Amelioration of the stability of polyunsaturated fatty acids and bioactive enriched vegetable oil: blending, encapsulation, and its application

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提高富含多不饱和脂肪酸和生物活性物质的植物油的稳定性:共混、包埋及其应用

作者 Monalisha Pattnaik; Hari Niwas Mishra 期刊 Critical Reviews in Food Science and Nutrition 发表日期 2021 ISSN 1040-8398 DOI 10.1080/10408398.2021.1899127 类型 原创研究 (Original Research)

📄 中文摘要 Chinese Abstract

中文
富含多不饱和脂肪酸(PUFAs)和单不饱和脂肪酸(MUFAs)的植物油容易发生氧化降解,导致酸败、异味和保质期缩短。为应对这些挑战,食品技术人员采用氢化、分提、酯交换和调配等改性技术。其中,将非常规油与常规油进行调配是一种经济有效的策略,可在不产生有害反式脂肪酸的前提下改善营养特性和氧化稳定性。然而,由于高不饱和度,调配油仍易发生氧化。微胶囊化技术通过在油滴周围形成保护屏障,为提高油脂的稳定性、耐热性和生物利用度提供了有前景的解决方案。本综述重点介绍了旨在提升食用油稳定性和营养价值的调配与微胶囊化技术的最新研究进展。

📋 英文结构化总结 English Structured Summary

全文整理

EN

Background:

Vegetable oils rich in polyunsaturated fatty acids (PUFAs) and monounsaturated fatty acids (MUFAs) are prone to oxidative degradation, leading to rancidity, off-flavors, and reduced shelf-life. To address these challenges, food technologists employ modification techniques such as hydrogenation, fractionation, interesterification, and blending. Among these, blending non-conventional and conventional oils is a cost-effective strategy to enhance nutritional profiles and oxidative stability without generating harmful trans fats. However, blended oils remain susceptible to oxidation due to their high unsaturation. Microencapsulation offers a promising solution by forming a protective barrier around the oil, improving its stability, thermo-resistance, and bioavailability. This review focuses on recent advances in blending and microencapsulation technologies aimed at enhancing the stability and nutritional value of edible oils.

Methods:

This is a review article that synthesizes findings from existing literature on vegetable oil blending and microencapsulation. The methodology involves a comprehensive analysis of studies related to the physicochemical, thermal, and oxidative properties of blended oils, as well as various encapsulation strategies including oleogels, oil beads, coacervation, and oil powder production. Techniques such as spray-drying, freeze-drying, coacervation, melt-extrusion, and emerging methods like microwave drying and spray chilling are discussed. The selection of wall materials—such as maltodextrin, proteins, gums, and polysaccharides—and their impact on encapsulation efficiency and stability are also evaluated based on published experimental data.

Results:

Blending vegetable oils significantly improves oxidative stability and nutritional balance. For example, combining flaxseed oil (FSO) with rice bran oil (RBO) in a 2:1 ratio reduced peroxide and acid values, while ternary blends (FSO:RBO:OO at 2:1:1) showed even greater stability due to synergistic antioxidant effects from oryzanol and tocopherols in RBO. Blending olive oil (OO) with sunflower or soybean oil increased total phenolic content and radical scavenging activity from ~55% to nearly 78%. A blend of 80% RBO and 20% sesame oil demonstrated antihypertensive and lipid-lowering effects in hypertensive patients. Microencapsulation further enhances protection: oleogels using waxes or ethylcellulose form thermoreversible gels that immobilize oil in 3D networks; oil beads made with alginate or pectin achieve encapsulation efficiencies >98%; complex coacervation using gelatin-gum Arabic yields up to 84% efficiency; and spray-dried oil powders improve handling and shelf-life. Encapsulated systems show reduced oxidation, better retention of bioactives, and controlled release.

Data Summary:

Key quantitative findings include: peroxide values as low as 0.33 mEq/kg in RBO–olive oil blends; induction periods of 18.7 h for RBO compared to 4.2 h for walnut oil; up to 43% reduction in polymer triacylglycerol formation in 50% RBO–sunflower oil blends after heating at 180°C; radical scavenging activity increasing from 55% to 78% with 20–40% olive oil addition; total phenolics rising from 10.5 to 51 mg/100g in soybean oil with olive oil blending; encapsulation efficiencies of 98.7% in alginate-shellac oil beads, >93.9% in chia seed gum–protein coacervates, and 84% in gelatin-gum Arabic capsules; and oil loads up to 75% in microparticles with >99.5% efficiency using Tween 20 and alginate.

Conclusions:

Blending vegetable oils is an effective, economical method to achieve balanced fatty acid profiles (MUFA:PUFA and ω-6:ω-3 ratios) aligned with WHO recommendations, while enhancing oxidative stability through natural antioxidants. Microencapsulation technologies—particularly oleogels, coacervation, and spray-drying—significantly improve the stability, shelf-life, and functionality of PUFA-rich oils. These approaches mitigate lipid oxidation, enable controlled release, and facilitate incorporation into diverse food matrices. The choice of wall material and encapsulation technique critically influences efficiency, stability, and application potential. Together, blending and microencapsulation offer scalable, clean-label strategies to produce healthier, more stable edible oils without hydrogenation.

Practical Significance:

The application of blended and microencapsulated oils spans the food, pharmaceutical, and nutraceutical industries. Omega-rich microcapsules are used in confectionery, dairy, ice cream, and dietary supplements to deliver essential fatty acids without compromising taste or stability. Oleogels serve as trans-fat-free solid fat alternatives in baked goods and chocolates. Encapsulated oils enable fortification of functional foods with bioactive compounds like γ-oryzanol and tocopherols, supporting cardiovascular health. These technologies support clean-label trends, extend product shelf-life, and enhance nutritional value, making them vital for developing next-generation healthy food products.

📋 中文结构化总结 Chinese Structured Summary

中文

背景:

富含多不饱和脂肪酸(PUFAs)和单不饱和脂肪酸(MUFAs)的植物油容易发生氧化降解,导致酸败、异味和保质期缩短。为应对这些挑战,食品技术人员采用氢化、分提、酯交换和调配等改性技术。其中,将非常规油与常规油进行调配是一种经济有效的策略,可在不产生有害反式脂肪酸的前提下改善营养特性和氧化稳定性。然而,由于高不饱和度,调配油仍易发生氧化。微胶囊化技术通过在油滴周围形成保护屏障,为提高油脂的稳定性、耐热性和生物利用度提供了有前景的解决方案。本综述重点介绍了旨在提升食用油稳定性和营养价值的调配与微胶囊化技术的最新研究进展。

方法:

本文为综述类文章,综合分析了植物油调配与微胶囊化领域的现有文献。研究方法包括对调配油的物理化学、热学及氧化特性相关研究进行全面分析,并探讨多种封装策略,如油凝胶、油珠、复凝聚及油粉制备。文中讨论了喷雾干燥、冷冻干燥、复凝聚、熔融挤出以及微波干燥和喷雾冷却等新兴技术。同时,基于已发表的实验数据,评估了壁材(如麦芽糊精、蛋白质、树胶和多糖)的选择对包封效率和稳定性的影响。

结果:

植物油调配显著提升了氧化稳定性和营养平衡性。例如,亚麻籽油(FSO)与米糠油(RBO)以2:1比例混合可降低过氧化值和酸值;三元调配(FSO:RBO:OO = 2:1:1)因RBO中谷维素和生育酚的协同抗氧化作用而表现出更优的稳定性。将橄榄油(OO)与葵花籽油或大豆油调配后,总酚含量和自由基清除率从约55%提升至近78%。80% RBO与20%芝麻油的调配油在高血压患者中显示出降压和降脂效果。微胶囊化进一步增强保护效果:使用蜡或乙基纤维素形成的油凝胶可构建热可逆凝胶,将油固定于三维网络中;以海藻酸盐或果胶制备的油珠包封效率超过98%;明胶-阿拉伯胶复凝聚体系包封率可达84%;喷雾干燥油粉则改善了操作性和货架期。封装体系表现出更低的氧化程度、更好的生物活性成分保留能力以及可控释放特性。

数据总结:

关键定量结果包括:RBO-橄榄油调配油的过氧化值低至0.33 mEq/kg;RBO的诱导期为18.7小时,而核桃油仅为4.2小时;在180°C加热后,50% RBO-葵花籽油调配油中聚合物三酰甘油生成量减少高达43%;添加20–40%橄榄油后,自由基清除率从55%提升至78%;大豆油中总酚含量从10.5 mg/100g增至51 mg/100g;海藻酸盐-虫胶油珠的包封效率达98.7%,奇亚籽胶水-蛋白质复凝聚体系超过93.9%,明胶-阿拉伯胶微胶囊为84%;使用Tween 20和海藻酸盐制备的微粒含油量高达75%,包封效率超过99.5%。

结论:

植物油调配是一种经济有效的方法,可实现符合WHO推荐的均衡脂肪酸比例(MUFA:PUFA 和 ω-6:ω-3 比值),并通过天然抗氧化剂提升氧化稳定性。微胶囊化技术——尤其是油凝胶、复凝聚和喷雾干燥——显著提高了富含PUFA油脂的稳定性、货架期和功能特性。这些方法可抑制脂质氧化、实现可控释放,并促进油脂在多种食品基质中的应用。壁材和封装技术的选择对包封效率、稳定性及应用潜力具有决定性影响。调配与微胶囊化相结合,为生产更健康、更稳定的食用油提供了可扩展的清洁标签策略,无需依赖氢化工艺。

实际意义:

调配油与微胶囊化油广泛应用于食品、制药和营养保健品行业。富含Omega脂肪酸的微胶囊可用于糖果、乳制品、冰淇淋和膳食补充剂中,在不影响口感或稳定性的前提下提供必需脂肪酸。油凝胶可作为烘焙食品和巧克力中无反式脂肪的固体脂肪替代品。封装油脂可用于强化功能性食品中的生物活性成分(如γ-谷维素和生育酚),支持心血管健康。这些技术契合清洁标签趋势,延长产品货架期并提升营养价值,是开发下一代健康食品的关键技术。

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Amelioration of the stability of polyunsaturated fatty acids and bioactive enriched vegetable oil: blending, encapsulation, and its application

Monalisha Pattnaik & Hari Niwas Mishra To cite this article: Monalisha Pattnaik & Hari Niwas Mishra (2021): Amelioration of the stability of polyunsaturated fatty acids and bioactive enriched vegetable oil: blending, encapsulation, and its application, Critical Reviews in Food Science and Nutrition, DOI: 10.1080/10408398.2021.1899127

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View related articles View Crossmark data REVIEW Amelioration of the stability of polyunsaturated fatty acids and bioactive enriched vegetable oil: blending, encapsulation, and its application

Monalisha Pattnaik and Hari Niwas Mishra Agricultural and Food Engineering Department, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, India

ABSTRACT Lipid oxidation in vegetable oils is the primary concern for food technologists. Modification of oils like hydrogenation, fractionation, inter-esterification, and blending are followed to improve nutri- tional quality. Blending non-conventional/conventional vegetable oils to obtain a synergistic oil mixture is commonly practiced in the food industry to enhance the nutritional characteristics and stability of oil at an affordable price. Microencapsulation of these oils provides a functional barrier of core and coating material from the adverse environmental conditions, thereby enhancing the oxidative stability, thermo-stability, shelf-life, and biological activity of oils. Microencapsulation of oils has been conducted and commercialized by employing different conventional methods including emulsification, spray-drying, freeze-drying, coacervation, and melt-extrusion compared with new, improved methods like microwave drying, spray chilling, and co-extrusion. The microen- capsulated oil emulsion can be either dried to easy-to-handle solids/microcapsules, converted into soft solids, or enclosed in a gel-like matrix, increasing the shelf-life of the liquid oil. The omega- rich microcapsules have a wide application in confectionery, dairy, ice-cream, and pharmaceutical industries. This review summarizes recent developments in blending and microencapsulation tech- nologies in improving the stability and nutritional value of edible oils.

KEYWORDS Application; blending; encapsulation; microcap- sules; oxidative stability

Introduction Vegetable oils extracted from various plant seeds are rich in polyunsaturated fatty acids (PUFAs) and monounsaturated fatty acids (MUFAs). These oils, due to their specific chem- ical and physical properties, are limited in technological application. Hence, modification like hydrogenation, frac- tionation, interesterification, and blending is mostly followed (Hashempour-Baltork et al. 2016). Hydrogenation utilizes catalysts such as hydrogen and nickel gas that saturates the unsaturated double bond and converts cis to a trans-state.

Trans fatty acids are supposed to have toxic effects on human health (Iqbal 2014). Interesterification is an elective procedure for hydrogenation. Unsaturated fats are redistrib- uted in the triacylglycerol structure amid this procedure, and no immersion or isomerization happens. In any case, this procedure needs uncommon and is costlier (Dijkstra

2015). Fractionation is a procedure in which a few fats/oils are isolated into two divisions with various dissolving and textural properties (Kellens et al. 2007). Fractionation can be utilized as a pretreatment preceding hydrogenation, interes- terification, or mixing (Shahidi 2005). Therefore, blending is the simplest method of mixing diverse fats/oils with unique physical and compound attributes. Mixing vegetable fats/oils with various properties is one of the least complex techni- ques to make new explicit items with wanted nutritional and oxidative properties. The blended oil is rich in MUFA/

PUFA, which makes it chemically unstable and susceptible to oxidation. The exposure of oxygen to these oils creates cleavage in the unsaturated bonds, thereby elevating the oil rancidity. The unpleasant odor has a negative impact on the sensory attributes and lowers the overall acceptability. Thus, microencapsulation innovation could be a reasonable alter- native to maintaining its textural, sensory, and oxidative characteristics.

