Modulating Functionality of Beverages Through Nanostructured Interventions

MODULATING FUNCTIONALITY OF BEVERAGES THROUGH NANOSTRUCTURED INTERVENTIONS

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Swati Pund⁎, Amita Joshi†, Vandana Patravale‡ ⁎

Nanomedicine Laboratory, Department of Biosciences and Bioengineering, Indian Institute of Technology-Bombay, Mumbai, India, †Department of Pharmaceutics, B.V. Patel PERD Centre, Ahmedabad, India, ‡Department of Pharmaceutical Sciences and Technology, Institute of Chemical Technology, Mumbai, India

7.1  Fortification of Beverages—Need and Challenges Liquids, more specifically liquids other than water, intended for human oral consumption are known as beverages. Broadly, beverages can be classified as—alcoholic, nonalcoholic, and dairy based (Day and McSweeney, 2016; Rocha et al., 2017). The former is composed of fermented beverages containing ethanol like beers, wines, and spirits, while soft drinks include tea, coffee, fruit juices, carbonated, and noncarbonated sweetened drinks. Nonalcoholic beverages can be further grouped based on their sugar content as either sugar-based or sugar-free beverages. Dairy-based beverages differ from the others by the high protein containing fat forming emulsions, for example, milk, fermented milk, yogurt drinks, and milkshakes (Rocha et  al., 2017). Common commercial beverages are vegetable juices, fruit juices, soft drinks, and energy drinks (Corbo et al., 2014). Over a last decade, there is an appreciable growth in the global sales of bottled waters, including enhanced, flavored, and fruit-flavored waters. Enhanced water is fortified with electrolytes, vitamins, and other nutraceuticals, whereas flavored and fruit-flavored waters are flavored with flavorants and fruit extracts. Rapid lifestyle change and higher consumption of fast food ­including beverages have been accounted for increase in chronic Nanoengineering in the Beverage Industry. https://doi.org/10.1016/B978-0-12-816677-2.00007-7 © 2020 Elsevier Inc. All rights reserved.

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lifestyle disorders. With the increasing public perception of a strong correlation between food and disease prevention, producers are trying to enrich beverages with nutraceuticals and produce functional beverages. Market for functionally fortified beverages has observed rapid growth in the last decade. The interest of beverage manufacturers in developing products with bio-functional ingredients to meet the consumer demand for nutritious beverages which promote health and well-being is continuously rising (Raikos, 2017). However, fortification of aqueous-based edible product with bioactive nutraceuticals is greatly limited owing to their various properties like poor aqueous solubility, chemical instability, low bioavailability, and disagreeable odor and taste (Tamjidi et al., 2013). These challenges are depicted in Fig. 7.1. Dietary consumption of flavonoids, carotenoids, vitamins, phenolic acids, minerals, amino acids, and fatty acids is known to reduce the risk of lifestyle chronic diseases (Zulueta et al., 2007). Beverages serve as a vehicle to deliver such nutritional bioactives. Consumer awareness regarding healthy lifestyle has led to increased consumer interest in functional beverages. Incorporation of lipophilic bioactives with aqueous beverages is a challenging task and requires either emulsification, suspension, or dissolution in the beverages (Martínez-Monteagudo et al., 2017). Fabrication of beverages needs to focus on practical aspects of manufacturing and packaging, marketing along with its formulation that helps to retain its sensory as well as ­nutritional properties (Chambers, 2014). Ideally, the manufacturing of beverages should be reliable, robust, and inexpensive. While the beverages should be formulated such that it remains unaffected by various stress parameters during transportation and storage, viz., temperature

Fig. 7.1  Challenges in fortification of beverages with variety of bioactives for improving functionality.

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a­ lterations, exposure to light, humidity, gases, mechanical vibrations, microorganisms, pH, and ionic strength (Piorkowski and McClements, 2014). Having an intended flavor and optical properties are the first impressions of the consumer. Therefore, to formulate a beverage with the desirable balanced flavor profile, well matching with the mouth feel, without any off-flavor and after-taste is the target. Fortification of beverages for improving the functionality with pharmaceuticals, phytochemicals, minerals, vitamins, etc. has to tackle inherent bitter, off-flavors, and/astringent taste of these materials. In addition, taints and off-flavors are often generated during manufacturing process, or transport or on storage. Hence, retaining sensory properties along with nutritional properties of beverages have become the current focus of research and development in the area of beverages and is one of the main challenges for the beverages industry.

7.2  Nanostructured Systems in Beverages Addition of pure form of nutraceuticals in beverages is challenging due to poor solubility of the lipophilic bioactive, deterioration during processing, poor shelf life and digestion, unacceptable sensory characteristics, and compromised bioavailability. This results in poor consumer acceptability and applicability of beverages as functional food. Use of novel nanostructure technology in beverage industry presents an attractive option that aid in addressing critical issues of beverages (Livney, 2015). Nanoemulsions, nanosuspensions, liposomes, and solid lipid nanoparticles (SLN)/nanostructured lipid carriers (NLCs) are the nanotechnology-based recipes extensively explored for improving the bioavailability and sensory attributes of beverages (Yao et al., 2014). Nanostructures broadly improve sensory properties as well as improved nutritional quality by improving solubility and bioavailability of the bioactives, thereby increasing consumer acceptability (Fig. 7.2).

7.2.1  Sensory Properties of Beverages Appearance, color, surface texture, mouth feel, clarity, odor and flavor, viscosity, consistency, and carbonation are few of the sensory attributes of beverages that strongly determine the consumer acceptability of the product and success of the product. Clarity of a solution is determined by the ability of the particles to disperse the light beam. Also, the ability of a system to disperse the particles determines the gravitational sedimentation of the particles in a solution over a period of time. Creation of nanoparticles facilitates control over these sensory attributes. Colloidal interaction can be used to adjust the sedimentation or flocculation behavior, over a period of time, which eventually

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Fig. 7.2  Advantages offered by nanoengineered fortification of beverages with examples.

determines the clarity of the solution. Brownian motion governs the movement of particles and is dominant than sedimentation velocity, when the particles are extremely small and in nanometric size range. Hence, manipulating interparticle colloidal interaction can result in achieving colloidal stability and longer dispersibility. In addition, size, distribution of the particles, concentration of the particles, and their refractive index determine the beverage quality. Visual color and the rheological properties of the beverages also can be tailored using nanostructures. Zhong and Jin (2009) attuned the viscosity of the beverage formulation using corn zein nanoparticle dispersed in carboxymethylcellulose solution thus providing structural stability. The odorless and tasteless zein offers an ideal alternative carrier for beverages. Turbidity and color are the two of the sensory attributes that are controlled by the dimension of the particle structure. On the basis of classical Mie theory, in general, particle/droplet diameter less than 80 nm results in a transparent dispersion (Lesmes and McClements, 2009). Addition of natural flavors and fruit extract in flavored water results in turbidity. Use of nanoemulsions helps to make dispersion more

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clear, by formation of extremely small droplet size (Piorkowski and McClements, 2014). Incorporation of flavors in nanostructures also extends the release of fragrance and aroma through their shelf life. Incorporation of flavors in the lipidic nanoparticle, like SLNs provide a unique opportunity to create a distinctive mouth feel/sensation, due to melting of lipids. Smaller particle size and thereby a larger surface area of SLNs, may expedite the melting process along with an enhanced interaction with the taste buds resulting in developing a unique flavor and mouth feel of a product (Zhong and Shah, 2012). Melting profile of lipid entrapped flavor can also be manipulated for a burst release effect (Burova et  al., 1999). Nanostructuring of water-soluble components also has impact on sensory qualities because of higher mass transfer from increased surface area of nanoparticles.

