FATS AND OILS

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In fats and oils, there contain minor components that can act as oleogels whereby an oleogel can be defined as a different category of Jello depending on the composition and bulding blocks and it is created using different strategies compared to typical Jello. There are several categories of oleogels such as crystalline particles, crystalline fibers, polymeric strands, particle-filled networks, and liquid crystalline mesophases. For the first category which is crystalline particles, it is categorize by the formation of liquid triacylglycerols (TAGs) entrapped inside the network of crystalline TAGs particles. Example of oleogelators for this category are Some of the common oleogelators in this category are diacylglycerols (DAGs), monoacylglycerols (MAGs), fatty acids, waxes and others. As for crystalline fiber oleogels, most of the gelators have low molecular weight and they can form together in fibrous network on their own. Besides, oleogels in polymeric strands is actually carry a meaning of biopolymer oleogels such as cellulose, starch, gelatin and others which has considerably weak gelling properties in food applications. In addition, particle filled network of oleogels is formed continuous liquid phase is filled with inert particles, be it is solid or liquid. The network forms a suspension system when the inert particles are solid and forms an emulsion when the inert particles are liquid. However, this type of oleogel has limited applications in food. The last category is liquid crystalline mesophase whereby the system involves the scaffolds that have oil as continuous phase with liquid crystals spaces (Nguyen,2015).
 Oleogels have attracted considerably high interest because they can be applied to many areas because of their solid structure at room temperature and thermally reversible properties and oleogelation is one of the promising strategies for lowering the saturated- and trans-fat content in food (Yi et al, 2017). Therefore, the most compatible minor components of fats and oils that can act as oleogels are from crystalline particles category which consist of simple and compound lipids such as monoacylglycerols (MAGs) and diacylglycerols (DAGs), and phytosterols as they are edible and have ability to form stable gels (Nguyen,2015).
Figure 1: MAG and DAG strusture
Figure 2: Phytosterol structure




























REACTION INVOLVED DURING EXTRACTION

1.      MONOACYLGLYCEROLS (MAGs) and DIACYLGLYCEROLS (DAGs) by ENZYMATIC GLYCEROLYSIS.

Figure 3: Flow chart of Enzymatic Glycerolysis



Enzymatic glycerolysis is the best alternative way in production of MAGs and DAGs because it generally involves less energy and chemical usage. It can also be conducted in mild reaction condition which results in purer products and less degradation products that are easily purified and reduced the problems of waste disposal. In this process, oil, glycerol as substrate and tertiary alcohol as solvent are mixed and added in the reaction vessel. They are stirred constantly at specific pressure to obtain homogenous mixture. Then, addition of enzyme such as lipase is introduced to the mixture. This reaction is conducted in pre-established condition. After that, lipase and solvent are removed by filtration and vacuum oven respectively prior to analysis of MAGs and DAGs by gas chromatography (Feltes et al, 2010).
Lipases are characterized as TAG hydrolases which the active sites will be opened upon enzyme activation and attract lipid substrates such as TAG, DAG and MAG where the acyl group is cleaved of, bonded to the lipase and then being esterified to available alcohols or water. That means that TAG in oil initially is attached to the lipase. Here the TAG is cleaved to an acyl-enzyme intermediate and DAG being released in its free form. Subsequently, the glycerol is attached to the enzyme and ester bonded to the acyl-enzyme intermediate to form MAG which is then released from the lipase. This reaction will only produce high yield of MAGs and DAGs under favourable condition for an enzyme. Gas chromatography is established because it is highly informative method that can separate and quantifyall major and minor products from the chemical catalysed glycerolysis reaction in approximately 30 minutes (Damstrup, 2008).
Figure 4: Reaction during enzymatic glycerolysis

2. PHYTOSTEROLS by SOXHLET EXTRACTION (MS et al, 2018).
Figure 5: Soxhlet apparatus
Figure 6: Flow chart of Soxhlet method
















Phytosterols present in all plant cell membranes and are especially enriched in vegetable oils and fats. Soxhlet extraction has been extensively and widely used to extract various compounds of interest from plant matrices and is indicated as conventional method for lipid extraction. After plant material is extracted using Soxhlet method, it will further analyse using gas chromatography to determine the phytosterols by flame ionization detection (FID). GC-FID has better identification and quantification of phytosterols.