Microencapsulation is the process of enveloping one sub- stance termed as core material into another called wall/coat- ing materials, improving stability and functional properties.

Microencapsulation and controlled release of flavors have too reformed the nourishment, enhancing the flavor, stabil- ity, nutritive value, and appearance of their products (Pattnaik et al. 2021). In these regions, the conversion of liquid to easy-to-handle dry powders, gels, or beads were the inspirations for the utilization of microcapsules. The dif- ferent types of microcapsules and microspheres are pro- duced from a wide range of wall materials like carbohydrates, proteins, gums, etc. There are several differ- ent microencapsulation processes, such as spray-drying, coaxial electrospray system, freeze-drying, coacervation, in situ polymerization, melt-extrusion, etc. (Albert, Vatai, and

Koris 2017; Bakry, Abbas, et al. 2016; Adelmann, Binks, and

Mezzenga 2012).

CONTACT Monalisha Pattnaik monalisha.pattnaik21@gmail.com; monalisha.pattnaik21@iitkgp.ac.in

Agricultural and Food Engineering Department, Indian

Institute of Technology Kharagpur, Kharagpur, West Bengal-721302, India.

 2021 Taylor & Francis Group, LLC CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION https://doi.org/10.1080/10408398.2021.1899127

There have been numerous review papers describing the blending of vegetable oils and their effect on their physico- chemical properties, the methodology of microencapsulation of different core materials like volatile flavors, probiotics, essential oils but none of them have focused on vegetable oil encapsulation and its related problems (Juric et al. 2020;

Bakry, Abbas, et al. 2016; Kaushik et al. 2015b). Hence, this review paper will provide a concise reading to the research- ers covering all the aspects starting from vegetable oil blend- ing to oil powder/gel through microencapsulation. The paper focuses on the impact of vegetable oil blending on the nutritional, compositional, thermal, oxidative, and physical properties of the edible oils; providing a clear understanding of the selection of wall materials for encapsulation of vege- table oil, and the advantages and disadvantages of various conventional and emerging encapsulation techniques.

Blending of vegetable oils Formulation of an admix of edible oil to improve the health and nutritional aspect of edible oil is seeking little attention.

To be counted as a healthy oil, the blending of vegetable oils has been a recent trend followed by most industries.

“Healthy oil” by definition is the edible cooking oil that sat- isfies the fatty acid compositions recommended by World

Health Organization (WHO) to prevent various diseases like diabetes, chronic heart disease, obesity (WHO 2008). Fats are an essential part of a healthy balanced diet; there is a shred of evidence to show that limiting saturated and trans fat intake is important since it contributes to the lessening of the build-up of fatty material (plaque) inside the blood vessels (arteries). This process is called atherosclerosis and is a major cause of heart disease. Saturated fatty acid (SFA) and trans fats increase low-density lipoprotein (LDL) choles- terol in the blood, which leads to plaque formation (Ference et al. 2017). PUFAs and MUFAs reduce LDL cholesterol and increase high-density lipoprotein (HDL) cholesterol (Manchanda and Passi 2016). MUFAs are beneficial in that they increase esterification of cholesterol in the liver, thereby reducing the free cholesterol pool and increasing receptor- mediated uptake of LDL cholesterol, resulting in a decrease in blood cholesterol levels as reported by the Dietary

Guidelines Advisory Committee on the Dietary Guidelines for Americans, 2010. It can be seen from the studies that even higher consumption of PUFA has an adverse impact on the health by weakening the capability of the antioxi- dants in the human body to tackle free radicles, thereby increasing the risk of aging, cardio-related issues, diabetes, and cancer (Choudhary and Grover 2013; WHO 2008; Vani,

Laxmi, and Sesikeran 2002). According to WHO, the total fat intake should be 30%–35% Total energy, SFA <10%,

MUFA 10%–14%, PUFA 6%–11% Total energy (WHO 2008). However, to maintain good heart health, x-6 and x-3 must vary between 1:1 and 4:1 (Mishra and Manchanda

2012). Henceforth, a balanced ratio of MUFA, PUFA as well as essential fatty acids like x-6 and x-3 is essential to main- tain a modulated lipid profile in the human body. A bal- anced fatty acid composition can be achieved by adopting vegetable oil blending practice, which will eliminate the need for hydrogenation or inter-esterification of oils.

Effect of blending on the physical, chemical, and thermal properties

Lipid oxidation of edible oil has resulted in the development of off-flavors and rancidity, drastically lowering the stability of these oils, thereby imposing a pronounced negative effect on human health (Adbel-Razek et al. 2011). Therefore, the mixing of various edible oils is an economical way of enhancing oxidative stability by strengthening their antioxi- dant potentials (Table 1). For instance, flaxseed seed oil (FSO) and olive oil (OO) are rich in unsaturated fatty acids in terms of x-3 and x-9, respectively, making it prone to oxidative and hydrolytic cleavage of the double bonds.

However, FSO, when combined with rice bran oil (RBO) in the ratio 2:1, exhibited a lower peroxide value, p-anisidine value, and acid value (Ghosh, Srivastava, et al. 2019).

Furthermore, a ternary blend of FSO, RBO, and OO in the ratio 2:1:1 showed an exceptionally lower value of peroxide, p-anisidine, and free fatty acid (Ghosh, Srivastava, et al.

2019). RBO is a non-conventional oil; it has oryzanol, toco- trienols, and tocopherols in abundance along with squalene and phytosterol. The presence of oryzanol and trienols in

RBO might have slowed down the formation of obnoxious compounds like aldehyde, ketones, and free radicles (Choudhary and Grover 2013; Reddy et al. 2013). Similarly, on blending RBO in different concentrations with OO, it showed the least peroxide value (0.53 and 0.33 mEq/kg), and highest when blended with mustard oil (MO), i.e., 1.73 and 1.33 mEq/kg. The possible reason for such disparity may be due to the variation in MUFA and PUFA in the respective oil blends. The blend containing a higher amount of MUFA or oleic acid than PUFA ought to slow down the oxidative degradation during shelf-life and frying (RBO þ OO: 42% oleic acid, 36.9% PUFA and RBO þ MO:

32.3% oleic acid and 50.8% PUFA) (Choudhary, Grover, and Kaur 2015). Although walnut oil (WO) and grape seed oil (GSO) has the same MUFA and PUFA content, the pres- ence of a lower quantity of x-3 in GSO doubles its oxidative stability. Given the MUFA content, both RBO and toasted sesame oil (TSO) possess a similar amount. However, due to the prevalence of potent antioxidant components in RBO, it has a slightly higher induction period than TSO and 4 times higher than WO (18.7 h vs. 18 h vs. 4.2 h). The antioxidants activity of TSO in terms of tocopherol, sesamol a potent antioxidant formed from sesamolin lies on the higher side than the refined sesame oil (Kochhar and Henry 2009).

Similar results were reported by Pattnaik and Mishra (2021), the addition of RBO (above 70%) to groundnut oil (GO) and FSO provided substantially higher oxidative stability.

Consequently, owing to the pre-dominant bio-active compo- nents, RBO is labeled as “heart oil” and also considered to satisfy the fatty acid composition recommended by WHO (Choudhary, Grover, and Kaur 2015). Sometimes, cold- pressed oil can be a great option to improve stability. The cold-pressed oils are more endowed with nutritive properties

2 M. PATTNAIK AND H. N. MISHRA as they do not undergo any chemical or heat treatment, keeping the antioxidants or antioxidant precursors intact.

Cold-pressed OO is the most desirable substitute for con- ventional oils because of its natural antioxidants, mainly phenols, and tocopherols. Thus, on mixing 20 and 40% of

OO with sunflower oil (SFO) and soybean oil (SBO), it increases the radical scavenging activity of the individual oils from 55% to nearly 78% and the total phenolic content of SBO to 10.5 to 51 mg/100g, SFO 20.5 to 69.5 mg/100g (Abdel-Razek et al. 2011). Another such blend between non- conventional RBO and traditional OO (70:30) showed a bet- ter oxidative and antioxidant stability even after 28days of storage, possessing 2525mg/kg of total natural antioxidants and 67.7% radical scavenging activity (Choudhary and Grover

2013). Several non-conventional oils like black cumin oil, gar- den cress oil (GCO), moringa oleifera oil, MO, and camellia oil have a substantial amount of antioxidative potentiality, hence, can be reviewed for judicious blending (Umesha and

Naidu 2015; Wang et al. 2016; Mohamed, Elsanhoty, and

Hassanien 2014; Anwar et al. 2007).

Color and viscosity are the prime attributes associated with the deep frying of oils. Higher viscosity denotes the formation of polymers or primary and secondary oxidation products. Low viscosity is indicative of unsaturation and

Table 1. Major findings of physicochemical properties and health benefits of various vegetable oil blends.

Oil blend MUFA:PUFA n6:n3 Findings Health benefits

References Flaxseed þ tomato seed oil; Flaxseed þ tomato seed oil þ rice bran oil

— — Highest antioxidant activity and phytochemical content with excellent oxidative stability

— Ghosh, Srivastava, et al. (2019) Sunflower oil þ sesame oil

0.70 — Increased stability of sunflower oil — Ghosh, Upadhyay, et al. (2019)

Olive oil þ sunflower oil þ cress oil 1.5 4.8 Improved the functional characteristics, thermal and oxidative stability of individual oils

Balanced MUFA, PUFA & essential fatty acids have beneficial effects on cardiovascular health

Nehdi et al. (2019) Rice bran þ sesame oil 1.19 88.9

Rich source of antioxidants and unsaturated fatty acids

Antihypertensive and lipid- lowering action Devarajan et al. (2016)

Canola oil þ palm oil 1.62 2.92 Enhanced oxidative stability

Improvement in biochemical parameters and serum fatty acids

Adeyemi et al. (2016) Rice bran oil þ partially hydrogenated oil

2.42 21.8 Increased the antioxidants majorly oryzanol content

Lowering of adverse effects and pro-inflammatory effects of pure partially hydrogenated oil

Rao, Kumar, and Lokesh (2016) Olive oil þ sunflower oil; olive oil þ soybean oil

3.33;4.14 13.43;12.24 Higher in dietary MUFA content

Cardioprotective activity through lipid-lowering and plasma cholesterol reduction causing hypolipidemia

Jan et al. (2016) Canola oil þ palm oil/ sunflower oil

2.62;1.10 12.5; 4.76 Frying stability of the blended oils

Improved lipid profile of dietary rats El-Reffaei et al. (2016)

Soybean oil þ camellia oil 1.17 6.4 Thermal and frying stability of soybean oil due to increased phenols and

MUFA in camellia oil — Wang et al. (2016) Rice bran oil þ peanut oil

0.75 — Thermally stable to high cooking and frying conditions

— Choudhary, Grover, and Kaur (2015) Rice bran þ garden cress oil; Sesame oil þ garden cress oil

1; 0.93 2.2; 2.4 Increase the antioxidant activity of oils

No significant change in serum and liver peroxide content; deceased total cholesterol and regulated lipid profile

Umesha and Naidu (2015) Sunflower oil þ garden cress oil

0.56 2.3 Balanced essential fatty acids Enhanced radical scavenging activity and decreased total cholesterol

Umesha and Naidu (2015) Canola oil þ olive oil þ palm oil

2.66 3.74 Increased stability by modifying the fatty acid composition

— Roiaini, Ardiannie, and Norhayati (2015) Soybean þ sesame oil

0.55 — Better oxidative stability at high temperatures

Prevention of chronic diseases associated with oxidative stress, such as in cancer and coronary artery disease

Li et al. (2014) Rice bran þ olive oil 1.42 2.14 High smoke point and frying temperature with good retention of antioxidants, lower acid value, and least peroxide formation

Favorable effects on cholesterol regulation and LDL cholesterol oxidation

Choudhary and Grover (2013) Rice bran þ flaxseed oil

1.1 4.0 Possessed good oxidative stability over the storage time

Functional and health- promoting oil blend with an ideal balance of fatty acids

Reddy et al. (2013) Palm oil þ olive oil 4.4 34.8 Better oxidative stability of the blend with 20% olive oil comparable to palm oil

Comparable health benefits linked to cholesterol, LDL,

HDL, and triglycerides De Leonardis and Macciola (2012)

CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION 3 average fatty acid carbon length. Similarly, the color of indi- vidual oils changes after blending and almost darken after repeated frying at high temperature because of the accumu- lation of oxidation compounds. The blend of RBO and GO shows an appreciable smoke and frying temperature ranging between 160 and 182 C (Choudhary, Grover, and Kaur

2015). As RBO is related to the high 4-monomethylsterols content with an ethylidene side chain, it may have contrib- uted to its high smoke point oxidative stability. Besides, ory- zanol is a combination of ester compounds that aid in stabilizing oils at frying temperatures. To meet the standards of frying oils, the frying temperature of vegetable oil should not exceed 180 C as high temperature accelerates oxidation, polymerization, and free fatty acid formation of oils. When an oil blend of 50% RBO and 50% SFO was heated at

180 C, it caused a 43% reduction in polymer triacylglycerol formation in the blend than SFO (Mezouari and Eichner

2007). A blend of canola oil and palm oil (1:1), when used for frying at 180 C, was acceptable up to 3 frying cycles with respect to its change in physical and chemical proper- ties (Enrıquez-Fernandez, Alvarez de la Cadena y Ya~nez, and Sosa-Morales 2011). Palm oil admixed with 20% OO led to a 32% reduction in the formation of short-chain fatty acids on heating at 130 C due to the saturated fats present in palm oil, which favored less PUFA loss in the blend (De

Leonardis and Macciola 2012). Henceforth, mixing OO more than 20% might lower the stability due to the excessive

PUFA content. SBO might be considered as one of the superior vegetable oil, but it is regarded to be inferior in thermal stability at high temperatures. A binary mixture of

SBO with sesame oil (SEO) (80:20 v/v) might enhance the lipid oxidative stability of fried products when fried at

160 C (Li et al. 2014). Therefore, a better choice of vege- table oils and careful oil blending will govern the change in fatty acid composition and antioxidants affecting the overall quality of oils.

