and Thermally Crosslinked PVA-Based Membranes: Effect on Swelling and Transport Behavior , 2019, Polymers.

[70]  Hasmukh A. Patel,et al.  Nanoclays for polymer nanocomposites, paints, inks, greases and cosmetics formulations, drug delivery vehicle and waste water treatment , 2006 .

[71]  A. R. Monteiro,et al.  A novel colorimetric indicator film based on chitosan, polyvinyl alcohol and anthocyanins from jambolan (Syzygium cumini) fruit for monitoring shrimp freshness. , 2020, International journal of biological macromolecules.

[72]  M. Tabatabaei,et al.  Encapsulation of Rosmarinus officinalis essential oils in chitosan-benzoic acid nanogel with enhanced antibacterial activity in beef cutlet against Salmonella typhimurium during refrigerated storage , 2017 .

[73]  Luiz H. C. Mattoso,et al.  Improved barrier and mechanical properties of novel hydroxypropyl methylcellulose edible films with chitosan/tripolyphosphate nanoparticles , 2009 .

[74]  Ricardo Stefani,et al.  Chitosan/corn starch blend films with extract from Brassica oleraceae (red cabbage) as a visual indicator of fish deterioration , 2015 .

[75]  Philippe Dubois,et al.  New prospects in flame retardant polymer materials: From fundamentals to nanocomposites , 2009 .

[76]  Lijuan Wang,et al.  Preparation of a visual pH-sensing film based on tara gum incorporating cellulose and extracts from grape skins , 2016 .

[77]  Silvana Andreescu,et al.  Colorimetric paper bioassay for the detection of phenolic compounds. , 2012, Analytical chemistry.

[78]  S. Ifuku,et al.  Sustainable Chitin Nanofibrils Provide Outstanding Flame-Retardant Nanopapers. , 2019, Biomacromolecules.

[79]  H. Ismail,et al.  Tensile, Swelling, and Oxidative Degradation Properties of Crosslinked Polyvinyl Alcohol/Chitosan/Halloysite Nanotube Composites , 2013 .

[80]  Yu Dong,et al.  Biodegradable and Water Resistant Poly(vinyl) Alcohol (PVA)/Starch (ST)/Glycerol (GL)/Halloysite Nanotube (HNT) Nanocomposite Films for Sustainable Food Packaging , 2019, Front. Mater..

[81]  Yu-Zhong Wang,et al.  Robust and fire retardant borate-crosslinked poly (vinyl alcohol)/montmorillonite aerogel via melt-crosslink , 2017 .

[82]  P. Hornsby,et al.  Thermal decomposition behaviour of polyamide fire-retardant compositions containing magnesium hydroxide filler , 1996 .

[83]  H. Sheen,et al.  Effects of added nanoclay for styrene-acrylic resin on intumescent fire retardancy and CO/CO2 emission , 2019, Journal of Coatings Technology and Research.

[84]  Mohammad A Al Karaawi,et al.  Antimicrobial potential of bacteriocins: in therapy, agriculture and food preservation. , 2017, International journal of antimicrobial agents.

[85]  J. Rhim,et al.  Anthocyanin food colorant and its application in pH-responsive color change indicator films , 2020, Critical reviews in food science and nutrition.

[86]  D. Vodnar,et al.  Applicability of Agro-Industrial By-Products in Intelligent Food Packaging , 2020, Coatings.

[87]  K. Pilarski,et al.  Functional polypropylene composites filled with ultra-fine magnesium hydroxide , 2014 .

[88]  T. Jesionowski,et al.  Recent development in the synthesis, modification and application of Mg(OH)(2) and MgO: A review , 2017 .

[89]  Henrik Stapelfeldt,et al.  Light and heat sensitivity of red cabbage extract in soft drink model systems , 2001 .

[90]  A. Chiralt,et al.  Physical, structural and antimicrobial properties of poly vinyl alcohol-chitosan biodegradable films , 2014 .

[91]  Wei Liu,et al.  Properties and Flammability of Electrospun PVA and PVA/Laponite® Membranes , 2010 .

[92]  Azman Hassan,et al.  On the use of magnesium hydroxide towards halogen-free flame-retarded polyamide-6/polypropylene blends , 2012 .

[93]  M. Mannan,et al.  Fire reaction properties of polystyrene-based nanocomposites using nanosilica and nanoclay as additives in cone calorimeter test , 2018, Journal of Thermal Analysis and Calorimetry.