7.2.2  Nutritional Quality by Enhancing Solubility, Stability, and Bioavailability of the Bioactives Bioavailability is the fraction of the ingested active that becomes available in the systemic circulation. Beverages especially functional beverages contain many lipophilic bioactives, viz., polyphenols, flavors, antioxidants, and many more, that are expected to function in a hydrophilic environment. As a result of their limited aqueous solubility, these bioactive fails to liberate into solution state and serve their purpose. An advantage of utilizing nanostructures is improvement in the solubility and water dispersibility, thereby improving biological functionality (Sotomayor-Gerding et  al., 2016). Engineered nanostructures can also be used to modulate the absorption pattern of the bioactives. Bioactives are either absorbed actively or passively. Reduced size of nanostructures enhances passive absorption, while the active absorption can be modulated by balancing the structural aspect of nanostructures with the biological requirement. Several examples of nanometric delivery of poorly soluble bioactives exclusively for beverage application are discussed later in this chapter. Improved aqueous solubility along with the larger surface area, nanostructures provide enhanced mass transfer results in improved absorption. Since lipophilic compounds have good permeability across intestine, they can be absorbed by actively as well as passively. However, hydrophilic compounds are absorbed only via active transportation process. This can be further limited by poor intestinal permeability of certain hydrophilic compounds. Formulating nanostructures of such components can result in improved permeability and thereby its absorption. Thus, nanostructure provides a potential solution for improving the bioavailability of bioactives in beverages and also a suitable platform for protecting the sensitive bioactives from the harsh environmental conditions, viz., temperature, ionic

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strength, pH, oxidation, etc., which can cause significant degradation of bioactives (Ozturk et al., 2015). Thus, protecting the bioactive from degradation may increase the bioavailability of the bioactive. He et al. (2017) reported reduced degradation of anthocynanins when formulated as chitosan nanoparticles. Several reports prove improved stability of bioactives through nanostructuring (Chen et  al., 2017; Luo et al., 2017; Walker et al., 2015a). Nanoparticles can be tailored for achieving a site-specific release of bioactives. Use of enteric polymer to encapsulate bioactive is one such approach that can be explored to give gastric acid-resistant coat so as to target release of bioactive in intestine for absorption. This approach is very well established for protecting the pharmaceuticals that are sensitive to the acidic environment. It is also useful for actives that are predominantly absorbed from the intestine (Zhong and Shah, 2012). Markman and Liveney (2012) synthesized casein-maltodextrin conjugates based on the Maillard reaction and explored as co-assembling nanoencapsulating emulsifier. The covalent chemical conjugation of an amine from a protein with an aldehyde group of reducing sugar from the polysaccharide was confirmed using gel electrophoresis and by o-phthaldialdehyde assay. Lipophilic vitamin D2 and hydrophilic epigallocatechin gallate were well protected after encapsulation performed using isoelectric protein precipitation. Nile red was used a fluorescent hydrophobic probe to monitor stability of enteric coat toward simulated gastric digestion. Use of mucoadhesive polymers increases residence time of particulate system at site of absorption and increases the probability of uptake and in turn improves the bioavailability. Mucoadhesive interaction can be nonspecific (electrostatic) or specific (receptor mediated) between the particulate system and the gastrointestinal mucosa. Nonimmunological origin, lectins, and lectin-like molecules specifically recognize sugar molecules and bind to the glycosylated membrane components. This binding acts as bioadhesion and also causes internalization into cells (Lehr, 2000). Campuzano et  al. (2012) developed new synthetic microengines, functionalized with lectin receptors, and demonstrated its application for the efficient isolation of Escherichia coli from beverages with low and high sugar concentration like water and apple juice, respectively. Chitosan coating of curcumin nanoliposomes significantly increased their mucin adhesion property by imparting positive charge to liposomes and interacting electrostatically with negatively charged mucin (Shin et  al., 2013). Use of chitosan also gives high gastric stability for acid labile compounds, providing controlled release in intestinal pH, thus improving the bioavailability (Fonte et al., 2011; Lee et al., 2017).

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7.3  Delivery Systems for Nanostructured Beverages Summary of different delivery systems explored with nanoengineering for fortification of beverages is tabulated in Table 7.1.

7.3.1  Emulsified Systems Typically, emulsions are dispersion of macroscopic droplets of one liquid in another liquid, with a droplet size of 1–10 μm consisting of water, oil, and emulsifier. They are semitransparent to cloudy, viscous liquid having tough interfacial film and are thermodynamically unstable. Emulsions can be oil-in-water, water-in-oil, or multiple emulsions. A dispersion of oil in water, of most interest for pharmaceutical applications, is referred to as o/w emulsion, requires the emulsifying agent having more solubility in the aqueous phase. The reverse emulsion, w/o is stabilized by surfactants that are soluble and stable in the oil phase. On the other hand, double emulsions are the ternary systems having either a w/o/w or o/w/o type, wherein the dispersed droplets contain smaller droplets of a different phase. Emulsions can further classified as microemulsion and nanoemulsions. Microemulsions are isotropic, thermodynamically stable systems composed of oil, water, surfactant and cosurfactants, or cosolvents. The main factor influencing the formation of microemulsion is the ultralow interfacial tension, which is usually achieved by the use of two or more emulsifiers. Out of the two emulsifiers used in microemulsion formation, one is predominantly water-soluble surfactant, while the other is predominantly oil-soluble cosurfactant. Cosurfactants reduce the interfacial tension to an ultralow value, required for microemulsion formation (Dokania and Joshi, 2015). On the other hand, nanoemulsions have a globule diameter in the nanometer range (below 100 nm, Walker et al., 2015b). The small size of nanoemulsion globules offers potential advantages like high optical clarity required for beverage fortification (Pund et  al., 2016), higher stability toward flocculation and coalescence, ability to modify product texture, mouth feel, and taste (McClements and Rao, 2011). The formation of nanoemulsion requires an input of energy. This energy can be supplied by either mechanical equipment or the chemical potential inherent within the components (Lawrence and Warisnoicharoen, 2006). Nanoemulsions can be fabricated either by high-energy equipments capable of causing powerful disruption of oil globules like high-pressure valve homogenizer, microfluidizer, and ultrasonic homogenizer, or by low-energy techniques like spontaneous emulsification and phase inversion emulsification (Pund et al., 2016). Ultrahigh-pressure homogenization beverages showed ­better

Table 7.1  Different Delivery Systems for Nanostructured Fortification of Beverage Nanostructure