Effect of blending on the nutritional value According to the World Health Organization, the most important criteria for the nutritional evaluation of oils are: (i) ratio of saturated, mono, and polyunsaturated fatty acids, (ii) ratio of Ꞷ-6 and Ꞷ-3, and (iii) presence of antioxidants.

As previously mentioned, the optimum ratio of saturated, mono, polyunsaturated fatty acids and Ꞷ-6, Ꞷ-3 to main- tain a healthy heart is 1:1.5:1, 1:1–4:1, respectively.

Ꞷ-6 and Ꞷ-3 are the essential fatty acids to regulate the body’s functioning. Due to the lack of omega-3 desaturase, a converting enzyme in human cells, they can neither convert

Ꞷ-6 to Ꞷ-3 nor can produce it. Hence, it needs to be pro- vided externally through dietary intake. Linoleic acid (LA) and eicosapentaenoic acid (EPA) are the parent x fatty acids

6 and 3, respectively, which produce eicosanoids responsible for the physiological changes in the human body. The eico- sanoids produced from both the x fatty acids have opposite properties. The larger quantities of Ꞷ-6 are a common problem in Western diets. It increases the eicosanoid meta- bolic products from LA, particularly hydroxy fatty acids, thromboxanes, lipoxins, prostaglandins, and leukotrienes than EPA. The eicosanoid produced from LA should be in lower quantities to become biologically active. On the con- trary, the larger quantities of eicosanoids formed from LA contribute to the formation of thrombus and atheromas with high blood viscosity, few allergic and inflammatory dis- orders leading to the proliferation of cells in most vulnerable people (Simopoulos 2016). A careful blending of oils will maintain a balanced fatty acid composition. Devarajan et al. (2016) claimed that a blend of 20% cold-pressed, unrefined

SEO with 80% RBO showed excellent results in lowering the blood pressure and modulating lipid profiles such as an increase in HDL and LDL decrease after treating hyperten- sive patients. Blending of Ꞷ-3 rich GCO with Ꞷ-6 rich

SFO, SEO, and RBO significantly reduced the radical scav- enging activity (IC50), improved the antioxidants, lowered the Ꞷ-6: Ꞷ-3 ratio in Wister rats. It is noteworthy that it also increased the Glutathione peroxidase and catalase activ- ity, protecting against oxidative damage (Umesha and

Naidu 2015).

A similar reduction of LDL cholesterol and triglycerides in rats was observed by Sharma and Lokesh (2013) on mix- ing Ꞷ-3 rich FSO with GNO. A significant reduction in serum cholesterol by 27%–29% in hamsters was achieved when fed with blended oils of OO with SFO and SBO, but higher intake of soybean oil beyond 20% can lead to exces- sive weight gain, hyper-sensitive, higher blood glucose level, increased risks of the tumor (Jan et al. 2016; Li et al. 2014).

Thence, OO has Ꞷ-3 in abundance and can be a potential oil for blending with other Ꞷ-6 rich oils such as SEO, RBO, or SFO. Apart from essential fatty acids, OO is a source of a wide variety of antioxidants, predominantly hydroxytyrosol, tocopherols, and oleuropein, which are primarily responsible for lowering LDL cholesterol, exhibit anti-inflammatory, anti-hypersensitive, and antithrombotic like health benefits (Choudhary and Grover 2013). Tocopherols, c-oryzanol, and phytosterol-rich vegetable oils possess a strong inhibition of oxygen radicles, risk of cancer, and anti-atherogenic effect.

This c-oryzanol particularly is associated with a strong inhibiting power against ADP and collagen-related platelet aggregation (Cicero and Derosa 2005). An effective blending of oils consisting of health-promoting antioxidants, several bioactive compounds, and Ꞷ-3, Ꞷ-6 incorrect amount will lessen mortality and facilitate more flexibility in contributing nutritional properties.

Encapsulation strategies for oils Encapsulation of vegetable oils means trapping liquid oil into a matrix to obtain the desired effect. Vegetable oils are encapsulated to mask its aroma, flavor, color, increase its oxidative stability, control its release, and increase its bio- availability (Sagiri, Anis, and Pal 2016; Adelmann, Binks, and Mezzenga 2012; Tonon, Grosso, and Hubinger 2011).

Hence, depending upon the desirability of the product, the liquid oil is either converted into gels, beads, or powder.

4 M. PATTNAIK AND H. N. MISHRA Oleogels One of the encapsulation methods of reducing the use of saturated fats in food applications is the formulation of oleo gels. Oleogels are mostly the structured oils that are pre- ferred to prevent fat migration or the fat bloom during the melting of chocolates or similar products (Hughes et al.

2009). These are prepared by gelation of vegetable oil with oleogelators like waxes, alcohols, phospholipids, mono-digly- cerides, and phytosterols. Oleogelators effectively trap and immobilize the liquid oil within a 3-D structure converting the resultant mixture from liquid to a hard gel-like structure (Figure 1a). Firstly, the oleogelators are heated at 50–170 C until it melts, then it is added to oil where the solution is homogenously mixed before cooling to set it down into gels.

There are three proposed methods for the formation of oleogel, namely; 1) self-assembled structures of polymers, 2) self-assembled structures of low molecular weight com- pounds, 3) other miscellaneous structuring materials (Patel et al. 2015; Co and Marangoni 2012). The first method involves gelation by hydrophobic polymers such as ethylcel- lulose, polysaccharides, or proteins as a gelling agent (Patel et al. 2015). In the second method, gelation is done by using low molecular weight phytosterols or entrapping oil within crystalline strands of monoacylglycerols (MAGs), diacylgly- cerols (DAGs), or triacylglycerols (TAGs) particles (Pehlivanoglu et al. 2018; Patel et al. 2015; Sahoo et al.

2011). Lastly, some other inorganic gelators like fumed silica are used for producing gelling networks in SFO (Patel et al. 2015).

Oleogelators play a vital role in entrapping oil into 3-D structures. The food-grade oleogelators must be GRAS and possess certain properties viz. thermoreversibility, surface activity, nontoxic, and lipophilic (Doan et al. 2015; Patel et al.

2013) (Table 2). There are several oleogelators available based on the gelling type namely; (i) low molecular weight com- pounds, e.g., phospholipids (lecithin), phytosterol or sterol esters (sorbitan monostearate, c-oryzanol, sorbitan tristearate, sitosterol), and fatty acids forming self-assembly fibrous net- work (sphingolipids, hydroxy stearic acid); (ii) polymers (ethyl cellulose [EC]), hydroxypropyl methylcellulose [HPMC], methylcellulose, chitosan, chitin, proteins [zein pro- teins, gelatin, b-lactoglobulins]); (iii) crystalline compounds (plant or natural waxes, MAG, DAG, cholesterol, policosanol) (Patel and Dewettinck 2016). Several studies suggest that waxes are very efficient in binding oils within crystal net- works at low concentrations (<10%) due to long-chain, high melting point, and low polarity (Patel et al. 2013). Identically, a thermos-reversible EC, when used as a gelator, results in hard oleogels because of a strong interaction between the oil phase and the gel phase through bonds. The increased gel strength of the oleogels with high setting temperature was associated with the strong network of polymer-polymer and hydrogen-bonding (Davidovich-Pinhas,

Barbut, and Marangoni 2015a). On the other hand, certain surfactants can be used in combination or alone based on their plasticizing properties. The addition of surfactants can considerably affect the sol-gel transition temperature and interactions, thereby changing the quality of the gels (Davidovich-Pinhas, Barbut, and Marangoni 2015b). In some cases, proteins have been used as surfactants through an emulsion-template approach to entrap a good amount of oil content in their high internal phase emulsions. Tavernier et al. (2017) prepared oleogels through a similar approach by forming a protein-polysacchar- ide network using soy protein isolate (SPI) and

Figure 1. Schematic illustration of different strategies for encapsulation processes (a) oleogel, (b) oil beads, (c) oil capsules by coacervation, and (d) oil powder.

CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION 5 Table 2. Different coating materials used for encapsulating PUFA rich edible oil.

Coating materials Preparation and properties Limitations

Benefits Application References Maltodextrin (MD) Acid- or enzyme-catalyzed starch hydrolysate with Mw

<4000 g/mol, white hygroscopic polysaccharide, easily digestible, soluble in water

Slightly sweet, increase the viscosity Forms a conjugate with protein, helps in emulsifying when used in combination, film-forming ability, thickener

Emulsification, microcapsules Nurhadi, Roos, and Maidannyk (2016)

Methyl cellulose Produced by heating cellulose with caustic solution and treating it with methyl chloride. Dissolves in cold water forming a clear, viscous solution, gel formation on heating above 50 C, gels are reversible on cooling

Insoluble in hot water and other solvents, high viscosity at low concentration

Stabilizes emulsion & foam, modify texture, act as thickener, adhesive, film- forming ability

Gelation, emulsification Nasatto et al. (2015) Ethylcellulose (EC)

Prepared by mixing the alkali cellulose with ethyl chloride in the presence of alkali at about 60 for 12 h under pressure. Solubility depends on degree of substitution (DoS):

1.0 < DoS < 1.5 soluble in water; 2.4 < DoS < 2.5 soluble in organic solvent

To entrap oil, EC needs to be heated above glass transition temperature and eventually cooled down

Forms elastic gels with surfactants, higher gel strength in the presence of oleic acid, acts as a stabilizer and film- forming agent, sustained release

Gelation, microcapsules Wasilewska and Winnicka (2019);

Singh, Auzanneau, and Roger (2017) HPMC Off-white/white nonionic cellulose powder prepared by etherification in alkaline condition, forms a non- flowable and semi-flexible mass when heated to critical temperature

Forms colloids on dissolving in cold water, soluble in polar organic but insoluble in diethyl ether, acetone, and anhydrous alcohol

Excellent film forming, act as stabilizer and surface tension enhancer, thickener, adhesive properties, water retention capacity

Thermal gelation, emulsification Ding, Zhang, and Li (2015); Novak et al. (2012)

Gum Arabic (GA) A mixed salt of a polysaccharidic acid (Arabic acid) with Ca2þ, Mg2þ, and

K. Readily soluble in water, low viscosity — Emulsifying agent, high water-holding capacity, binding agent, degrades oxidation

Used as a thickener in oil gels and emulsions Naeli et al. (2020);

Mariod (2018) Galactomannans b-(1–4)-D-mannan (M) backbone with single D- galactose (G) branches linked a-(1–6). Water solubility increases with an increase in galactose

Film-forming properties vary with M/G ratio Thickeners, excellent stiffeners and act as an emulsion stabilizer

Used with other polymers for film coating, or gels

Dos Santos et al. (2015); Silveira and Bresolin (2011)

Pectin A methylated ester of polygalacturonic acid a-(1- >4)-linked D-galacturonic acid; LMP (<50% esterified), HMP (>50% esterified), Dissolves in water

Forms clumps during dispersion; HMP- forms gels with sugar and acid, LMP forms gels with divalent cation

Gelling agent, thickener, water binder, and colloidal stabilizer

Beads or capsules Sundar Raj et al. (2012) Carrageenan

The number and position of ester sulfate groups influence structure; Kappa:

25%–30% ester sulfate groups; Iota: 28%–35% ester sulfate groups;

Lambda: 32%–39% ester sulfate groups. In reaction with water, it forms a gel, whereas when added to milk it reacts with proteins and stabilizes

KAPPA – rigid and brittle gel, thermo- reversible, high gel strength, shows syneresis.

IOTA – elastic gel, thermo-reversible, no syneresis, thixotropic.

LAMBDA – cold soluble, non-gelling, high viscosity.

Emulsification, foam stabilization, thickening, gelling, and suspending agent in water and milk systems

Gelation Kariduraganavar, Kittur, and Kamble (2014)

Alginate The anionic polymer obtained from seaweed. Sodium and potassium alginate dissolves in hot and cold water with agitation

Ionic cross-linked gels by divalent ions are less stable but can be cross-linked by cell or covalent reagents

Acts as stabilizing, viscosifying, and gelling agent

Gelation Lee and Mooney (2012) Xanthan gum (XG) High-molecular weight extracellular heteropolysaccharide produced by fermentation of Xanthomonas campestris.

