Emulsion-based coatings for preservation of meat and related products
Abstract
Tomas Bata University in Zlin, TBU: IGA/FT/2023/007; Univerzita Palackého v Olomouci: IGA_PrF_2023_024
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Citation: Gautam, S.; Lapˇcík, L.; Lapˇcíková, B.; Gál, R. Emulsion-Based Coatings for Preservation of Meat and Related Products. Foods 2023,12, 832. https://doi.org/10.3390/ foods12040832 Academic Editor: JoséManuel Benito Received: 2 January 2023 Revised: 6 February 2023 Accepted: 14 February 2023 Published: 15 February 2023 Copyright: © 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). foods Review Emulsion-Based Coatings for Preservation of Meat and Related Products Shweta Gautam 1, Lubomír Lapˇcík1,2,* , Barbora Lapˇcíková1,2 and Robert Gál1 1Department of Foodstuff Technology, Faculty of Technology, Tomas Bata University in Zlin, Nam. T.G. Masaryka 275, 762 72 Zlin, Czech Republic 2Department of Physical Chemistry, Faculty of Science, Palacky University in Olomouc, 17. Listopadu 12, 771 46 Olomouc, Czech Republic *Correspondence: [email protected] Abstract: One of the biggest challenges faced by the meat industry is maintaining the freshness of meat while extending its shelf life. Advanced packaging systems and food preservation techniques are highly beneficial in this regard. However, the energy crisis and environmental pollution demand an economically feasible and environmentally sustainable preservation method. Emulsion coatings (ECs) are highly trending in the food packaging industry. Efficiently developed coatings can preserve food, increase nutritional composition, and control antioxidants’ release simultaneously. However, their construction has many challenges, especially for meat. Therefore, the following review focuses on the essential aspects of developing ECs for meat. The study begins by classifying emulsions based on composition and particle size, followed by a discussion on the physical properties, such as ingredient separation, rheology, and thermal characteristics. Furthermore, it discusses the lipid and protein oxidation and antimicrobial characteristics of ECs, which are necessary for other aspects to be relevant. Lastly, the review presents the limitations of the literature while discussing the future trends. ECs fabricated with antimicrobial/antioxidant properties present promising results in increasing the shelf life of meat while preserving its sensory aspects. In general, ECs are highly sustainable and effective packaging systems for meat industries. Keywords: emulsion coatings; rheology; phase separation; thermal analysis; antimicrobial agents; meat 1. Introduction Fresh meat is a highly perishable food due to its complex composition and animal variety (Table 1). It attracts a wide variety of microbes and pathogens. Its freshness is impacted by the slaughtering conditions, gut microflora, storage parameters (moisture, atmospheric oxygen, light, and temperature) and internal enzymatic reactions of the animal [1]. Table 1. Composition of meat from different animals. Meat Nutritional Composition (per 100 g) Energy (kJ/100 g) References Water Protein Fat Ash Beef (lean) 75.0 22.3 1.8 1.2 485 [2] Beef carcass 54.7 16.5 28.0 0.8 1351 Pork (lean) 75.1 22.8 1.2 1.0 469 Pork carcass 41.1 11.2 47.0 0.6 1975 Veal (lean) 76.4 21.3 0.8 1.2 410 Chicken 75.0 22.8 0.9 1.2 439 Mutton carcass 73.9 20.2 4.86 1.18 524 [3] Chevon carcass 75.6 20.3 3.68 4.09 - [4] Buffalo carcass 76.3 20.4 1.37 0.98 724 [5] Foods 2023,12, 832. https://doi.org/10.3390/foods12040832 https://www.mdpi.com/journal/foods
Foods 2023,12, 832 2 of 15 Meat decay is a rapid process and begins as soon as the animal is slaughtered. The three main spoilage mechanisms are microbial, enzymatic, and lipid oxidation spoilage. The skin, intestinal tract, and the slaughtering and storage conditions of the animal are foremost sources of microbial spoilage. Spoilage bacteria most found include species of Pseudomonas and Streptococcus, among other classes, whereas the most commonly found spoilage molds are Cladosporium and Sporotrichum, among other classes. The intestinal enzymes that chemically combine with organic compounds and initiate deterioration reactions in