Bioactive

References

Emulsified systems

Carotenoids—Lutein, Lycopene and β-carotene Flaxseed oil Fish oil Vitamin E

Kim et al. (2014), Luo et al. (2017), Mao et al. (2013), Qian et al. (2012a,b), Vishwanathan et al. (2009) Chen et al. (2017) Komaiko et al. (2016), Walker et al. (2015a) Chen and Wagner (2004), Dasgupta et al. (2016), Saberi et al. (2013), Saberi et al. (2014), Yang and McClements (2013) Anu Bhushani et al. (2016), Gadkari et al. (2017), Tsai and Chen (2016) Donsì et al. (2011), Chang and McClements (2014), McClements et al. (2014), Rao and McClements (2011, 2013), Sugumar et al. (2016), Yang et al. (2017) Li et al. (2012b) Jo et al. (2015) Xue et al. (2017) Ghosh et al. (2014) Nazemiyeh et al. (2016) Tamjidi et al. (2014a,b, 2017) Lee et al. (2017) Liu et al. (2012) Ni et al. (2015) Babazadeh et al. (2016) Mohammadi et al. (2017) He et al. (2017) Kusuma et al. (2015) Zimet and Livney (2009) Khan et al. (2017), Zohri et al. (2010) Markman and Liveney (2012)

Catechins Essential oils Lemon oil, Orange oil, citrus oil

SLNs/NLCs

Polymeric Nanoparticles

Nanosuspensions Liposomes

5-Hydroxy-6,7,8,4′-tetramethoxyflavone Trans-cinnamaldehyde Thymol Eugenol Lycopene Astaxanthin Ferric pyrophosphate Coenzyme Q10 Quercetin Rutin Vitamin D3 Anthocyanins Chitosan Docosahexaenoic acid Nisin Vitamin D2 Epigallocatechin gallate Curcumin Vitamin D3 Nisin Z Ferrous sulfate

Aditya et al. (2015) Mohammadi et al. (2014) Laridi et al. (2003) Xia and Xu (2005)

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c­ olloidal and oxidative stability, improved microbiological shelf life and good sensorial characteristics than the conventional treated (Codina-Torrella et  al., 2017, 2018). Unlike microemulsions, nanoemulsions are thermodynamically unstable, however, kinetically stable systems. Like conventional emulsions, both emulsions and nanoemulsions are in thermodynamic nonequilibrium state, however, the kinetics of destabilization of nanoemulsion is very slow and hence they are considered as kinetically stable (Rao and McClements, 2012). As a result of this, nanoemulsion droplets remain stable in conditions of stress like temperature changes, dilutions, etc. On the other hand, microemulsions are strongly affected by temperature changes and/ or dilutions and are even broken up by these alterations. Selection of appropriate emulsifier or its combination with co-emulsifier or cosolvent is very crucial in maintaining the stability of nanoemulsion for long-term use as well as against various environmental stresses during processing (pH, ionic strength, heating, and cooling). To stabilize newly generated oil-water interface, emulsifiers/stabilizers are essential. Food-grade surfactants and emulsifiers for nanoemulsions are selected depending on the emulsion composition, active ingredient, and processing parameters (Qian and McClements, 2011). Higher molecular weight biopolymers, like polysaccharides (gum arabic and modified starch) and amphiphilic proteins (e.g., casein, lactoferrin, β-lactoglobulin, protein isolates, and whey proteins) are widely used (Mao et  al., 2013). Small-molecule surfactants (e.g., Tween 20, 40, 80, and Span 80), phospholipids (e.g., soy lecithin), quillaja saponins, and sucrose esters are amphiphilic molecules (Lee et al., 2010; Xue and Zhong, 2014). Proteins are less effective than small-molecule surfactants, with depletion flocculation as a major drawback observed. To promote utilization of healthy proteins in beverages, and for long-term stabilization of nanoemulsions in beverages, Yerramilli et  al. (2017) suggested partial replacement of sodium caseinate with pea protein isolate in high-pressure homogenization manufacturing of beverage nanoemulsions for assuring long-term stability. Apart from polymeric surfactants, nanoparticles also stabilize oil droplets in water and form emulsions that are known as the Pickering emulsions. Irreversible adsorption of nanoparticles on oil-water interface provides high dynamic stability. Chaudhari et  al. (2015) formulated pear juice emulsion using pear juice concentrate (1%) and medium-chain triglycerides (5%), along with sweetener and preservative. Relative effectiveness of silica nanoparticle-based emulsifiers with surfactant (Tween 20) and biopolymer-based emulsifier (modified starch) in influencing physical stability of emulsion was analyzed. Droplet size and visible evaluation of pear juice emulsion demonstrated more effective stabilization of silica and starch-stabilized

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emulsions on storage as well after thermal processing. Stable turbidity as analyzed from absorbance measurements at 500 nm was observed for silica-stabilized emulsion as compared to starch and tween 20 stabilized emulsion. Specific applications of nanoemulsion fortified beverages are discussed in detail.

7.3.1.1 Carotenoids Carotenoids are synthesized only by plants, not by animals. Their presence in animal tissues is entirely of dietary origin. Although animals cannot synthesize carotenoids de novo, they can convert them into other carotenoids or can metabolize them. Carotenoids are classified as carotenes comprised entirely of carbon and hydrogen, for example, α-carotene, β-carotene, and lycopene; and xanthophylls comprised of carbon, hydrogen, and oxygen, for example, lutein and zeaxanthin (Pund et  al., 2016). Lutein, a lipid soluble, oxygenated carotenoid, exhibits beneficial pharmacological effects against damaging UV radiation, age-related macular degeneration, and cardiovascular diseases. Vishwanathan et  al. (2009) prepared stable lutein nanoemulsion with 150-nm globule size using soybean oil, Xangold oil, vitamin E oil, and phospolipon 85G by high shear microfluidizer processor. This nanoemulsion was used for demonstrating enhanced bioavailability after dispersing it in orange juice as a delivery vehicle. Lycopene, hydrophobic carotenoid, imparts deep red color to fresh tomatoes and tomato-based products. Lycopene is antioxidant and its ability to quench singlet oxygen is twice as high as β-carotene. Qian et al. (2012b) and Salvia-Trujillo et al. (2013) modulated the bioaccessibility of β-carotene using simulated digestion model by fine tuning of carrier oil concentration and composition of mediumand long-chain triglycerides. High β-carotene bioaccessibility can be achieved either by using low-fat long-chain triglycerides or highfat medium-chain triglycerides nanoemulsions. Kim et  al. (2014) prepared transparent lycopene emulsion for fortification of clear liquid drinks without affecting the optical characteristics. The lycopene nanoemulsion with droplets less than 100 nm was prepared by ­emulsification-evaporation technique with tween 20 as stabilizer. A model aqueous beverage containing 8% sucrose, 0.15% citric acid, and 0.1% ascorbic acid and 0.07% orange flavor was fortified with 20 g of lycopene nanoemulsion. Accelerated shelf life analysis was carried out at 30°C and 40°C to predict shelf life of the lycopene-added beverage at 4°C and 20°C. Half-life of lycopene emulsion was found to be 1302 d at 4°C and 206.66 d at 20°C. Salvia-Trujillo and McClements (2016) demonstrated higher bioaccessibility of lycopene from tomato juice by addition of excipient nanoemulsion. The excipient nanoemulsion was prepared using corn oil and tween 80 using microfluidizer. Small excipient emulsion mixed with tomato juice was completely digested

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under simulated gastrointestinal conditions, facilitating the transfer of lycopene into the mixed micelles in the small intestine phase. Recently, Luo et  al. (2017) fabricated β-carotene oil-in-water nanoemulsions by high-pressure dual-channel microfluidization using two natural “label-friendly” emulsifiers, quillaja saponins, and whey protein isolate with improved physical and chemical stability.