Soluble in cold and hot High viscosity at low concentration

Acts as thickener and stabiles emulsion, suspension and foams, have a synergistic effect with other gums

Microcapsules Bascuas et al. (2020); Cai et al. (2019) (continued)

6 M. PATTNAIK AND H. N. MISHRA j-Carrageenan (charged polysaccharide) in the ratio 15:1 that showed a long-term emulsion (with 60% oil) stability. The dried oleogel had a unique honeycomb-like structure without any oil leakage for several months of storage. Similarly,

Tavernier et al. (2018) demonstrated better oil retention in oleogels formed by SPI (2.5 wt%)—candelilla wax (1–5 wt%) than oleogels prepared by only candelilla wax due to the com- bination of both internal crystalline network and protein stabilized compartments. Patel et al. (2015) reported high oleogel strength that contained >97 wt% oil using biopoly- mers like gelatin and xanthan gum (non-surface-active). They did not observe any coalescence of the oil droplets, addition- ally, there was tight packing of oil droplets within the polymer.

Besides emulsion-template approach, the solvent exchange method is another procedure to disperse proteins

Table 2. Continued.

Coating materials Preparation and properties Limitations

Benefits Application References water, dissolves in most acids and bases

Chitosan The deacetylation of chitin derives a linear polysaccharide. The weak base having solubility < pH 6.5

Poor encapsulating properties, insoluble in water or organic solvents

Act as an emulsifying and stabilizing agent in combination with proteins

Used in conjunction with proteins Kumar et al. (2020)

Milk protein concentrate or isolate (MPI/MPC) MPI contains high protein

>90%; MPC has protein <90% dry matter, Off white powders with sweet and milky aroma produced by spray drying of ultra or diafiltrated skim milk

MPC/MPI with high protein content has poor solubility

Emulsifying and oil binding capacity provides heat stability

Emulsification Meena, Singh, Arora, et al. (2017); Meena,

Singh, Panjagari, et al. (2017) Sodium/ potassium caseinate

White or pale yellow, odorless powder formed by the reaction of casein with alkali. Soluble in boiling water, insoluble in ethanol

Slowly disperses in water with turbidity, Poor acid stability

Emulsifying properties, heat, acid, foam and freeze stability, water binding capacity, high surface activity, water- soluble emulsifier

Emulsification Meena, Singh, Panjagari, et al. (2017)

Whey protein isolate/ concentrate (WPI/WPC) Pale yellow or white mixture of proteins obtained from spray drying of whey, soluble in water

Poor heat and freeze stability and poor water binding capacity

High surface activity, good emulsifying & foaming agent, excellent emulsion and acid stability

Emulsification when used in a composite blend Meena, Singh, Panjagari, et al. (2017)

Soy protein isolate/ concentrate (SPI/SPC) Light brown powder prepared from defatted soy flour or by immobilization of soy globulin proteins; SPI:

>90% proteins dry basis, SPC  70% proteins dry basis

Low gel intensity and porous structure; solubility varying with pH

Good emulsifying and water retention capacity, provides colloidal and foam stability, shows high viscosity, plasticity and elasticity properties, gelation in the presence of salts

Emulsification, soft gelation Wang et al. (2019); Tang (2017); Xu and

Liu (2016) Gelatin An admixture of peptides and proteins produced by partial hydrolysis of collagen. Soluble in the water at temperatures above 35–40 C, sets when cooled

Swells at low temperature absorbing more water Acts as a stabilizer, thickener, and texturizer

Gelation Kanwate and Kudre (2017); Haddar et al. (2011)

Lentil protein Prepared by extraction from lentils and other pulses.

Solubility varies with the type of lentil and pH Weak gelling, foaming, and emulsifying capacity when used alone

Excellent nutritional factors, high digestibility, good oil binding capacity, act as an extender

Used for emulsification in conjunction with other proteins or polysaccharides

Jarpa-Parra (2018); Chang, Varankovich, and Nickerson (2016)

Cyclodextrin Non-reducing carbohydrate obtained from enzymatically modified starches consisting of a-1,4- linked glucose monomers.

Water solubility varies as c > a > b –cyclodextrin, and solubility increases with temperature

Insoluble in organic solvents Forms self-assembled aggregates, enhances penetration through a biological membrane

Encapsulation by complexation Rakmai et al. (2018);

Jansook, Ogawa, and Loftsson (2018); Marques (2010)

Carboxymethyl cellulose (CMC) White to slight yellow modified cellulose powder produced by carboxymethylation,

Soluble at any temperature Low surface activity and non-foaming

Excellent film-forming capacity, good water retention but pH- dependent, good binding, stability, and emulsifying ability

Emulsification, coacervation, microcapsules, or micro/nanobeads

Bakry, Fang, et al. (2016); Ngamakeue and Chitprasert (2016); Devi and

Maji (2011) CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION

7 in oil via strong protein networks in a hydrophobic environ- ment. In this technique, the protein is initially denatured to form disulfide bridges and hydrophobic interactions between proteins. Thereafter, the polarity is reduced first by replacing water with intermediate solvents (acetone, oxolane) then fur- ther by oil (Scholten 2019). De Vries et al. (2015) reported successful oleogel formation using solvent exchange method with heat-set whey protein isolate (WPI) and SFO. They reported stiffer oleogels with proper networks conferring good oil holding capacity (up to 91%). Similar studies were conducted by De Vries et al. (2017) using the same approach on denatured WPI and SFO (1:10). They claimed that the WPI aggregates showed gel-like properties and formed a gel network with the oil even at low protein con- centration (3%).

The type and concentration of oil and oleogelators influ- ence the textural, thermal, and rheological properties of the oleogels (Patel et al. 2015). The gelling ability of various waxes is affected by the vegetable oils’ fatty acid composition and acyl chain length (Demirkesen and Mert 2020). For instance, with the increase in SFA content, the gelling con- centration gradually decreases due to the high melting rate of TAG, ultimately strengthens the oleogel structure. A lower gelling concentration of bee wax was observed for

RBO because of high saturation than rapeseed oil. Similarly, keeping the bee wax concentration the same, a higher crys- talline mass of wax was formed in RBO with the high latent heat of crystallization (Patel et al. 2015). Therefore, oleogels containing high melting TAG and SFAs produce rigid gels with high viscosity. Studies show that in comparison to heterogenous waxes, homogenous waxes having less minor components and higher ester concentration possess lower critical gelling concentration. Due to this lower critical gel- ling concentration, it requires a minimum amount of oleo- gelator to form oleogel that provides good oil binding capacities (Demirkesen and Mert 2020). Consequently, from an economic point, a lower concentration of oleogelators (0.5–7% w/w) can be utilized to prepare firm oleogels with vegetable oils consisting of high oleic content such as RBO,

SFO, and OO. Oleogels can be used for developing func- tional foods by entrapping bioactive compounds without requiring a large amount of saturated fat because of their distinctive solid-like-fat attributes that confer better protec- tion and higher stability.

Oil beads Oil beads are typically like hydrogel beads wherein the core material is a liquid oil. The basic preparation of such beads involves the dispersion of vegetable oil into the solution of wall materials, after that thoroughly mixed to form a homo- genous solution (Figure 1b). The oil load differs and can reach up to 50% of the final product or beyond depending upon the oil-to-wall weight ratios. The oil-to-wall ratios nor- mally vary from 0.1 to 1.0; however, 0.2 to 0.5 are more common (Chan 2011). There is a large variety of proteins, carbohydrates, and gums used as wall materials (Table 2).

Gums have an excellent stabilizing property but exhibit poor encapsulating ability (Mahdavi et al. 2016; de Oliveira,

Paula, and de Paula 2014; Ramırez et al. 2002). A cyclic polymer of six alpha-1,4-linked glucopyranosyl units known as a-Cyclodextrin (a-CD) is utilized as an encapsulating medium due to its amphiphilic behavior. It self-aggregates to form oil beads on continuous shaking at low temperature (25–37 C) with the triglycerides. The absence of any chem- ical solvent, low temperature, and good encapsulation effi- ciency (80%–87%) make this polymer suitable for the development of soft beads (Bochot et al. 2007). However, minimal knowledge about its toxicity and the dosage limits its use in food products. Sodium alginate has been a classic example of gelling and thickening agents for a longer time.

It is a copolymer with two monomeric units of D-mannur- onic acid and a-L-guluronic acid. The ability to reduce the interfacial tension between the oil and water phase makes it an efficient wall material for bead preparation. They form thermo-irreversible and water-insoluble gel beads on chemically reacting with calcium ions. The calcium cations cross-link to the guluronic sequences to form gel networks; therefore, high guluronic acid content (M/G ratio ¼ 0.59, G type), have better encapsulation efficiency than high man- nuronic acid content (M/G ratio ¼ 1.56, M type) (Chan

2011). Pectin extracted from citrus fruits is associated with similar gelling properties, which can be used alone or in combination with alginate to form gel beads. Depending upon the methyl esterification of the galacturonic acid in the chains, pectin can be classified into low-methoxy (LMP) or high-methoxy (HMP). HMP is conventionally used as a thickening agent, and the formation of gel occurs only by hydrogen-bonding and hydrophobic interactions in the pres- ence of acids and a high amount of sugar. On the contrary,

LMP forms thermo-reversible gel beads with calcium ions and does not require high sugar content. LMP has a less demarked dimerization step than alginates, due to the ran- dom distribution of ester and amide groups along the pectin chain. Additionally, the gel strength is influenced by cross- links and concentration of calcium divalent ions while reduces with an increase in temperature and acidity (Yang et al. 2018; Capel et al. 2006). The calcium-pectin oil gel beads have gained popularity for their sustained release and targeted drug delivery.

Various studies have been conducted in recent years on the oil beads prepared from different wall materials. To improve the encapsulation efficiency, polysaccharides are used as structural strengthening agents, while proteins act as emulsifiers (Corstens et al. 2017). For instance, Morales et al. (2017) observed an encapsulation efficiency of 98.7% in oil beads prepared by a protein-polysaccharide complex of sodium alginate—shellac and SFO in the ratio of 80:20.

They also observed a smooth and non-aggregated oil bead surface with an encapsulation efficiency of 98.7% (oil load:

38.6% w/w), which showed swelling properties under basic conditions (pH 7). Lin et al. (2020) investigated the inter- action of

SPI and alginate with varying oil content (10%–40%). They found that emulsion stability decreased on increasing the alginate concentration to 1.5%, oil to 40%, and limiting SPI to 1%, due to high viscosity that hindered

8 M. PATTNAIK AND H. N. MISHRA the movement of SPI to the oil-water interface. However, more SPI concentration led to better absorption to the oil- water surface but favored some flocculation of oil droplets.

In another study, Lin et al. (2021) reported that the presence of WPI established stronger interactions with alginate than

SPI during gel beads formation via hydrogen bonds between polar amino acids and alginate molecules that helped in pre- venting water loss and SFO loss from the beads. To obtain oil beads with high oil loads some researchers have sug- gested the addition of emulsifiers or adoption of emulsifica- tion technique in combination with ionic gelation. For example, e Silva et al. (2019) demonstrated that 1% Tween

20 exhibited stable emulsion through alginate interaction.

They also observed high encapsulation efficiency (>99.5%) of the microparticle for oil loads up to 75%. On the other hand, Piornos et al. (2017) obtained beads with high oil load (66.37% linseed oil) using Lupin protein isolate (LPI) (56 g/

L) and alginate beads (47 g/L) by allowing gelation for

30 min. They further observed a high encapsulation effi- ciency (98.30%), due to the emulsifying properties of LPI.

Nonetheless, the bead size, water/oil content, and mechan- ical properties (shrinkage, compressibility, elasticity) of the oil beads can be controlled by maintaining the gelation time, optimizing the formulation, regulating the process technolo- gies and preparation methods (Lin et al. 2020).

Oil capsules by coacervation Coacervation in the colloidal solution is defined as the phase separation between two liquids caused by a change in pH, temperature, ionic strength, and the carrier medium’s solu- bility. When the coacervation takes place or is completed, a visible separation of two phases occurs. One phase is called coacervate, and another is known as the equilibrium phase.

When the coacervation is conducted using one polymer solution, it is a single coacervation, whereas the presence of two oppositely charged polymer solutions (preferably pro- teins and polysaccharides) is termed as complex coacerva- tion (Timilsena et al. 2017; Schmitt and Turgeon 2011). The main driving force for complex coacervation is the electro- static interaction between two charged particles, along with hydrophobic interactions and

Van der Walls forces (Timilsena et al. 2017). The microencapsulation of oils by complex coacervation is carried out by three basic steps (Figure 1c) (Ruiz, Ortiz, and Segura 2017). Firstly, a pro- tein-based polymer solution is dispersed into an aqueous medium by adjusting its pH beyond the isoelectric point and temperature above the gelling point. Secondly, the homogeneous oil-in-water emulsion is prepared by homoge- nizing oil in the prepared protein solution. Thirdly, another polymer solution is prepared by dispersing polysaccharides in an aqueous solution, which is followed by blending with the above O/W emulsion. The coacervates instantaneously form a coating around oil particles if there is adequate opposite charge density. In case of insufficient charge dens- ity, the polymer solution’s temperature or pH is adjusted to a satisfactory charge level for the induction of coacervates.

