Improved texture pectin emulsion gel
Pectin-based emulsions with controlled pH and ion content address the limitations of existing emulsions by providing improved cooking performance and mouth coating without additional emulsifiers.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- SOCIETE DES PRODUITS NESTLE SA
- Filing Date
- 2024-06-14
- Publication Date
- 2026-06-30
AI Technical Summary
Existing emulsions used in food matrices lack improved cooking performance, shape retention, and mouth coating properties, and often require undesirable emulsifiers like ethylcellulose or methylcellulose.
Development of pectin-based emulsions with controlled pH and ion content, containing small oil droplets, which are stable without additional emulsifiers, and can maintain shape and provide strong mouth coating.
The pectin emulsions exhibit improved cooking performance, shape retention, and enhanced mouth coating, suitable for use as binders, fillings, and flavor carriers, while being free from undesirable additives.
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Figure 2026521492000001_ABST
Abstract
Description
[Technical Field]
[0001] [Background technology] Emulsions and emulgels (also known as emulsion-filled gels) are frequently used in food matrices to impart fat-like properties, such as mouth coating and tackiness. Emulsions often consist of proteins as hydrophilic colloids, being highly hydrophilic and non-surface-active. Chemically modified hydrophilic colloids, such as cellulose, and further examples methylcellulose or ethylcellulose, are surface-active and can lead to oleogel formation, but are not well-received by consumers. Current emulsions used in cooking processes also tend not to retain their shape during cooking and do not possess good mouth coating properties. There is a clear need to develop novel emulsions that not only have improved cooking performance but also better mouth coating and tackiness properties. [Overview of the Initiative]
[0002] This invention describes pectin emulsions containing up to 40% oil and varying pectin content. By adjusting the pH and ion content, a surprisingly wide range of textures could be obtained. The emulsions can melt upon cooking, with or without oil release, and can retain their shape depending on their composition. The emulsions also possess an unexpectedly strong mouth coating, which is far stronger than that of conventional emulsion gels produced from proteins. Pectin emulsions are suitable for use as improved binders, meltable fillings, or flavor carriers.
[0003] Natural pectin, obtained from vegetables and fruits, for example, allows for the creation of clean-label food products with improved sensory characteristics without the need for other existing emulsifiers that are often perceived as undesirable by consumers, such as ethylcellulose or methylcellulose, gum arabic, and lecithin.
[0004] The present invention provides a stable emulsion in which small oil droplets with an average size of less than 20 μm are uniformly dispersed and homogenized in a continuous aqueous phase. This stable emulsion can be clearly distinguished from gelling matrices in which much larger oil droplets are simply encapsulated. Such gelling matrices generally require the addition of other emulsifiers or calcium ions for stabilization. As will be discussed in the following examples, the present invention enables an emulsion that can maintain improved stability without the addition of other emulsifiers or calcium ions. [Brief explanation of the drawing]
[0005] [Figure 1] This figure shows the force-displacement curve obtained from a probe tack test. Y-axis = force (g). [Figure 2] This figure shows the parameters and stability results investigated for emulsion formulations. Legend: Black circles = stable emulsion; Stripes = unstable emulsion; Gray = stable only without calcium addition; White = not tested. [Figure 3] This figure shows the predicted values of the measurement parameters (tack force, G' at 40°C, tanδ during heating or cooling) as a function of the emulsion gel composition. [Figure 4A] This figure shows the storage modulus and loss modulus of a 4% pectin system as functions of calcium concentration at 25°C and 80°C. [Figure 4B] This figure shows the storage modulus and loss modulus of a 6% pectin system as functions of calcium concentration at 25°C and 80°C. [Figure 5A]This figure shows the oil droplet measurement of an emulsion gel formulated with 4% pectin and 20% sunflower oil, before heat treatment. [Figure 5B] This figure shows the oil droplet measurement of an emulsion gel formulated with 4% pectin and 20% sunflower oil after heating at 80°C. [Figure 6A] This figure shows the oil droplet measurement of an emulsion gel formulated with 4% pectin, 20% sunflower oil, and 20 mM calcium salt, before heat treatment. [Figure 6B] This figure shows the oil droplet measurement of an emulsion gel formulated with 4% pectin, 20% sunflower oil, and 20 mM calcium salt, after heating at 80°C. [Figure 7A] This figure shows the oil droplet measurement of an emulsion gel formulated with 6% pectin and 20% sunflower oil, before heat treatment. [Figure 7B] This figure shows the oil droplet measurement of an emulsion gel formulated with 6% pectin, 20% sunflower oil, and 20 mM calcium salt, before heat treatment. [Figure 8] This figure shows the storage modulus of emulsion gels with increasing concentrations of unsaturated palm stearin as the temperature is raised from 25°C to 80°C. [Figure 9] This figure shows the probe tack test results for samples P1 (dissolved at 50°C for 15 minutes) and P2 (dissolved at 50°C for 2 hours) during measurement. [Figure 10] This figure shows the results of the heating and cooling rheology tests for P1 and P2. [Figure 11] This figure shows the probe tack test results during measurement for samples P2 (dissolved at 50°C for 2 hours) and P4 (dissolved at 50°C for 15 minutes and pH 2). [Figure 12] This figure shows the results of the heating and cooling rheology tests for P2 and P4. [Figure 13] This figure shows the loss coefficient of an emulsion gel containing 4% pectin, 20% high-oleic sunflower oil, and additional fiber and starch. [Figure 14]It is a diagram showing the principal component (PC) analysis of the sensory characteristics of the recipe designed in Example 2. [Figure 15] It is a diagram showing the effect of water content on the sensory characteristics of the pectin gel in Example 2. [Figure 16] It is a diagram showing the effect of pectin content on the sensory characteristics of the pectin gel in Example 2. [Figure 17] It is a diagram showing the effect of oil content on the sensory characteristics of the pectin gel in Example 2. [Figure 18A] It is a diagram showing the storage modulus and loss modulus of the sample stored at 4°C in Example 11 by the rheology method of modulating frequency. [Figure 18B] It is a diagram showing the storage modulus and loss modulus of the sample stored at 20°C in Example 11 by the rheology method of modulating frequency. [Figure 19A] It is a diagram showing the storage modulus and loss modulus of the sample stored at 4°C in Example 11 by the rheology method of modulating amplitude. [Figure 19B] It is a diagram showing the storage modulus and loss modulus of the sample stored at 20°C in Example 11 by the rheology method of modulating amplitude. [Figure 20A] It is a diagram showing the viscosity of the sample stored at 4°C in Example 11. [Figure 20B] It is a diagram showing the viscosity of the sample stored at 20°C in Example 11. [Figure 21A] It is a diagram showing the texture analysis results of the carrot gel stored at 4°C in Example 11: hardness (positive force) and tack force (negative force). [Figure 21B] It is a diagram showing the texture analysis results of the carrot gel stored at 4°C in Example 11: positive and negative areas [Figure 22A] It is a diagram showing the texture analysis results of the carrot gel stored at 20°C in Example 11: hardness (positive force) and tack force (negative force). [Figure 22B]Texture analysis results of carrot emulsion gels stored at 20°C in Example 11: A diagram showing positive and negative areas. [Figure 23A] A diagram showing tribology measurement of carrot emulsion gels stored at 4°C in Example 11. [Figure 23B] A diagram showing tribology measurement of carrot emulsion gels stored at 20°C in Example 11. [Figure 24] A diagram showing oil-binding capacity of carrot emulsion gels stored at 4°C and 20°C in Example 11. [Figure 25] A diagram showing oleic acidification of carrot emulsion gels stored at 4°C and 20°C in Example 11. [Figure 26] A diagram showing oil droplet measurement after heat treatment of carrot emulsion gels in Example 11. [Figure 27A] A diagram showing oil droplet measurement of carrot emulsion gels in Example 11 after storage at 4°C for 2 months. [Figure 27B] A diagram showing oil droplet measurement of carrot emulsion gels in Example 11 after storage at 4°C for 6 months. [Figure 28A] A diagram showing oil droplet measurement of carrot emulsion gels in Example 11 after storage at room temperature for 2 months. [Figure 28B] A diagram showing oil droplet measurement of carrot emulsion gels in Example 11 after storage at room temperature for 6 months. [Figure 29A] A diagram showing texture characteristics of recipes R1 - R5 described in Example 12. [Figure 29B] A diagram showing texture characteristics of recipes R1 and R6 - R8 described in Example 12. [Figure 30A] A diagram showing sensory characteristics of recipes R1 - R5 described in Example 12. [Figure 30B] A diagram showing sensory characteristics of recipes R6 - R8 described in Example 12. [Figure 31] A diagram showing sensory mapping of recipes R1 - R8 described in Example 12. [Figure 32]This figure shows the rheology of emulsion gels C1 and C2 described in Example 15. [Figure 33A] This figure shows the oil droplet size of emulsion C1 described in Example 15. [Figure 33B] This figure shows the oil droplet size of emulsion C2 described in Example 15. [Figure 34] This figure shows the evaluation of the acidity of the pectin emulsion described in Example 16.