7.3.1.2  ω-3 Fatty Acids Fat consumption is necessary for human development, health, and longevity. There are two fatty acids that have been identified as being essential in the human diet: linoleic acid and α-linolenic acid, known as ω-6 and ω-3 fatty acid, respectively (Walker et  al., 2015b). Due to the important role in the brain development, improving cardiovascular health, and considerably low levels of ω-3 fatty acids in western diets, consumers are demanding ω-3 fatty acids supplemented functional beverages. Canola, soy, flaxseed, and walnuts are the land plant sources, whereas, sardine, mackerel, herring, and halibut are the fish sources of ω-3 fatty acids. However, incorporation of these oils in beverages is a challenge due to their hydrophobicity, poor oxidative stability, and variable bioavailability (Walker et al., 2015b). Colloidal delivery is essential for encapsulation of hydrophobic and oil-soluble constituents. Nanoemulsions are a promising way to incorporate these oils into liquid food systems like beverages. Flaxseed oil, a natural source of improved oxidative stability after nanoemulsification using caseinate as a natural antioxidant for improved oxidative stability (Chen et al., 2017). Walker et al. (2015a) nanoemulsified fish oil by blending it with lemon oil by low-energy spontaneous emulsification as well as by microfluidizer to form optically transparent, physically stable nanoemulsion with oxidative stability. Blending essential oil used along with fish oil lowered the viscosity of oil phase, added flavor, and provided additional benefit of antioxidant effect (Rao and McClements, 2013). Later, in Komaiko et al. (2016) suggested the use of sunflower phospholipids as a natural emulsifier for fish oil nanoemulsion for beverage application. At high phosphatidylcholine amount (surfactant to oil ratio >1), nanoemulsification using microfluidization produced globule size less than 150 nm.

7.3.1.3  Lipophilic Vitamins Being essential micronutrients, lipophilic vitamins A, D, E, and K play an important role in human body functions. Vitamin A is responsible of the vision, normal embryonic development, and growth. Vitamin D is a steroid hormone which has ergocalciferol (vitamin D2) and cholecalciferol (vitamin D3) components among which the latter has the highest bioactive role in bone metabolism, boosting the immune system and prevention of rickets disease in children. Vitamin D

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is abundant in seafoods, however, other natural sources of the vitamin are mushrooms and egg yolk. Vitamin E has two main groups, such as tocopherols and tocotrienols. The bioactive compounds α-tocopherol and γ-tocotrienol have high antioxidant activity exhibiting anticarcinogenic roles. Vitamin K functions in calcium metabolism in blood circulating system which may affect the human bone health (Öztürk, 2017). α-tocopherol is the most naturally abundant and biologically active form of vitamin E in humans. It has antioxidant activity in food as well as in vivo and helps to prevent cardiovascular disease and carcinogenesis. However, heat sensitivity, oxidation susceptibility, poor aqueous solubility, deterioration during processing and storage, and low and variable bioavailability has limited its easy utilization as a functional ingredient for fortification of beverages (Saberi et al., 2013). A possible way to overcome these challenges is to incorporate vitamin E into a colloidal dispersion consisting of small lipophilic particles suspended within an aqueous medium. Emulsified vitamin E generally show upward flocculation called as ringing and increased turbidity creating negative impact for clear beverages. Ultrahigh-pressure homogenization and encapsulation in starch resulted in nanoparticles with size less than 100 nm and also improved stability and clarity of beverages after fortification at a level of 62.5 ppm (Chen and Wagner, 2004). Saberi et al. (2013, 2014) studied feasibility of low-energy spontaneous emulsification technique for formulating vitamin E nanoemulsion and also studied effect of several parameters on stability like effect of surfactant type and concentration, stirring speed and temperature on particle size and effect of cosurfactant on thermal and storage stability. Yang and McClements (2013) prepared vitamin E nanoemulsion using natural surfactant, Q-Naturale, based on the quillaja saponin and food-grade MCT oil as oil phase and compared efficacy with emulsion prepared with tween 80. Tween 80 was more effective in reducing the globule size, however, small droplets at relatively low vitamin loadings (40%), whereas Q-Naturale was more effective in vitamin E loading. Air-driven microfluidizer was used for emulsification. Use of glycerol in aqueous phase helped to reduce the globule size by increasing the viscosity of the continuous phase and reducing the interfacial tension. This study suggested effective use of a natural surfactant, Q-Naturale for making edible vitamin E emulsions for beverage applications. Dasgupta et al. (2016) prepared vitamin E nanoemulsion by low-energy wash-out method using mustard oil and tween 80. Use of mustard oil was on the basis of its nonphenolic volatile constituent allylisothiocyanate, which has significant antibacterial activity against various pathogenic microorganisms at very low concentrations. The nanoemulsion exhibited narrow globule-size distribution with mean size of 86 nm and was stable for 15 days without any visible flocculation. Nanoemulsion increased the shelf life of mango juice and also showed improved bioactivity,

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antioxidant, and antimicrobial actions. Raikos (2017) developed orange oil in water-flavored beverage emulsion encapsulating vitamin E and analyzed stability of vitamin E from whey-protein stabilized beverage during a chilled storage after thermal treatment of varying temperatures and exposure. Emulsions were subjected to 63°C for 30 min, 80°C and 90°C for 45 s. The physical stability was assessed by multiple light scattering (Turbiscan) and optical microscopy and the vitamin E content was estimated by reverse-phase high-performance liquid chromatography (RP-HPLC) analysis. Heat treatment had a significant beneficial effect on emulsion stability as indicated by the Turbiscan stability index. Due to mild denaturation whey proteins, an effective rearrangement at the interface had significant beneficial effect on stability of emulsion. All heated beverages were fairly stable for a month. Shu et al. (2016) prepared o/w nanoemulsions for improving the stability of ergocalciferol (vitamin D2) in beverages. Researchers investigated the effect of different stabilizers on the formulation and stability of ergocalciferol-loaded nanoemulsions. Lecithin, an electrostatic stabilizer, sodium caseinate, an electrosteric stabilizer, and decaglycerol monooleate, a stearic stabilizer were explored for the formulation of nanoemulsion by high-pressure homogenization. The stability of nanoemulsions to different environmental stresses was highly dependent on the emulsifier type. No particular emulsifier could provide absolute stability to the nanoemulsions when exposed to different environmental stresses like pH (2–8), ionic strength (0–500 nM), freezethaw cycles (−20°C to 30°C), and high-temperature treatment (80°C, 100°C, or 120°C for 1 h). The nanoemulsions exhibited good physical and chemical stability during storage at 25°C up to 30 days, independent of type of emulsifier. This study gave an insight into selection of appropriate stabilizer considering the commercial processing steps for functional beverages.