meat cause enzymatic spoilage [ 6 , 7 ]. Lipid autoxidation begins when blood circulation and metabolic processes cease. Meat preservation aims to prevent detrimental reactions (lipid and protein oxidation and microbial decay) increase meat’s shelf-life and freshness, conserve nutrients, and most importantly, protect consumers. Furthermore, it aims to produce meat that meets and exceeds consumer expectations [ 8 ]. Multiple preservation methods have been thoroughly researched, including smoking, chilling, modified atmosphere packaging, active packaging, chemical preservatives, freezing, pickling, and edible packaging, all of which are advantageous according to the requirements of the consumer market. The increase in pollution demands environmentally sustainable methods and novel packaging systems for meat and associated products. Edible films (EFs) and coatings (ECs) are food-based packaging systems applied to food to safeguard it from detrimental changes and ensure preservation. The concept of EFs and ECs can be dated back to ancient China, where lipid coating was applied on lemons and oranges. Lipid coating was also used similarly in the sixteenth century in the US to preserve fruits. Since then, the idea of edible films and coatings has achieved incredible advancements. The principal difference between EFs and ECs lies in the application method. EFs are first prepared as a laminate in one or multiple layers, dried, and then applied on the food products, whereas ECs are either sprayed on the products, or the products are immersed in the EC and then dried. The major challenge in preparing the films and coatings is the selection of appropriate raw materials that will serve all the required mechanical and barrier properties and their optimum ratio. Suffice it to say that one composition cannot be generalized for a food class, creating a spacious area for the researchers to explore. An EC is a blend of two or more immiscible liquids made miscible by adding an emulsifier. Emulsions can be classified conventionally based on their composition as O/W (oil-in-water) or W/O (water-in-oil). They can also be classified based on the number of phases as a double phase/multiple phase emulsion, wherein one emulsion is dispersed into another liquid or another emulsion, for example, O/W/O (oil-in water in-oil), or W/O/W (water-in oil in-water) emulsion. From the food packaging aspect, multiple emulsions are more advantageous than conventional ones. Multiple emulsions can be used efficiently to hold more than one functional ingredient, formulated strategically for the controlled release of certain ingredients, and they can be developed to isolate certain ingredients that might react otherwise. The food industry exploits these qualities of multiple emulsions to make complex food ECs. The following review presents a brief classification of ECs based on the composition of the emulsions and on the particle size, followed by a comprehensive study of the three most essential physical properties (ingredient separation, rheology, and thermal stability) of consideration to prepare an efficient emulsion. Lastly, the advantages of ECs, limitations in current research, and scopes for future prospects are briefly discussed. The data collected have been limited to those from the past 12 years, i.e., 2010 to 2022, from prominent research websites, namely Web of Science, Scopus, and Google Scholar. ECs for other food categories have not been covered here. 2. Classification of ECs 2.1. Based on Composition The properties (physical and mechanical) are exclusively dependent on the ingredient of choice. Proteins provide barrier protection that is distinct from that provided by