[0006] Embodiments of the present invention This invention generally relates to pectin-based emulsions.
[0007] In particular, the present invention relates to a pectin-based emulsion comprising pectin, oil, and water, having a pH of less than 5.
[0008] In particular, the present invention relates to a pectin-based emulsion comprising pectin, oil, and water, wherein the emulsion has a pH lower than the pKa of pectin.
[0009] In particular, the present invention relates to a pectin-based emulsion comprising 0.5 to 6% by weight of pectin, oil, and water, and having a pH of less than 5.
[0010] In particular, the present invention relates to a pectin-based emulsion comprising pectin, 3 to 40% by weight of oil, and water, wherein the emulsion has a pH of less than 5.
[0011] In particular, the present invention relates to a pectin-based emulsion comprising 0.5 to 6% by weight of pectin, 3 to 40% by weight of oil, and water, wherein the emulsion has a pH of less than 5, the average oil droplet size in the emulsion is less than 20 μm, and the pectin is a high-methoxyl pectin with a methoxyl degree (DM) > 60.
[0012] In one embodiment, the emulsion has a pH of less than 4.5, less than 4.2, less than 4, or about 3.5.
[0013] In one embodiment, the average oil droplet size in the emulsion is less than 19 μm, or less than 18 μm, or less than 17 μm, or less than 16 μm, or less than 15 μm.
[0014] In one embodiment, the pectin is high-methoxyl pectin with a methoxy degree (DM) of 70.
[0015] In one embodiment, the emulsion contains a polyvalent ion. In one embodiment, the polyvalent ion contains calcium, magnesium, or iron. In one embodiment, the polyvalent ion is preferably a calcium ion.
[0016] In one embodiment, the emulsion contains up to 80 mM of polyvalent ions.
[0017] In one embodiment, the emulsion contains 5 to 40 mM of polyvalent ions.
[0018] In one embodiment, the emulsion comprises about 2% by weight of pectin and about 15% by weight of oil.
[0019] In one embodiment, the pectin may be purified or unpurified. For example, unpurified pectin is unrefined citrus fiber.
[0020] In one embodiment, the emulsion further comprises fruit powder, vegetable powder, such as soybean flour, refined fiber, or refined starch.
[0021] In one embodiment, the water is deionized water, tap water, or mineral water.
[0022] In one embodiment, water is replaced with a cooked puree, such as a vegetable puree, or a fruit puree, or a bean puree.
[0023] In one embodiment, the pectin is citrus pectin, beet pectin, apple pectin, or amidated pectin.
[0024] In one embodiment, the pectin is citrus pectin.
[0025] The present invention further relates to a method for producing a pectin-based emulsion according to the present invention, the method comprising the steps of: heating pectin in water to at least 50°C; adding oil; and high-shear mixing for about 5 minutes.
[0026] The present invention further relates to a method for producing a pectin-based emulsion, A step of heating 0.5-6% by weight of pectin in water to at least 50°C to obtain a hydrated pectin solution, The process involves adding 3-40% by weight of oil to a hydrated pectin solution, The process involves mixing a mixture of hydrated pectin solution and oil by high-shear mixing for approximately 5 minutes. Includes, The present invention relates to a method wherein the emulsion has a pH of less than 5, the average oil droplet size in the emulsion is less than 20 μm, and the pectin is a high-methoxyl pectin with a methoxyl degree (DM) > 60.
[0027] In one embodiment, high-shear mixing is carried out while heating the mixture to at least 50°C, preferably about 75°C.
[0028] In one embodiment, high-shear mixing is performed for 170-3400 seconds. -1 This is carried out at a shear rate. This shear rate corresponds to a rotational speed of 100 to 2000 RPM.
[0029] In one embodiment, the method further includes adjusting the pH of the pectin emulsion to less than pH 5, preferably less than pH 4.5, more preferably less than pH 4.2, and more preferably less than pH 3.5.
[0030] In one embodiment, the pH is adjusted to approximately pH 3.5.
[0031] In one embodiment, the method further comprises adding polyvalent ions, preferably calcium ions, to the pectin-based emulsion after high-shear mixing.
[0032] In one embodiment, after high-shear mixing, polyvalent ions are added to the pectin-based emulsion so that the final concentration of polyvalent ions in the pectin-based emulsion reaches a maximum of 80 mM, preferably 5 to 40 mM.
[0033] In one embodiment, in the step of mixing a mixture of hydrated pectin solution and oil by high-shear mixing, the oil is added at a constant flow rate of approximately 100 mL / min.
[0034] The present invention further relates to the use of a pectin-based emulsion according to the present invention, wherein the emulsion is a. Binding agent, b. Filling, c. Flavoring agent, d. fat substitutes, e. Spreadable products, f. puree, g. dip, h. Toppings, or i.Frozen dessert It is, regarding use. [Modes for carrying out the invention]
[0035] pectin The pectin may be high-methoxyl pectin. The methoxyl content (DM) may be 60-70%. The methoxyl content (DM) of the pectin may be 70%. The pectin may be low-methoxyl pectin. The methoxyl content may be about 33% methoxyl. The pectin may be amidated pectin. The methoxyl content may be about 27% methoxyl. Amidated pectin may contain about 20% amide. The pectin may be beet pectin. The pectin may be apple pectin. Low-methoxyl pectin has been found to produce a firm, less viscous gel.
[0036] The pectin-based emulsion may contain about 0.5% by weight, or about 1% by weight, or about 1.5% by weight, or about 2% by weight of pectin, or about 3% by weight of pectin, or about 4% by weight of pectin, or about 5% by weight of pectin, or about 6% by weight of pectin, or about 7% by weight of pectin, or about 8% by weight of pectin, or about 9% by weight of pectin, or about 10% by weight of pectin. Preferably, the pectin-based emulsion contains about 2% by weight of pectin or about 4% by weight of pectin.
[0037] starch The starch may be waxy corn starch. The starch may be potato starch.
[0038] fiber The fiber may be citrus fiber. Citrus fiber may contain approximately 30% pectin. The fiber may also be wheat fiber. Citrus fiber can be used in addition to or as a pectin source in the emulsion. Wheat fiber can also be used in addition to citrus fiber.