Gelatin is the most commonly used shell material for the formation of complex coacervates. Flaxseed oil capsules formed from gelatin-gum Arabic (GA) matrix had an effi- ciency of 84% and transitioned from spherical mononuclear to irregular multinuclear when the rpm of the homogenizer was changed (Liu, Low, and Nickerson 2010). However, to increase the stability of the coacervates, either mild heat is applied, or some cross-linkers are added. The degree of solidification depends on the concentration of cross-linkers used in the process. Several cross-linkers include tannic acid, transglutaminase, glutaraldehyde, Gallic acid, or for- maldehyde. Despite the strong linkage ability, the toxicity of the cross-linkers should be studied before its application.

Timilsena et al. (2016) prepared complex coacervates from chia seed gum-chia seed protein isolates complex (wall material) and chia seed oil (core) using transglutaminase as a cross-linking agent. He observed the highest encapsulation efficiency (>93.9%) and longer storage stability almost 6 times than unencapsulated oil when the core: wall ratio was kept at 1:2. Kaushik et al. (2015a) studied the effect of pH alteration over a range of 8 to 1.5 and claimed that at pH

3.1, flaxseed protein isolate configured its helix structure, thus, provided a stable and strong linkage with flaxseed gum. It can be concluded that the strength of coacervates depends on the process parameters, charge density, concen- tration of the polymers, pH, and temperature. In compari- son to other microencapsulation techniques, this process can take a high payload up to 90% for single nuclear and 60% for multi-core by producing micro particles of the wide par- ticle size range (1–1000 mm) (Kaushik et al.

2015b).

Conversely, it is a batch process that wastes time and the ionic charge and pH of the material govern microcapsules’ stability. Hence, a limited variety of wall materials and cross-linkers can be utilized for this process.

Oil powder Vegetable oils rich in PUFA are prone to oxidative degrad- ation, which can deliberately shorten its shelf-life.

Encapsulation of such oils can prevent untimely lipid oxida- tion and preserve the quality of the oils. It serves several benefits, such as protection from environmental conditions, increasing the stability of the oils, and the controlled release of omega fatty acids into the food product (Kaushik et al.

2015b). The encapsulated liquid oil can be converted into stable powders by following few steps viz. as shown in

Figure 1d: (i) Emulsification is the process by which the core or active material (oil) is dispersed in the solution of wall materials and then thoroughly homogenized by a shear blender or homogenizer to form an emulsion, (ii) Solvent evaporation is used to remove the solvents used in the solu- tion to dissolve the wall materials. Different drying methods can be employed for the conversion of an emulsion into powder such as spray drying, microwave drying, freeze-dry- ing, fluidized bed drying, etc. which will be discussed in

Bulk encapsulation of oil. Consequently, it produces micro- spheres of oil powder enveloped in the matrix of wall mate- rials. Depending on the physico-chemical properties of the core, the wall composition, and the used microencapsulation

CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION 9 technique, different types of particles can be obtained such as a simple sphere surrounded by a coating of uniform thickness, a particle containing an irregular shape core, sev- eral core particles embedded in a continuous matrix of wall material, several distinct cores within the same capsule, and multi-walled microcapsules. The selection of wall materials is based on the emulsifying activity, stability, solubility, properties of the core, and desired final product. They actively influence the physico-chemical properties of the microcapsule viz. encapsulation efficiency, particle size, pow- der morphology, and lipid oxidation. The commonly used wall materials can be broadly classified into carbohydrates, proteins, gums, and wax (Table 2). Polysaccharides provide stability to emulsion by forming a network in the continu- ous phase (Kumar et al. 2020). The polysaccharides like GA and gelatin have emulsifying capacity due to interfacial properties but possess low encapsulation efficiency (Mahdavi et al. 2016). Modified starches, like maltodextrin, have poor emulsifying activity and low oil retention.

Conversely, sodium caseinate has excellent emulsifying activity and sta- bilizes the emulsion but lacks in entrapping liquid oil.

However, a combination of maltodextrin with protein or gums has been observed to show better results (Pattnaik and

Mishra 2020; Mahdavi et al. 2016). Furthermore, the add- ition of a surfactant like a lecithin or a caseinate to the above solution might provide a better result (Salminen et al.

2014). Recent studies suggest that microcapsules with better encapsulation efficiency and stability can be achieved by forming a conjugate between protein-polysaccharide via

Maillard reaction. Li et al. (2017) reported great emulsion stability at pH 11 and efficiency of about 95% with high oil loading up to 80% on using sodium caseinate-lactose conju- gate formed through Maillard reaction. The use of low molecular weight carbohydrates in encapsulation is linked with caking and re-crystallization problems on storage (Gharsallaoui et al. 2007). Milk-based proteins should often be used as encapsulating material as they show good func- tional and film-forming properties (Gharsallaoui et al. 2007).

Aberkane, Roudaut, and Saurel (2014) reported that pea protein could also be considered as a good coating material for encapsulation. The use of lentil protein as effective wall material is also supported by findings reported by Chang,

Varankovich, and Nickerson (2016). In this study, the solu- tion of the lentil protein, maltodextrin, and sodium alginate produced rigid microparticles with enhanced oxidative sta- bility and entrapment efficiency (88%).

Gomes and Kurozawa (2020) claimed that rice protein after enzymatic hydrolysis by flavourzyme protein hydrolysate demonstrated excellent emulsion stability and had a maximum encapsula- tion efficiency of 89.5% when used for microencapsulation of linseed oil. Nonetheless, certain protein-based entrapping agents have allergens, precipitate at long-term storage, and denature at high drying temperature depending on drying technique (Haque and Adhikari 2015; Zhao et al. 2013).

Besides the wall materials, the particle size of the micro- capsules also governs the oxidation process.

Sanchez, Cuvelier, and Turchiuli (2016) affirmed that surface to vol- ume ratio is the main factor influencing the oxidation, because of exchange surface area. Linke, Hinrichs, and

Kohlus (2020) observed higher oxidation in smaller particles than larger ones, as the surface to volume ratio was smaller that caused a higher particle-air interface. The larger par- ticle-air interface exposed the surface to oxygen and led to more oxygen diffusion resulting in detrimental changes by reacting with the oil droplets. However, by modifying the encapsulation procedure, the particle properties (porosity, density, size) can be changed which might affect the oxida- tive stability of oil powders.

Bulk encapsulation of oil Traditionally, there are several drying methods practiced for the encapsulation of PUFA rich edible oil. However, due to the inherent unsaturation of the oils, some techniques failed to provide efficient protection against lipid oxidation. The primary reason for the reduced stability is the lower encap- sulation efficiency, resulting in the exudation of un-encapsu- lated oil to the surface. Furthermore, the drying temperature of certain methods caused antioxidant depletion, followed by shelf-life deterioration. In recent years, many novel tech- niques and technological advancements have emerged to eliminate existing issues (Table 3). This section deals with the working principles, problems, and their related solution of novel technologies along with the most widely used encapsulation methods.

Spray drying Spray drying (SD) is the most commonly used drying tech- nique for emulsions. They are widely used by food and pharmaceutical industries for encapsulating flavors, essential oils, fats/omega-rich oil, etc. The ease of scale-up, flexibility of the process, good powder quality, and cost-effectiveness of this method make it a popular one (Kaushik et al.

2015b). The basic steps of spray drying involve dispersion of core material into the wall material solution, formation of a homogenous emulsion, transferring into the feeding pump if the spray dryer, atomization of spray through pressure noz- zles, collection of the dried powder microcapsules (Figure

2a) (Albert, Vatai, and Koris 2017). The processing condi- tions of the spray dryer, such as inlet temperature, feed flow rate, composition, and homogeneity of feed solution influen- ces the size of the dried microcapsules varying from 0.1 to

100 mm fine particles to 2–3 mm coarse ones (Nedovic et al.

2011; Gharsallaoui et al. 2007). Viscosity of the emulsion has a direct effect on the powder particle size. High viscosity emulsions not only interfere in the atomization process but also cause air inclusion inside particles leading to larger sizes (Bakry, Abbas, et al. 2016). The effectiveness of the process depends on the encapsulation efficiency (%EE) of the micro- capsules and their related operating conditions. Ghosh,

Srivastava, et al. (2019) reported a decrease in %EE when the feed rate and the inlet air temperature of the spray dryer were increased beyond 35 mL/min and 175 C. The increased feed rate and the high inlet temperature might have encoun- tered insufficient air volume for solvent evaporation and

10 M. PATTNAIK AND H. N. MISHRA Table 3. Different techniques for encapsulation of PUFA rich edible oil and their operating conditions.

Drying techniques Oil Drying conditions Oil: wall ratio

Wall materials Microencapsulation efficiency (%) References

Spray drying Feed rate (L/h) Inlet temperature (C)

Outlet temperature (C) Sesame oil 2.4 135 80 1:1, 2:1

Tamarind seed mucilage 91, 81 Alpizar-Reyes et al. (2020)

Rice bran 1; — 180; 155 90; 92–96 1:4; 1:2–4 MD, GA, WPC; Pea protein, MD

78; 74 Atta et al. (2020); Benito- Roman, Sanz, and

Beltran (2020) Flaxseed 0.2–0.3; 1.8 120–160; 150

60–80; 75 1:4; 1:0.8 Polysaccharide gums (PSG) 90.78; 99.7

Shahid et al.(2020); Domian et al. (2018) Tailored PUFA rich

0.33 150, 180 80, 98 1:4 WPC, pectin, MD, modified starch

89–93 Velez-Erazo, Consoli, and Hubinger (2020) Soybean

0.485; — 130; 110 — 1:4; 1:2.3 MD, modified starch; sodium caseinate, kafirin

95; 40.15 da Silva James et al. (2019); Bai et al. (2019)

Sunflower — 150 60 1.22 WPI, sodium caseinate 96–99

Domian et al. (2014) Freeze drying Freezing temperature (C), Time (h)

Pressure (mbar) Drying time (h) Rice bran 80, 2 0.15

48 1:2–4 Pea protein, MD 96 Benito-Roman, Sanz, and

Beltran (2020) Sunflower 32, 24 — 48 1:2 Sodium caseinate, lactose;

MD, sucrose, gelatin 61.2; 77.1 Holgado et al. (2020)

Echium 18, — 1 24 1:2, 1:3 GA, sinapic acid 83.27

Comunian et al. (2019) Flaxseed 20, —; 70, 24 0.1; —

36; — 0.47; 1:1.5 Sodium octenyl succinate starch, trehalose; WPI,

MD, sodium alginate 95.7; 95.4 Domian et al. (2018);

Fioramonti, Rubiolo, and Santiago (2017) Microwave drying

PUFA rich oil blend Microwave power (W): 180 0.2 1:1.85

MD, sodium caseinate, MPI 89 Pattnaik and Mishra (2020)

Coacervation pH Temperature (C) Rpm Flaxseed 9.0; 3.1

40; 50 800; — 1:2; 1:4 Flaxseed protein isolate, flaxseed gum, transglutaminase;

Flaxseed protein isolate, flaxseed gum, glutaraldehyde

95.4; 87 Pham et al. (2020); Kaushik et al. (2016)

Pequi 4.5 40 — 1:4 Cashew gum, gelatin, tannic acid

70.98 Alexandre et al. (2019) Echium — 15 600 1:2, 1:3

GA, sinapic acid 83.27 Comunian et al. (2019) Linseed

3.5 30 200 50% oil load Gelatin-flaxseed mucilage (FM)-oxidized tannic acid

>95 Mohseni and Goli (2019) Chia seed 2.7 40 — 1:2

Chia seed protein, chia seed gum, transglutaminase

93.9 Timilsena et al. (2016) Spray cooling/chilling

Feed temperature (C) Inlet & outlet air temperature (C)

Feed flow rate (L/h) Ascorbic acid 80 4,7.5 0.6 1:4

Palm oil, fully hydrogenated palm oil 93.5 dos Santos Carvalho et al. (2019)

Co-extrusion Core flow rate (L/h) Shell flow rate (L/h)

Hardening time (min) Kenaf seed 0.012 0.42 10 1:3 Alginate, HMP

67.9 Chew and Nyam (2016) Canola 0.03; 0.03 0.2; 0.2

120; 10 —; — Alginate, quercetin; alginate, HMP, quercetin

78.3; 68 Waterhouse, Wang, and Sun-Waterhouse (2014);

Wang, Waterhouse, and Sun-Waterhouse (2013) Olive —

— 10 0.05 Alginate, caffeic acid 60.6 Sun-Waterhouse et al. (2011)

CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION 11 protein denaturation, respectively. Encina et al. (2016) reported that microcapsules produced with low outlet tem- perature has high moisture content and a rubbery state while high outlet temperature results in dents and cracks that aids oxidative deterioration along with excess oil release. The wall material composition also governs the qual- ity of the powders obtained from spray drying. Drusch et al. (2006) observed the crystallization of the low molecular weight carbohydrates used as wall materials when the inlet temperature was raised beyond the glass transition tempera- ture, thereby exposing the core substance out of the matrix.