Foods 2023,12, 832 3 of 15 polysaccharides or lipids. Their combination in coatings (composites) may offer a variety of properties. Polysaccharides, proteins, and/or their blends form the base with some included functional ingredients such as antimicrobial agents. In some cases, the coating is made with essential oils (EOs) as the main ingredient and the polysaccharide or (rarely) protein acts as a carrier in the emulsion. The complexity of meat demands a packaging material capable of serving multiple functions at once. Therefore, no single ingredient can satisfy all the purposes and there must be a blend of ingredients to meet the needs of an ideal packaging material. 2.1.1. Polysaccharide Coatings Cellulose, native and modified starch, pectins, seaweed extracts (alginates, carrageenan, and agar), gums (acacia, tragacanth, and guar), pullulan, and chitosan are primarily used to make coatings [ 9 ]. These compounds impart hardness, crispness, compactness, viscosity, adhesiveness, and gel-forming ability while preventing dehydration, oxidative rancidity, and surface browning. Although some gums have a negative charge, most are neutral [ 10 , 11 ]. Hydrogen bonds play a crucial role in forming films and their final characteristic due to the presence of several hydroxyl and other polar groups in their structures. Negatively charged gums such as alginate, pectin, and carboxymethyl cellulose (CMC) typically have pH-dependent properties [ 12 , 13 ]. Hydrophobicity and poor mechanical strength are the two significant downsides of having a purely polysaccharide-based coating. 2.1.2. Protein Coatings Casein, whey protein (concentrate and isolate), collagen, gelatin, egg albumin, corn, soybean, wheat, cottonseed, peanut, and rice are the most popular examples of proteins used for coatings [ 14 – 16 ]. Proteins provide good gas barrier properties but poor moisture diffusion resistance. Their ductility is another problem which can be improved by gelatinization of protein. Studies on the effect of denaturation degree on the physical and mechanical properties of the edible film have reported that protein denaturation reduces the vapor and oxygen permeability; however, the protein orientation at the molecular level remains unclear. In contrast, the instability of protein-based films poses risks in package breakage during transportation, handling, and sale, resulting in limited packaging applications [14,17,18]. 2.1.3. Lipid Coatings Lipids for coatings can be divided into vegetable fats and oil, waxes, natural resins, and EOs. However, all of them are not suitable for meat due to the spoilage caused by lipid oxidation. Pure lipids with proteins or polysaccharides as a carrier are a more effective method to obtain gas barrier and moisture barrier properties. This can further improve the color, appearance, texture, aroma, and simultaneously prevent microbial spoilage [19]. 2.2. Based on Particle Size Emulsions can be categorized as macroemulsions (0.1–0.5 µ m), nanoemulsions (20–100 nm) , and microemulsions (5–50 nm). The particle size of the emulsion droplets influences the properties or behavior of the emulsions. For emulsions to function as a coating, it is crucial to consider the relation of particle size to the release mechanism and the fate of the droplets throughout the storage life. Homogenization devices are best suited to obtain an emulsion of particular particle size. During homogenization, the large droplets undergo size reduction upon applying mechanical sheer force. This yields uniformly distributed droplets in the dispersed medium. Since the emulsion is thermodynamically unstable, surfactants are introduced to reduce the interfacial tension between the dispersed phase and the dispersed medium [ 20 ]. This implies that the particle size (influenced by homogenization and the process conditions) impacts the emulsion stability and, thereby, its encapsulation efficiency [ 21 ], more of which will be covered in the subsequent sections. An example of this correlation is the study of O/W system with droplet size <200 nm,
Foods 2023,12, 832 4 of 15 encapsulating resveratrol. It was found that the emulsion system was stable for 4 weeks while preserving resveratrol from lipid oxidation and its antimicrobial properties [22]. 