[0039] oil For the purposes of this application, the terms “oil” and “fat” are used interchangeably. Fats or oils may include animal fats or animal oils, vegetable fats or vegetable oils, such as coconut oil or coconut fat, sunflower oil, and milk fat.
[0040] The oil may be sunflower oil, for example, high-oleic sunflower oil. The pectin-based emulsion may contain palm stearin oil. The pectin-based emulsion may contain about 3% by weight, or about 5% by weight, or about 10% by weight, or about 15% by weight, or about 20% by weight, or about 30% by weight, or about 40% by weight, or about 50% by weight of oil. Preferably, the pectin-based emulsion contains 3-40% by weight of oil, or 5-40% by weight of oil, or 5-30% by weight, or 5-20% by weight of oil, or 10-30% by weight of oil, or 10-20% by weight of oil, or 10-15% by weight of oil. Pectin-based emulsions may contain palm stearin oil and high-oleic sunflower oil in a palm stearin oil:high-oleic sunflower oil ratio of approximately 25:75, 50:50, or 75:25.
[0041] polyvalent ions The pectin-based emulsion may contain polyvalent ions, such as magnesium ions, iron ions, or calcium ions, preferably calcium chloride dihydrate. The pectin-based emulsion may contain about 1% calcium chloride dihydrate. The pectin-based emulsion may contain about 5 mM, or about 6 mM, or about 7 mM, or about 8 mM, or about 9 mM, or about 10 mM, or about 11 mM, or about 12 mM, or about 13 mM, or about 14 mM, or about 15 mM, or about 16 mM, or about 17 mM, or about 18 mM, or about 19 mM, or about 20 mM calcium chloride. Preferably, the pectin-based emulsion contains 5 to 40 mM of polyvalent ions.
[0042] For example, after mixing the oil with the pectin solution and emulsifying it by high-shear mixing, polyvalent ions, such as calcium ions, may be added to the pectin-based emulsion. For example, after mixing the oil with the pectin solution and emulsifying it, polyvalent ions, preferably calcium ions, are added to the pectin-based emulsion so that the final concentration of polyvalent ions in the pectin-based emulsion reaches a maximum of 80 mM, preferably 5 to 40 mM.
[0043] When vegetable puree and / or fruit puree is used as the aqueous phase to replace at least a portion of the water in a pectin-based emulsion, the vegetable puree and / or fruit puree may contain multiple types of polyvalent ions, such as magnesium ions, iron ions, or calcium ions, and at least a portion of the final concentration of polyvalent ions in the pectin-based emulsion may be derived from the vegetable puree and / or fruit puree.
[0044] For example, the calcium ion content in vegetable puree and / or fruit puree may be, on average, 10 to 40 mg per 100 g, or 0.2 to 0.8 mmol per 100 g.
[0045] Other pectin-based emulsion ingredients Pectin-based emulsions may contain approximately 50% by weight of water, approximately 60% by weight of water, approximately 70% by weight of water, approximately 80% by weight of water, approximately 90% by weight of water, or 50-90% by weight of water. Deionized water has been found to provide a viscoelastic fluid, which has been found to be useful in controlling mouthfeel properties. The use of mineral water provides a gel-like material. Mineral water can be used as a calcium source.
[0046] The pectin-based emulsion may contain potato starch, for example, about 3% by weight of potato starch. The pectin-based emulsion may contain waxy corn starch, for example, about 3% by weight of waxy corn starch. The pectin-based emulsion may contain wheat fiber, for example, about 3% by weight of wheat fiber, or about 6% by weight of wheat fiber. Preferred starches are waxy starch or potato starch. Starch has been found to improve binding properties in both high and low temperature applications. Potato starch has been found to provide very good sensory properties.
[0047] The pectin-based emulsion may contain soybean flour, preferably micronized soybean flour. It has been found that micronizing the flour prevents granularity caused by aggregation.
[0048] Pectin-based emulsion recipe A pectin-based emulsion may, for example, contain about 1.5 to 2.0% by weight of pectin and about 10 to 15% by weight of oil. A pectin-based emulsion may, for example, contain about 4% by weight of pectin and about 20% by weight of oil. A pectin-based emulsion may, for example, contain about 4% by weight of pectin and 20% by weight of oil in deionized water. A pectin-based emulsion has a pH of less than 5, preferably less than 4.5, preferably less than 4.2, preferably less than 4, and preferably less than 3.5. The pH may be about pH 2.
[0049] A pectin-based emulsion may contain approximately 3% by weight of pectin, approximately 8% by weight of soy flour, and approximately 20% by weight of fat. A pectin-based emulsion may contain approximately 8% by weight of pectin and approximately 10% by weight of fat. A pectin-based emulsion may contain approximately 4% by weight of pectin and approximately 40% by weight of fat.
[0050] Food products containing pectin emulsions Food products containing pectin-based emulsions may also be vegetable puree spreads. The purees may include red pepper puree, carrot puree, or broccoli puree. The food products may have recipes substantially similar to those shown in Table 16.
[0051] The food product may be a spreadable liquid-like matrix, wherein the product comprises an emulsion having about 2% by weight of pectin and about 15% by weight of oil.
[0052] Pectin-based emulsions can be used as flavor enhancers. Flavor enhancers may have recipes substantially similar to those shown in Table 19 (R8).
[0053] Pectin-based emulsions can be used as purees, for example, as baby food purees. An example of a baby food puree may contain about 0.5–1.5% by weight of pectin and about 3–7% by weight of fat or oil.
[0054] Pectin-based emulsions can be used as ice cream, gelato, or frozen desserts. An example of a frozen dessert may contain about 1-2% by weight of pectin, about 3-20% by weight of fat or oil, and about 60-95% by weight of vegetable and / or fruit puree. An example of a frozen dessert may further contain sugar.
[0055] Method for producing pectin-based emulsions Pectin can be hydrated with water. The water may be mineral water, such as Vittel® water. The water may be tap water. The water may be deionized water. Pectin can also be hydrated with water contained in vegetable puree and / or fruit puree. The hydration step may be carried out for about 15 minutes and may be carried out at about 50°C. The pasteurization step may be carried out at about 75°C for about 5 minutes. Both may be carried out at a rate of about 2.5 in Thermomix (350 RPM). The pasteurization step may be carried out optionally for food safety purposes only, and the pectin-based emulsion according to the present invention is stable even without such optional pasteurization step. After hydration, oil may be added to the pectin solution, and this pectin solution can be emulsified for about 5 minutes, for example by high-shear mixing. High-shear mixing may be carried out while heating the mixture to at least 50°C, preferably about 75°C. High-shear mixing may be carried out for 170-3400 seconds. -1 The process may be carried out at a shear rate of 100-2000 RPM, which corresponds to a rotational speed of 100-2000 RPM. The shear rate of the Thermomix may be increased to approximately 4.5 (1550 RPM), and oil may be added at a constant flow rate of approximately 100 mL / min. Depending on the sample formulation, calcium chloride may be added during the last minute of emulsification or after emulsification.
[0056] This method may further include a step of retorting a pectin-based emulsion. The retorting step may be carried out at 95°C for 5 minutes.
[0057] Use of pectin-based emulsions Pectin-based emulsions include (i) binding agents, for example, those that can be used as binding agents to hold products in place during cooking so that they can be flipped over in a frying pan during cooking. Typically, emulsions include calcium and starch; (ii) fillers, for example, those located inside a matrix that reduce the thickness of the emulsion during cooking without phase separation (e.g., croquettes and burrata); (iii) flavor carriers, for example, by incorporating spices inside a food matrix; (iv) fat substitutes, for example, those that destabilize the emulsion during cooking and enhance the juiciness of the final food product; (v) spreadable products; (vi) purees; (vii) dips; (viii) toppings; or (ix) frozen desserts.