However, the crystallization can be avoided by the optimum mixing of low molecular weight carbohydrates with proteins due to their high glass transition temperature (Adhikari et al. 2009). Islam, Edrisi, and Langrish (2013) found an increase of %EE from 20 to 60 at high humid conditions on adding whey protein isolate to lactose solution. The presence of protein film reduces the particle-air also particle-particle interaction due to its surface activity and low diffusivity of the molecules.Additionally, the emulsification process also determines the droplet size, which has a noticeable impact on the %EE. The processes resulting in smaller oil droplet sizes are responsible for high %EE due to the perfect enclos- ing of the core within the polymer matrix. Few researchers have investigated the effect of mechanical homogenization (MH; rotor-stator), micro fluidization (MF), membrane emulsification (ME), and ultra-sonication (US) on the sur- face oil content and its %EE. They have claimed smaller and monodisperse particle size with low surface oil and high

%EE in the order: MF > US > ME > MH (Albert, Vatai, and

Koris 2017; Ramakrishnan et al. 2014; Jafari et al. 2008).

Many studies show that an increase in the homogenization pressure (>80 MPa) and homogenization cycles (>5) cause a rise in temperature and decrease in particle size which leads to the aggregation of particles along with the forma- tion of primary oxidation products (Kuhn and Cunha 2012).

Additionally, El-Messery et al. (2020) compared spray-dried (inlet, outlet temperature—130 C, 71%–75 C, respectively) and freeze-dried (50 C condenser temperature, 0.04 Mbar vacuum pressure) microcapsules produced from maltodex- trin, gum Arabic, and krik oil. Their findings suggest that the spherical-shaped spray-dried particles (62.2%–78.8%) had better encapsulation efficiency than irregular-shaped porous freeze-dried particles (51.9%–58.2%) owing to lower gas permeability and provided extra protection to the core.

However, spray drying has few limitations, such as high product temperature accelerates powder porosity and lipid oxidation. Increased oil loading beyond 20%–25% is associ- ated with an increase in wall materials concentration which leads to high viscosity, higher viscosity emulsion arises prob- lem during atomization through nozzles, crystallization of sugars, and sticking of powder on to the dryer chamber reduces the yield (Kaushik et al. 2015b; Ramakrishnan et al.

2014). Several researchers have prepared multilayered emul- sions to promote better lipid protection that also contributed to high oil loading (Velez-Erazo, Consoli, and Hubinger

2020; Jimenez-Martın et al. 2015; Carvalho, Silva, and

Hubinger 2014). Fioramonti et al. (2019) claimed that spray- dried flaxseed oil powder prepared by layer-by-layer depos- ition technology of double emulsion contained a high oil load (up to 66%), whey protein concentrate (WPC), and sodium alginate that had an encapsulation efficiency of 

84%. The prepared particles showed good oxidative stability than the liquid oil for up to 6 months at 18 & 4 C storage temperature. Similarly, Chang, Varankovich, and Nickerson (2016) entrapped an extra 20% canola oil by adding sodium

Figure 2. Schematic illustration of different encapsulation processes (a) spray drying, (b) spray chilling/cooling, (c) microwave drying, and (d) co-extrusion.

12 M. PATTNAIK AND H. N. MISHRA alginate in conjunction with lentil protein isolate (LPI) and maltodextrin. Despite high emulsion viscosity and larger droplet size, they observed a high encapsulation efficiency ( 88%) due to a strong electrostatic complex between LPI and sodium alginate. Moreover, the drying of microcapsules through cross-linking and different techniques can be uti- lized to eliminate the problems of aggregation and adher- ence of the microparticles on the walls of the spray dryer.

Spray chilling/cooling The basic process of spray chilling is similar to spray drying.

The steps consist of dispersion of core into encapsulating matrix, preparation of homogenous emulsion, feeding the emulsion through nozzles, atomization of the solution, solid- ifying the matrix, and collecting through the cyclone and fil- ter bags. The main difference lies in the drying chamber; here, the atomized particles through the nozzle fall into the cooling chamber where the particles are gelled or solidified (Figure 2b). In spray drying, energy is applied for solvent evaporation, whereas, spray chilling involves energy removal for solidification. The solidification process is the function of cooling chamber and its material properties. The tem- perature in the cooling chamber must be regulated below the melting point or gelling point of the solid. Moreover, the matrix materials in the solution must quickly solidify in the chamber before reaching the collection chamber. The cooling capacity and chamber size depend on the size and surface area of the atomized particle (Oxley 2012). The lipid particles produced by the spray cooling process had a wrinkled but spherical surface, possessing a high entrapment efficiency of 92%–96% (Ribeiro, Arellano, and Grosso 2012).

This process can also be utilized for encapsulating tempera- ture-sensitive materials in a lipid matrix as it does not require organic solvents, for instance, Matos et al. (2015) prepared solid lipid particles loaded with ascorbic acid by spray cooling technique. He claimed increased storage stabil- ity of the loaded material and better encapsulation efficiency up to 84%. Similarly, Xiao et al. (2020) investigated docosa- hexaenoic acid (DHA) microcapsules enclosed within dode- cenyl succinic anhydride-esterified agarose (DSAG) having a good entrapment efficiency (65%–85%), They claimed that

0.03 MPa atomization pressure is optimum for producing larger and uniform sized microcapsules, on contrary, micro- particles tend to aggregate and they are difficult to prepare with a spray pressure beyond 0.04 MPa. Few studies have shown that the modulation of the atomization process in the spray cooling technique the polymeric forms of hydrogen- ated fats could be changed to a-form, hence this could potentially be used in confectionery or as enhancers for the crystallization process (Lopes et al. 2015).

The spray chilling process has been effectively used to encapsulate heat-sensitive PUFA rich oils to delay oxidation, in pharmaceutical industries, or for enclosing probiotics and enzymes for minimal thermal loss. The absence of organic solvents makes this process inexpensive. In comparison to spray drying, it has a higher production rate and reduced exposure to elevated temperature (Oxley 2012). Moreover, the process yield of spray chilled microcapsules was found to be higher than spray dried microcapsules (60% vs. 45%) without the occurrence of any agglomeration in the micro- particles (Fadini et al. 2018). However, the process has a limitation of the coating matrix with respect to viscosity and solid concentration. The solid concentration in the slurry should be optimized to minimize the viscosity for the pro- duction of small atomized droplets, and this will enhance the production rate and cooling capacity of the chamber.

Freeze drying Freeze drying (FD) is a simple and less complicated process usually preferred for encapsulation of heat-sensitive materi- als and essential oils. The PUFA rich oil emulsion is first frozen at a low temperature between 90 and 40 C, then the frozen mixture is sublimed from solid to a gaseous state at reduced pressure. Although it is a batch process, yet it has high nutrient retention than the spray drying process.

Therefore, it is suitably used for Ꞷ-rich oils like fish, lin- seed, virgin olive, and WO. A good encapsulation efficiency of about 99 and 84% was observed for extra-virgin oil and flaxseed oil, respectively, with protein as wall constituents (Calvo et al. 2012; Karaca, Nickerson, and Low 2013). The microcapsules formed by the freeze-drying process show an exceptionally high protective effect against lipid oxidation because of the antioxidants retention during the storage period at ambient temperature (Karaca, Nickerson, and Low

2013). The combination of various wall materials (maltodex- trin: whey protein: arrow root; maltodextrin: whey protein; whey protein: arrow root) was investigated and compared by Charles et al. (2021). They claimed that the micropar- ticles produced from the combination of maltodextrin, arrowroot, and whey protein showed better oxidative stabil- ity with improved entrapment efficiency (>80%) of fish oil for 90 days at 25 C storage temperature due to the cryo- protective behavior of arrowroot which aided stabilization and protection of air-sensitive fish oil. On the other hand,

Perrechil et al. (2021) experimented with rice protein con- centrate (RPC) and modified starch for producing freeze- dried flaxseed oil microcapsules. They discerned that RPC had a poor emulsifying ability (encapsulation efficiency, EE

<1%), while on increasing the content of modified starch, the EE improved from 12.9 to 90.6%.Besides displaying good oxidation stability, few studies show low microencap- sulation efficiency due to the presence of a porous, irregular flaky structure (Anwar and

Kunz 2011; Velasco, Dobarganes, and Marquez-Ruiz 2003). Similar porous struc- tures were observed by Rodriguez et al. (2019) on encapsu- lating chia seed oil in sodium caseinate and lactose (core:wall—1:2) possessing an excellent encapsulation effi- ciency (84%). The porous structure of such oil powders favor easy ingress to oxygen, thereby accelerates the oxida- tion process. To include higher oil content, Fioramonti,

Rubiolo, and Santiago (2017) prepared multi-emulsion by ultrasonication (75% Amplitude, 150 s, 20 kHz) using malto- dextrin, sodium alginate, and

WPI as wall materials.

Although, they observed a significant increase in CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION

13 encapsulation efficiency from 27% to 95% on increasing the maltodextrin content (0 to 20%), yet, 10% maltodextrin con- centration showed excellent oxidative stability. The presence of thicker interfacial layers at high maltodextrin concentra- tion might inhibit the interaction between the continuous phase and liquid oil, additionally, emulsification by ultraso- nication triggers lipid oxidation due to high local intensities caused by cavitation.

In a study conducted by Gonzalez et al. (2016), the EE did not show any significant difference regardless of the dry- ing methods, i.e., spray and freeze-drying, mainly because of the high solids concentration (wall materials: oil—2:1) that prevented the migration of oil particles on to the surface.

Conversely, Domian et al. (2018) reported a higher EE in spray-dried linseed oil powder (EE >95.88%) than freeze- dried microcapsules (EE <95.73%). The major drawback of this process, in contrast to other processes, is the long proc- essing time, high energy use, and production cost (Prosapio,

Norton, and De Marco 2017). Howbeit, the use of low tem- perature in freeze-drying process would be beneficial for microencapsulation of unsaturated fatty acids by overcoming the porosity issue with certain technical advancements like temperature-regulated nucleation during freezing. The spray and freeze-drying can be combined to obtain fine unagglom- erated powder without any heat damage. The spray-freeze drying (SFD) is relatively a new technique that involves rapid freezing of atomized droplets in cryogenic gas or liquid, later the frozen water is sublimed to produce final dry microparticles (Ishwarya, Anandharamakrishnan, and

Stapley 2015). Pang et al. (2017) compared spray drying, freeze-drying, and spray-freeze drying of fish oil microcap- sules developed using acacia gum, sodium alginate, and

Tween-80 (3:1:0.1). From their study, they concluded that freeze-drying takes a longer time (36 h) and high overall cost, while spray drying has a shorter drying time (2 h) and poor powder quality affecting its yield. Contrarily, SFD pro- duced uniform-sized microparticles with larger surface area, excellent powder quality, and better entrapment efficiency (EE of SD, FD, SFD—72.64%, 49.7%, 90.8%, respectively).

Microwave drying Microwaves are electromagnetic radiation produced by mag- netron in the presence of both electric and magnetic fields.

Microwave drying of agricultural food products is a familiar technique often employed for heat-sensitive food products because of its low product temperature, shorter drying time, energy efficiency, and higher drying rate (Chandrasekaran,

Ramanathan, and Basak 2013). Theoretically, microwave drying is a volumetric direct heating method that produces heat by the rapid movement of polar molecules. The polar molecules re-orient themselves in the direction of an electric field. However, due to high electric field frequency, these polar molecules align and realign themselves rapidly about million times per second, generating heat by internal fric- tion, thus resulting in volumetric heating (Chandrasekaran,

Ramanathan, and Basak 2013). This phenomenon builds up a vapor pressure gradient between the external and internal surrounding, which up thrusts the moisture out, hence, accelerates the drying rate and shortens the drying time.

The application of microwave for drying of microencap- sulated oil emulsion is a relatively novel idea. Limited litera- ture suggests that microwave drying of microencapsulated emulsions is less explored. Hassan and Muhamad (2017) attempted drying of oil emulsion containing perah seed oil with a high amount of Ꞷ-3 fatty acid by combining freeze- drying with microwave technique. He reported that the pro- duced microencapsulated oil powder had an irregular porous surface; however, they effectively protected the oil inside the solid matrix due to lower gas permeability.

Similarly, Pattnaik and Mishra (2020) claimed improved physicochem- ical properties of microencapsulated oil powder by using only the microwave technique to dry oil-in-water emulsion.

They have demonstrated a comparatively excellent entrap- ment efficiency (nearly 90%) despite porous structure with improved antioxidants retention and powder flowability with other conventional drying methods. The selective heat- ing of coating and core materials in the emulsion causes sig- nificant entrapment of active ingredients within the microcapsule (Figure 2c). For successful encapsulation of oil, the wall and core materials’ dielectric constants and dissipa- tion factors must be substantially different. This differential dielectric factor causes the heating of wall materials alone, which upon cooling diffuses around the core to form a hard shell (Pattnaik and Mishra 2020). Besides the numerous advantages, microwave drying produces a porous powder structure, and at higher microwave power levels, there might be an occurrence of some non-enzymatic browning or pro- tein denaturation. Nevertheless, the above issue can be easily controlled by fine-tuning the optimum operating conditions.

Extrusion Extrusion has been potentially used to produce high-density microencapsulated products like omega-rich oils, flavor, essential oils, and enzymes. This process involves the mixing of molten wall materials with the core materials followed by solidification. The dispersed core in the hot melt is extruded through a single or twin-screw system at high pressure (Akoh 2017). This process increases the storage stability of the less porous microparticles due to their glassy state, but it requires a lower oil load during encapsulation. Moreover, it is an expensive technique when compared to spray drying, and the high shearing caused by high pressure during extru- sion might affect the stability of sensitive materials like unsaturated oil (Kaushik et al. 2015b; Saerens et al. 2011).