3. The Complexity of ECs for Meats: Essential Properties of Consideration 3.1. Ingredient Separation The most common phenomenon disrupting the emulsion is the ingredient separation occurring due to gravitation, coalescence, flocculation, or phase separation. The phases orient themselves according to their concentration and polarity [ 23 – 25 ]. Separation may also occur due to environmental changes such as temperature, pressure, and pH. Ingredient separation can be monitored by creaming stability analysis and thermal analysis via DSC; it is also reflected in the microstructure analysis of the coating. At a molecular level, the separation occurs due to the difference in the type of chemical bond that an ingredient can make. Emulsions separate due to the difference in the type of bonds they can make with each other. Water can make strong hydrogen bonds, whereas the oil phase makes only relatively weak van der Waals bonds [ 26 , 27 ]. This creates a thermodynamically unstable environment that can be stabilized by providing free energy to increase the area of interaction between the ingredients. This energy can be estimated by the following equation [28]: ∆G=γi∆A where ∆ Gis the free energy required to increase the area of contact between two immiscible liquids by ∆ A(at constant temperature and pressure) and γi is the constant of proportionality called as the interfacial tension. McClements [ 23 ] claims that the magnitude of imbalance in the molecular interaction across the interface determines the interfacial tension; the greater the imbalance, the higher the interfacial tension. In this way, emulsifiers are used to act as a border between the two phases and create uniformity. The most common emulsifiers reportedly used are tween 80 [ 29 – 32 ] (concentration varying from 0.2–25 wt% of oil/v, tween 20 [ 30 , 33 , 34 ] (concentration same as tween 80), polyglyceryl-6-dioleate (3–7% w/w) [ 35 ] and lecithin (10% w/v) [ 29 , 36 ] with tween 80 being the most common one reported. Some researchers have skipped using an emulsifier and instead used a high-velocity homogenizer to obtain a uniform emulsion [37,38]. The emulsion’s flow behavior (laminar or turbulent) affects the particle coalescence. The partition and blending of the dispersed phase and dispersed medium to achieve uniform mixing is the first step of homogenization [ 39 , 40 ]. The remaining part of the process involves disruption of larger droplets into smaller ones. Therefore, an understanding of the forces responsible for the droplet disruption during homogenization is important. According to Mc Clements [ 23 ] the fate of the droplets formed during homogenization depends on the balance between the interfacial forces holding the droplets together and disruptive forces generated in the homogenizer separating them [41,42]. The literature indicated that emulsions prepared using a homogenizer produced extremely uniform emulsion in the particle size range of 250–2000 nm. Some experiments have also used an ultrasonicator to prepare emulsions; however, the particle sizes were lower than those produced by homogenizers (particle size range: 50–300 nm) [ 30 , 43 – 45 ]. The selection of a homogenizer depends on the desired particle size, the amount of product to be homogenized, the physicochemical properties of the components and the characters required in finished product, and most importantly, the energy costs. Table 2summarizes the particle size in nanometers (nm) as reported by some of the authors in their studies. Since homogenizers have high energy costs, researchers have tried to achieve similarly stable emulsions using low-energy-cost methods such as spontaneous emulsification, the phase inversion method, the phase inversion temperature method, spontaneous ultrasonication, etc. [ 46 , 47 ]. Despite being low energy methods, they have the major disadvantage of using a high ratio of emulsifier and oil.
Foods 2023,12, 832 5 of 15 Table 2. Summary of the composition, particle size, antimicrobial/antioxidant compound, target microorganisms, production, and shelf life conditions studied in the literature. Product Coating Material Particle Size (nm) Antimicrobial/Antioxiadnt Compound Target Microorganisms Conditions Reference Chicken Gelatin and chitosan nanoemulsion coating 1122.4 Rosemary extract in corn germ oil and ε-poly-L-lysine Coliforms, E-coli, molds, yeast 4◦C, 16 days (d) Coated by soaking, covered with cling film and stored [43] Eggs Chitosan 1483–983 Beeswax-basil EO E-coli, S. aureus Room temperature, 35 d 2 mL coating sprayed and dried. [44] Turkey breast fillets Chitosan 342–5149 Zataria Multiflora Boiss EO and Bunium persicum Boiss EO Salmonella enteritidis, Listeria monocytogenes, TVC (total