[0058] As used herein, the singular form "one" ("a," "an," and "the") also includes multiple references unless otherwise indicated.
[0059] The terms “comprise,” “comprises,” and “comprising” should be interpreted as not being exclusive but potentially encompassing others. Similarly, the terms “include,” “including,” and “or” should all be interpreted as potentially encompassing others unless such interpretation is clearly prevented by the context.
[0060] The compositions disclosed herein may not contain any elements not specifically disclosed. Accordingly, disclosures of embodiments using the term “comprising” include disclosures of embodiments that “consist essentially of” a specified component, and disclosures of embodiments that “consist of” a specified component. Similarly, the methods disclosed herein may not contain any steps not specifically disclosed herein. Accordingly, disclosures of embodiments using the term “including” include disclosures of embodiments that “consist essentially of” a specified step, and disclosures of embodiments that “consist of” a specified step.
[0061] The term "and / or" as used in the context of "X and / or Y" should be interpreted as "X" or "Y" or "X and Y". As used herein, the terms "example" and "such as" are for illustrative and explanatory purposes only, and should not be considered exclusive or comprehensive, especially when followed by a list of terms. Unless otherwise stated, any embodiment disclosed herein may be combined with any other embodiment disclosed herein.
[0062] As used herein, “about” and “approximately” are understood to mean a number within a numerical range, for example, a range of -10% to +10% of the referenced number, preferably a range of -5% to +5% of the referenced number, more preferably a range of -1% to +1% of the referenced number, and most preferably a range of -0.1% to +0.1% of the referenced number.
[0063] Vegan products are defined as those that do not contain animal products, such as dairy and meat products. The vegan analogue products of the present invention have an appearance, taste, and texture similar to real animal products.
[0064] The present invention will be described below with reference to several examples, but these examples are not intended to limit the scope of the present invention as described herein. [Examples]
[0065] Preparation of emulsion The pectins used in the following examples were (i) high-methoxyl pectin (derived from citrus fruits, methoxyl (DM) = 70%); (ii) low-methoxyl pectin (derived from citrus fruits, DM = 33%); (iii) amidated pectin (derived from citrus fruits, 27% methoxyl and 20% amide); (iv) beet pectin; and (v) apple pectin. Soy flour, starch (waxy corn and potato starch), citrus fiber (30% pectin), and wheat fiber were also used.
[0066] The first step in producing the emulsion gel was to hydrate the pectin with water (Vittel water, tap water, or deionized water) at 50°C for 15 minutes, and then pasteurize the gel at 75°C for 5 minutes for food safety. Both steps were performed at a speed of 350 RPM. After the hydration process, the pectin solution was emulsified by high-shear mixing for 5 minutes. During high-shear mixing, the shear rate was increased from 350 RPM to 1550 RPM, and oil was added at a constant flow rate of 100 mL per minute. Depending on the composition of the sample, CaCl2 was added during the last minute of emulsification.
[0067] analysis The tackiness and hardness of the samples were evaluated using a texture analyzer (TA HD plusC-, Stable Micro Systems Ltd, Godalming, UK) by adapting the probe tack test method. A cylindrical plate with a height of 12.5 mm was filled to its maximum capacity with the freshly prepared sample, ensuring a flat surface. The plate was then covered and refrigerated at 4°C for 24 hours before analysis. Each sample was measured eight times in all experiments. A 45 mm diameter cylindrical plexiglass probe was moved downward at 0.5 mm / s until it penetrated 2 mm into the sample. The probe was then moved upward at 10 mm / s for 5 seconds. Hardness (N) was measured as the peak force when the probe penetrated 2 mm into the sample. Tack (N), the maximum strength required to separate the binder and the adhesive force obtained when separating the probe from the sample, and Wahesion (N), the total work required to separate the probe from the sample and also known as adhesion, were measured. * We also obtained s).
[0068] Figure 1 shows the force-displacement curve of a probe tack test measurement, which represents the force (in g, but converted to N during data processing using a conversion factor of 1N = 101.97g) against time (s) and various parameters (hardness, ftack, and wadhesion) obtained from it.
[0069] In the oil binding method, the sample (4-4.5 g) was placed in a 15 mL polypropylene tube and centrifuged at 11000 g (7993 rpm) at 20°C for 15 minutes using a Sorvall Lynx 6000 centrifuge (ThermoFisher Scientific, Waltham, USA). After centrifugation, the leached oil was removed and the OBC was calculated. OBC is the ratio (percentage) of the oil retained by the emulsion-gel sample after centrifugation to the oil initially present in the sample.
[0070]
number
[0071] In this equation, m is the mass of the empty tube, m1 is the total mass of the tube with the emulsion-gel sample added, m2 is the total mass of the emulsion-gel sample, and X oil This represents the initial oil content (%) of the initial sample.
[0072] Rheological analysis was performed using a rotating rheometer with the following geometry (MCR 502, Anton Paar, Graz, Austria): Solid-like sample: A 50mm diameter stainless steel parallel plate with a 1mm gap distance and a serrated surface (PP50 / SS / P2) was used to prevent slippage. To prevent water evaporation from the sample, paraffin oil was applied and a cooling cover hood system was used. For liquid-like samples, use a CC-27 sanded cylinder.
[0073] The sample was loaded at 4°C, heated to 90°C (5°C / min, 0.2% strain, 1Hz), cooked at 90°C for 1 minute, cooled to 60°C (5°C / min, 0.2% strain, 1Hz; holding time 3 minutes), and then cooled to 40°C (5°C / min, 0.2% strain, 1Hz; holding time 3 minutes). Frequency sweeps (0.02%γ, 0.01~10Hz) were performed at 4°C and at 40°C after cooling. The storage modulus G', loss modulus G'', and loss coefficient tanδ were recorded at 4°C, 40°C during the heating process, and 90°C and 40°C during the cooling process.
[0074] The effect of calcium on thermal stability was investigated by heating the sample from 25°C to 90°C in a shorter heating process (5°C / min, 0.2% strain, 1 Hz). Frequency sweeps were performed at 25°C and 90°C (0.02% γ, 100~0.1 Hz).
[0075] The color was measured using the DigiEye system as recommended by the supplier. The instrument measured transparency (L) and color along the green-red axis (a) and the blue-yellow axis (b). The color difference between the two samples, 1 and 2, is expressed by ΔE as follows:
[0076]
number
[0077] The oxidation of oil was measured using ML Oxipress (MikroLab Aarhus A / S, Denmark). Briefly, 50g of emulsion gel was weighed into a glass container and oxidized at 5 bar and 90°C. The oxidation curve was recorded as the pressure generation over time. The breakpoint time at which the pressure began to decrease was recorded as the time required to detect oxidation and rancidity.
[0078] The oil droplet size was measured using confocal laser scanning microscopy, with Nile Red used to stain the droplets. An LSM 710 microscope equipped with Zeiss Airyscan was used, excited at 561 nm, and images were obtained. The oil droplet size was measured using ImageJ.
[0079] Example 1 Physical properties of pectin emulsions To logically interpret the effects of oil, pectin, and ion content on emulsion properties, an experimental design was implemented. High methoxypectin (derived from citrus fruits, DM=70%) was varied between 2-10%, oil between 10-50%, and additional CaCl2 dihydrate was varied from 0 to 1%. Emulgels were formed as described in the previous section. Emulgels could be formed with most formulations. The results of the formulation tests are shown in Figure 2.