7.3.1.4 Catechins Chemically flavanols, catechins, are either epistructured (epicatechin, epicatechin gallate, epigallocatechin, and epigallocatechin gallate) or nonepistructured (catechin, catechin gallate, gallocatechin, and gallocatechin gallate) (Senanayake, 2013). Catechins are not essential to human nutrition, however, have gained importance as they protect human health by preventing diseases. Catechins inhibit carcinogenesis of the skin, esophagus, bladder, prostate colon, liver, lung, stomach, small intestine, and mammary glands and have also shown memory enhancing effect (Gadkari and Balaraman, 2015). Catechins are highly susceptible to change in pH, temperature, moisture, exposure to light, and oxygen (Li et al., 2012a). Nanoemulsification of green tea catechins have shown improved bioaccessibility (Anu Bhushani et al., 2016).

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Tsai and Chen (2016) suggested an advantageous technique for the tea beverage industry to isolate catechins from tea leaf waste and its further utilization by nanoemulsification. Nano-emulsified anionic catechin, 11.4 nm in size, was produced using prolonged sonication lecithin and tween 80. High encapsulation efficiency of 88% and stability for 120  days at 4°C exhibited in improved in  vitro cytotoxicity against prostate cancer cells. To improve physicochemical stability and release profile of green tea catechin, Gadkari et al. (2017) carried out nanoemulsification with sunflower oil with 1-dodecanol as carrier and tween 80 as stabilizer using high-pressure homogenization technique. Carrier lipid and encapsulated catechins were compatible and nanoemulsions with 280 nm globule size were stable for 8 weeks against environmental stress (pH, temperature, and salt concentration). Slow and sustained release of polyphenols was observed from lipid matrix in simulated gastric fluids.

7.3.1.5  Essential Oils The essential oils are naturally occurring highly aromatic volatile antioxidant liquids, usually extracted from parts of plant (flowers, fruits, bark, leaves, stem, fruits, and roots) and are composed lipophilic, poorly water-soluble compounds like aldehydes, carotenoids, flavonoids, isoflavones, terpenoids, and phenolic acids (Seow et  al., 2014). Essential oils are popular flavoring agents in pharmaceuticals, cosmetics as well as in food and beverage industry (Dima and Dima, 2015). Apart from bioactivities like antiinflammatory, antiallergic, and anticancer, essential oils also exhibit antifungal and antimicrobial activity due to the presence of terpenoids and phenolic compounds (Donsì and Ferrari, 2016; Rasooli, 2007; Weiss et al., 2009). Therefore, essential oils are popularly explored as natural preservatives to avoid microbial spoilage of food and beverages (Guerra-Rosas et al., 2017). However, hydrophobic properties of essential oils reduce solubilization effect and create a negative impact on the quality of edible item as well as its antimicrobial efficacy (Sugumar et  al., 2016). Nanoemulsification of volatile oils or their constituents has significantly improved the antimicrobial efficacy (Donsì et al., 2012; Lu et al., 2017; Moghimi et al., 2017; Salvia-Trujillo et al., 2015). Donsì et  al. (2011) investigated nanoemulsion-based delivery of two essential oils, a terpenes mixture extracted from Melaleuca alternifolia and d-limonene, for improving the safety and quality of orange and pear juice while minimally altering the organoleptic characteristics. Lecithin-stabilized nanoemulsion was found to be efficient carrier for the terpenes mixture, while d-limonene was successfully nanoencapsulated with palm oil by high-pressure homogenization. The minimum inhibitory concentration and minimum bactericidal concentration for nanoencapsulated terpenes for E. coli, Lactobacillus

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delbrueckii, and Saccharomyces cerevisiae was significantly lower than that of unencapsulated mixture. Whereas, nanometric encapsulation of d-limonene reduced minimum inhibitory concentration, without any significant variation of the minimum bactericidal concentration in comparison to the unencapsulated d-limonene. Rao and McClements (2013) examined effect of glycerol and propylene glycol as cosolvents and lysolecithin as cosurfactant on the formation and stability of sucrose monopalmitate stabilized lemon oil nanoemulsions. Cosurfactants support stability of emulsion when used along with main surfactant by co-adsorbing at interface and alter various interfacial characteristics like tension, rheology, charge, curvature, thickness, and polarity. Cosolvents are hydrophilic components, easily miscible with water that affects physicochemical and structural properties of the aqueous solutions, thereby altering the performance of the colloidal systems. Lemon oil nanoemulsions with 3% oil phase, 1.4% sugar monopalmitate, and 60.5% sucrose, prepared by high-speed stirring followed by high-pressure homogenization were characterized for particle size, charge, refractive index, and turbidity. Addition of high levels of polar cosolvents made emulsions optically transparent, by reducing the refractive index rather than reducing the globule size. Addition of lysolecithin as a cosurfactant improved stability on storage by influencing optimum curvature and thus preventing coalescence. Researchers attempted making concentrated emulsion by using lemon oil 10%, however, could not fabricate it with low turbidity. Li et al. (2012b) nanoemulsified highly hydrophobic polymethoxyflavones extracted from citrus peel. Being high melting point substance and highly hydrophobic, it is difficult to use for fortification of beverages, dietary supplements, and even in pharmaceuticals. Corn oil, ­medium-chain triglycerides, and orange oil were explored for dissolving 5-hydroxy-6,7,8,4′-tetramethoxyflavone under heating. However, the compound showed tendency to crystallize on cooling to ambient temperature. Nanoemulsions were prepared using different surfactants β-lactogloulin, tween 20, lyso-lecithin, tween 20 or tween 85, and highspeed homogenization followed by high-pressure homogenization. However, 5-hydroxy-6,7,8,4′-tetramethoxyflavone showed tendency to crystalize and sediment in the nanoemulsion. Chang and McClements (2014) and McClements et  al. (2014) designed orange oil nanoemulsion by isothermal low-energy emulsification and high-­pressure homogenization respectively, and studied effect of various formulation, process parameters, and environmental stress on stability of the product. Sugumar et al. (2016) prepared nanoemulsion of orange oil in water with tween 80 as surfactant using ultrasonic processor. Antiyeast activity of this orange oil nanoemulsion was tested in real food system, apple juice against food spoilage yeast, S. cerevisiae and was found to be effective antiyeast even after being diluted in apple juice.

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Trans-cinnamaldehyde a main component of cinnamon oil is commonly used in beverages as a fragrance element. Jo et al. (2015) nanoemulsified trans-cinnamaldehyde with tween 20 as emulsifier using microfluidizer. This nanoemulsion successfully inhibited growth of Salmonella typhimurium and Staphylococcus aureus growth in watermelon juice and thus extending its shelf life. Moghimi et  al. (2017) showed significant antibacterial activity nanoemulsion of trans-cinnamaldehyde and 1,8 cineol against E. coli and S. aureus and Pseudomonas aeruginosa. Xue et al. (2017) emulsified thymol by high-speed homogenization at 12,000 rpm using gelatin and soy lecithin. The nanoemulsion of thymol was found to be more effective antimicrobial than free thymol in milk as well as in cantaloupe juice. Similarly, Ghosh et al. (2014) designed sesame oil nanoemulsion by probe sonication, for the delivery of eugenol to preserve the orange juice. Eugenol-loaded nanoemulsion emulsified with tween 80 and 20, exhibited bactericidal activity against S. aureus. Staining with acridine orange and ethidium bromide for preferential identification of dead bacteria confirmed that eugenol-loaded nanoemulsion altered membrane permeability of bacterial cell resulting in cell death.