viable count), total Pseudomonas spp., Enterobacteriaceae, LAB (lactic acid bacteria), and yeast and mold count 4◦C, 18 d Coated with nano-emulsion for 2 min, drained for 1 h, and packed in zip lock bags. [29] Chicken breast fillet Sodium caseinate 57.4 Ginger EO Listeria monocytogenes and Salmonella typhimurium 4◦C, 12 d Coating by direct immersion and packed in LDPE [30] Raw goat meat Gum arabic 220–260 geraniol and carvacrol Bacillus cereus and E-coli 4◦C, 9 d Coating by direct dipping. [45] Pork loin Pectin 48.5–335.9 Oregano EO and resveratrol TVC 4◦C, 20 d Coating by direct immersion for 30 s, air drying, and sealed hermetically in plastic trays with 20% CO2 and 80% O2. [31] Shrimps Oil-in-water nanoemulsion 10.2–11 Saffron EO E-coli and S aureus 4◦C and 8 ◦C 14 d Coating by direct immersion, draining, and sealing in PE (polyethylene) bags. [34] Red sea bream Oil-in-water nanoemulsion 799.5–114.7 Ginger EO E-coli and S aureus 4◦C, 10 d Coating by direct dipping. [48] Fresh pork tenderloin Gelatin 4000–6000 Eugenol EO TVC, Enterobacteriaceae lactic acid bacteria, Pseudomonas spp. 4◦C, 15 d Coating by soaking for 30 s and covered with cling films. [49] Chicken fillets Basil seed gum - Shirazi thyme EO and summery savory EO Mesophilic, psychrotrophic and LAB 4◦C, 12 d Coating by soaking for 120 s, drain for 2 min ×2. [32] Scopthalmus Maximus Locust bean gum and sodium alginate - Daphnetin TVC, psychrophiles, and Pseudomonas spp. 4◦C, 18 d Coating by direct dipping for 20 min at 4◦C, drying for 60 min in air flow at 4◦C and then individually packed in PE. [36] Chicken fillet Konjac glucomannan/carrageenan - Camellia EO TVC, psychrophiles, and LAB 4◦C, 10 d Coating by direct immersion for 10 s, drying at ambient temp. for 10 min, and covering with plastic wrap. [50] Turkey fillets Alginate 156.2 Trachyspermum ammi EO Listeria monocytogenes 4◦C, 12 d Coating by direct dipping, dipping in 2% CaCl2solution for 30 s and, packed in sterile zipper packs. [51] Sliced bolognas Pectin - Thymus vulgaris and Thymbra spicata EO Mesophilic and LAB 4◦C, 21 d Coating by dipping for 2 min and draining for 3 min before storage. [52]
Foods 2023,12, 832 6 of 15 Table 2. Cont. Product Coating Material Particle Size (nm) Antimicrobial/Antioxiadnt Compound Target Microorganisms Conditions Reference Pork meat Chitosan - Thyme EO Pseudomonas, Lactococcus, and Acinetobacter 4◦C, 12 d Coating by alcohol spraying, air drying for 5 min, and packed in plastic bags. [53] Ready to eat chicken patties Chicken bone gelatin–chitosan 1370.8–183.6 Cinnamon EO and rosemary extract E. coli,Bacillus subtilis, and S aureus 4◦C, 16 d Coating by direct dipping for 3 min, drained for 10 min and sealed in PE bags. [38] Crayfish meat Chitosan - Propolis extract Total aerobic mesophilic, psychrotrophic and H2S-producing bacteria, yeastsmolds 4◦C, 16 d Coating by direct dipping for 2 min, drying for 60 min in air flow at 10 ◦C and then individually packed in sterile PE. [54] Chicken meat Chitosan - Duck fat TVC and Listeria spp. 4◦C, 15 d Coating by direct dipping for 2 min under magnetic stirring at 800 rpm, dried in laminar hood at 25 ◦C for 2 h and packed in PE bags. [55] Pork Chitosan 389.7–45.3 Schizonepeta tenuifolia EO TVC, Pseudomonas spp., LAB, and Enterobacteriaceae 4◦C, 16 d Coating by direct dipping for 30 s) ×2 with 2 min break, draining for 10 min, and packed in oxygen-permeable PE film. [56] Fresh meat Chitosan >1000 Eugenol EO E. coli and S. aureus 4◦C, 14 d Coating by direct dipping for 1 min and draining. [57] Chicken breast Calcium alginate - Artemisia fragrance EO TVC, coliforms, molds and yeast 4◦C, 12 d Coating by direct dipping for 60 min at 4◦C, draining and packing in PE bags. [58] Silver carp fillet Sodiumalginate– carboxymethyl cellulose - Ziziphora clinopodioides EO, apple peel extract, and zinc oxide nanoparticles (alone and in combination) Listeria monocytogenes 4◦C, 14 d Coating by direct immersion at room temperature for 30 s, drained for 15 min, and dried under refrigeration for 2 h. [59] Chicken breast Whey protein isolate - Oregano and clove EO Total aerobic mesophilic bacteria, Enterobacteriaceae, total aerobic psychrotrophic bacteria, LAB, and Pseudomonas spp. 4◦C, 13 d Coating