[0080] The measured parameters were oil bonding, TA (adhesion, tack force, and hardness), and rheology (G' and tanδ at 4°C and 40°C after heating). Several relationships were observed. The parameters of the texture analyzer were correlated (e.g., tack force was positively correlated with hardness (r=0.91) and with adhesion (r=0.88)). Tack force could be predicted using a linear model (R²=0.76). The model coefficients were (i) using high pectin levels (p<10 -4(ii) and (ii) high tack strength (absolute value) was achieved when a low oil content was used (p=0.06), however, this effect was shown to apply only when a high level of pectin was used (≧8%). The linear additive model was sufficient to explain the influence of formulation on gel properties. Good predictive accuracy was achieved for rheological and texture analysis (Figure 3).
[0081] We identified pathways that enable the production of gels with desired properties: (i) TA, high tack force and adhesive work → combination of high pectin level and low oil level; (ii) [rheology] high G' and low tanδ at 40°C cooling → combination of high oil level and calcium addition; and (iii) [rheology] high G' and low tanδ at 90°C → combination of high oil level and calcium addition.
[0082] Table 1 shows the effect of increasing the content of formulation parameters (pectin, oil, and calcium) on emulsion-gel properties, and the R-value of linear model regression for each analytical parameter. 2 The values are shown. A downward arrow indicates a decrease in that parameter, and an upward arrow indicates an increase. The type and number of arrows indicate the level of significance.
[0083] [Table 1]
[0084] The overall results are shown in Table 2 (Texture Analysis), Table 3a, and Table 3b (Rheology). [Table 2] TIFF2026521492000006.tif226147
[0085] [Table 3a]
[0086] [Table 3b]
[0087] Example 2 The effect of pectin emulsion formulation on sensory properties The effect of pectin emulsion gel composition on functional properties was systematically studied. The recipes are summarized in Table 4. High methoxypectin (DM 70%) derived from citrus fruits was used. All formulations were prepared with mineral water, except for sample S15, which used deionized water.
[0088] [Table 4]
[0089] The samples were tasted and evaluated by a trained panel at ambient temperature (25°C) or heated (60°C). The evaluation used a rating system, which involved first listing all characteristics related to the sample, and then rating each characteristic on a scale from 1 (slightly strong) to 5 (very strong). The sensory characteristics terminology used is shown in Table 5.
[0090] [Table 5]
[0091] Almost no difference was observed between the high-temperature (60°C) sample and the ambient temperature (25°C) sample. All properties differed significantly between the samples (p-value < 0.001). Three main groups were obtained, as shown in Figure 14. Group 1: High melt-in-the-mouth properties and slipperiness. Group 2: High density, adhesion, and homogeneity. Group 3: High brittleness, hardness, and surface oiliness.
[0092] The influence of each individual component on the sensory properties was examined individually (Figures 15-17). As shown in Figure 15, high water content was strongly correlated with high homogeneity, low bubbles, a non-oily surface, and a denser texture.
[0093] As shown in Figures 16 and 17, when the same procedure was performed on pectin and oil, it was shown that a higher pectin content resulted in a firmer texture, higher thermal stability, higher tackiness, and better mouth coating. On the other hand, a higher oil content resulted in an oily, glossy surface, but reduced uniformity of appearance.
[0094] Furthermore, the use of demineralized water has been shown to significantly increase slipperiness and mouthfeel while simultaneously reducing oil leakage, hardness, stickiness, and mouth coating. Therefore, when the presence of minerals is advantageous for thermal stability and more suitable for binding applications, it should be preferable to use demineralized water in the filling formulation.
[0095] Example 3 Effects of calcium addition and heating In this Example 3, the recipe shown in Table 6 below was used.
[0096] [Table 6]
[0097] To better visualize the effect of calcium concentration on the thermal stability of the gel, the storage modulus at a frequency of 68 rad / s was selected as a single reference point. This selection is motivated by an interest in the properties of the elastic solid state, which can be seen in the G' value. The G' values obtained from calcium additions of 0 mM to 80 mM at temperatures of 25°C and 80°C can be seen in Figures 4A and 4B. Figure 4A shows the results for a sample containing 4% pectin (Recipe 1), and Figure 4B shows the results for a sample containing 6% pectin (Recipe 2).
[0098] At 25°C, without calcium addition, the loss modulus is greater than the storage modulus, indicating that the gel behaves more like a liquid. This behavior manifests as a much less viscous fluid, like an emulsion, rather than a more solid-like gel as seen with higher calcium additions. Adding a 10 mM calcium solution dramatically increases the solid-like behavior, with the storage modulus in the 4% mixture more than tripling from 91 Pa to 289 Pa. In particular, rheological measurements demonstrate that the storage modulus is greater than the loss modulus, suggesting that the gel exhibits more solid-like behavior. This dramatic increase is attributed to dimerization within the pectin, where positively charged divalent calcium electrostatically bonds to negatively charged carboxyl groups within the pectin skeleton. This reaction leads to the formation of a network following the eggbox model, ultimately resulting in a structure much rigider than the pectin structure in the absence of cationic charges. Rheological measurements reveal that a small amount, as low as 10 mM, may be sufficient to initiate this gelation mechanism.
[0099] For the 4% and 6% pectin systems at 25°C, the highest G' values were observed at 20 mM. At both percentages, the addition of excess calcium above 20 mM did not have a beneficial effect on gel strength. Higher concentrations of 40 mM and 80 mM showed higher storage modulus values than gels without calcium, but these values were lower than those at lower concentrations of 10 mM and 20 mM. The presence of cationic charge at this maximum level is likely due to the pectin's tendency to localize within the aqueous matrix. Aggregation of pectin as a result of excess positive charge hinders the formation of continuous long-range networks, resulting in weaker gels than those with lower calcium concentrations.
[0100] When heated from 25°C to 80°C, the gel strength decreased with the application of heat, resulting in an overall decrease in G' and G'' values at each calcium concentration. Corresponding to the most solid-like behavior at high temperatures, the measure of heat resistance was interpreted as the maximum value of G' at 80°C. Similar to the G' values observed at 25°C, the strongest gel and highest heat resistance were again observed for the 4% and 6% pectin systems at calcium concentrations of 10 mM and 20 mM, respectively. This behavior is consistent with the observation that stronger gels are obtained at lower calcium concentrations.
[0101] The effects of heating and calcium addition on emulsion stability were also evaluated by measuring oil droplet size using confocal microscopy. Surprisingly, the oil droplet size was found to be very small, well below 20 μm, and this diameter was hardly affected by calcium addition or heat treatment. The oil droplet diameters are shown in Figures 5A and 5B (4% pectin, 20% oil, no calcium added, before and after heat treatment up to 80°C), Figures 6A and 6B (4% pectin, 20% oil, 20 mM Ca, before and after heat treatment up to 80°C), and Figures 7A and 7B (6% pectin, 20% oil, no calcium added or 20 mM Ca, before heat treatment). Increasing the pectin concentration resulted in smaller oil droplets ranging from approximately 15 μm (4% pectin) to less than 10 μm (6% pectin).
[0102] This third example demonstrates that the pectin-based emulsion according to the present invention provides a fluid-like emulsion in which small oil droplets having an average size of less than 20 μm are sufficiently dispersed and homogenized in a continuous aqueous phase. In contrast to gelling matrices in which much larger oil droplets are simply encapsulated, the emulsion according to the present invention allows for improved stability, such as versatility for liquid or fluid applications, and a more controllable texture. Notably, the present invention provides such a stable and homogeneous emulsion without the addition of calcium. The fact that the small oil droplet size was not significantly affected by heating and calcium addition means that the present invention may provide a stable food product without high-temperature heat treatment when used in several applications, and that such stability will not be impaired by any heat treatment that may be required in some applications for food safety or operational reasons. The addition of calcium after emulsification of the oil and pectin favorably modifies the texture of the emulsion while maintaining a stable emulsion state.