7.3.1.6 Curcumin Curcumin, a diferuloylmethane is yellow hydrophobic polyphenol derived from the herb Curcuma longa and has numerous health-­ promoting activities such as antioxidant, antiinflammatory, anticancer, antimicrobial, and free radical scavenger properties (Yu and Huang, 2012). It is a regular component of Indian spice, however, cannot be readily added into beverages due to its aqueous insolubility, which leads to its degradation, low, and variable bioavailability. Joung et al. (2016) formulated curcumin nanoemulsions by varying surfactant concentrations by high-speed homogenization followed by high-pressure homogenization using microfluidizer at 1000 bar for five cycles. MCT oil containing 45% capric acid and 55% caprylic acid was used as oil phase and tween 20 as surfactant. The globule size of emulsion was inversely proportional to surfactant concentration, whereas radical scavenging activity was directly proportional to surfactant concentration. This may be because of generation of more surface area and by facilitating dissolution of more curcumin in oil phase. Higher surfactant concentration retarded the lipid degradation and fortification of milk with curcumin nanoemulsion significantly reduced the lipid oxidation too, showing the potential application of curcumin nanoemulsion for the beverage industry.

7.3.1.7  Coenzyme Q10 Coenzyme Q10 is lipophilic nutraceutical with health benefits for cardiovascular diseases, energy-boosting, has rather low bioavailability in common supplements. A stable, easily redispersible, and

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transparent nanoemulsion of coenzyme Q10 was prepared using high-pressure homogenization at 150 MPa with C valve, for three cycles (Lim et  al., 2010). The coenzyme Q10 nanoemulsion with average globule size of 40 nm did not show flocculation, sedimentation, or creaming when stored at either 4°C or 25°C for 12 weeks. The study indicates the suitability of coenzyme Q10 for nanoemulsification by high-pressure homogenization for preparing beverages in the food industry. Zhao (2016) developed a functional beverage prototype infused with citral and coenzyme Q10 with a specific objective to improve both citral’s stability and coenzyme Q10’s bioavailability by using nanoemulsion-based delivery systems. Citral is a flavor with strong lemon aroma, however, gets easily degraded and oxidized in the acidic beverage applications. Nanoemulsion was prepared using MCT oil and by high-speed homogenization followed by high-­pressure homogenization. Use of saponin and lysolecithin significantly protected sensitive aroma of citral by inhibiting formation of major off-flavors (p-cresol, α,p-dimethylstyrene, p-­ methylacetophenone). Oral pharmacokinetic studies of the developed product in mice showed improved bioavailability of coenzyme Q10 not only in blood stream but also resulted in increased uptake levels in major organ tissues.

7.3.2  SLNs and NLCs SLNs are lipid-based colloidal carrier systems developed as an alternative to liposomes, emulsions, and polymeric nanoparticles (Müller et al., 2002). SLNs typically are spherical particles with average diameters between 50 and 500 nm. SLNs possess a solid core matrix of cost-effective solid biodegradable lipids that solubilize lipophilic molecules, stabilized by surfactants (emulsifiers). They were produced by replacing the liquid lipid (oil) of an o/w emulsion by a solid lipid or a blend of solid lipids and are solid at room temperature. SLNs are composed of 0.1% (w/w) to 30% (w/w) solid lipid dispersed in an aqueous medium and if necessary stabilized with preferably 0.5% (w/w) to 5% (w/w) surfactant. SLNs are manufactured by techniques like high-pressure homogenization, solvent diffusion method, etc. They modulate the release of hydrophilic as well as hydrophobic components, improve their bioavailability, protect the chemically labile molecules, and promote the absorption of lipid matrix through intestinal lymphatics (Makwana et al., 2015). The potential application of SLN includes the encapsulation of bioactive compounds, antimicrobials, or antioxidants (Oehlke et  al., 2017). Nazemiyeh et al. (2016) prepared physicochemicaly stable anionic SLNs of lycopene using Precirol ATO5, Compritol 888 ATO, and myristic acid by hot homogenization for beverage application.

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Due to limited loading capacity and expulsion of entrapped active substance during storage, next-generation SLNs were developed as NLCs. Preferably, solid lipids and liquid lipids are mixed in the range of 70:30–99.9:0.1, in order to obtain blend for particles matrix. The presence of liquid lipid in the particle matrix leads to melting point depression in NLC. NLCs have partially crystalized and controlled nanostructure of mixture of solid and liquid lipids for improved loading and firm hold of active substance during storage (Muchow et al., 2008; Müller et al., 2002; Shidhaye et al., 2008). SLNs have higher water content compared to NLCs, while NLCs have higher lipid content (Pardeike et al., 2009). Also, NLCs show a higher loading capacity for a number of active compounds, a lower water content of the particle suspension, and avoid/minimize potential expulsion of active compounds during storage (Wissing et al., 2004). Astaxanthin, a pink-colored ketocarotenoid produced by fungi, demonstrates wide range of physiological functions due to its antioxidant capacity. Astaxanthin was loaded into NLCs composed of glyceryl behenate as solid lipid, oleic acid as liquid lipid, and α-tocopherol and EDTA as antioxidants (Tamjidi et  al., 2014a,b, 2017). Technique used was melt-emulsification and ultrasonication using tween 80 as hydrophilic and lecithin as hydrophobic emulsifier. Stability of astaxanthin NLCs was analyzed in a model beverage composed with sucrose, 0% or 12% sucrose at pH 3 and 7, in semiactual beverage of whey and actual nonalcoholic beer for up to 2 months at 6°C or 20°C. Adverse effect of carbonation and thermal pasteurization suggested addition of NLCs after carbonation and pasteurization. Ferric pyrophosphate-loaded NLCs were prepared with a view of iron fortification of beverages. NLCs were prepared using palm oil, polyvinyl alcohol, lecithin, and tween 80 by high-speed homogenization followed by coating with chitosan. Coating of NLCs with chitosan, increased the iron encapsulation efficiency, slowed in simulated gastric and intestinal fluids, and protected the NLCs from lipid digestion by lipase, suggesting its applicability for iron fortification of milk, yogurt, fruit juice, and other beverages (Lee et al., 2017). Coenzyme Q10 NLCs with enhanced physicochemical stability and bioavailability were developed for fortification of beverages (Liu et al., 2012). NLCs were prepared by hot high-pressure homogenization at 700 bar for three cycles using mixture of lipids, glycerol monolaurate, acetylated mono- and diglycerides, and octyl and decyl glycerate. Polyglyceryl-10 laurate, gum arabic, and powder soybean lecithin were used as emulsion stabilizers. The NLCs were stable after addition to a model acid beverage with pH 3.4 containing sugar and iron and also after lyophilization. The steric hindrance provided by arabic gum played important role in the stability.