by immersion, draining, and drying under sterilized conditions. [15] Paínho and alheira Portuguese sausage Whey protein - Origanum virens EO Salmonella spp. And L. monocytogenes 4◦C, 106–126 d Coating by applying 1 mL of emulsion by silicone brush and packing in LDPE films by thermal vacuum sealing (30 s at 120 ◦C) [16] Chicken breast Pomegranate juice–chitosan -Zataria multiflora EO TVC, Pseudomonas spp., lactic acid bacteria, Enterobacteriaceae, Psychrotrophic bacteria and yeasts– molds 4◦C, 20 d Coating by direct immersion for 2 min twice with a short interval, drained for 5 h at 10 ◦C, and packing in sterilized LDPE packages. [60] Rainbow trout fillet Chitosan - Mentha spicata EO TVC, psychrotrophic bacteria, Pseudomonas spp. and Enterobacteriaceae 4◦C, 14 d Coating by direct immersion for 1 min, draining for 5 min, and packing in sterile stomacher bags. [61]
Foods 2023,12, 832 7 of 15 Table 2. Cont. Product Coating Material Particle Size (nm) Antimicrobial/Antioxiadnt Compound Target Microorganisms Conditions Reference Silver carp fillet Methylcellulose - Pimpinella affinis EO TVC and psychrotrophic bacteria 4◦C, 20 d Coating by direct immersion for 30 s ×2, and drained for 5 h at 10 ◦C. [62] Bighead carp fillet Sodium Alginate - Horsemint (Mentha longifolia) EO TVC and psychrotrophic bacteria 4◦C, 16 d Coating by direct immersion for 30 s and drained for 30 min at ambient conditions, [63] Rainbow trout fillet Fish gelatin - Oregano EO TVC 4◦C, 16 d Coating by direct immersion for 2 min ×2 with 1 min draining interval and drying for 1 h under sterile laminar hood. [64] Shrimp Chitosan - Garlic EO Aerobic plate count 4◦C, 11 d Coating by direct immersion for 5 min, drained and dried for 4hat4◦C, and packed in plastic wrap. [65] Lamb meat Chitosan 96–93 Satureja plant EO TVC, Pseudomonas spp. and LAB 4◦C, 20 d Coating by direct immersion for one min) ×2, drained and dried for 15 min at 25 ◦C [66] Rainbow trout fillet Carboxymethyl cellulose -Zataria multiflora Boiss EO and grapeseed extract TVC, Pseudomonas spp. and LAB 4◦C, 20 d Coating by direct immersion and drained. [67] Refrigerated bream (Megalobrama amblycephala) Sodium alginate - Vitamin C and tea polyphenols TVC 4◦C, 20 d Coating by direct immersion for 1 min, air dried for 1 min, and immersed in CaCl2and packed in PE bags. [68] Trout (Oncorhynchusmykiss) fillets Carrageenan - Lemon EO TVC, Pseudomonas spp. and Enterobacteriaceae 4◦C, 15 d Coating by direct immersion. [69] 3.2. Rheology The study of an emulsion’s rheological properties is crucial in understanding the protective ability of the coatings for meat or any other food product. The fluidity and spreadability of the emulsions are the most consequential rheological characteristics of consideration. It was surprising for the authors to find that only 13% of research (as per the previously mentioned criteria) conducted rheological studies of the coating emulsions for meat. Since meat has an irregular surface, it becomes highly pertinent to investigate the viscosity and spreadability index of the emulsions. The literature indicated that the coating emulsions manufactured for meat and products exhibited a decrease in viscosity with increasing shear rate and shear thinning properties [ 44 , 49 , 69 , 70 ]. Coatings prepared with EOs revealed an increase in apparent viscosity with increasing oil concentrations. It was also observed that the viscosity of the coatings reduced significantly after 30–32 days of storage for the samples prepared with the highest amounts of gelling agent and fat (beeswax and animal fat in a fat blend) [37,70]. On a much deeper level, one must understand the rheological behavior of the interfacial layer that surrounds the emulsion droplets [ 71 , 72 ]. According to Murray and Dickenson [ 73 ], interfacial rheology is defined as the “study of the mechanical and flow properties of adsorbent layers at fluid interfaces” whereas the stresses responsible for the movement of the interfacial regions (relative to one another) without disruption of overall surface are called interfacial shear deformation. However, they may cause the surface area to expand or contract, which is termed the interfacial dilational deformation [ 27 , 74 , 75 ].