[0103] Example 4 Influence of pectin type The citrus-derived high-methoxypectin used was replaced with citrus-derived low-methoxypectin, apple pectin, beet pectin, citrus-derived amidated pectin, and unrefined citrus fiber. Citrus fiber can also be considered unrefined pectin compared to refined citrus-derived high-methoxypectin. The emulsion was prepared from MQ water, 4% pectin, and 20% oil.
[0104] [Table 7a]
[0105] All formulations exhibited very good oil-binding ability. Apple pectin could not form an emulsion due to its high pH, but a stable emulsion could be formed by lowering the pH to 3.5. However, these emulsions were very liquid and lacked viscosity compared to those formed from citrus pectin. While emulsions could be formed from citrus pectin, it was quite surprising that emulsions could also be formed using pectins with different methoxylation and amidation patterns. The sugar beet pectin gel had lower hardness and tackiness compared to the citrus derivatives.
[0106] [Table 7b]
[0107] The emulsion gels were heated to 90°C and then cooled to 40°C to evaluate their stability. High-methoxyl and beet pectin emulsion gels exhibited strong liquid-like behavior (tanδ > 1), while citrus fiber and low-methoxyl pectin emulsion gels. All materials decreased in viscosity upon heating (increased tanδ), but the beet fiber formulation was the least affected of all materials. Using pectin-rich citrus fiber (40% pectin) significantly improved gel-like characteristics and thermal stability. This improvement suggests that emulsion gel properties and heat resistance can be adjusted by modifying the pectin structure and degree of methoxylation, in addition to the calcium content. No emulsion gel phase separated upon heating, but the apple pectin phase decreased in viscosity considerably.
[0108] Example 5 Effect of oil on the composition The recipes in Table 8 below were investigated in this Example 5.
[0109] [Table 8]
[0110] To evaluate the effect of oil saturation on the thermal stability and strength of gels, saturated fats were selected and added to emulsion gels at various concentrations. Palm stearin contains up to 50% palmitic acid, a fully saturated fatty acid that keeps the oil in a solid state at room temperature. Palm stearin is in contrast to high-oleic sunflower oil, which consists almost entirely of unsaturated oleic acid and exists as a liquid at room temperature. To incorporate the solid fat into the gel, the oil mixture was heated to 55°C, well above the melting point of palm stearin. The oil was then incorporated under high shear in the same manner as the gel containing only high-oleic sunflower oil.
[0111] Figure 8 shows rheological data that highlights the effect of saturated oil addition on gel strength at room temperature and high temperatures. The storage modulus (G') is chosen for the plot because it represents the solid behavior of the gel. Notably, the storage modulus at room temperature differs as the amount of saturated oil in the gel matrix increases. When the temperature is fixed at 25°C, the lowest G' values are observed when palm stearin is added to high oleic acid oil at 0% and 25%. Above 25% addition, a tendency is observed for the G' value to increase with increasing amounts of saturated fat, and 100% palm stearin gel shows a dramatically high G' value at 25°C. The solid properties of fat were found to impart rigidity to the gel matrix at temperatures below its melting point. As the temperature is raised to 80°C, the solid fat begins to melt, which manifests as a decrease in the G' value. At the final temperature of 80°C, the opposite trend is observed. Gels containing a larger amount of saturated fat show lower G' values.
[0112] These behaviors demonstrate the importance of fatty acid saturation for gel stiffness at both high and low temperatures. To maintain strength at both high and low temperatures, a mixture of both saturated and unsaturated fatty acids may be required.
[0113] Example 6 Effects of pH, temperature, and extended dissolution time The potential effects of extended solubilization time on pectin chain conformation, and the resulting functional properties of the emulsion gel, were investigated using the recipes in Table 9 below.
[0114] [Table 9]
[0115] Figure 9 shows the results of the probe tack test and the appearance of the samples. Samples P1 and P2 differed in the dissolution time for hydrating pectin. For P1, dissolution was performed using Vittel® water at 50°C for 15 minutes, while for P2, dissolution was performed using Vittel® water at 50°C for 2 hours. There was no visual difference in the gel, but sample P2 had a shorter solubilization time than P1 (1.10 ± 0.14 N). * Significantly higher adhesion (1.617±0.27N) compared to s). * This showed s), while the tack force remained the same.
[0116] Furthermore, the sample with a longer solubilization time (P2) showed a higher oil-binding capacity (90.8±3.1%) compared to P1 (76.8±3.3%) (Table 9). Therefore, extending the hydration time directly improved the emulsion properties of the pectin emulsion gel.
[0117] The improved oil-binding capacity observed in this study is thought to be due to increased polymer elongation of pectin chains as a result of prolonged hydration time. The elongated polymer chains expose methyl groups that may have been previously trapped within the pectin structure, creating a chain configuration that can be described as a "hydrophobic pocket." As the solubilization time increases, this pocket moves and becomes available for interaction with oil droplets. The enhanced interaction between the exposed hydrophobic pocket and the oil droplet strengthens binding and stabilization within the gel structure.
[0118] However, as shown in Figure 10, the rheological properties during heating and cooling did not show any significant differences between the samples.
[0119] To investigate the effect of pH on the stability of pectin emulgels, samples P3 and P4 were prepared by changing the pH to 2 or 5 (the reference sample had a pH of approximately 3.5). P3 (pH = 5) did not produce a stable emulsion and immediately phase-separated. Since the pKa of pectin is typically about 3.5 - 4, the carboxyl groups of pectin are deprotonated, thereby reducing the oil affinity, i.e., emulsion stability.
[0120] On the other hand, at pH 2 (sample P4), a stable emulsion was produced, but the physical properties were significantly different compared to P1 or P3. As seen in Figure 11, P4 showed an increase in the adhesiveness (W adhesion ) of the emulgel and a decrease in hardness compared to P2. In this case, since the pH is lower than the pKa of pectin, all the chains are fully protonated and lose the binding affinity for calcium. This is the reason for the measured decrease in gel strength. This is further confirmed by the fact that P4 shows an increase in liquid behavior compared to P2, which shows G’ > G” typical of a gel material, as P4 shows G” > G’ in rheological measurements (Figure 12). Furthermore, the oil-binding capacity was more strongly improved in P4 than in P2 (P2 = 90.8 ± 3.1% and P4 = 100.0 ± 0.0%, see Table 9), highlighting the pectin oil affinity more prominently compared to the gelling ability of pectin.
[0121] This confirms that the greater the presence of ionic cross-links, the lower the oil-binding capacity. The long junction regions of calcium cross-links in the pectin chains form rigid regions with reduced molecular mobility, resulting in a decrease in the accessibility of hydrophobic groups when they interact with oil droplets to stabilize the oil droplets.
[0122] Furthermore, it is emphasized that when the carboxyl groups are charged, the formation of ionic cross-links at higher pH may be thermodynamically more favorable compared to hydrophobic interactions between pectin chains and oil droplets.
[0123] The results demonstrated that pH plays a crucial role in the overall properties of the system. Higher pH values lead to the formation of ionic crosslinks, resulting in decreased oil-binding capacity and even emulsion decomposition due to phase separation. Lower pH resulted in increased adhesion and decreased hardness, suggesting changes in the gelation mechanism and a shift towards hydrogen bonding interactions. This pH-induced change led to enhanced oil-capturing and stabilizing properties at low temperatures.