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Quercetin, a common dietary bioactive polyphenol has numerous beneficial effects to human body. However, slow solubility and unstability in alkaline pH, photo, and warm temperature limited its use in beverages. For improving bioaccessibility and use in soft beverages, NLCs of quercetin were prepared by dissolving quercetin in mixture of glyceryl monostearate, glycerolmonolaurate, and caprylic capric triglyceride followed by high-pressure homogenization with aqueous phase containing polyglyceryl-10 laurate, polyglycerol-6 monostearate, and sucroseesters-11 (Ni et al., 2015). The resultant anionic NLCs showed 129 nm diameter and 93.5% entrapment efficiency. These NLCs were added (5%) to simulated aqueous beverage composed of 10% glucose, 0.1% sodium benzoate, 1.56% citric acid, and 0.17% sodium citrate and stored at 4°C, 25°C, and 40°C. The particle sizes increased in the first 15 days rapidly and remained stable for next 2 months, indicating stability. The initial growth in size is attributed to the change in surrounding media. Babazadeh et  al. (2016) fortified three beverages namely, milk, orange, and apple juices with optimum formulation of rutin NLC. Rutin, quercetin-3-rutinoside hydrate, an antioxidant has significant free radical scavenging activity along with nutritional and health-­ promoting effects. Rutin was encapsulated in lipid matrix of cacao butter and oleic acid by high shear homogenization in molten state followed by probe sonication in aqueous tween 80 solution resulting into NLCs with size less than 100 nm. Three beverages were fortified with rutin NLCs namely, low-fat milk, orange juice, and the pH of fortified beverages was adjusted to 6.51, 3.27, and 3.73, respectively, using citric acid. NLCs were found to be stable during processing and storage and had no impact on the appearance of enriched food beverages.

7.3.3  Polymeric Nanoparticles Polymeric nanoparticles encapsulate and protect the bioactives and modulate their release in a temporally or spatially controlled manner. Mucus, a complex hydrogel composed of proteins mainly mucin, lipids, salts, carbohydrates, antibodies, bacteria, and cellular debris, covers the entire gastrointestinal tract and present the potential barrier for uptake of nanoparticles delivered by oral route (Ensign et al., 2012). The surface and surface charge of nanoparticles can be tailored to enhance mucoadhesion for prolonging the residence time at mucosal surface. Chitosan, derived from deacetylated chitin, is a cationic polysaccharide composed of (1,4)-linked 2-amino-2-deoxy-β-d-glucose units. Being nontoxic, biodegradable, biocompatible, and mucoadhesive, chitosan is widely used to prepare nanoparticles (Agnihotri et al., 2004). Chitosan nanoparticles have been explored as fermentation inhibitor of

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legen, a traditional refreshing drink served in Indonesia (Kusuma et al., 2015). Legen is known to have therapeutic benefits like prevention of stomach ulcers and hemorrhoids disease. Legen has a short shelf life of just 2 days and turns alcoholic thereafter. Chitosan nanoparticles of size 50 nm synthesized by reacting chitosan with concentrated ammonia, successfully prevented fermentation of legen for up to 5 days without affecting the aroma and flavor of the drink (Kusuma et al., 2015). Anthocyanins, natural, water-soluble pigments are increasingly being used as natural colorant in food products (Martins et al., 2016). Antocyanins have antioxidant properties and can fight against various neurodegenerative diseases, cancer, diabetes, and inflammation. Use of anthocyanins in functional foods is limited by their instability and low bioavailability. Anthocyanins are sensitive to change in pH, temperature and exposure to oxygen, enzymes, light, and ascorbic acid (Hernandez-Herrero and Frutos, 2015). He et  al. (2017) used carboxymethyl chitosan, a chemical derivative of chitosan with improved solubility for improving stability of anthocyanin. Anthocyanin nanoparticles were prepared by ionic-gelation of negatively charged carboxymethyl chitosan and positively charged chitosan hydrochloride. These two polymers formed a polyelectrolyte film around anthocyanin core, thus delaying its release and maintaining its stability in gastrointestinal tract after oral administration. In addition, these two chitosans are mucoadhesive, having an affinity to intestinal mucosa, prolonging the residence time in the intestinal lumen, thus improving its biological functionality. Optimal preparation parameters were set using statistical and mathematical, Box-Behnken design and response surface methodology to get particles of 219.53 nm size and 63.15% encapsulation efficiency. These polymeric nanoparticles retarded degradation of anthocyanin in simulated gastrointestinal fluid. Stability of anthocyanin was increased when analyzed in artificial model beverage composed of sucrose, citric acid, glucose, sodium chloride, sodium citrate, and potassium monophosphate (He et al., 2017). Zimet and Livney (2009) designed stable nanocomplexes of docosahexaenoic acid, ω-3 polyunsaturated fatty acid by electrostatic interaction of β-lactoglobulin, the major whey protein of cow milk and pectin, a polysaccharide. Entrapped docosahexaenoic acid, showed a mean particle size of 100 nm with good colloidal stability and a transparent dispersion, suitable for enrichment of clear acid nonfat beverages. High affinity of docosahexaenoic acid for β-lactoglobulin resulted higher encapsulation efficiency and strong binding even at low pH. These nanocomplexes were also stable to oxidation during accelerated stress tests of heat stability, indicating its suitability for industrial beverage pasteurization, and cold storage. Chitosan-monomethyl fumaric acid was synthesized by chemical modification of chitosan with monomethyl fumaric acid in the

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presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and explored for nanodelivery of nisin. Nisin, a polycyclic antibacterial peptide produced by the bacterium Lactococcus lactis used to extend the shelf life of the food products, was loaded into chitosan and chitosan-monomethyl fumaric acid nanoparticles were prepared by ionic interactions between the positive amino group of chitosan, chitosan-monomethyl fumaric acid, and negative tripolyphosphate ions (Khan et  al., 2017). Chitosan-nisin and chitosan-monomethyl fumaric acid nanoparticles showed mean particle size of 134.3 and 207.9 nm, encapsulation efficiency of 71.48% and 60.32%, and zeta potential +39.4 and +31.5 mV, respectively. Addition of nisin-loaded chitosan-monomethyl fumaric acid nanoparticles in orange juice significantly improved antimicrobial activity against Gram-positive and Gram-negative bacteria, thus suggesting a potential alternative preservative for beverages. Chitosan-monomethyl fumaric acid can be successfully used as carrier for nanometric delivery of actives in beverages and nisin-loaded chitosan-monomethyl fumaric acid nanoparticles can be used as a novel and direct beverage additive. Previously, Zohri et al. (2010) synthesized nisin-loaded chitosan/ alginate nanoparticles. Chitosan and alginate form polyionic complexes through ionic gelation due to interaction between the amine groups of chitosan and carboxyl groups of alginate which are biocompatible, biodegradable, and efficiently protect the encapsulated actives better than individual polymer. Nisin-loaded nanoparticles were more efficient antibacterial on the growth of S. aureus in raw and pasteurized milk. Recently, Mohammadi et al. (2017) prepared NLCs of lipopholic vitamin D3 for fortification of beverages. Vitamin D plays key role in the development of matrix and mineralization of cartilage and bones and adjusts the serum phosphorus and calcium levels within narrow limits. Because of limited sun-exposure and inadequate dietary intake, there is a high prevalence of vitamin D insufficiency and deficiency worldwide likely. Using Precirol and Compritol as solid lipids, Miglyol and Octyloctanoat as liquid lipids, tween 80, tween 20, and poloxamer 407 as surfactants, Mohammadi et al. (2017) prepared vitamin D3 NLCs by hot homogenization method. After oral administration to male Wistar rats, the NLC formulation exhibited the faster appearance of vitamin D3 in the plasma and also prolonged the plasma levels.