Foods 2023,12, 832 8 of 15 The interfacial rheology is, consequentially, controlled by the factors (emulsifier concentration, pH, temperature, and ionic strength) that influence the character and strength of the interactions between the molecules absorbed at the interface [76,77]. 3.3. Thermal Stability Thermal analysis is not a usual technique chosen by researchers; however, the data give significant results concerning the fate of emulsion droplets and their nature. Emulsion systems are known to be unstable, and therefore they unwind irreversibly into respective bulk phases. However, one can obtain a kinetically stable system that enables analysis via calorimetry, but only if it accompanies the adsorption and release of energy. The primary purpose of thermal analysis is to study the melting and crystallization behavior of emulsion droplets, which is possible by differential scanning calorimetry (DSC) and differential thermal analysis (DTA) [ 23 ]. The analysis takes place based on detecting the energy adsorbed (melting) or released (crystallization) by the emulsion systems under the specified temperature conditions. These measurements help monitor the influence of ingredients and experiment conditions on the melting and crystallization behavior of the bulk phases [ 70 , 78 ]. Furthermore, thermal analysis also gives a detailed insight into the polymorphic forms of the triacylglycerols and the glass transition state of the polysaccharides and proteins. It also helps determine the droplets’ stability to coalescence when the bulk phases melt or crystallize; this is because the droplet crystallization temperature is directly proportional to its size owing to the supercooling effects. A droplet’s energy release during crystallization is instantaneous because it occurs far from thermodynamic equilibrium, whereas the energy absorption occurs at the fixed temperature of melting and its kinetics are determined by interactions with the medium surrounding it [79]. 3.4. Antioxidant and Antimicrobial Properties Essential requirements for ECs in enhancing the shelf life of meat and products are antimicrobial and antioxidant properties. The importance of discussing the parameters of the aforementioned properties lies in the fact that they influence the efficacy of ECs for meat considerably and ECs without them are rendered less effective. As previously established, the high susceptibility of meat to spoilage demands that its shelf life be considered the highest priority. Since fresh meat is highly susceptible to oxidation (lipid and protein), it is one of the major parameters of concern. Hydroperoxides are produced through lipid peroxidation, and when these compounds are broken down, secondary oxidative products are produced, resulting in unpleasant odors and flavors in meat [ 32 , 80 , 81 ]. Oxidative damages due to uncontrolled formation of free radicals result in quality decay, loss of flavor, texture, color, and nutritive values of the meat due to PUFA (polyunsaturated fatty acids) degrading [1,82–84]. Natural antioxidants from plants and extracts thereof have been of interest to researchers; however, ECs’ effectiveness against lipid and protein oxidation has not yet been studied extensively. Natural antioxidants prevent the formation and spread of reactive species and free radicals by acting as hydrogen donors and scavengers of free radicals [85]. Step 1 Initiation: Heat, metal ions, and irradiation act as catalysts and form lipid free radicals that react with oxygen to produce peroxy radicals. R+O2→R•+•OOH (1) Step 2 Propagation: Peroxide radicals react with other lipid molecules to produce hydroperoxides and more free radicals as follows: R•+O2→ROO•(2) RH +ROO• → ROOH +R•(3) ROOH →RO•+•OH (4)