Co-extrusion is an alternative extrusion technology which applies a jet atomizer equipped with concentric nozzles to form emulsion droplets (Figure 2d). The matrix solution is extruded through the outer tube, and the core material is extruded out of the inner tube, then the formed droplets are passed into a carrier fluid for hardening of the microcap- sules (Whelehan 2011). Chew and Nyam (2016) extruded emulsion containing alginate and kenaf seed oil through vibrating nozzles into calcium chloride solution for gel hard- ening. They reported stable microspheres with 0.2 water

14 M. PATTNAIK AND H. N. MISHRA activity (aw) and 76.62% encapsulation efficiency. The use of concentric nozzles can induce higher oil loading in the microcapsules ( 90%). Alginate is commonly used for co- extrusion since it has lower toxicity, chemical stability, and good cross-linking capacity in the presence of calcium ions.

The entrapment efficiency is influenced by the extent of cross-linking at the surface of the extruded droplet and the emulsion stability (Dolc¸a et al. 2015). The experimentation conducted by Chan (2011) demonstrated a high encapsula- tion efficiency and good emulsion stability when the oil-to- wall weight ratio was kept up to 15 g/g. However, the particle size of the microcapsules produced by the gravita- tional force is reported to range between 2 and 7 mm, which might affect the food product’s mouthfeel (Martins,

Poncelet, Rodrigues, et al. 2017). Besides, the nozzle diam- eter and feed flow rate can be regulated to obtain the desired size particles. In some cases, electrostatic dripping is adopted to produce smaller uniform-sized microcapsules where the oil emulsion is extruded by placing the nozzle under an electrical potential difference. The electrostatic forces accelerate the droplet fall rate that is comparatively faster than other dripping processes (i.e., under gravitational force) (Martins, Poncelet, Rodrigues, et al. 2017). Droplets fallen are collected in a bath where it is hardened through the cross-linking method. Martins et al. (2015) stated the influence of curing time and alginate-calcium chloride con- centration on the membrane thickness and diameter of the oil microcapsules. They noted the formation of a thicker membrane after 20 min of curing with the maximum amount of calcium ions released from the oil core. This thicker membrane is beneficial for providing excellent pro- tection to the core material (Abang, Chan, and Poncelet

2012). However, a longer curing time results in a weaker membrane structure due to the migration of calcium ions from the membrane to the solution (Martins, Poncelet,

Marquis, et al. 2017). Lower alginate content (<15 g/L) did not affect membrane thickness, similarly, higher calcium chloride concentration (<4.6 g/L) produced well-structured microcapsules (Martins et al. 2015).

Extruded microcapsules can be further dried by various drying methods to improve the integrity of the structured microparticles. For example, Menin et al. (2018) prepared flaxseed oil microcapsules using low methoxyl pectin (15% oil/pectin) by vibrational extrusion technology, followed by active drying (fluidized bed drying) and passive air drying.

The fluidized-bed dried micro particles possessed higher sur- face oil owing to the porous structure, while both the drying techniques displayed good encapsulation efficiency (>96%).

The major limitation of this encapsulation technique is the frequent clogging of the nozzles because of the viscous poly- mer solution, thus interferes in the drop generation.

Application of microencapsulated oils Food industry

The growing awareness about the benefits of consuming

PUFA enriched food products has urged the food industries to incorporate them into the food product. Marine animals like fish are endowed with omega fatty acids, but the con- cern of the vegan race limits its use in the food product.

Therefore, most food technologists have switched over to vegetable-based omega-rich oils. However, the underlying problem with the inclusion of PUFA enriched vegetable oil is their susceptibility to oxidation during storage.

Henceforth, microencapsulated oil in the form of gel or powder has been successfully utilized in food products.

The oleogels were associated with the replacement of trans and saturated fats in breakfast spreads, confectionery, dairy products, meat products, and sweets. Oleogels pre- pared with SFO and 2% shellac without any emulsifiers were stable for around 4 months, the crystallization of shellac wax aided in the stabilization of the oleogel (Patel et al. 2014).

Similarly, spreads obtained from virgin OO with 7% mono- glycerides (MG) had similar textural and thermal properties to commercial margarine with storage stability of about

3 months (€Oǧ €utc€u and Yı lmaz 2014). The replacement of shortening in muffins with foam oleogels of SFO with 4%

HPMC up to 50% level displayed acceptable physical, tex- tural and sensorial properties (Oh and

Lee 2018).

Furthermore, a full replacement of margarine in muffins with high oleic SFO and 4%, 7%, or 10% MG provided desired results of lowering saturated fats, acceptable proper- ties, and lowered migration of oil up to 50% (Ergun,

Thomson, and Huebner-Keese 2016). Zulim Botega et al. (2013) explored the replacement of dairy fat (4%, 8%, 15%) with rice bran wax and glycerol monooleate-based oleogels.

He claimed that glycerol monooleate was responsible for fat networks forming during ice-cream preparation with favored desirable characteristics like overrun and melting. The restriction of fat migration on to the surface of halva was achieved by adding oleogelators made up of sunflower wax, bee wax, and shellac wax (€Og€utc€u, Arifoglu, and Yı lmaz

2017). Lim et al. (2017) deep-fried instant noodles in oleo- gels made up of soybean oil and carnauba wax instead of soybean or palm oil. He reported that there was no adverse change in the texture of the noodles and the noodles also absorbed less oil.

Fortification of food products with oil powder was also reported in the literature. For instance, Goyal et al. (2015) reported that the fortification of milk with flaxseed oil pow- der showed comparable sensorial aspects with storage for up to 5 days. He also stated that this flaxseed oil powder, when added to milk, met the nutritional necessity of x  3 fatty acids in non-fish eating or vegan eaters. The microspheres of linseed oil dried by spray drying when incorporated in soup formulation at 14% fulfilled 80% of the daily require- ment of a-linolenic acid. In addition to it, the oil powder showed excellent oxidative stability for 8.78 months (Rubilar et al. 2012). RBO powder, when added to yogurt, increased the acidity and water holding capacity during storage; how- ever, the product was acceptable from sensorial aspects (Atta et al. 2020). Yogurt and bread fortified with palm oil powder using complex coacervation method and chitosan/xanthan gum and chitosan/pectin as wall materials show appreciable stability and release in the gastrointestinal fluids (Rutz et al. 2017).

CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION 15 Pharmaceutical industry

The poor bioavailability and absorption of some compounds/drugs in the human digestive system have encouraged the need for a proper delivery system. The lipid-soluble compounds can be effectively structured into a matrix of crystalline sphere. While formulating any deliv- ery system, one must consider the solubility and micellari- zation of the enveloping material and its effect on nutrient bioaccessibility and digestibility. Most of the lipid digestion and absorption occurs in the stomach and small intestines (Mei et al. 2006). Therefore, the micelles are formed when vegetable oil comes out of the enveloping matrix, and these micelles serve as the drug vehicle in the gastrointestinal fluid carrying the active component (Davidovich- Pinhas 2016).

The carotene from 12-hydroxystearic acid canola gel showed release of carotene from oil between 0 to 30 min during the digestion in intestine, whereas the same had a controlled release between 30 to 75 min when an oleogel was used (Stortz et al. 2012). A similar oleogel emulsion was prepared from zein protein and used for delivery of carotene demonstrated good color stability, protection, and retention of active compounds (Chen et al. 2016). An oleo- gel composed of canola, corn, or coconut oil with mono- stearin and Span 20 enclosing 2.6% curcuminoids showed high bioaccessibility than curcumin powder on dispersing in water and nearly 5 times higher during the fasted state.

The storage stability improved, and there was no occur- rence of precipitation (Yu et al. 2012). Almeida et al. (2008) formulated a bi-gel for topical application com- posed of oleogel and hydrogel, which showed good spread- ability and stability for up to 6 months. Besides this, it provided enhanced cooling and moisturizing effect in the absence of tensoactives. Bochot et al. (2007) claimed an efficient delivery of Isotretinoin, a poorly soluble lipophilic molecule into a self-assembling lipid bead system consist- ing of soybean oil and a-cyclodextrin. The soybean oil beads could potentially be used in pharmaceutical applica- tions (oral or topical) as well as in cosmetics. Microspheres of alginate-pectin and calcium-pectinate prepared from the emulsion-gelation method were capable of forming floating beads of Ranitidine hydrochloride or other oils for intra- gastric conditions (Jaiswal et al.

2009; Sriamornsak, Thirawong, and Puttipipatkhachorn 2004). The oil-loaded calcium-alginate beads produced from the emulsion-extru- sion method had a positive antifungal effect against

Aspergillus niger and Fusarium verticillioides fungi species (Soliman et al. 2013). Marefati et al. (2015) reported a promising Pickering double emulsion to prepare the oil powders from octenyl succinic anhydride (OSA) modified quinoa starch with high encapsulation efficiency and oil content of about 97% and 70 wt.% respectively for its effective use in pharmaceutical industries. There is also development of several non-chemical-based mosquito repellents and ointment containing encapsulated essential oil microcapsules encouraged as a promising alternative offering a longer duration of action with desirable charac- teristics (Solomon et al. 2012).

Pesticides, fungicides, and insecticides Pesticides and fungicides are used enormously to minimize post-harvest losses and food deterioration. However, due to the well-known adverse impact of these pesticides and fungi- cides on the environment and human health, there is an urgent need for alternative practices. The delay of postharv- est decay can be achieved by applying encapsulated essential oils extracted from various plants which are environment friendly as well as biodegradable. For instance, encapsulated essential oils from Rosmarinus officinalis, Salvia mirzayanii,

Artemisa persica, and Thymus vulgaris were applied to mango fruit for controlling its decay caused by A. niger, thereby enhancing the storage life and maintaining the internal quality of mango fruits (Javadpour et al. 2018).

Many insect-resistant packaging for food products has attracted attention from the food industry, such as thyme oil and cinnamon oil used as microcapsules or as films contain- ing microcapsules for effective repelling of insects and/or moth larvae by releasing an effective insecticide (e.g., cinna- maldehyde in cinnamon). These films have excellent tensile properties helpful in preventing the invasion of larvae about

90% into food products (Chung et al. 2013). Additionally, an improved anti-fungal activity by slow-release of

Cuminum cyminumc essential oil encapsulated in chitosan- caffeic acid nanogel was presented by Zhaveh et al. (2015).

Kulkarni et al. (2000) prepared neem seed oil beads encap- sulated in sodium alginate-glutaraldehyde polymers incorpo- rated in liquid pesticide for controlled release in soil. A green approach involving environmentally friendly pesticides against the insect pest Myzus persicae was developed by encapsulating Pennyroyal (M. pulegium) essential oil into baker’s yeast via diffusion through the cell membrane that showed efficient insecticidal activity for a period of 3 days (Kavetsou et al. 2019).

Lubricants, textile, and personal care Nowadays, mineral oil-based lubricants have created a nega- tive impact on society owing to their toxicity and inhibition of plant growth. There is more demand for eco-friendly, bio-degradable, and pollution-free lubricants. Vegetable oils can be a promising alternative to mineral oils for boundary and hydrodynamic lubricants because of their high viscosity index, low volatility, biodegradability, and nontoxicity (Sharma, Adhvaryu, and Erhan 2009; Suzuki, Ulfiati, and

Masuko 2009). Compared to traditional soap-based lubricat- ing greases, the oil gels do not demand sophisticated manu- facturing equipment or expertise.

Martın-Alfonso and Valencia (2015), reported such potential oleogel for lubricat- ing grease manufactured from ethylene-vinyl acetate copoly- mer (EVA) copolymer with

28% vinyl acetate (VAc) content, SFO, and high oleic SFO. EVA is a thickener agent possessing flexibility, adhesive, and fracture toughness prop- erties. Linear viscoelasticity with a frequency of oleogels was similar to the commercially available lithium greases. The increase of linear elasticity with EVA concentration indi- cated a strong microstructural network. However, more related data about the tribological behavior of EVA with

16 M. PATTNAIK AND H. N. MISHRA vegetable oils are needed to be studied to find out its various applicability. Some aromatic oil encapsulated within the polymer matrix could be potentially used as a functional textile product at spa centers, personal cares, or for aroma- therapy (Carvalho, Estevinho, and Santos 2016). Sarı ı s¸ı k,

Okur, and Asma (2012) reported similar use of berry oil capsules encapsulated by b-cyclodextrin and later incorpo- rated into 100% cotton towel fabric. Insect repellant cotton fabrics are manufacture by including microencapsulated bio- pesticides through impregnation or surface coating of the textiles. Similar experiments were conducted by Miro Specos et al. (2017) to contain microencapsulated citriodiol or cit- ronella essential oil pads within cotton woven fabrics. These cotton fabrics exhibited extended durability and 100% repel- lency for more than 30 days.

Future scope Future research must be more focused on the technological advancement of existing methods like spray drying. The improvization of pressure nozzles to withhold high viscosity without creating lumps can be attempted. The modification of nozzles successively can support a higher oil load.

Nonetheless, microwave drying favors high oil load; a future suggestion would be to model this process as a continuous one. Spray cooling is generally preferred for encapsulation of probiotics, essential oils, or bioactive compounds; hence, future research can be conducted on vegetable oils. In this way, a better powder product can be obtained without com- promising the other properties.