7.3.4 Nanosuspensions Nanosuspensions are the colloidal dispersions stabilized using surfactants or polymers or a combination thereof. Nanosuspensions are commonly referred to as a carrier-free delivery system since it has 100% active substance without any carrier or vehicle. Use of low

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amount of excipients reduces the risk of excipient-associated toxicity. Nanosuspensions are produced either by bottom-up processes by controlled precipitation and crystallization or by top-down nanosizing (Shegokar, 2013). A major advantage of nanosuspension is their ability of loading large amount of drug (Wang et  al., 2013). Nanoparticles in nanosuspension exhibit remarkably enhanced drug solubility and dissolution velocity, due to small particle size. They offer unique advantages, viz., ease of manufacturing and scale-up, reduced batch-to-batch variation in comparison to the other approaches for manufacturing nanostructures (Zhang et  al., 2014). Aditya et  al. (2015) designed novel amorphous curcumin nanosuspensions by avoiding undesired recrystallization by molecularly dispersing the nanosuspension within β-lactoglobulin as stabilizer for incorporation into beverages. Amorphous curcumin nanosuspension was prepared by antisolvent precipitation followed by lyophilization with trehalose as cryoprotectant and added (100 μg/mL) to a model beverage composed of sucrose %w/v, vitamin C 0.1%w/v, and citric acid 0.15% w/v in water. Improved chemical stability of curcumin was attributed to the presence of vitamin C. Maximum solubility and stability at acidic pH indicated its suitability for fortification of fruit juices and carbonated beverages.

7.3.5 Liposomes Liposomes are microscopic vesicles of an aqueous core surrounded by one or more lipid bilayers. The hydration of surfactants such as phospholipids under low-shear force results in liposome formation. Amphiphilic phospholipid molecules arrange themselves in sheets or lamellae to form a bilayer or multilayer membrane around an aqueous core (Tamjidi et  al., 2013). On the basis of their size and lamellarity, liposomes are multilamellar vesicles (five or more concentric aqueous and lipid layers and size 100–1000 nm), or small unilamellar vesicles (comprise a single bilayer surrounding an aqueous compartment and size range 25–100 nm) or large unilamellar vesicles (large aqueous compartment surrounded by a single bilayer and size 100– 1000 nm). Liposomes are a flexible carrier system that can encapsulate both ­water-soluble and water-insoluble compounds simultaneously (Samad et al., 2007). Liposomes are thermodynamically unstable and have tendency to aggregate, fuse, flocculate, or precipitate during storage. Increasing the surface zeta potential and/or coating of liposomes with bulky nonionic polymers provide electrostatic and steric stabilization, respectively. Addition of cholesterol to lipid bilayer also provides physicochemical stabilization by reducing flexibility and fluidity of liposomes (Liu et al., 2017). With a growing understanding of functional behavior, physicochemical, kinetic, and thermodynamic stability of liposomes, along with improved ­manufacturing ­technologies

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and cheap raw materials, it has become feasible to use liposomal products in food and beverages (Khanniri et al., 2016; Taylor et al., 2005). Nonphospholipid paucilamellar vesicles of size 0.1–1.0 μm, with two to five bilayer shells surrounding an unstructured space, termed as Novasomes, were explored for encapsulation of flavors for beverages (Mathur and Capasso, 1997). Laridi et al. (2003) encapsulated nisin Z in liposomes composed of various commercially prepared proliposomes namely, hydrogenated PC, soybean PC, charged phospholipids, and various other soy-based unsaturated phospholipids. Nisin-Z encapsulated liposomes in milk were able to withstand the cheese manufacture temperature cycle without statistically significant losses of entrapped material. Longterm stability for 27 days was observed for liposome-encapsulated nisin Z at 4°C in milk with different fat levels (3.25%, 2.0%, and 1.0%), skim milk, sweet whey, and phosphate buffer saline. Xia and Xu (2005) prepared liposomes of ferrous sulfate using egg lecithin, cholesterol, and tween 80 by four different methods namely thin film hydration, thin film sonication, freeze thawing, and reverse-phase evaporation. Ascorbic acid was added as an antioxidant to protect the ferrous ion against oxidation. Reverse-phase evaporation technique exhibited highest encapsulation efficiency of 67% among the four techniques employed. Milk fortified with ferrous sulfate liposomes added was boiled for 30 min without any visible heat instability like coagulation or aggregation. One-week storage at 4°C revealed stability without any precipitation and coagulation. The sensory evaluation of fortified milk showed no significant different difference in color and off-flavor compared to control milk. Nanoliposomal vitamin D3 was prepared by Mohammadi et al. (2014) for addition to beverages. Vitamin D3 was encapsulated in anionic liposomes composed of soy lecithin and cholesterol using thin film hydration and probe sonication process with very high entrapment efficiency.

7.4  Concluding Remarks Evidently, beverage industry is getting inclined toward the design and production of food-grade nanostructures in order to encapsulate, protect, and enhance the functionality of bioactives in beverages. Fortification of beverages with nanoscaled bioactives is increasingly the focus of research and development efforts of beverage industry because of the obvious benefits offered by nanoengineering over the conventional delivery, like transparency, increased bioavailability, and improved physicochemical stability. Nanometric size, not only improves nutritional benefits but also adds to sensory qualities during

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storage and consumption, which is ultimately responsible for the success of a new product development. However, there are certain critical aspects that need to be thoroughly investigated prior to its wide spread usage in beverages (Fig. 7.3). Nevertheless, beverage industry would prefer to use nanostructures derived from commonly used edible ingredients like milk proteins, polysaccharides, aromatic oils, and natural extracts. Different chemical properties of variety of bioactives need detailed experimentation for fortification to avoid change in sensory and nutritional value of original beverage over the desired shelf life. Process of manufacture should be robust and economical too. In addition, reported examples are from research laboratories and may be challenging for scale-up for commercial application. It would be advisable and beneficial to use techniques and equipments of commercially scalable manufacturing, in order to minimize the lead time. Manipulation of material in nanometer range results in novel properties, however, may also result in toxicity after consumption of nanostructures. Therefore, detailed clinical investigations are required to establish the safety of these nanostructures in beverages. Apart from scientific constraints and practicality of manufacturing, beverages also have to comply regulatory recommendations with respect to ingredients like preservatives, sweeteners, health promotional claims, and tolerable upper intake levels of the added nutraceuticals. This scenario indicates tremendous opportunities exist in design and development of nanoengineered nutraceuticals for tailoring the functionality of beverages.

Fig. 7.3  Attributes for successful development of nanostructures fortified beverages.

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Acknowledgments The authors SP and AJ gratefully acknowledge funding from the Department of Science and Technology (DST), Govt. of India and Science and Engineering Research Board (SERB, DST, Govt. of India), respectively, during the completion of the chapter.

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