Foods 2023,12, 832 9 of 15 Step 3 Termination: Reaction between two free radicals results in the termination of the reaction. R•+R• → R–R (5) R+ROO• → ROOR (6) ROO•+ROO• → ROOR +O2(7) Lobo et al. [ 84 ] explained the three distinct methods of oxidative protein modification: through a specific amino acid’s oxidative modification; by breaking the peptide caused by free radicals; and by the reaction with the products of lipid peroxidation, which results in the formation of the transverse binding protein. The protein’s susceptibility to oxidation and enzymatic proteolysis increases with the presence of amino acids such as cysteine, histidine, methionine, and arginine, which are modified by free radicals [ 86 – 89 ]. Carbonyl formation is a common reaction pathway in the oxidation process, and the same oxidants that start lipid oxidation also cause and propagate protein oxidation. Carbonyl derivatives and protein–lipid and protein–protein complexes are also produced when proteins react with secondary lipid peroxidation products such as ketones and aldehydes [ 90 – 93 ]. • OH is readily produced in meats when hydrogen peroxide or lipid peroxide reacts with copper or iron to modify amino acids such as lysine and methionine in specific locations. H2O2+ Fe(II)/Cu(I) → •OH + OH−+ Fe(III)/Cu(II) (8) •OH + Protein (lysine)-NH2→Protein-COH (carbonyl) (9) Currently the EOs from plants, their extracts, and by-products are gaining much attention. Typically, EOs are a source of phenolic and polyphenolic substances with potent antioxidant properties [ 92 ]. The functional properties of emulsions can be improved by the synergistic effects of the EOs and their constituents, which in turn can successfully extend the shelf life of meat, particularly that high in fat such as pork. Due to the strong radical scavenging properties of phenolic compounds, the antioxidant activity of EOs is associated with mechanisms such as interaction with free radicals, hydroperoxide decomposition, inhibition of chain reactions, and transitional binding of metals [ 93 , 94 ]. The thermodynamic stability of phenolic radicals can be attributed to their resonant structures, according to Majdinasab [ 32 ]. This implies that the CHO fraction of EOs is a more effective antioxidant than the phenolic content [84]. The oxidation extent can be evaluated by peroxide value (PV) determination or by the thiobarbituric acid reactive substances (TBARS) method. In a study, shrimp samples treated with 3% and 5% saffron EO emulsions were found to have significantly low PV in comparison to the untreated samples, especially at the end of the 14th day of the study. A TBARS assay also revealed a huge difference in the TBA value of the emulsion coated samples and the uncoated ones [ 34 ]. Similar results were discovered in a study on nanoemulsion prepared from oregano EO and resveratrol in PEctin EC. It was found that the coated pork loin samples reached close to the threshold spoilage value (4.20 mg MDA (malonaldehyde)/kg) on day 20 of the study, whereas the uncoated samples crossed the threshold value on the 5th day of study [ 31 ]. Emulsions prepared from lipopeptides and BHA in sunflower coating for raw beef patties revealed that the TBARS value of the uncoated samples increased rapidly on storage and reached a value of 2.8 mg MDA/kg on the 12th day of storage. The value was much lower for the emulsion-coated samples (0.35 and 0.25 for lipopeptides and BHA coating, respectively) [ 33 ]. The TBARS value of chicken meat coated with rosemary extract and ε -poly-L-lysine was found to be significantly lower (1.523–1.97 mg MDA/kg) than that of the uncoated samples (2.27 mg MDA/kg) [ 48 ]. Chicken fillets coated with BSG-based coatings had a peroxide value of 5 meq active O 2 /kg lipid after 12 days whereas the uncoated samples had a value of 8.07 meq active O 2 /kg lipid. The authors reported that the formation of hydroperoxides was low due to the antioxidant properties of thyme EO and summer savory EO. They attributed this to thyme’s higher amounts of phenolic compounds, such as carvacrol and thymol, and their