REGULATIONS ON MINOR COMPONENTS AS OLEOGEL

Monoacylglycerols (MAGs), Diacylglycerols (DAGs) and phytosterols are the minor component in fats and oils which exhibit same properties as oleogels. These minor components involved in various food applications such as emulsifiers in margarine, mayonnaise and salad dressing (MAGs and DAGs). Phytosterols is a plants sterol that is usually added to fatty and oily food to lower the cholesterol intake as phytosterols has cholesterol-lowering properties. Based on Malaysian Food Regulations 1985 (subregulations that include fats and oils part only),

Margarine follows Regulation 185 which stated:
(1) Margarine shall be the plastic or fluid emulsion of edible fat or edible oil and is capable of being used for the same purpose as butter. It may contain milk and milk sugars.
(2) Margarine -
(a) shall contain not less than 80 per cent of fat; and
 (5) In addition to the requirements specified above, polyunsaturated margarine shall also comply with the general standard prescribed for polyunsaturated fat and oil in subregulation 179(6), and the particular labelling requirement as specified in subregulation 208 (4).
 Mayonnaise follows Regulation 345 that stated:
(1) Mayonnaise shall be a mixture of edible vegetable oil, liquid egg or liquid egg yolk with vinegar or citrus fruit juice or both, with or without other food. It shall contain not less than 65 per cent of edible vegetable oil.
Salad dressing follows Regulation 344 that stated:
(1) Salad dressing shall be a mixture of edible vegetable oil or milk fat with vinegar or citrus fruit juice or both, with or without other food. It includes tartar sauce.
If the food product has made phytosterol’s nutrient function claim on the label as stated in Regulation 18E 4(k), then the food product containing this phytosterols should also follow Regulation 18E (4B) where
(a) there shall be written on the label of food making such nutrient claim the following statements:
(i) “Not recommended for pregnant and lactating women, and children under the age of five years”;
(ii) “Persons on cholesterol-lowering medication must seek medical advice before consuming this product”;
(iii) a statement to the effect that the product is consumed as part of a balanced and varied diet and shall include regular consumption of fruits and vegetables to help maintain the carotenoid level; and
(iv) “With added plant sterols” or “With added plant stanols” in not less than ten point lettering;
(b) the total amount of plant sterol or plant stanol contained in the product shall be expressed in metric units per 100 g or per 100 ml or per package if the package contains only a single portion and per serving as quantified on the label;
(c) only the terms “plant sterols” or “plant stanols” shall be used in declaring the presence of such components; and
(d) the claim may only be made for milk, milk product, soya bean milk and soya bean drink as prescribed in regulations 82, 83, 357 and 358 respectively.



REFERENCES
Nguyen, Z. Q. (2015). Analysis and characterization of oleogel consisting of beta-sistosterol and gamma-oryzanol in soybean oil. Graduate Theses and Dissertations. 14477. doi:10.31274/etd-180810-4029
Yi, B., Kim, M.-J., Lee, S. Y., & Lee, J. (2017). Physicochemical properties and oxidative stability of oleogels made of carnauba wax with canola oil or beeswax with grapeseed oil. Food Science and Biotechnology, 26(1), 79–87. doi:10.1007/s10068-017-0011-8
Feltes, M. M. C., Vladimir Oliveira, J., Treichel, H., Block, J. M., de Oliveira, D., & Ninow, J. L. (2010). Assessment of process parameters on the production of diglycerides rich in omega-3 fatty acids through the enzymatic glycerolysis of fish oil. European Food Research and Technology, 231(5), 701–710. doi:10.1007/s00217-010-1325-4
Damstrup, M. L. (2008). Process Development of Enzymatic Glycerolysis for Industrial Monoacylglycerol Production. National Food Institute Food Production Engineering Technical University of Denmark. Retrieved from http://orbit.dtu.dk/fedora/objects/orbit:82493/datastreams/file_4985265/content
MS, U., Ferdosh, S., Haque Akanda, M. J., Ghafoor, K., A.H., R., Ali, M. E., … Islam Sarker, M. Z. (2018). Techniques for the extraction of phytosterols and their benefits in human health: a review. Separation Science and Technology, 53(14), 2206–2223. doi:10.1080/01496395.2018.1454472
Food Act 1983 (Act 281) & Regulations 1985(20 April 2016). (n.d.). Laws of Malaysia.