[0124] Example 7 Addition of other raw materials To examine the effects on gel rigidity and texture, several types of starch and fiber were added at various concentrations. Figure 13 shows the loss coefficients of 4% pectin, 20% oil emulsion gels containing various fibers and starches. The addition of these fibers has a significant effect on gel rigidity, as seen in the decrease in the loss coefficient at room temperature. Potato starch showed the smallest decrease, followed by wheat fiber. Waxy corn starch showed the largest decrease in the loss coefficient at both low and high temperatures. Furthermore, with regard to the addition of wheat fiber, it can be seen that increasing the amount of fiber further reduces the loss coefficient. These results demonstrate that the addition of fibers and starch to emulsion gels can improve rigidity and thermal stability.
[0125] The addition of starch and fiber affects not only the stiffness but also the texture of the emulsion gel. The addition of these fibers significantly impacts hardness, tack force, and adhesive work. As seen in Table 10, the addition of starch and fiber yields similar trends to those observed in rheological tests. Potato starch shows the smallest change, followed by wheat fiber and waxy corn. These results indicate that the addition of fiber and starch can increase the tackiness of the gel, resulting in a much firmer texture overall.
[0126] [Table 10]
[0127] Example 8 Formulation and texture In this example, the recipes shown in Table 11 below were prepared.
[0128] [Table 11]
[0129] Six internal participants were recruited for the test. Samples were provided at ambient temperature and were not preheated.
[0130] The panelists were asked to check the appropriate characteristics (multiple selections allowed) to describe each sample. They also had to identify which of the three samples was the strongest and which was the weakest. Panelists were also asked to provide comments on characteristics not listed in the glossary.
[0131] Based on the data collected from the entire panel, we were able to draw the following conclusions.
[0132] [Table 12]
[0133] [Table 13]
[0134] Example 9 Recipes for meltable fillers and binders The following recipes were prepared as binders or fillers by hydrating pectin in a mixture of puree and water, as described in the Experiment section.
[0135] [Table 14]
[0136] Examples of food products having a meltable core are described herein. A soy protein gel was prepared by hydrating 20% soy protein in water for 15 minutes. The soy protein mixture was placed on a plastic film to form layers, then an emulsion gel filling (recipe disclosed in Table 14) was added to the center, the film was closed to form a small ball, which was then cooked in a steam oven. After cooking, the ball was opened and cut, allowing the liquid filling to drain out. The sample had the appearance of a burrata with a liquid core trapped within a solid shell. The sample could be heated without melting.
[0137] In another example, the recipes given for the fillings in Table 14 were placed in several hemispherical silicone molds and frozen overnight. The next day, the hemispheres were removed from the molds, assembled into a single sphere, coated with egg and breadcrumbs, and then deep-fried. This croquette successfully provided a liquid core when fried. The ball could also contain pieces of vegetables.
[0138] In another embodiment, a binder was prepared as disclosed in Table 14, then combined with the raw materials disclosed in Table 15 to form a moist dough, which was then shaped into croquettes and deep-fried in a frying pan. The croquettes maintained their shape even after being deep-fried and turned over, and the vegetable or TVP pieces did not fall off, confirming the binding properties of the pectin emulsion gel. Unlike the dry texture often found in plant-based meat substitutes, the croquettes exhibited an indulgent texture derived from the pectin.
[0139] [Table 15]
[0140] Example 10 A healthy spread with a high vegetable content.
[0141] [Table 16]
[0142] Using puree instead of water, an emulsion gel with a high puree content was prepared as described above. Since vegetables with a high pH (e.g., above pH 5) do not emulsify efficiently and may lead to oil separation as reported in the previous section, the pH was adjusted to 4.2 with vinegar to ensure the emulsion formulation was obtained.
[0143] The emulsion exhibited vibrant color, excellent stability, and a satisfying mouthfeel due to the pectin-based mouth coating. Samples prepared using only vegetables and oil felt oily but lacked strong mouth coating and satisfaction.
[0144] Example 11 Shelf life stability of vegetable spreads The recipes in Table 17 below were tested for healthy vegetable spreads.
[0145] [Table 17]
[0146] The spread was prepared as described in Example 10. The amount of acid was increased to ensure food safety. The emulsion was transferred to a glass jar, sealed, and retorted in a steam oven until the core temperature reached 95°C for 5 minutes.
[0147] The glass jars were stored for 6 months at either 4°C in a refrigerator or 25°C at room temperature. Stability was evaluated before and after heat treatment, and at 2 weeks, 1 month, 1.5 months, 2 months, 3 months, and 6 months later. The stability of the gel was investigated by a shelf-life test using the method described below. A rheological measurement method that modulates the frequency and monitors the storage modulus and loss modulus for both samples stored at 4°C and samples stored at 20°C (Figures 18A and 18B). A rheological measurement method that monitors the storage modulus and loss modulus for both samples stored at 4°C and samples stored at 20°C by adjusting the amplitude (Figures 19A and 19B). Viscosity for both samples stored at 4°C and samples stored at 20°C (Figures 20A and 20B) Texture analysis (Figures 21A, 21B, 22A, 22B) Tribology (Figures 23A and 23B) Oil bonding (Figure 24) Oil oxidation (Figure 25)
[0148] Overall, the samples showed little change in these properties immediately after manufacturing and after heat treatment, with only slight decreases in viscosity and gel strength. No further deviations were observed up to 6 months when stored at room temperature.
[0149] The oil droplet size in the carrot puree was measured immediately after heat treatment and at the shelf life of 2 months or 6 months at room temperature (25°C) or 4°C. Immediately after heat treatment, the oil droplet size was approximately 10 μm (Figure 26), showed little development during the first 2 months, and increased slightly at 6 months (Figures 27A and 27B). On the other hand, the sample stored at room temperature showed a greater increase in oil droplet size, reaching a visible size of approximately 15 μm, even at 2 months (Figures 28A and 28B). However, the average oil droplet size of the sample stored at room temperature was still less than 20 μm even after 6 months. As discussed in Example 3 above, the pectin-based emulsion according to the present invention enables an emulsion that can maintain good stability even after 6 months under room temperature conditions.
[0150] [Table 18]
[0151] Example 12 Pectin emulsion gels, and their effects on flavor and texture perception. The functional properties of acidified pectin emulsion gels were evaluated using the recipes in Table 19 below.
[0152] [Table 19]
[0153] A panel of 10 people was trained on the product categories and various characteristics listed in Table 20.
[0154] [Table 20]
[0155] The samples were stored in a refrigerator and tasted at ambient temperature.
[0156] Samples prepared using oil but without pectin showed phase separation, with the oil layer clearly visible at the top.
[0157] As shown in Figure 29A, the addition of pectin significantly affected the texture of the recipe by increasing viscosity, stickiness, and mouth coating compared to carrot puree (R4 and R5 compared to R1, R2, and R3). However, the pectin emulsion gel offered further benefits in reducing the perception of astringency and bitterness compared to puree thickened with pectin alone (R4 and R5, Figures 29A and 29B). The addition of curry spices did not affect the texture properties of the emulsion gel recipe (Figure 29B).
[0158] The addition of pectin reduced the perception of overall flavor, including lactic acid-induced bitterness and vegetable flavors. The emulsion gel sample (R5) was perceived as slightly less acidic than the acidified puree, but the difference was not statistically significant (Figure 30A). The addition of pectin to the curry-flavored puree (R7) increased both the perceived spiciness and bitterness, whereas the pectin emulsion gel maintained a strong curry flavor while exhibiting significantly less bitterness (Figure 30B). Grouping of all products revealed that, unlike the acidified puree, the pectin sample was not described as having acidity (Figure 31). This demonstrates the benefit of pectin emulsion gel in masking off-flavors.
[0159] Example 13 Recipes for frozen desserts Pectin emulsion gels can also be formulated using fruit puree. An example recipe is shown in Table 21. The emulsion gels were prepared as described in the previous example and then frozen. The frozen desserts were freshly prepared using a Pacojet. The pectin used in this example was a citrus-derived high-methoxyl pectin with a degree of methoxylation of approximately 70%.