Despite the methods described above, the use of supercritical fluid (specifically carbon dioxide) for the production of atomized spray par- ticles can be explored in the near future. This supercritical carbon dioxide will not only eliminate the solubility issue but also produce particles of low temperature. The authors also suggest the adoption of biopolymers prepared from industrial or agricultural waste products to be utilized as carrier material. In addition to their abundance availability, they are also biodegradable and nontoxic. The employment of such polymers will lessen the environmental pollution load to some extent.

Conclusion The gradual shift of the population toward vegan products has urged the food industries to look for alternative vege- table oils rich in omega fatty acids than marine oils. Marine oils (mostly fish) have long-chain fatty acids such as EPA and DHA, while vegetable oils are endowed with short-chain fatty acids like linoleic and linolenic acid. Moreover, the fatty acid composition of vegetable oils varies based on ori- gin and source. The vegetable oils have to be tailored for balancing their fatty acids without producing any unwanted or toxic compounds like trans-fats. Henceforth, blending is the most economical way of achieving the desired balanced fatty acids with improved nutritional, functional, and ther- mal properties. The use of ternary blending should be explored more than binary blending since they deliver better characteristics than the latter. The susceptibility of such

PUFA enriched vegetable oils to oxidative degradation has beseeched the technologists toward its preservation through encapsulation. The liquid oil can be effectively entrapped into a matrix of gel or powder in numerous ways. Spray drying and coacervation are considered to be the most com- monly used techniques. Nonetheless, there has been an emergence of a few other novel methods like microwave, spray cooling, spray-freeze drying . The encapsulated oil microparticles in the form of gel or powder have a wide application in all the fields viz. food, pharmaceutical, and textile industries along with personal care products and agri- culture because they are environment friendly, pollution- free, biodegradable, and favor controlled release of core particles.

Author contributions Monalisha Pattnaik: conceptualization, co-developed the methodology, drafted the manuscript by analyzing the litera- ture and heavily involved in curating the manuscript. Hari

Niwas Mishra: Supervision, conceptualized the idea, co- developed the methodology, involved in review & editing.

Conflicts of interest The authors have declared no conflicts of interest for this article.

Funding Indian Institute of Technology Kharagpur, Ministry of

Human Resource Development (MHRD) Fellowship to the first author.

ORCID Monalisha Pattnaik http://orcid.org/0000-0002-8219-8852

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24 M. PATTNAIK AND H. N. MISHRA

📖 中文全文 Chinese Full Text

中文

# 综述

## 富含多不饱和脂肪酸和生物活性物质的植物油稳定性改善:调配、包埋及其应用

**莫纳莉莎·帕特奈克** 与 **哈里·尼瓦斯·米什拉**

印度理工学院卡拉格普尔分校农业与食品工程系,西孟加拉邦,印度

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## 摘要

植物油中的脂质氧化是食品技术人员关注的主要问题。氢化、分提、酯交换和调配等油脂改性方法被用于改善油脂的营养品质。将非常规/常规植物油进行调配以获得协同混合油,是食品行业中常用的做法,可在合理成本下提升油脂的营养特性和稳定性。对这些植物油进行微胶囊化,可在芯材与壁材之间形成功能性屏障,使其免受不利环境条件的影响,从而增强油脂的氧化稳定性、热稳定性、保质期和生物活性。植物油的微胶囊化已通过多种传统方法实现并得到商业化应用,包括乳化法、喷雾干燥法、冷冻干燥法、复凝聚法和熔融挤出法,同时也涌现出微波冷却喷雾、喷雾冷却和共挤出等新型改进方法。微胶囊化油乳液可被干燥为易于操作的固体/微胶囊、转化为软固体,或包裹于凝胶状基质中,从而延长液态油的保质期。富含omega脂肪酸的微胶囊在糖果、乳制品、冰淇淋及制药行业具有广泛的应用前景。本综述总结了调配与微胶囊化技术在改善食用油脂稳定性和营养价值方面的最新研究进展。

**关键词:** 应用;调配;包埋;微胶囊;氧化稳定性

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## 引言

从各种植物种子中提取的植物油富含多不饱和脂肪酸(PUFAs)和单不饱和脂肪酸(MUFAs)。这些油脂由于其特定的化学和物理性质,在技术应用方面受到限制。因此,通常采用氢化、分提、酯交换和调配等方法进行改性(Hashempour-Baltork et al. 2016)。氢化过程利用氢气和镍等催化剂使不饱和双键饱和,并将顺式结构转化为反式结构。反式脂肪酸被认为对人体健康具有毒性作用(Iqbal 2014)。酯交换是氢化的替代方法。在此过程中,不饱和脂肪酸在三酰甘油结构中重新分布,且不发生异构化。然而,该方法需要特殊条件且成本较高(Dijkstra 2015)。分提是将某些油脂分离为具有不同溶解性和质构特性的两个组分的工艺(Kellens et al. 2007)。分提可作为氢化、酯交换或混合的前处理步骤(Shahidi 2005)。因此,调配是将具有不同物理和化学性质的各类油脂进行混合的最简单方法。将具有不同性质的植物油脂进行混合,是制造具有理想营养和氧化特性的新型特定产品的最简单技术之一。调配油富含MUFA/PUFA,这使得其在化学上不稳定且易受氧化。氧气与这些油脂接触会导致不饱和键断裂,从而加速油脂酸败。不良气味对感官特性产生负面影响,降低了整体可接受度。因此,微胶囊化技术可能是维持其质构、感官和氧化特性的合理替代方案。

微胶囊化是将一种称为芯材的物质包裹在另一种称为壁材/包衣材料中的过程,从而改善其稳定性和功能特性。微胶囊化及风味物质的控释技术也已革新了食品领域,提升了食品的风味、稳定性、营养价值和外观(Pattnaik et al. 2021)。在这些领域中,将液态油脂转化为易于操作的干粉、凝胶或微珠是应用微胶囊技术的驱动力。由碳水化合物、蛋白质、胶体等多种壁材可制备不同类型的微胶囊和微球。微胶囊化的方法多种多样,包括喷雾干燥、同轴静电喷雾、冷冻干燥、复凝聚、原位聚合、熔融挤出等(Albert, Vatai, and Koris 2017; Bakry, Abbas, et al. 2016; Adelmann, Binks, and Mezzenga 2012)。

已有大量综述论文描述了植物油的调配及其对理化性质的影响,以及不同芯材(如挥发性风味物质、益生菌、精油等)的微胶囊化方法,但其中没有一篇聚焦于植物油的包埋及其相关问题(Jurić et al. 2020; Bakry, Abbas, et al. 2016; Kaushik et al. 2015b)。因此,本综述将为研究人员提供从植物油调配到通过微胶囊化获得油粉/凝胶的全面概述。本文重点讨论了植物油调配对食用油脂的营养、组成、热学、氧化和物理性质的影响;为植物油包埋壁材的选择提供了清晰的认识,并阐述了各种传统和新兴包埋技术的优缺点。

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## 植物油的调配

调配食用油混合物以改善其健康和营养特性正受到越来越多的关注。将植物油进行调配以符合"健康油脂"标准,已成为大多数行业近期遵循的趋势。根据定义,"健康油脂"是指满足世界卫生组织(WHO)推荐的脂肪酸组成、可预防多种疾病(如糖尿病、慢性心脏病、肥胖症)的食用烹饪油(WHO 2008)。脂肪是健康均衡饮食的重要组成部分;有证据表明,限制饱和脂肪和反式脂肪的摄入很重要,因为这有助于减少血管(动脉)内脂肪物质(斑块)的积聚。这一过程称为动脉粥样硬化,是心脏病的主要原因。饱和脂肪酸(SFA)和反式脂肪会提高血液中低密度脂蛋白(LDL)胆固醇水平,从而导致斑块形成(Ference et al. 2017)。PUFAs和MUFAs可降低LDL胆固醇并提高高密度脂蛋白(HDL)胆固醇(Manchanda and Passi 2016)。MUFAs的益处在于其能促进肝脏中胆固醇的酯化,从而降低游离胆固醇库并增加受体介导的LDL胆固醇摄取,最终降低血液胆固醇水平——这一结论来自美国膳食指南咨询委员会2010年发布的《美国居民膳食指南》。研究表明,过量摄入PUFA也会对健康产生不利影响,削弱人体抗氧化剂清除自由基的能力,从而增加衰老、心脏相关疾病、糖尿病和癌症的风险(Choudhary and Grover 2013; WHO 2008; Vani, Laxmi, and Sesikeran 2002)。根据WHO的建议,脂肪总摄入量应占总能量的30%–35%,SFA <10%,MUFA 10%–14%,PUFA 6%–11%(WHO 2008)。然而,为维持良好的心脏健康,ω-6与ω-3的比例应在1:1至4:1之间(Mishra and Manchanda 2012)。因此,MUFA、PUFA以及ω-6和ω-3等必需脂肪酸的平衡比例对于维持人体内调节良好的脂质谱至关重要。采用植物油调配方法可以实现脂肪酸组成的平衡,从而无需对油脂进行氢化或酯交换处理。

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## 调配对物理、化学和热学性质的影响

食用油脂的脂质氧化导致异味和酸败的产生,严重降低了这些油脂的稳定性,从而对人体健康产生显著的负面影响(Adbel-Razek et al. 2011)。因此,将各种食用油脂进行混合是通过增强其抗氧化潜力来提高氧化稳定性的经济有效方法(表1)。例如,亚麻籽油(FSO)和橄榄油(OO)分别富含ω-3和ω-9不饱和脂肪酸,这使得它们容易发生不饱和键的氧化和水解断裂。然而,当FSO与米糠油(RBO)以2:1的比例混合时,其过氧化值、对茴香胺值和酸值均较低(Ghosh, Srivastava, et al. 2019)。此外,FSO、RBO和OO以2:1:1比例形成的三元混合物在过氧化值、对茴香胺值和游离脂肪酸值方面表现出极低的数值(Ghosh, Srivastava, et al. 2019)。RBO是一种非常规油脂,富含谷维素、生育三烯酚和生育酚,以及角鲨烯和植物甾醇。RBO中谷维素和三烯酚的存在可能减缓了醛类、酮类和自由基等有害化合物的形成(Choudhary and Grover 2013; Reddy et al. 2013)。同样,将RBO以不同浓度与OO混合时,其过氧化值最低(0.53和0.33 mEq/kg),而与芥子油(MO)混合时最高,分别为1.73和1.33 mEq/kg。造成这种差异的原因可能是各混合油中MUFA和PUFA含量的差异。含有较高MUFA或油酸含量(相对于PUFA)的混合油在保质期和煎炸过程中应能减缓氧化降解(RBO + OO:42%油酸,36.9% PUFA;RBO + MO:32.3%油酸,50.8% PUFA)(Choudhary, Grover, and Kaur 2015)。尽管核桃油(WO)和葡萄籽油(GSO)具有相同的MUFA和PUFA含量,但GSO中ω-3含量较低使其氧化稳定性提高了一倍。就MUFA含量而言,RBO和烘烤芝麻油(TSO)含量相近。然而,由于RBO中存在强效抗氧化成分,其诱导期略高于TSO,且是WO的4倍(18.7 h vs. 18 h vs. 4.2 h)。TSO的抗氧化活性体现在其生育酚含量上,以及由芝麻素转化而成的强效抗氧化剂芝麻酚的含量高于精炼芝麻油(Kochhar and Henry 2009)。Pattnaik和Mishra(2021)也报道了类似结果,在花生油(GO)和FSO中添加超过70%的RBO可显著提高氧化稳定性。因此,由于RBO中富含生物活性成分,其被誉为"心脏之油",并被认为可满足WHO推荐的脂肪酸组成(Choudhary, Grover, and Kaur 2015)。有时,冷榨油也是提高稳定性的绝佳选择。冷榨油由于未经过任何化学或热处理,保留了抗氧化剂或抗氧化剂前体,因而具有更丰富的营养特性。

**表1. 各种植物油混合物的理化性质及健康益处的主要发现**

| 油脂混合物 | MUFA:PUFA | n6:n3 | 研究发现 | 健康益处 | |---|---|---|---|---|

冷榨OO是常规油脂最理想的替代品,因其含有天然抗氧化剂,主要是酚类和生育酚。因此,将20%和40%的OO分别与葵花籽油(SFO)和大豆油(SBO)混合,可使各油脂的自由基清除活性从55%提高至近78%,SBO的总酚含量从10.5 mg/100g提高至51 mg/100g,SFO从20.5 mg/100g提高至69.5 mg/100g(Abdel-Razek et al. 2011)。另一项研究显示,非常规RBO与传统OO的混合物(70:30)在储存28天后仍表现出更好的氧化和抗氧化稳定性,总天然抗氧化剂含量达2525 mg/kg,自由基清除活性为67.7%(Choudhary and Grover 2013)。多种非常规油脂,如黑孜然油、独行菜草油(GCO)、辣木油、MO和山茶油,均具有显著的抗氧化潜力,因此可用于合理调配的研究(Umesha and Naidu 2015; Wang et al. 2016; Mohamed, Elsanhoty, and Hassanien 2014; Anwar et al. 2007)。

颜色和粘度是与油脂深度煎炸相关的主要属性。较高的粘度表明形成了聚合物或初级和次级氧化产物。较低的粘度则表明不饱和度较高。