[0160] [Table 21]
[0161] Recipe D was perceived as glossy, fruity, fatty, rich, and hearty.
[0162] Recipe E was airy and had a satisfying texture. Recipe E can be used as a coating.
[0163] Recipes F and G exhibited a wonderfully satisfying texture and a strong fruity flavor. Coconut fat provided a more airy texture than sunflower oil and was preferred over all other recipes.
[0164] Example 14 Baby puree To improve stability and texture, a baby puree was prepared from pectin emulsion gel. The pectin used in this example was a high-methoxyl pectin derived from citrus fruits with a degree of methoxylation of approximately 70%. A low pectin concentration was preferred in the formulation to adjust the texture to a satisfying puree. The recipe is summarized in Table 22.
[0165] [Table 22]
[0166] The emulsion gel was prepared as described above, then the sample was heated at 90°C for 5 minutes, filled into a glass jar, closed, and inverted for 90 seconds to ensure storage stability.
[0167] Two weeks after heat treatment, the samples were evaluated for color and viscosity.
[0168] The color results are shown in Table 23. The color difference of the heat-treated puree is shown compared to the untreated puree. A color difference is perceptible when the ΔE value is greater than 4, and a higher ΔE value indicates a greater color difference. The reference carrot puree was more strongly affected by heat treatment (ΔE > 12) compared to the emulsion recipe (ΔE > 8). Lower oil content resulted in less impact on color.
[0169] [Table 23]
[0170] The reference carrot puree clearly formed two phases after heat treatment, while the Emulgel puree remained homogeneous. As shown in Table 24, immediately after heat treatment, the viscosity decreased slightly and remained stable for three weeks. This demonstrates that the Emulgel puree is superior to the baby food puree in terms of stability.
[0171] [Table 24]
[0172] Example 15 A healthy, satisfying, and spicy cooking sauce. The cooking sauces were prepared according to the recipes disclosed in Table 25.
[0173] [Table 25]
[0174] Emulsion gels with a high puree content were prepared as described above by adjusting the pH to approximately 3.5 using lactic acid. The spice mixes used in each recipe are disclosed in Table 26.
[0175] [Table 26]
[0176] The products obtained from these recipes had lower viscosity than the dip given in Example 10. The products were less sticky and less mouth-coating. The mouthfeel was rich and satisfying, and the spices were perceived for a long time in the mouth. The texture and viscosity were similar to barbecue sauce or ketchup.
[0177] Example 15 Process influence on oil droplet size and emulsion stability To evaluate the effect of process parameters, the following recipe (Table 27) was prepared.
[0178] [Table 27]
[0179] The sample was prepared as described above, with only minor modifications. In C1, pectin was hydrated at room temperature (25°C), then a CaCl2 1M solution was added to reach a final concentration of 5 mM; and finally, emulsification was carried out at 25°C. In C2, pectin was hydrated at 50°C and emulsified at 75°C; after emulsification, CaCl2 solution was added.
[0180] Samples C1 and C2 exhibited different viscoelastic properties, as shown in Figure 32. The low-temperature emulsified sample (C1) exhibited weak gel-like behavior, while C2 exhibited viscoelastic fluid-like behavior. Such a large difference in rheological properties was not expected from a simple change in emulsification temperature. The oil droplet size was compared for both samples. The high-temperature emulsified sample (C2) provided oil droplet sizes of less than 20 μm, while the sample emulsified at 25°C (C1) provided larger oil droplet dimensions of approximately 25 μm (Figures 33A and 33B). High-temperature emulsification reduces the viscosity of the pectin continuous phase and the oil phase, resulting in smaller oil droplets that disperse more easily under shear and have a significant impact on material properties.
[0181] Example 16 Emulgel puree acidity masking In this embodiment, the following recipe (Table 28) was prepared as described above.
[0182] [Table 28]
[0183] All products have the same acidity (target pH 4.2).
[0184] A panel of nine participants was trained on product categories and acidity. Panelists were asked to rate the acidity on a linear scale from 0 (no acidity) to 10 (maximum acidity). The products were consumed in a random order at room temperature (20°C) under red light.
[0185] The scores are shown in Figure 34. * This indicates products that are significantly different from product D03 (lower score) and have ANOVA significance in the 1%. **This indicates a product that is significantly different from products D02 and D01, with ANOVA significance at 1%.
[0186] Sample D01 was the most acidic (score 7.1), while both emulsion gel samples were significantly less acidic (scores D02 4.4 and D03 2.1). D03 was significantly less acidic than D02.
[0187] Given a pH of 4.2, increasing the amounts of pectin and sunflower oil significantly reduces the perceived sourness in sensory evaluation.
[0188] This Example 16 demonstrates that the pectin-based emulsion according to the present invention provides a significant acidity masking effect.
Claims
1. A pectin-based emulsion comprising 0.5 to 6% by weight of pectin, 3 to 40% by weight of oil, and water, wherein the emulsion has a pH of less than 5, the average oil droplet size in the emulsion is less than 20 μm, and the pectin is high-methoxyl pectin with a methoxyl degree (DM) > 60.
2. The pectin-based emulsion according to claim 1, wherein the emulsion has a pH of less than 4.5, preferably less than 4.2, and more preferably about 3.
5.
3. The pectin-based emulsion according to claim 1 or 2, wherein the emulsion comprises about 1.5 to 2.0% by weight of pectin and about 10 to 15% by weight of oil.
4. The pectin-based emulsion according to any one of claims 1 to 3, wherein the pectin is a high-methoxyl pectin having a DM of 70.
5. The pectin-based emulsion according to any one of claims 1 to 4, wherein the emulsion further comprises fruit powder, vegetable powder, such as soy flour, refined fiber, or refined starch.
6. The pectin-based emulsion according to any one of claims 1 to 5, wherein the water is deionized water, tap water, or mineral water.
7. The pectin-based emulsion according to any one of claims 1 to 6, wherein the water is replaced by a puree, for example, a vegetable puree, or a fruit puree, or a bean puree.
8. The pectin-based emulsion according to any one of claims 1 to 7, wherein the pectin is citrus pectin, beet pectin, apple pectin, or amidated pectin.
9. The pectin-based emulsion according to any one of claims 1 to 8, wherein the pectin is citrus pectin.
10. A method for producing a pectin-based emulsion according to any one of claims 1 to 9, comprising the steps of: heating pectin in water to at least 50°C; adding oil; and high-shear mixing for about 5 minutes.
11. The method according to claim 10, wherein the high-shear mixing step is carried out while heating the mixture of pectin and oil to at least 50°C, preferably about 75°C.
12. The method according to claim 10 or 11, wherein the high-shear mixing step is performed at a rotational speed of 100 to 2000 RPM.
13. The method according to any one of claims 10 to 12, further comprising adjusting the pH of the pectin-based emulsion to less than pH 5, preferably less than pH 4.5, more preferably less than pH 4.2, and more preferably about pH 3.
5.
14. The method according to any one of claims 10 to 13, further comprising the step of adding polyvalent ions, preferably calcium ions, to the pectin-based emulsion after performing the high-shear mixing so that the final concentration of polyvalent ions in the pectin-based emulsion reaches a maximum of 80 mM, preferably 5 to 40 mM.
15. Use of a pectin-based emulsion according to any one of claims 1 to 9, wherein the emulsion is a. Binding agent, b. filling, c. Flavoring carriers, d. fat substitute, e. Spreadable products, f. Puree, g. Dip, h. Toppings, or i. frozen dessert It is used.